CN107539966A - The preparation method of HAS - Google Patents
The preparation method of HAS Download PDFInfo
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- CN107539966A CN107539966A CN201710912030.3A CN201710912030A CN107539966A CN 107539966 A CN107539966 A CN 107539966A CN 201710912030 A CN201710912030 A CN 201710912030A CN 107539966 A CN107539966 A CN 107539966A
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Abstract
The invention discloses a kind of preparation method of HAS, comprise the following steps：1) enter after, being well mixed as the acid solution of raw material and oxime in reactive distillation column and carry out rectifying, tower reactor obtains the mixed solution of HAS and unreacted oxime and acid；2) mixed solution obtained by tower reactor, is delivered to stripper with pump portion and carries out stripping removing organic matter and partial moisture, is partly delivered in the reactor equipped with catalyst and is further reacted；The liquid material of reaction gained is back to the tower reactor of rectifying column, and gas phase is back to rectifying column middle and upper part；3), by crystallization, solid-liquor separation, drying, HAS is obtained from HAS solution after the concentration of stripper tower reactor outflow.
Description
Technical field
The present invention relates to the preparation method of chemical field, particularly HAS.
Background technology
HAS is a kind of very extensive chemical products of purposes, available for synthetic pesticide raw material, medical material, rubber
Auxiliary agent raw material, natural rubber stabilizer, metal conditioner, fiber modification agent, developer, reducing agent and polyalcohol catalyst
Deng.The preparation method of traditional HAS mainly has nitromethane method, acetoxime method, nitric oxide reduction method, disulfonic acid ammonium
Salt solution solution etc..
Prepared by nitromethane need to use toxic articles dimethyl suflfate, and when hydrolysis prepares azanol, accessory substance is a hypertoxic oxygen
Change carbon；During hydrolysis, alkane and other materials are in two-phase in reaction system, and have sharp interface, and due to hydro carbons, to be in interface anti-
Should, so speed is low, reaction time length, total recovery is 75% or so.
Traditional acetoxime method, first reacted with natrium nitrosum, sodium pyrosulfite, after sulfuric acid acidifying, generate azanol disulfonic acid
Salt, then reacted with acetone, then azanol is prepared with sour water solution, yield only has 60%, therefore process route complexity, technological process be present
Long, production cost is high, and raw material dosage is high, and azanol per ton needs 6 tons of sodium sulfites and a large amount of acetone, and three wastes discharge amount is big, product matter
Measure the shortcomings of unstable.
Nitric oxide reduction method is to mix ammonia, oxygen and water vapour with certain volume ratio, is preheating to certain temperature, is passed through
Carries out oxidation reaction on the rhodium catalyst of platinum one in reactor, can obtain nitric oxide after processing, then by nitric oxide and hydrogen
Mixing, imports in the sulfuric acid containing platinum catalyst and reacts to obtain HAS, yield 70% or so, and this process equipment requires higher,
Expensive catalyst, vent gas treatment are difficult.
Though disulfonic acid ammonium salt hydrolysis method production technology is ripe, integrated mill's production is suitable only for, cost of investment is big, and
The product arrived is the mixture of ammonium sulfate and HAS, and it is extremely difficult to isolate commerical grade solid sulphuric acid azanol product.
The problem of existing for above conventional method, Chinese patent application CN 200910096601.6 disclose a kind of hydroxyl
The preparation method of amine salt, it is in rectifying column, and 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 in above-mentioned steps and inorganic acid aqueous solution are 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, wash
Wash, be dried to obtain hydroxylamine salt solid.
Chinese patent application CN201310097499.8 enters on the basis of CN200910096601.6 discloses method
The improvement of one step, the backflow in tower reactor is carried out on the basis of adjusting process parameter.Specially：
The first step：Oxime (C=NOH) in molar ratio:Sour (H) is 1:(1~1.3), appropriate acid solution and oxime are got out, acid
The mass fraction of solution is (10%~35%)；
Second step：The ready solution of the first step is added into rectifying column, control rectifying column absolute pressure 0.095~
0.1MPa and bottom temperature are to be distilled at 20~130 DEG C, and it is 0~4 to control tower top reflux ratio, timely separate fraction, control
Tower reactor reflux ratio is 0~100, cyclic part kettle liquid, and circulation fluid entrance can be in feed position with height or upper-lower position, extraction
Tower bottom product；
3rd step：Product is concentrated, crystallized, being filtered, is dried to obtain the solid hydroxylamine salt of high-quality.
Ketoxime is acetoxime, diacetylmonoxime, cyclohexanone oxime, methyl isobutyl ketoxime.Acid is hydrochloric acid, sulfuric acid or phosphoric acid.
The chemical reaction process of oxime hydrolysis Sulphuric acid azanol is really carried out in two steps：
1. oxime hydrolyzes to form azanol and corresponding ketone in the presence of acid catalyst, the reaction is reversible reaction；
2. azanol further combines to form hydroxylamine salt with inorganic acid；
Specific reaction equation is as follows：
Chemical equation after merging is：
The method for promoting balance to move right is typically that ketone is removed into reaction system in time, as above-mentioned Chinese patent is retouched
The rectifying mode for the use stated removes ketone from tower top.The inorganic-liquid in equimolar (oxime and hydrogen ion equimolar amounts) course of reaction
On the one hand body acid is catalyst, while be also reaction raw materials, and the azanol ultimately produced will combine to form HAS with sulfuric acid.Body
Sulfuric acid in system is gradually consumed, oxime hydrolysis influenceed finally also to be up to balance by catalytic amount, will have part oxime with
Acid can not be reacted completely, and a part of sulfuric acid (free acid) will be remained in kettle liquid.
The patents such as Chinese patent application CN201310097499.8, CN200910096601.6 and CN201710138089.1
Liquid mineral acid (hydrochloric acid, sulfuric acid or phosphoric acid) hydrogen ion mole and ketoxime mole ratio is used to be more than 1 to promote to react,
Excessive inorganic acid in reactive distillation tower bottoms be present.Although the filtrate obtained after Crystallization Separation can return to reaction system
System, wastage of material is there is theoretically no, but because the inorganic acid of excess is present, on the one hand can increase equipment selection difficulty, separately
On the one hand the free acid containing high content in the HAS that crystallizes out can be caused, the free acid of high content in solid sulphuric acid azanol
A series of adverse consequences can be caused：
1) high contents free acid can not be removed in the drying process, while can also cause moisture high, and final product is deposited
It is particularly easy to lump during storage, is unfavorable for the safe handling of downstream client；
2) high contents free acid requires higher to equipment material, it is easy to causes equipment corrosion；
3) high contents free acid can make product quality be badly damaged, and almost deteriorate all-mass index.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of method is simple, technological process is short, and product quality is stable, production
The low HAS preparation method of cost.
In order to solve the above-mentioned technical problem, the present invention provides a kind of preparation method of HAS, comprises the following steps：
1), according to H+：C=NOH is 1:1~1.3 mol ratio, it is laggard using being well mixed as the acid solution of raw material and oxime
Enter in reactive distillation column (reactive distillation column for carrying reboiler), control reactive distillation column is in 5~100KPa of absolute pressure and tower reactor temperature
Rectifying is carried out at 50~110 DEG C of degree, it is 0.5~5 to control tower top reflux ratio, and separation (separation in time) cut, tower reactor obtains sulfuric acid
The mixed solution of azanol and unreacted oxime and acid；The distillate on kettle top is ketone, and the ketone of gained is reclaimed；
Sour mass concentration is 8~42% in the acid solution as raw material；
Explanation：Reboiler is mainly to provide energy and partial material is vaporized and (undergone phase transition, no temperature change)；
2) mixed solution obtained by tower reactor, is delivered to stripper with pump portion and carries out stripping removing organic matter and part water
Divide (so as to realize concentration), be partly delivered in the reactor equipped with catalyst and further reacted, it is described to be delivered to stripping
The mixed solution of tower：It is delivered to mixed solution=1 of reactor:1~20 volume ratio；
Reaction temperature in reactor is higher than the bottom temperature of rectifying column 0.5~15 DEG C, the filling of catalyst reactor
The mass ratio of amount and raw material diacetylmonoxime sample size hourly is 0.1~10：1；The liquid material of reaction gained is back to rectifying
The tower reactor of tower, gas phase are back to rectifying column middle and upper part；
Explanation：
The input and output of reactive distillation column are conservation of mass relation；
In the present invention, the mixed solution of reactor is delivered to by control and is delivered to the body of the mixed solution of stripper
Product ratio, to adjust reaction time of the mixed solution in reactor；
Caused liquid material is in addition to hydroxylamine salt after above-mentioned reactor reaction, in addition to water, a small amount of sulfuric acid and fourth
Ketoxime, liquid material are back to the tower reactor of rectifying tower reactor；After reactor reaction caused gas phase include vaporization caused by water vapour,
Diacetylmonoxime and the butanone of reaction generation；Reaction pressure in reactor is typically about 5~200Kpa of absolute pressure；
The temperature of stripper is 85~90 DEG C, and pressure of stripping tower is about 20~30Kpa；
3), from stripper tower reactor outflow concentration after HAS solution by crystallization, solid-liquor separation (including centrifugation point
From)；
Solid obtained by the solid-liquor separation obtains HAS (HAS of high-quality) through drying.
Improvement as the preparation method of the HAS of the present invention：Liquid caused by the step 3) solid-liquor separation returns
It is back to rectifying column.
Explanation：The composition of the liquid is hydroxylamine sulfate solution and a small amount of free acid；Its return rectifying column middle and lower part or
Tower reactor, usually it is back to rectifying tower reactor.
Further improvement as the preparation method of the HAS of the present invention：The catalyst is that acid ion exchanges tree
At least one of fat or silicon dioxide carried sulfuric acid (that is, one or two kinds of mixtures)；
The silicon dioxide carried sulfuric acid, the load capacity of sulfuric acid is 5%~36% (weight %).
Further improvement as the preparation method of the HAS of the present invention：The acid as raw material is sulfuric acid, or
The mixed solution of sulfuric acid and HAS；The oxime as raw material is acetoxime, diacetylmonoxime.
In the present invention,
Acid-exchange resin can be obtained by conventional mode purchased in market, and for example, the production of Britain Piao Laite companies is strong
Acid cation exchange resin C100 × 10, Anhui Province east resin Science and Technology Ltd. or Zhejiang Province Zhengguan Industry Co., Ltd
D001 large hole strong acid styrene system cation exchange resins etc. production of units etc..
Silicon dioxide carried sulfuric acid can be prepared by following conventional method：
From the chromatographic silica gel of 20~400 mesh, by 200 DEG C of calcination process, after being cooled to room temperature, hot concentrated sulfuric acid is added
Immersion 5~10 minutes, place naturally and be cooled to room temperature.It is isolated by filtration the unnecessary concentrated sulfuric acid, then with distilled water flushing Silica Surface
Attachment acid, decompressing and extracting moisture, dries, obtains the support type SiO 2 catalyst of sulfur acid 5%~36%.
Raw material acid (pressing H+ densimeters) and the control of the mol ratio of oxime (C=NOH) are 1:(1~1.3).
Reactor carries heating function, and material (mixed solution obtained by tower reactor) is heated up so as to realize, or,
Heater is installed before reactor additional, so as to realize the heating to material.
Compared with prior art, the technology of the present invention has following technical advantage：
It is higher that the present invention solves free acid in rectifying kettle liquid and solid sulphuric acid azanol product in the presence of prior art
The problem of.
A kind of liquid acid of innovative development of the present invention is catalyzed oxime hydrolysis process altogether with solid acid, by liquid inorganic acid catalysis mistake
The rectifying kettle liquid obtained in journey allows solid acid to provide H+ and is catalyzed oxime hydrolysis again, promote again by solid acid catalysis reactor
Chemical balance further produces mobile here to azanol, promotes reaction rate, hydrolyzes obtained azanol and is remained in system
Liquid acid combines to form hydroxylamine salt, improves inorganic acid utilization rate, excellent so as to reduce residual of the liquid mineral acid in hydroxylamine solution
Change solid sulphuric acid azanol product quality.
The HAS solution post processing obtained after distillation hydrolysis of the present invention is simple, it is only necessary to which concentration control HAS is molten
After liquid concentration (being realized by stripper), then crystallized, separated, dry can be obtained by high-quality solid sulphuric acid azanol production
Product.Isolated crystalline mother solution continues return rectifying tower reactor and applied mechanically.The distillate containing a large amount of butanone that rectifying tower top obtains
Can reuse diacetylmonoxime.
In summary, the present invention can low cost, the situation of low energy consumption reduction rectifying column kettle liquid middle reaches from acid content,
Slow down corrosion of the material to equipment.The present invention can significantly improve solid sulphuric acid azanol product quality, contain free acid in product
Amount and moisture significantly reduce.The method of the present invention is discharged without technique waste water, and energy-saving and emission-reduction are environment-friendly, and product purity is high,
It is prevented from caking.
Brief description of the drawings
The embodiment of the present invention is described in further detail below in conjunction with the accompanying drawings.
Fig. 1 is the process flow diagram of the present invention.
Embodiment
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in
This.
In following case, reactive distillation column each means the reactive distillation column with reboiler.
Embodiment 1, a kind of preparation method of HAS, are followed the steps below successively：
1) it is, 1 by diacetylmonoxime and sulfuric acid molar ratio:0.5 (that is, C=NOH：H+=1:1) it is 99.9%, to control purity
The flow 871kg/h of diacetylmonoxime, the flow of 28% sulfuric acid is 1750kg/h, after above-mentioned material is sufficiently mixed, is added
Rectifying is carried out in the middle part of reactive distillation column, rectifying column 30~32Kpa of absolute pressure is controlled, 85~90 DEG C of rectifying tower reactor temperature, controls tower top
Reflux ratio 1.2 is produced, and butanone obtained by kettle top is reclaimed；
2), the mixed solution obtained by tower reactor is divided into following two-way：
Stripper is delivered to 1500~1600kg/h flow with pump control and carries out stripping removing organic matter and part water
Divide (so as to realize concentration)；It is delivered to pump control with 15000kg/h flow in the reactor equipped with catalyst and enters traveling one
Step reaction；
The temperature of stripper is 85~90 DEG C, and pressure of stripping tower is about 20~30Kpa；
Reaction temperature in reactor is higher than rectifying tower reactor temperature 2 DEG C (that is, 87~92 DEG C)；
Reactor built with 0.5 ton of acid-exchange resin as catalyst (production of Britain Piao Laite companies
Storng-acid cation exchange resin C100 × 10), i.e. the loadings of catalyst and the matter of raw material diacetylmonoxime sample size hourly
Amount is than being 0.57：1；The liquid material of reaction gained is back to the tower reactor of rectifying column, and gas phase is back to rectifying column middle and upper part；
3), from HAS solution after the concentration of stripper tower reactor outflow by crystallization, centrifugation；Centrifuge gained
Solid through drying, obtain HAS (HAS of high-quality).For example, it is specially：From the dense of stripper tower reactor outflow
HAS solution enters crystallization cylinder crystallisation by cooling after contracting, 20~35 DEG C of control material temperature, will contain a large amount of solid sulphuric acid hydroxyls
The solution of amine delivers to centrifuge and is centrifuged (centrifuge for selecting separation factor 500~1000), centrifuges the solid of gained
HAS is dried by conventional heated air, and it is 80~90 DEG C to control air themperature；After drying 30 minutes, when final products.
Filtrate is back to rectifying column caused by centrifugation.
Separately sampled analysis rectifying column kettle liquid (that is, the mixed solution obtained by tower reactor) and solid sulphuric acid azanol product, through certainly
Electrokinetic potential titrator is analyzed, and rectifying column kettle liquid middle reaches are 2.51% from acid content, and HAS content is 41.2%, solid sulphuric acid
Free acid content is 0.15% in azanol product, and HAS content is 99.65%, moisture 0.16%.
Comparative example 1-1, for embodiment 1, step 2) is made into：
2), the mixed solution obtained by tower reactor is all delivered to stripper with 1500~1600kg/h flow and entered with pump control
Row stripping is de-；
That is, the setting of catalytic reactor is eliminated, reactor gains is also accordingly eliminated and is back to rectifying column；
Remaining is equal to embodiment 1.
Separately sampled analysis tower bottoms and solid sulphuric acid azanol product, are analyzed, tower bottoms middle reaches through automatical potentiometric titrimeter
It is 5.24% from acid content, HAS content is 40.3%, and free acid content is 0.32% in solid sulphuric acid azanol product, sulphur
Sour hydroxylamine content is 99.36%, moisture 0.31%.
Comparative example 1-2,
Mixed solution obtained by tower reactor is delivered to stripper with 1500~1600kg/h flow with pump control and carries out vapour
Put forward removing organic matter and partial moisture；Controlled with pump and the reactor equipped with catalyst is delivered to about 750~800kg/h flow
It is middle further to be reacted；
Remaining is equal to embodiment 1.
Separately sampled analysis tower bottoms and solid sulphuric acid azanol product, are analyzed, tower bottoms middle reaches through automatical potentiometric titrimeter
It is 4.78% from acid content, HAS content is 40.9%, and free acid content is 0.28% in solid sulphuric acid azanol product, sulphur
Sour hydroxylamine content is 99.48%, moisture 0.28%.
Comparative example 1-3,
It is 1 by diacetylmonoxime and sulfuric acid molar ratio:0.515 (that is, C=NOH：H+=1:1.03) it is 99.9%, to control purity
Diacetylmonoxime flow 871kg/h, the flow of 28% sulfuric acid is 1803kg/h, after above-mentioned material is sufficiently mixed, is added
Enter and rectifying is carried out in the middle part of reactive distillation column, control rectifying column 30~32Kpa of absolute pressure, 85~90 DEG C of rectifying tower reactor temperature, control tower
Top reflux ratio 1.2 is produced, and butanone obtained by kettle top is reclaimed；
Stripper is delivered to 1500~1600kg/h flow with pump control and carries out stripping removing organic matter and part water
Divide (so as to realize concentration).
That is, the setting of catalytic reactor is eliminated, reactor gains is also accordingly eliminated and is back to rectifying column；And by original
Expect excess sulfuric acid 3%；Remaining is equal to embodiment 1.
Separately sampled analysis tower bottoms and solid sulphuric acid azanol product, are analyzed, tower bottoms middle reaches through automatical potentiometric titrimeter
It is 5.98% from acid content, HAS content is 40.2%, and free acid content is 0.38% in solid sulphuric acid azanol product, sulphur
Sour hydroxylamine content is 98.85%, moisture 0.36%.
Embodiment 2, a kind of preparation method of HAS, are followed the steps below successively：
1) it is, 1 by diacetylmonoxime and sulfuric acid molar ratio:0.45, control the flow 871kg/ for the diacetylmonoxime that purity is 99.9%
H, the flow of 28% sulfuric acid is 1575kg/h, after above-mentioned material is sufficiently mixed, adds in the middle part of reactive distillation column and carries out
Rectifying, rectifying column 30~32Kpa of absolute pressure, 85~90 DEG C of rectifying tower reactor temperature being controlled, control tower top reflux ratio 1.2 is produced,
Butanone obtained by kettle top is reclaimed；
2), the mixed solution obtained by tower reactor is divided into following two-way：
Stripper is delivered to 1500~1600kg/h flow with pump control and carries out stripping removing organic matter and part water
Divide (so as to realize concentration)；It is delivered to pump control with 15000kg/h flow in the reactor equipped with catalyst and enters traveling one
Step reaction；
The temperature of stripper is 85~90 DEG C, and pressure of stripping tower is about 20~30Kpa；
Reaction temperature in reactor is higher than rectifying tower reactor temperature 2 DEG C (that is, 87~92 DEG C)；
Reactor is built with 0.4 ton of silicon dioxide carried sulfuric acid (load capacity of sulfuric acid be 30%), i.e. the dress of catalyst
The mass ratio of the amount of filling out and raw material diacetylmonoxime sample size hourly is 0.46：1；The liquid material of reaction gained is back to rectifying column
Tower reactor, gas phase is back to rectifying column middle and upper part；
3), from HAS solution after the concentration of stripper tower reactor outflow by crystallization, centrifugation；
The solid of gained is centrifuged through drying, obtains HAS (HAS of high-quality).
Filtrate is back to rectifying column caused by centrifugation.
Separately sampled analysis tower bottoms and solid sulphuric acid azanol product, are analyzed, tower bottoms middle reaches through automatical potentiometric titrimeter
It is 2.41% from acid content, HAS content is 41.3%, and free acid content is 0.14% in solid sulphuric acid azanol product, sulphur
Sour hydroxylamine content is 99.68%, moisture 0.15%.
Comparative example 2, for embodiment 2, step 2) is made into：
2), the mixed solution obtained by tower reactor is all delivered to stripper with 1500~1600kg/h flow and entered with pump control
Row stripping is de-；
That is, the setting of catalytic reactor is eliminated, reactor gains is also accordingly eliminated and is back to rectifying column；
Remaining is equal to embodiment 2.
Separately sampled analysis tower bottoms and solid sulphuric acid azanol product, are analyzed, tower bottoms middle reaches through automatical potentiometric titrimeter
It is 4.83% from acid content, HAS content is 40.4%, and free acid content is 0.28% in solid sulphuric acid azanol product, sulphur
Sour hydroxylamine content is 99.45%, moisture 0.27%.
Embodiment 3, a kind of preparation method of HAS, are followed the steps below successively：
1) it is, 1 by diacetylmonoxime and sulfuric acid molar ratio:0.5, the flow 871kg/h for the diacetylmonoxime that purity is 99.9% is controlled,
The flow of 15% sulfuric acid is 3267kg/h, after above-mentioned material is sufficiently mixed, adds and essence is carried out in the middle part of reactive distillation column
Evaporate, control rectifying column 30~32Kpa of absolute pressure, 85~90 DEG C of rectifying tower reactor temperature, control tower top reflux ratio 1.2 is produced, kettle
Top gained butanone is reclaimed；
2), the mixed solution obtained by tower reactor is divided into following two-way：
Stripper is delivered to 2800~3500kg/h flow with pump control and carries out stripping removing organic matter and part water
Divide (so as to realize concentration)；It is delivered to pump control with 20000kg/h flow in the reactor equipped with catalyst and enters traveling one
Step reaction；
The temperature of stripper is 85~90 DEG C, and pressure of stripping tower is about 20~30Kpa；
Reaction temperature in reactor is higher than rectifying tower reactor temperature 2 DEG C (that is, 87~92 DEG C)；
Reactor is built with 0.2 ton of silicon dioxide carried sulfuric acid (load capacity of sulfuric acid is 30%) and 0.3 ton of D001 macropore
Strongly acidic styrene type cation exchange resin；That is, the loadings of catalyst and the matter of raw material diacetylmonoxime sample size hourly
Amount is than being 0.57：1；The liquid material of reaction gained is back to the tower reactor of rectifying column, and gas phase is back to rectifying column middle and upper part；
3), from HAS solution after the concentration of stripper tower reactor outflow by crystallization, centrifugation；
The solid of gained is centrifuged through drying, obtains HAS (HAS of high-quality).
Filtrate is back to rectifying column caused by centrifugation.
Separately sampled analysis tower bottoms and solid sulphuric acid azanol product, are analyzed, tower bottoms middle reaches through automatical potentiometric titrimeter
It is 1.4% from acid content, HAS content is 22.3%, and free acid content is 0.14% in solid sulphuric acid azanol product, sulphur
Sour hydroxylamine content is 99.65%, moisture 0.16%.
Comparative example 3, for embodiment 2, step 2) is made into：
2), the mixed solution obtained by tower reactor is all delivered to stripper with 2800~3500kg/h flow and entered with pump control
Row stripping is de-；
That is, the setting of catalytic reactor is eliminated, reactor gains is also accordingly eliminated and is back to rectifying column；
Remaining is equal to embodiment 3.
Separately sampled analysis tower bottoms and solid sulphuric acid azanol product, are analyzed, tower bottoms middle reaches through automatical potentiometric titrimeter
It is 2.91% from acid content, HAS content is 21.9%, and free acid content is 0.30% in solid sulphuric acid azanol product, sulphur
Sour hydroxylamine content is 99.38%, moisture 0.31%.
Finally, it is also necessary to it is noted that listed above is only several specific embodiments of the invention.Obviously, this hair
It is bright to be not limited to above example, there can also be many deformations.One of ordinary skill in the art can be from present disclosure
All deformations for directly exporting or associating, are considered as protection scope of the present invention.
Claims (4)
1. the preparation method of HAS, it is characterized in that comprising the following steps：
1), according to H+：C=NOH is 1:1~1.3 mol ratio, enter after being well mixed as the acid solution of raw material and oxime anti-
Answer in rectifying column, control reactive distillation column carries out rectifying, control tower at 50~110 DEG C of 5~100KPa of absolute pressure and bottom temperature
It is 0.5~5 to push up reflux ratio, and separate fraction, tower reactor obtains the mixed solution of HAS and unreacted oxime and acid；Kettle top evaporates
It is ketone to go out liquid, and the ketone of gained is reclaimed；
Sour mass concentration is 8~42% in the acid solution as raw material；
2) mixed solution obtained by tower reactor, is delivered to stripper with pump portion and carries out stripping removing organic matter and partial moisture,
Part, which is delivered in the reactor equipped with catalyst, is further reacted, the mixed solution for being delivered to stripper：Conveying
To mixed solution=1 of reactor:1~20 volume ratio；
Reaction temperature in reactor is higher than the bottom temperature of rectifying column 0.5~15 DEG C, the loadings of catalyst reactor with
The mass ratio of raw material diacetylmonoxime sample size hourly is 0.1~10：1；The liquid material of reaction gained is back to rectifying column
Tower reactor, gas phase are back to rectifying column middle and upper part；
3), from HAS solution after the concentration of stripper tower reactor outflow by crystallization, solid-liquor separation；
Solid obtained by the solid-liquor separation obtains HAS through drying.
2. the preparation method of HAS according to claim 1, it is characterized in that：Produced by the step 3) solid-liquor separation
Liquid be back to rectifying column.
3. the preparation method of HAS according to claim 1 or 2, it is characterized in that：The catalyst is acid ion
At least one of exchanger resin or silicon dioxide carried sulfuric acid；
The silicon dioxide carried sulfuric acid, the load capacity of sulfuric acid is 5%~36%.
4. the preparation method of HAS according to claim 3, it is characterized in that：
The acid as raw material is sulfuric acid, or the mixed solution of sulfuric acid and HAS；
The oxime as raw material is acetoxime, diacetylmonoxime.
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| CN110845323A (en) * | 2019-11-15 | 2020-02-28 | 山东省化工研究院 | Preparation method of hydroxylamine formate |
| CN111285338A (en) * | 2020-03-12 | 2020-06-16 | 浙江锦华新材料股份有限公司 | Preparation method of solid hydroxylamine sulfate |
| CN111320152A (en) * | 2020-03-06 | 2020-06-23 | 山东省化工研究院 | Method for preparing hydroxylamine hydrochloride by gas-phase continuous hydrolysis of ketoxime |
| CN112591721A (en) * | 2021-01-05 | 2021-04-02 | 浙江锦华新材料股份有限公司 | Preparation method of solid hydroxylamine sulfate |
| CN117269415A (en) * | 2023-11-17 | 2023-12-22 | 江苏艾科维科技股份有限公司 | Method for simultaneously measuring content of free acid, hydroxylamine and ammonium salt by potentiometric method |
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| CN110845323A (en) * | 2019-11-15 | 2020-02-28 | 山东省化工研究院 | Preparation method of hydroxylamine formate |
| CN110845323B (en) * | 2019-11-15 | 2022-04-26 | 山东省化工研究院 | Preparation method of hydroxylamine formate |
| CN111320152A (en) * | 2020-03-06 | 2020-06-23 | 山东省化工研究院 | Method for preparing hydroxylamine hydrochloride by gas-phase continuous hydrolysis of ketoxime |
| CN111320152B (en) * | 2020-03-06 | 2023-03-10 | 山东省化工研究院 | Method for preparing hydroxylamine hydrochloride by gas-phase continuous hydrolysis of ketoxime |
| CN111285338A (en) * | 2020-03-12 | 2020-06-16 | 浙江锦华新材料股份有限公司 | Preparation method of solid hydroxylamine sulfate |
| CN112591721A (en) * | 2021-01-05 | 2021-04-02 | 浙江锦华新材料股份有限公司 | Preparation method of solid hydroxylamine sulfate |
| CN117269415A (en) * | 2023-11-17 | 2023-12-22 | 江苏艾科维科技股份有限公司 | Method for simultaneously measuring content of free acid, hydroxylamine and ammonium salt by potentiometric method |
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