CN107539966B - The preparation method of hydroxyl sulfate - Google Patents
The preparation method of hydroxyl sulfate Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of hydroxyl sulfate, comprising the following steps: 1), will enter after mixing as the acid solution of raw material and oxime and carry out rectifying in reactive distillation column, tower reactor obtains the mixed solution of hydroxyl sulfate and unreacted oxime and acid；2) the resulting mixed solution of tower reactor, is delivered to stripper with pump portion and carries out stripping removing organic matter and partial moisture, is partially delivered in the reactor equipped with catalyst and is further reacted；The tower reactor that resulting liquid material is back to rectifying column is reacted, gas phase is back to rectifying column middle and upper part；3), pass through crystallization, solid-liquor separation, drying from hydroxyl sulfate solution after the concentration that stripper tower reactor flows out, obtain hydroxyl sulfate.
Description
Technical field
The present invention relates to the preparation methods of chemical field, especially hydroxyl sulfate.
Background technique
Hydroxyl sulfate is a kind of chemical products that purposes is very extensive, can be used 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 hydroxyl sulfate mainly has nitromethane method, acetoxime method, nitric oxide reduction method, disulfonic acid ammonium
Salt water solution etc..
Nitromethane preparation need to use toxic articles dimethyl suflfate, and when hydrolysis prepares azanol, by-product is an oxygen of severe toxicity
Change carbon；When hydrolysis, alkane and other materials are in two-phase in the reaction system, and have sharp interface, since to be in interface anti-for hydro carbons
It answers, so rate is low, the reaction time is long, total recovery is 75% or so.
Traditional acetoxime method is first reacted with sodium nitrite, sodium pyrosulfite, after sulfuric acid acidification, generates azanol disulfonic acid
Salt, then reacted with acetone, then prepare azanol with sour water solution, yield only has 60%, therefore there are process route complexity, process flows
Long, high production cost, 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 disadvantages 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 one rhodium catalyst of platinum 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 hydroxyl sulfate, and yield 70% or so, this process equipment is more demanding,
Expensive catalyst, vent gas treatment are difficult.
Though disulfonic acid ammonium salt hydrolysis method production technology is mature, it is suitable only for integrated mill's production, cost of investment is big, and
The product arrived is the mixture of ammonium sulfate and hydroxyl sulfate, and it is extremely difficult to isolate commerical grade solid sulphuric acid azanol product.
The above conventional method there are aiming at the problem that, Chinese patent application CN 200910096601.6 discloses a kind of hydroxyl
The preparation method of amine salt is that ketoxime is hydrolyzed to reaction in an acidic solution and generates hydroxylamine salt and ketone in rectifying column, from
The ketone of the top of the distillation column output is discharged in time, specific preparation step are as follows: and the mol ratio of ketoxime and inorganic acid is 1:0.4~3, point
Ketoxime and inorganic acid are not taken；By in above-mentioned steps ketoxime and inorganic acid aqueous solution feed in the middle part of the rectifying column, and Decompression Controlling
Tower temperature in the kettle is 40~100 DEG C, and overhead reflux ratio is 1~6；When distillating to tower top without ketone, cooling kettle liquid crystallization, filtering is washed
It washs, is dried to obtain hydroxylamine salt solid.
Chinese patent application CN201310097499.8 done on the basis of CN200910096601.6 published method into
The improvement of one step has carried out the reflux in tower reactor on the basis of adjusting process parameter.Specifically:
Step 1: oxime (C=NOH): sour (H) is 1:(1~1.3 in molar ratio), suitable acid solution and oxime are got out, acid
The mass fraction of solution is (10%~35%)；
Step 2: 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 control tower top reflux ratio is 0~4, 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 and lower position, extraction
Tower bottom product；
Step 3: product is concentrated, is 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 under the action of acid catalyst, which is reversible reaction；
2. azanol further forms hydroxylamine salt in conjunction with inorganic acid；
Specific reaction equation is as follows:
Chemical equation after merging are as follows:
The method for promoting balance to move right is usually that ketone is removed 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) reaction process
On the one hand body acid is catalyst, while being also reaction raw materials, and the azanol ultimately produced will form hydroxyl sulfate in conjunction with sulfuric acid.Body
Sulfuric acid in system is gradually consumed, oxime hydrolysis influenced finally also to be up to balance by catalytic amount, will have part oxime with
Acid cannot react 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
It is all made of liquid mineral acid (hydrochloric acid, sulfuric acid or phosphoric acid) hydrogen ion mole and ketoxime mole ratio and is greater than 1 to promote to react,
There is excessive inorganic acid in reactive distillation tower bottoms.Although the filtrate obtained after Crystallization Separation can return to reaction system
System, there is theoretically no wastage of material, but since excessive inorganic acid exists, on the one hand will increase equipment selection difficulty, separately
On the one hand it will lead to the free acid in the hydroxyl sulfate crystallized out containing high-content, the free acid of high-content in solid sulphuric acid azanol
It can cause a series of adverse consequences:
1) high-content free acid cannot remove in the drying process, while can also cause moisture content high, and final product is deposited
It is particularly easy to agglomerate during storage, is unfavorable for the safe handling of downstream client；
2) high-content free acid requires equipment material higher, it is easy to equipment be caused to be corroded；
3) high-content free acid can make product quality be badly damaged, and almost deteriorate all-mass index.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method is simple, process flow is short, stable product quality, production
Hydroxyl sulfate preparation method at low cost.
In order to solve the above technical problem, the present invention provides a kind of preparation methods of hydroxyl sulfate, comprising the following steps:
1), according to H+: C=NOH is the molar ratio of 1:1~1.3, laggard by being uniformly mixed as the acid solution of raw material and oxime
Enter in reactive distillation column (reactive distillation column with reboiler), controls reactive distillation column in 5~100KPa of absolute pressure and tower reactor temperature
Rectifying is carried out at 50~110 DEG C of degree, control tower top reflux ratio is 0.5~5, and separation (separation in time) fraction, tower reactor obtains sulfuric acid
The mixed solution of azanol and unreacted oxime and acid；The distillate of kettle top is ketone, and resulting ketone is recycled；
Sour mass concentration is 8~42% in the acid solution as raw material；
Illustrate: reboiler is mainly to provide energy and partial material is vaporized (undergoing phase transition, no temperature change)；
2) the resulting mixed solution of tower reactor, is delivered to stripper with pump portion and carries out stripping removing organic matter and part water
Divide (thus realizing concentration), is partially delivered in the reactor equipped with catalyst and is further reacted, it is described to be delivered to stripping
The mixed solution of tower: it is delivered to mixed solution=1:1~20 volume ratio of reactor；
Reaction temperature in reactor is 0.5~15 DEG C higher than the bottom temperature of rectifying column, the filling of catalyst reactor
The mass ratio of amount and raw material diacetylmonoxime sample volume hourly is 0.1~10:1；It reacts resulting liquid material and is back to rectifying
The tower reactor of tower, gas phase are back to rectifying column middle and upper part；
Illustrate:
The input and output of reactive distillation column are conservation of mass relationship；
In the present invention, by controlling the body for being delivered to the mixed solution of reactor and being delivered to the mixed solution of stripper
Product ratio, to adjust reaction time of the mixed solution in reactor；
The liquid material generated after above-mentioned reactor reaction further includes water, a small amount of sulfuric acid and fourth other than hydroxylamine salt
Ketoxime, liquid material are back to the tower reactor of rectifying tower reactor；The gas phase generated after reactor reaction include vaporization generate water vapour,
The butanone that diacetylmonoxime and reaction generate；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 flow out concentration after hydroxyl sulfate solution by crystallization, solid-liquor separation (including centrifugation point
From)；
The resulting solid of solid-liquor separation obtains hydroxyl sulfate (hydroxyl sulfate of high-quality) through drying.
The improvement of preparation method as hydroxyl sulfate of the invention: liquid caused by the step 3) solid-liquor separation returns
It is back to rectifying column.
Illustrate: the ingredient 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 is usually back to rectifying tower reactor.
The further improvement of preparation method as hydroxyl sulfate of the invention: the catalyst is acid ion exchange tree
At least one of rouge 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 are 5%~36% (weight %).
The further improvement of preparation method as hydroxyl sulfate of the invention: the acid as raw material is sulfuric acid, or
The mixed solution of sulfuric acid and hydroxyl sulfate；The oxime as raw material is acetoxime, diacetylmonoxime.
In the present invention,
Acid-exchange resin can be obtained by way of regular market purchase, and for example, the production of Britain's Purolite Company is strong
Acid cation exchange resin C100 × 10, Anhui Province east resin Science and Technology Ltd. or Zhejiang Province Zhengguan Industry Co., Ltd
Etc. the D001 large hole strong acid styrene system cation exchange resin of production of units etc..
Silicon dioxide carried sulfuric acid can be prepared by following conventional method:
After being cooled to room temperature, hot concentrated sulfuric acid is added by 200 DEG C of calcination process in the chromatographic silica gel for selecting 20~400 mesh
It impregnates 5~10 minutes, places naturally and be cooled to room temperature.It is isolated by filtration the extra concentrated sulfuric acid, then with distilled water flushing Silica Surface
Attachment acid, decompressing and extracting moisture dry, and obtain the support type SiO 2 catalyst of sulfur acid 5%~36%.
Raw material acid (pressing H+ densimeter) and the molar ratio of oxime (C=NOH) are controlled in 1:(1~1.3).
Reactor carries heating function, heats up to realize to material (the resulting mixed solution of tower reactor), alternatively,
Heating device is installed before reactor additional, 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 the prior art
The problem of.
A kind of liquid acid of innovative development of the present invention and solid acid are catalyzed oxime hydrolysis process altogether, by liquid inorganic acid catalysis mistake
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 movement here to azanol, promotes reaction rate, remaining in the azanol and system hydrolyzed
Liquid acid, which combines, forms hydroxylamine salt, improves inorganic acid utilization rate, so that residual of the liquid mineral acid in hydroxylamine solution is reduced, it is excellent
Change solid sulphuric acid azanol product quality.
The hydroxyl sulfate solution post-processing obtained after distillation hydrolysis of the present invention is simple, it is only necessary to which concentration control hydroxyl sulfate 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 applies.The distillate containing a large amount of butanone that rectifying tower top obtains
It can reuse diacetylmonoxime.
In conclusion the present invention can reduction rectifying column kettle liquid middle reaches the low cost, low energy consumption the case where 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 content significantly reduce.Method of the invention is discharged without technique waste water, and energy-saving and emission-reduction are environmental-friendly, and product purity is high,
It is prevented from caking.
Detailed description of the invention
Specific embodiments of the present invention will be described in further detail with reference to the accompanying drawing.
Fig. 1 is process flow diagram of the invention.
Specific embodiment
The present invention is described further combined with specific embodiments below, 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 hydroxyl sulfate, successively follow the steps below:
It 1) is, 1:0.5 (that is, C=NOH:H+=1:1) by diacetylmonoxime and sulfuric acid molar ratio, control purity is 99.9%
The flow of the flow 871kg/h of diacetylmonoxime, 28% sulfuric acid are 1750kg/h, after above-mentioned material is sufficiently mixed, are added
Rectifying is carried out in the middle part of reactive distillation column, is controlled 30~32Kpa of rectifying column absolute pressure, 85~90 DEG C of rectifying tower reactor temperature, is controlled tower top
Reflux ratio 1.2 is produced, and butanone obtained by kettle top is recycled；
2), the resulting mixed solution of tower reactor is divided into following two-way:
Stripper is delivered to the flow of 1500~1600kg/h with pump control and carries out stripping removing organic matter and part water
Divide (thus realizing concentration)；It is delivered in the reactor equipped with catalyst and is carried out into one with the flow of 15000kg/h with pump control
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 be provided with 0.5 ton as catalyst acid-exchange resin (Britain's Purolite Company production
Storng-acid cation exchange resin C100 × 10), that is, the loadings of catalyst and the matter of raw material diacetylmonoxime sample volume hourly
Amount is than being 0.57:1；The tower reactor that resulting liquid material is back to rectifying column is reacted, gas phase is back to rectifying column middle and upper part；
3), from hydroxyl sulfate solution after the concentration that stripper tower reactor flows out by crystallization, centrifuge separation；Centrifuge separation gained
Solid through drying, obtain hydroxyl sulfate (hydroxyl sulfate of high-quality).For example, specifically: it is flowed out from stripper tower reactor dense
Hydroxyl sulfate solution enters crystallization cylinder crystallisation by cooling after contracting, controls 20~35 DEG C of temperature of charge, will contain a large amount of solid sulphuric acid hydroxyls
The solution of amine send to centrifuge and is centrifuged (centrifuge for selecting separation factor 500~1000), is centrifugated resulting solid
Hydroxyl sulfate is dry by conventional heated air, and control air themperature is 80~90 DEG C；After 30 minutes dry, final products are waited until.
Filtrate caused by being centrifugated is back to rectifying column.
Separately sampled analysis rectifying column kettle liquid (that is, the resulting mixed solution of tower reactor) and solid sulphuric acid azanol product, through certainly
The analysis of electrokinetic potential titrator, rectifying column kettle liquid middle reaches are 2.51% from acid content, and hydroxyl sulfate content is 41.2%, solid sulphuric acid
Free acid content is 0.15% in azanol product, and hydroxyl sulfate content is 99.65%, moisture content 0.16%.
Comparative example 1-1, for embodiment 1, step 2) is changed to:
2), the resulting mixed solution of tower reactor all with pump control with the flow of 1500~1600kg/h be delivered to stripper into
Row stripping is de-；
That is, eliminating the setting of catalytic reactor, also accordingly eliminates reactor gains and be 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, hydroxyl sulfate 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 content 0.31%.
Comparative example 1-2,
The resulting mixed solution of tower reactor is delivered to stripper with pump control with the flow of 1500~1600kg/h and carries out vapour
Propose removing organic matter and partial moisture；The reactor equipped with catalyst is delivered to the flow of about 750~800kg/h with pump control
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, hydroxyl sulfate 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 content 0.28%.
Comparative example 1-3,
It is 1:0.515 (that is, C=NOH:H+=1:1.03) by diacetylmonoxime and sulfuric acid molar ratio, control purity is 99.9%
Diacetylmonoxime flow 871kg/h, the flow of 28% sulfuric acid is that 1803kg/h adds after being sufficiently mixed above-mentioned material
Enter and carry out rectifying in the middle part of reactive distillation column, controls 30~32Kpa of rectifying column 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 recycled；
Stripper is delivered to the flow of 1500~1600kg/h with pump control and carries out stripping removing organic matter and part water
Divide (thus realizing concentration).
That is, eliminating the setting of catalytic reactor, also accordingly eliminates reactor gains and be back to rectifying column；And it will be former
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, hydroxyl sulfate 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 content 0.36%.
Embodiment 2, a kind of preparation method of hydroxyl sulfate, successively follow the steps below:
It 1) is, 1:0.45, the flow 871kg/ for the diacetylmonoxime that control purity is 99.9% by diacetylmonoxime and sulfuric acid molar ratio
The flow of h, 28% sulfuric acid are 1575kg/h, after above-mentioned material is sufficiently mixed, is added in the middle part of reactive distillation column and carries out
Rectifying controls 30~32Kpa of rectifying column absolute pressure, and 85~90 DEG C of rectifying tower reactor temperature, control tower top reflux ratio 1.2 is produced,
Butanone obtained by kettle top is recycled；
2), the resulting mixed solution of tower reactor is divided into following two-way:
Stripper is delivered to the flow of 1500~1600kg/h with pump control and carries out stripping removing organic matter and part water
Divide (thus realizing concentration)；It is delivered in the reactor equipped with catalyst and is carried out into one with the flow of 15000kg/h with pump control
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 provided with 0.4 ton of silicon dioxide carried sulfuric acid (load capacity of sulfuric acid is 30%), that is, the dress of catalyst
The mass ratio of the amount of filling out and raw material diacetylmonoxime sample volume hourly is 0.46:1；It reacts resulting liquid material and is back to rectifying column
Tower reactor, gas phase is back to rectifying column middle and upper part；
3), from hydroxyl sulfate solution after the concentration that stripper tower reactor flows out by crystallization, centrifuge separation；
Resulting solid is centrifugated through drying, obtains hydroxyl sulfate (hydroxyl sulfate of high-quality).
Filtrate caused by being centrifugated is back to rectifying column.
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, hydroxyl sulfate 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 content 0.15%.
Comparative example 2, for embodiment 2, step 2) is changed to:
2), the resulting mixed solution of tower reactor all with pump control with the flow of 1500~1600kg/h be delivered to stripper into
Row stripping is de-；
That is, eliminating the setting of catalytic reactor, also accordingly eliminates reactor gains and be 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, hydroxyl sulfate 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 content 0.27%.
Embodiment 3, a kind of preparation method of hydroxyl sulfate, successively follow the steps below:
1) it is, 1:0.5 by diacetylmonoxime and sulfuric acid molar ratio, controls the flow 871kg/h for the diacetylmonoxime that purity is 99.9%,
The flow of 15% sulfuric acid is 3267kg/h, after above-mentioned material is sufficiently mixed, is added in the middle part of reactive distillation column and carries out essence
It evaporates, controls 30~32Kpa of rectifying column 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 recycled；
2), the resulting mixed solution of tower reactor is divided into following two-way:
Stripper is delivered to the flow of 2800~3500kg/h with pump control and carries out stripping removing organic matter and part water
Divide (thus realizing concentration)；It is delivered in the reactor equipped with catalyst and is carried out into one with the flow of 20000kg/h with pump control
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 provided 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 matter of the loadings of catalyst and raw material diacetylmonoxime sample volume hourly
Amount is than being 0.57:1；The tower reactor that resulting liquid material is back to rectifying column is reacted, gas phase is back to rectifying column middle and upper part；
3), from hydroxyl sulfate solution after the concentration that stripper tower reactor flows out by crystallization, centrifuge separation；
Resulting solid is centrifugated through drying, obtains hydroxyl sulfate (hydroxyl sulfate of high-quality).
Filtrate caused by being centrifugated is back to rectifying column.
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, hydroxyl sulfate 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 content 0.16%.
Comparative example 3, for embodiment 2, step 2) is changed to:
2), the resulting mixed solution of tower reactor all with pump control with the flow of 2800~3500kg/h be delivered to stripper into
Row stripping is de-；
That is, eliminating the setting of catalytic reactor, also accordingly eliminates reactor gains and be 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, hydroxyl sulfate 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 content 0.31%.
The above list is only a few specific embodiments of the present invention for finally, it should also be noted that.Obviously, this hair
Bright to be not limited to above embodiments, acceptable there are many deformations.Those skilled 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 (3)
1. the preparation method of hydroxyl sulfate, it is characterized in that the following steps are included:
1), according to H+: C=NOH is the molar ratio of 1:1~1.3, will be entered after mixing instead as the acid solution of raw material and oxime
It answers in rectifying column, control reactive distillation column carries out rectifying, control tower at 5~100KPa of absolute pressure and 50~110 DEG C of bottom temperature
Pushing up reflux ratio is 0.5~5, and separate fraction, tower reactor obtains the mixed solution of hydroxyl sulfate and unreacted oxime and acid；Kettle top evaporates
Liquid is ketone out, and resulting ketone is recycled；
Sour mass concentration is 8~42% in the acid solution as raw material；
2) the resulting mixed solution of 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=1:1~20 volume ratio of reactor；
Reaction temperature in reactor is 0.5~15 DEG C higher than the bottom temperature of rectifying column, the loadings of catalyst reactor with
The mass ratio of oxime sample volume hourly as raw material is 0.1~10:1；It reacts resulting liquid material and is back to rectifying column
Tower reactor, gas phase is back to rectifying column middle and upper part；
The catalyst is at least one of acid-exchange resin or silicon dioxide carried sulfuric acid；The silica is negative
Sulfuric acid is carried, the load capacity of sulfuric acid is 5%~36%；
3), from hydroxyl sulfate solution after the concentration that stripper tower reactor flows out by crystallization, solid-liquor separation；
The resulting solid of solid-liquor separation obtains hydroxyl sulfate through drying.
2. the preparation method of hydroxyl sulfate 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 hydroxyl sulfate according to claim 1 or 2, it is characterized in that:
The acid as raw material is the mixed solution of sulfuric acid or sulfuric acid and hydroxyl sulfate；
The oxime as raw material is acetoxime, diacetylmonoxime.
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| 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 |
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| US5510097A (en) * | 1994-05-19 | 1996-04-23 | Olin Corporation | Hydroxylammonium nitrate free of ammonium nitrate |
| DE19733681A1 (en) * | 1997-08-04 | 1999-02-11 | Basf Ag | Process for the preparation of an aqueous solution of free hydroxylamine |
| CN101497433B (en) * | 2009-03-08 | 2011-01-05 | 宁波欧迅化学新材料技术有限公司 | Method for preparing hydroxylammonium salt |
| CN103483221A (en) * | 2012-06-12 | 2014-01-01 | 刘建青 | Preparation method of cyclohexanone oxime |
| CN103159191B (en) * | 2013-03-25 | 2016-04-06 | 浙江圣安化工有限公司 | A kind of preparation method of hydroxylammonium salt |
| CN107089924B (en) * | 2016-09-23 | 2019-03-05 | 河北美邦工程科技股份有限公司 | A kind of azanol, hydroxylamine salt, cyclohexanone oxime combined producing process |
| 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 |
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