CN106946234A - A kind of preparation method of HAS - Google Patents
A kind of preparation method of HAS Download PDFInfo
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- CN106946234A CN106946234A CN201710138089.1A CN201710138089A CN106946234A CN 106946234 A CN106946234 A CN 106946234A CN 201710138089 A CN201710138089 A CN 201710138089A CN 106946234 A CN106946234 A CN 106946234A
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- Prior art keywords
- reactive distillation
- preparation
- ketoxime
- sulfuric acid
- distillation system
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to chemical field, it is related to a kind of preparation method of HAS.Described preparation method is, using sulfuric acid and ketoxime as raw material, to prepare HAS in reactive distillation system, comprise the following steps：(1) sulfuric acid solution and ketoxime are added in reactive distillation system and carry out reactive distillation；(2) distillate distillated is produced successively from reactive distillation system tower top, it is synchronous to carry out crystallization filter operation when HAS concentration reaches 2~8.5mol/L in reaction solution；(3) reaction solution is further cooled, carries out crystallization filtering.HAS is prepared with the method for the present invention, energy consumption can be greatly reduced, and the zero-emission of technique waste water can be realized.
Description
Technical field
The invention belongs to chemical field, it is related to a kind of preparation method of HAS.
Background technology
HAS is that one kind has the extensive chemical products of purposes, is helped available for synthetic pesticide raw material, medical material, rubber
Agent raw material, natural rubber stabilizer, metal conditioner, fiber modification agent, developer, reducing agent and polyalcohol catalyst etc..
The preparation method of traditional HAS mainly has nitromethane method, natural gas (methane) nitrification process, nitric oxide
Reducing process, disulfonic acid ammonium salt hydrolysis method etc..But nitromethane method product yield is low, by-product species are more, and separation equipment investment is big；
Though disulfonic acid ammonium salt hydrolysis method production technology is ripe, integrated mill's production is suitable only for, cost of investment is big；Remaining method is then equal
There is technological process length, unstable product quality, post processing trouble, the low problem of yield.
The problem of existing for above conventional method, Chinese patent application CN 200910096601.6 discloses a kind of hydroxyl
The preparation method of amine salt, it is that in rectifying column, ketoxime is hydrolyzed to reaction generation hydroxylamine salt and ketone in an acidic solution, from
The ketone of rectifying column tower top output is discharged in time, and specific preparation process is:The mol ratio of ketoxime and inorganic acid is 1:0.4~3, point
Ketoxime and inorganic acid are not taken；Ketoxime and inorganic acid aqueous solution in above-mentioned steps is fed in the middle part of rectifying column, and Decompression Controlling
Tower temperature in the kettle is 40~100 DEG C, and overhead reflux ratio is 1~6；When being distillated to tower top without ketone, cooling kettle liquid crystallization, filtering is washed
Wash, be dried to obtain hydroxylamine salt solid.
Chinese patent application CN 201310097499.8 is done on the basis of method disclosed in CN 200910096601.6
Further improvement, has carried out the backflow in tower reactor on the basis of adjusting process parameter.
Although above-mentioned two pieces Chinese patent application all discloses the method that HAS is prepared by reactive distillation, whole
The sour oxime of individual preparation process causes the waste of raw material than larger, reactant excessive acid, and steaming water consumption is all larger, also needs
Cooling carries out the crystallization of HAS, and rectifying and crystallization process energy consumption are higher.
The content of the invention
It is an object of the invention to provide a kind of method that reactive distillation by ketoxime and sulfuric acid prepares HAS, with big
Width reduces energy consumption of rectification, and realizes the zero-emission of technique waste water.
In order to achieve this, in the embodiment on basis, the present invention provides a kind of preparation method of HAS, and it is
Sulfuric acid and ketoxime are prepared into HAS in reactive distillation system, comprised the following steps：
(1) sulfuric acid solution and ketoxime are added in reactive distillation system and carry out reactive distillation；
(2) distillate distillated is produced successively from reactive distillation system tower top, when HAS concentration reaches in reaction solution
It is synchronous to carry out crystallization filter operation during to 2~8.5mol/L；
(3) reaction solution is further cooled, carries out crystallization filtering.
In a preferred embodiment, the present invention provides a kind of preparation method of HAS, wherein in step (1)
The mass percent concentration of described sulfuric acid solution is 50~65%.
In a preferred embodiment, the present invention provides a kind of preparation method of HAS, wherein institute in rapid (1)
The ketoxime stated is the mixed liquor of acetoxime, diacetylmonoxime or two kinds of oximes.
In a preferred embodiment, the present invention provides a kind of preparation method of HAS, wherein in step (1)
Ketoxime is (0.31~0.76) with the mol ratio of the water in sulfuric acid solution:1.
In a preferred embodiment, the present invention provides a kind of preparation method of HAS, wherein in step (1)
Ketoxime is (0.31~0.55) with the mol ratio of the water in sulfuric acid solution:1.
In a preferred embodiment, the present invention provides a kind of preparation method of HAS, wherein in step (1)
Described sulfuric acid and the mol ratio of ketoxime are (0.45~0.6):1.
In a preferred embodiment, the present invention provides a kind of preparation method of HAS, wherein in step (1)
Described sulfuric acid and the mol ratio of ketoxime are (0.5~0.6):1.
In a preferred embodiment, the present invention provides a kind of preparation method of HAS, wherein in step (1)
The absolute pressure of reactive distillation system is 0.02~0.1MPa.
In a preferred embodiment, the present invention provides a kind of preparation method of HAS, wherein in step (1)
The bottom temperature of reactive distillation system is 40~90 DEG C.
In a preferred embodiment, the present invention provides a kind of preparation method of HAS, wherein in step (1)
The overhead reflux ratio of reactive distillation system is 0~6.
In a preferred embodiment, the present invention provides a kind of preparation method of HAS, wherein in step (2)
Filtered solution after crystallizing filtration treatment is transmitted back into reactive distillation system to be utilized, or added in the lump in next reactive distillation
The reactive distillation operation of step (1) is carried out in reactive distillation system.
In a preferred embodiment, the present invention provides a kind of preparation method of HAS, wherein to step
(2), HAS crystal obtained by step (3) further washed, drying process.
The various advantages of the preparation method of the present invention include：
1) ketoxime is hydrolyzed, reaction rectification and reaction-crystallization efficient coupling, by time by ketone and HAS crystal
Continuous in-situ is removed, and improves ketoxime conversion ratio and HAS yield (HAS single yield >=90%)；Adjust simultaneously
Reflux ratio reduces distillating for ketoxime, increases raw material availability, therefore technique has very high economy；
2) initial concentration for adding acid is higher, water content is reduced, so as to reduce energy consumption of rectification and discharge of wastewater；
3) to have in time cool after crystal precipitation in reactive distillation processes and promote to crystallize and filter the crystal of precipitation, to avoid
Reaction system influences mass transfer and heat transfer because viscosity is too high, prevents hot-spot, it is to avoid side reaction occurs, it is ensured that HAS
Product quality；
4) reusable edible crystallization filtered solution, improves HAS total recovery；
5) accessory substance ketone by simple process can reuse prepare ketoxime, it is environment-friendly；
6) filtering gained crystal obtains the HAS solid product of high-quality after washing, drying, and its purity is high, production
Quality is stable.
Brief description of the drawings
Fig. 1 is the schematic diagram for the reaction unit for realizing the preparation method of the present invention.
Embodiment
The embodiment to the present invention is further illustrated with reference to embodiments.
The method of example 1 below -6 is implemented in the device shown in Fig. 1, wherein 1 is ketoxime charging aperture, 2 be sulfuric acid
Charging aperture, 3 be rectifying column, and 4 be overhead condenser, and 5 is connect vacuum pumping hole, and 6 be tower bottom of rectifying tower, and 7 be condenser, and 8 be filtering
Device.
Embodiment 1：
By diacetylmonoxime, 50wt% aqueous sulfuric acids according to diacetylmonoxime and H2SO4Mol ratio is 1:0.5 (diacetylmonoxime and sulfuric acid water
The mol ratio of solution reclaimed water is 0.367:1) 435.6g, 490g are weighed respectively, and addition carries out reactive distillation into reactor, controls
Tower reactor reactive distillation system pressure is 0.028~0.055MPa, and bottom temperature is 80~85 DEG C, and overhead reflux ratio is 0~6, and
When the butanone that distillates rectifying column tower top remove.Reactive distillation after four hours regular (for example per hour) from tower reactor sample once,
Titration determination wherein sulfuric acid and HAS concentration.After reaction seven hours, reaction solution is turned when HAS concentration is 5mol/L
Enter crystallizing tank to be crystallized.Filtering is crystallized twice, and it is 99.65% to determine crystal purity.Crystal and crystal filtered solution are common after measured
Containing 374.47g HASs, thus calculated yield is 91.25%.
Embodiment 2：
By diacetylmonoxime, 55wt% aqueous sulfuric acids according to diacetylmonoxime and H2SO4Mol ratio is 1:0.5 (diacetylmonoxime and sulfuric acid water
The mol ratio of solution reclaimed water is 0.449:1) 348.48g, 356.36g are weighed respectively, and addition carries out reactive distillation into reactor,
Control tower reactor reactive distillation system pressure be 0.030~0.055MPa, bottom temperature be 80~85 DEG C, overhead reflux ratio be 0~
6, the butanone in time distillating rectifying column tower top is removed.Reactive distillation after four hours regular (for example per hour) from tower reactor sampling one
It is secondary, titration determination wherein sulfuric acid and HAS concentration.After reaction seven hours, by reactant when HAS concentration is 5mol/L
It is that temperature is reduced to 50 DEG C and reaction solution is transferred into crystallizing tank and crystallized.Primary crystallization is filtered, determining crystal purity is
99.13%.Crystal and crystal filtered solution contain 303.09g HASs altogether after measured, and thus calculated yield is 92.32%.
Embodiment 3：
By diacetylmonoxime, 60wt% aqueous sulfuric acids according to diacetylmonoxime and H2SO4Mol ratio is 1:0.5 (diacetylmonoxime and sulfuric acid water
The mol ratio of solution reclaimed water is 0.551:1) 435.6g, 408.33g are weighed respectively, and addition carries out reactive distillation into reactor,
Control tower reactor reactive distillation system pressure be 0.025~0.055MPa, bottom temperature be 80~90 DEG C, overhead reflux ratio be 0~
6, the butanone in time distillating rectifying column tower top is removed.Reactive distillation after four hours regular (for example per hour) from tower reactor sampling one
It is secondary, titration determination wherein sulfuric acid and HAS concentration.After reaction seven hours, by reaction solution when HAS concentration is 4mol/L
Crystallizing tank is transferred to be crystallized.Filtering is crystallized twice, and it is 99.13% to determine crystal purity.Crystal and crystal filtered solution are after measured
Contain 377.34g HASs altogether, thus calculated yield is 91.95%.
Embodiment 4：
By diacetylmonoxime, 55wt% aqueous sulfuric acids according to diacetylmonoxime and H2SO4Mol ratio is 1:0.6 (diacetylmonoxime and sulfuric acid water
The mol ratio of solution reclaimed water is 0.374:1) 87.12g, 106.99g are weighed respectively, and addition carries out reactive distillation into reactor,
Control tower reactor reactive distillation system pressure be 0.025~0.040MPa, bottom temperature be 80~90 DEG C, overhead reflux ratio be 0~
6, the butanone in time distillating rectifying column tower top is removed.Reactive distillation after four hours regular (for example per hour) from tower reactor sampling one
It is secondary, titration determination wherein sulfuric acid and HAS concentration.After reaction seven hours, by reactant when HAS concentration is 2mol/L
It is that temperature is reduced to 50 DEG C and reaction solution is transferred into crystallizing tank and crystallized.Primary crystallization is filtered, determining crystal purity is
99.27%.Crystal and crystal filtered solution contain 74.77g HASs altogether after measured, and thus calculated yield is 91.10%.
Embodiment 5：
By acetoxime, 50wt% aqueous sulfuric acids according to acetoxime and H2SO4Mol ratio is 1:0.59 (acetoxime and sulfuric acid
The mol ratio of aqueous solution reclaimed water is 0.311:1) 84.74g, 134.08g are weighed respectively, add and reaction essence is carried out into reactor
Evaporate, it is 0.022~0.040MPa to control tower reactor reactive distillation system pressure, bottom temperature is 70~85 DEG C, and overhead reflux ratio is 0
~6, the acetone in time distillating rectifying column tower top is removed.Reactive distillation after four hours regular (for example per hour) from tower reactor sample
Once, titration determination wherein sulfuric acid and HAS concentration., will reaction when HAS concentration is 5mol/L after reaction seven hours
Liquid is transferred to crystallizing tank and crystallized.Filtering is crystallized twice, and it is 99.08% to determine crystal purity.Crystal and crystal filtered solution are through surveying
Contain 86.20g HASs altogether calmly, thus calculated yield is 90.59%.
Water consumption is steamed to above-mentioned 5 embodiment distillation processes to calculate, surplus water is theoretical calculation base using in solution
Plinth, often produces the steaming water consumption of 1kg HASs in the range of 8~893KJ, more conventional production method significantly reduces energy
Consumption.
Above-described embodiment is for example, the present invention can also be with other ad hoc fashions or others to the present invention
Particular form is implemented, without departing from idea of the invention or substantive characteristics.Therefore, from the point of view of the embodiment of description is in terms of any
It is regarded as illustrative and non-limiting.The scope of the present invention should illustrate by appended claims, any and claim
Intention and the equivalent change of scope also should be within the scope of the present invention.
Claims (9)
1. a kind of preparation method of HAS, it is that sulfuric acid and ketoxime are prepared into HAS in reactive distillation system, is wrapped
Include following steps：
(1) sulfuric acid solution and ketoxime are added in reactive distillation system and carry out reactive distillation；
(2) distillate is produced from reactive distillation system tower top, 2 are reached when the HAS concentration in reactive distillation tower reactor~
It is synchronous to carry out crystallization filter operation during 8.5mol/L；
(3) reaction solution is further cooled, carries out crystallization filtering.
2. preparation method according to claim 1, it is characterised in that：The quality hundred of sulfuric acid solution described in step (1)
It is 50~65% to divide specific concentration.
3. preparation method according to claim 1, it is characterised in that：Ketoxime described in step (1) is acetoxime, butanone
The mixed liquor of oxime or two kinds of oximes.
4. preparation method according to claim 1, it is characterised in that：Ketoxime and the water in sulfuric acid solution in step (1)
Mol ratio is (0.31~0.76):1.
5. preparation method according to claim 1, it is characterised in that：Mole of sulfuric acid and ketoxime described in step (1)
Than for (0.45~0.6):1.
6. preparation method according to claim 1, it is characterised in that：The absolute pressure of reactive distillation system in step (1)
For 0.02~0.1MPa.
7. preparation method according to claim 1, it is characterised in that：The bottom temperature of reactive distillation system in step (1)
For 40~90 DEG C.
8. preparation method according to claim 1, it is characterised in that：The overhead reflux of reactive distillation system in step (1)
Than for 0~6.
9. preparation method according to claim 1, it is characterised in that：By the filtration after crystallizing filtration treatment in step (2)
Liquid adds in reactive distillation system the reactive distillation operation for carrying out step (1) in the lump in next reactive distillation.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710138089.1A CN106946234B (en) | 2017-03-09 | 2017-03-09 | A kind of preparation method of hydroxyl sulfate |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710138089.1A CN106946234B (en) | 2017-03-09 | 2017-03-09 | A kind of preparation method of hydroxyl sulfate |
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| CN106946234A true CN106946234A (en) | 2017-07-14 |
| CN106946234B CN106946234B (en) | 2019-07-30 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107539966A (en) * | 2017-09-29 | 2018-01-05 | 江苏艾科维科技有限公司 | The preparation method of HAS |
| CN109250694A (en) * | 2018-08-24 | 2019-01-22 | 北京化工大学 | A method of hydroxylamine hydrochloride is prepared using hydrogen chloride dry gas |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080193362A1 (en) * | 2003-08-13 | 2008-08-14 | Takanori Aoki | Process for Producing Hydroxylamine |
| 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 |
-
2017
- 2017-03-09 CN CN201710138089.1A patent/CN106946234B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080193362A1 (en) * | 2003-08-13 | 2008-08-14 | Takanori Aoki | Process for Producing Hydroxylamine |
| 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107539966A (en) * | 2017-09-29 | 2018-01-05 | 江苏艾科维科技有限公司 | The preparation method of HAS |
| CN109250694A (en) * | 2018-08-24 | 2019-01-22 | 北京化工大学 | A method of hydroxylamine hydrochloride is prepared using hydrogen chloride dry gas |
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| CN106946234B (en) | 2019-07-30 |
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