CN100497166C - Method for preparing salt of hydroxylamine by using coupled technique of reaction-extraction - Google Patents
Method for preparing salt of hydroxylamine by using coupled technique of reaction-extraction Download PDFInfo
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- CN100497166C CN100497166C CNB2006100894033A CN200610089403A CN100497166C CN 100497166 C CN100497166 C CN 100497166C CN B2006100894033 A CNB2006100894033 A CN B2006100894033A CN 200610089403 A CN200610089403 A CN 200610089403A CN 100497166 C CN100497166 C CN 100497166C
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Abstract
This invention provides a method for preparing hydroxylamine salt by reaction-extraction 'coupled' technique. The method utilizes hydroxylamine hydrochloride and HNO3, H2SO4 or H3PO4 as the reactants to prepare hydroxylamine nitrate, hydroxylamine sulfate or hydroxylamine phosphate. During the reaction, a mixture of amide and diluting agent is utilized as the extraction phase to extract byproduct HCl generated during the reaction to obtain high-concentration hydroxylamine salt mother liquor. Then multi-stage cross-flow or vacuum distillation is performed to obtain concentrated hydroxylamine salt solution or crystal. During the reaction, byproduct inorganic acid can be extracted into the organic phase, which can reduce the amount of inorganic acid in aqueous phase, and break the previous thermodynamic equilibrium limit so that the reaction advances toward the positive reaction direction, and the yield is increased. The method has such advantages as simple process, few buproducts and easy operation, and is suitable for industrialization production.
Description
Technical field:
The present invention relates to the method that a kind of utilization reaction-extraction " coupling " technology prepares hydroxylammonium salt, belong to the fine chemical product technical field.
Background technology:
Hydroxylammonium salt is the fine chemical product of having many uses.Oxammonium sulfate and phosphatic hydroxylamine are mainly used in the production caprolactam, in producing important use are arranged also at agricultural chemicals, medicine; Hydroxylamine nitriate is mainly used in weary nuclear matter and handles and the liquid casting charge.
At present, the method for preparing oxammonium sulfate mainly contains NO reduction method, acetone oximate method, calcium oxide method, hydrolysis method etc.The preparation hydroxylamine nitriate method mainly contain catalytic reduction method, ion exchange method, electroosmose process, the precipitator method, neutralisation, electrolytic process, double decomposition etc.Prepare the main hydrogenation catalyst reduction method of method of phosphatic hydroxylamine and hydrolysis method etc.
Document 1: Liu Siquan, Xue Yaosen, Yang Lirong. synthetic [J] of oxammonium sulfate. the chemical engineer, 2004,102 (3): 9～10, be that the Sodium Nitrite that will measure adds in the 1000mL flask with four necks,round bottom, add a certain amount of water dissolution, keep certain temperature, drip certain density bisulfite ammonium solution, after being added dropwise to complete, the control certain temperature feeds the sulfur dioxide gas sulfonation, after reaching regulation pH value, the above-mentioned acid solution of heating hydrolysis obtains oxammonium sulfate.The author has obtained using the top condition of bisulfite amine, Sodium Nitrite, the synthetic oxammonium sulfate of sulfur dioxide liquid to be: NH through repeatedly experiment
4HSO
3: NaNO
2(mol/mol) be 1:1.1, sulfonation temperature is lower than 5 ℃, sulfonation pH value 3～4, and hydrolysis temperature is higher than 105 ℃, and the time is not less than 3h.
Document 2: neat through moral, Zhang Xuzhu, Jin Chong etc. neutralisation prepares the technical study [J] of hydroxylamine nitriate. fiery explosive journal, 2003,26 (1): 53～55, the author adds the strong amine of 41g sulfuric acid in the 500ml flask with three necks,round bottom of agitator and thermometer is housed, and adds the dissolving of 100ml deionized water and stirring, places subzero 5 ℃ cryosel water-bath to cool off, add 50% NaOH solution 31ml then, control reaction temperature is no more than 10 ℃, and reinforced finishing continues to stir 5min, leave standstill 5min, be cooled to 5 ℃ of suction filtrations,, get filtrate 188ml (quality is 214g) and 51.9g white solid (sodium sulfate) at last with 50ml deionized water wash solid.Filtrate added in the 500ml single port flask carry out underpressure distillation, the prolong temperature will remain on below 0 ℃, and cut is HA solution.Measure the salpeter solution of 15ml concentration 50%, add and be equipped with in the 250ml flask with three necks,round bottom of agitator and thermometer, place 0 ℃ ice-water bath to cool off.By waiting amount of substance to feed intake, calculate the volume of required HA, control reaction temperature is no more than 25 ℃.Behind reinforced the finishing, regulate endpoint pH to 1.0～1.3.
Document 3: Zhang Hui, military .HPO technology azanol reaction dynamics research of beam will and process optimization are inquired into [J]. the chemical industry progress, and 2003,22 (1): 83～86, the author has carried out lab scale research to the reaction that HPO technology nitrate hydrogenating reduction prepares phosphatic hydroxylamine.The batch test process of author's research is: carry out the experiment of different mixing speed in batch reactor, to get rid of the influence of hydrogen mass transfer to speed of reaction.A certain amount of catalyzer and inorganic process liquor are placed in the high pressure stirring tank, reactant gases (hydrogen, nitrogen) is controlled by mass flowmeter by steel cylinder, reactant gases after the metering enters reactor continuously, directly emptying after reacting, the pressure of reactive system is regulated automatically by the back pressure valve in reactor exit, and the temperature of reactive system is controlled automatically by temperature controller.Continuous stirred tank test: the simulation test of in continuous-stirring reactor, having carried out improving industrial reactor outlet azanol concentration.Raw material adopts the inorganic process liquor on the production equipment, adds a certain amount of nitric acid with volume pump in continuous-stirring reactor.
Above-mentioned these method ubiquity operational path complexity, technical process is long, unstable product quality, aftertreatment trouble, defective such as yield is low.And hydroxylammonium salt application at home and abroad more and more widely, and the personage of boundary is constantly exploring its reasonable synthetic route in the industry.Therefore, the new technology of further exploring the production hydroxylammonium salt is highly significant.
Summary of the invention:
The purpose of this invention is to provide the method that a kind of utilization reaction-extraction " coupling " technology prepares hydroxylammonium salt, is a kind of method that chemical reaction and liquid-liquid extraction process are coupled.
Hydroxylammonium salt and the hydrochloric acid that reversible chemical reaction generates strong acid (M) can take place in oxammonium hydrochloride and strong acid (M) in the aqueous solution, reaction equation is as follows:
nNH
2OH·HCl+M→(NH
2OH)
n·M+nHCl
M is a kind of in nitric acid, sulfuric acid or the phosphoric acid, n=1～3.
If in reaction solution, add the organic extraction phase, by-product hydrochloric acid is extracted in the organic phase, will makes the aqueous phase concentration of hydrochloric acid reduce, can break the suffered thermodynamics equilibrium limit of reaction, impel reaction to carry out, can improve the production rate of product significantly towards the direction that generates product.
The present invention utilizes above-mentioned principle, in the aqueous solution of oxammonium hydrochloride and strong acid (M), adds the extraction agent that can be used for by-product hydrochloric acid in the water phase separated, be extracted into organic phase, can obtain the hydroxylammonium salt of high density, by the underpressure distillation operation, promptly obtain this sour hydroxylammonium salt product again.
The concrete steps of preparation hydroxylammonium salt are:
A. with the amine substance extraction agent of deciding, be positioned in the clean container, be mixed with the hybrid extraction agent solution to wherein adding thinner again, the mixed extractant solution ratio is:
Main extraction agent volume fraction: 5%～70%
Diluent volume mark: 30%～95%
Preferable proportioning is:
Main extraction agent volume fraction: 25%～50%
Diluent volume mark: 50%～75%
Main extraction agent is any or several mixing solutions in aniline, pentanoic, xylidine, o-toluidine, N-butylaniline, tri-n-butylamine, n-octyl amine, two n-octyl amine, tri-n-octyl amine, the trialkyl tertiary amine etc.; Preferably any in aniline, pentanoic, tri-n-butylamine, trialkyl tertiary amine or the tri-n-octyl amine; Main extraction agent purity can be better greater than 95% effect.
Thinner is any or several mixing solutions in kerosene, primary isoamyl alcohol, toluene, trichloromethane, the tetracol phenixin etc., preferably primary isoamyl alcohol or and kerosene; Thinner purity can be better greater than 95% effect.
B. be 0.2molL according to the concentration that makes oxammonium hydrochloride in the reaction solution
-1～6.0molL
-1Quantitatively, accurately take by weighing the oxammonium hydrochloride crystal, joining volumetric molar concentration is 0.2molL
-1～5.0molL
-1Strong acid aqueous solution in prepare reaction solution; Strong acid is a kind of in nitric acid, sulfuric acid or the phosphoric acid.
C. the volume ratio according to hybrid extraction agent solution (oil phase) and reaction solution (water) is the ratio of 0.5:1～15:1, the mixed extractant and the reaction solution of steps A, B preparation are joined respectively in the reactor that has whipping appts, under 15～65 ℃ of temperature, react, react while stirring, reaction times is 15～30 minutes, keep that temperature of reaction is constant to leave standstill about 10 minutes, make oil, the abundant layering of water two-phase, separating oil, water two-phase, obtain the water of enrichment hydroxylammonium salt, collect water and obtain the hydroxylammonium salt mother liquor.
The used oxammonium hydrochloride crystalline of step B purity is more preferably greater than 95%, and used strong acid concentration is 0.2molL
-1～3.0molL
-1, oxammonium hydrochloride concentration is 0.2molL in the reaction solution of configuration
-1～4.0molL
-1
Preferable oil, the water volume ratio of step C is 1:1～10:1, and better oil, water volume ratio are 1:1～5:1.
When the preparation hydroxylammonium salt, be the hydroxylammonium salt mother liquid concentration that raising obtains, adopt operating method such as multistage cross flow, multi-stage countercurrent, continuous cross-flow and continuous countercurrent, can obtain the hydroxylammonium salt solution of high density.And, can obtain the hydroxylammonium salt mother liquor or the hydroxylammonium salt crystal of greater concn by low-pressure distillation, RO distillation procedure.
Utilize acid ion and Cl in the ion chromatograph analysis hydroxylammonium salt mother liquor
-Ionic concentration, result show that the mass concentration of hydroxylammonium salt is 8.08gL
-1～251.31gL
-1, the production rate of hydroxylammonium salt is 16%～90% in the reaction.
The invention has the beneficial effects as follows: utilize reaction-extraction " coupling " technology to prepare the method for hydroxylammonium salt, choose organic amine as main extraction agent, with kerosene or primary isoamyl alcohol is that thinner is mixed with mixed extractant, in reaction, the by-product hydrochloric acid that generates is extracted into organic phase, broken the thermodynamics equilibrium limit of reacting suffered, reaction is carried out towards the direction that generates product, and the hydroxylammonium salt of generation constantly accumulates at aqueous phase, can obtain the hydroxylammonium salt mother liquor of higher concentration.This method technological process is simple, operation easily, and by product is less, is easy to realize large-scale commercial production.
Embodiment
Embodiment 1
A. measure purity places 2L greater than 95% tri-n-butylamine 250mL Erlenmeyer flask with graduated cylinder, getting 750mL purity again joins in this Erlenmeyer flask as thinner greater than 95% primary isoamyl alcohol, being mixed with main extraction agent volume fraction is 25%, and the diluent volume mark is 75% the organic extraction phase solution of mixing.
B. be that 95%～99% the vitriol oil is slowly poured in the 2L beaker that fills deionized water with mass content, stir with glass stick simultaneously that the heat of generation is scattered and disappeared rapidly, and being mixed with the 1L volumetric molar concentration is 0.300molL
-1Aqueous sulfuric acid,, join and be mixed with reaction solution in the aqueous sulfuric acid greater than 99% oxammonium hydrochloride crystal with AR2140 type electronic analytical balance accurate weighing purity, the concentration of oxammonium hydrochloride is 0.601molL in the reaction solution
-1
C. be 1:1 according to the profit volume ratio, the mixed extractant and the reaction solution adding 3L that have configured are had in the reactor of whipping appts, control reaction temperature is 25 ℃, react while stirring, reaction times is 20 minutes, under uniform temp, leave standstill after reaction finishes and made the abundant layering of profit two-phase in 10 minutes, utilize separating funnel to separate the water that the profit two-phase obtains the enrichment oxammonium sulfate, be the oxammonium sulfate mother liquor.
D. utilize ion chromatograph to analyze in the oxammonium sulfate mother liquor
Ion and Cl
-Ionic concentration, the mass concentration that calculates oxammonium sulfate in the mother liquor is 60.13gL
-1, the transformation efficiency of oxammonium sulfate is 60.93%.
Embodiment 2:
A. according to the method for embodiment 1, being mixed with main extraction agent volume fraction is 50%, and the diluent volume mark is 50% the organic extraction phase solution of mixing.
B. being mixed with the 1L volumetric molar concentration is 1.200molL
-1Aqueous sulfuric acid, the oxammonium hydrochloride crystal of accurate weighing joined preparation oxammonium hydrochloride concentration is 0.802molL in the aqueous sulfuric acid
-1Reaction solution.
C. according to the method for embodiment 1, the mixed extractant that configured and reaction solution are positioned over 3L have in the reactor of whipping appts, be 25 ℃, react and obtained the oxammonium sulfate mother liquor in 20 minutes.
D. utilize ion chromatograph to analyze in the oxammonium sulfate mother liquor
Ion and Cl
-Ionic concentration, the mass concentration that obtains oxammonium sulfate in the mother liquor is 82.35gL
-1, the transformation efficiency of oxammonium sulfate is 62.59%.
Embodiment 3:
A. according to the method for embodiment 1, being mixed with main extraction agent volume fraction is 30%, and the diluent volume mark is 70% the organic extraction phase solution of mixing.
B. being mixed with the 1L volumetric molar concentration is 2.00molL
-1Aqueous sulfuric acid, the oxammonium hydrochloride crystal of accurate weighing joined preparation oxammonium hydrochloride concentration is 3.50molL in the aqueous sulfuric acid
-1Reaction solution.
C. according to the method for embodiment 1, the mixed extractant that configured and reaction solution are positioned over 3L have in the reactor of whipping appts, be 25 ℃, react and obtained the oxammonium sulfate mother liquor in 20 minutes.
D. utilize ion chromatograph to analyze in the oxammonium sulfate mother liquor
Ion and Cl
-Ionic concentration, the mass concentration that obtains oxammonium sulfate in the mother liquor is 113.56gL
-1, the transformation efficiency of oxammonium sulfate is 73%.
Embodiment 4:
A. with embodiment 1
B. being mixed with the 1L volumetric molar concentration is 0.500molL
-1Aqueous sulfuric acid, the oxammonium hydrochloride crystal of accurate weighing joined preparation oxammonium hydrochloride concentration is 0.960molL in the aqueous sulfuric acid
-1Reaction solution.
C. be 4:1 according to the profit volume ratio, the mixed extractant that configured and reaction solution be positioned over 3L have in the reactor of whipping appts that control reaction temperature is 30 ℃, the reaction times is 20 minutes.
D. the mass concentration that records oxammonium sulfate in the mother liquor is 99.09gL
-1, the transformation efficiency of oxammonium sulfate is 62.88%.
Embodiment 5:
A. adopting tri-n-octyl amine is main extraction agent, and kerosene is thinner, and according to the method for embodiment 1, being mixed with main extraction agent volume fraction is 25%, and the diluent volume mark is 75% the organic extraction phase solution of mixing.
B. being mixed with the 1L volumetric molar concentration is 1.00molL
-1Aqueous sulfuric acid, the oxammonium hydrochloride crystal of accurate weighing joined preparation oxammonium hydrochloride concentration is 1.00molL in the aqueous sulfuric acid
-1Reaction solution.
C. be 1:1 according to the profit volume ratio, the mixed extractant that configured and reaction solution be positioned over 3L have in the reactor of whipping appts that control reaction temperature is 30 ℃, the reaction times is 20 minutes.
D. the mass concentration that records oxammonium sulfate in the mother liquor is 111.52gL
-1, the transformation efficiency of oxammonium sulfate is 68.15%.
Embodiment 6:
A. adopting aniline is main extraction agent, and kerosene is thinner, and according to the method for embodiment 1, being mixed with main extraction agent volume fraction is 25%, and the diluent volume mark is 75% the organic extraction phase solution of mixing.
B. being mixed with the 1L volumetric molar concentration is 1.00molL
-1Aqueous sulfuric acid, the oxammonium hydrochloride crystal of accurate weighing joined preparation oxammonium hydrochloride concentration is 1.40molL in the aqueous sulfuric acid
-1Reaction solution.
C. be 1:1 according to the profit volume ratio, the mixed extractant that configured and reaction solution be positioned over 3L have in the reactor of whipping appts that control reaction temperature is 30 ℃, the reaction times is 20 minutes.
D. the mass concentration that records oxammonium sulfate in the mother liquor is 101.4gL
-1, the transformation efficiency of oxammonium sulfate is 62%.
Embodiment 7:
A. adopting the N-butylaniline is main extraction agent, and kerosene is thinner, and according to the method for embodiment 1, being mixed with main extraction agent volume fraction is 25%, and the diluent volume mark is 75% the organic extraction phase solution of mixing.
B. being mixed with the 1L volumetric molar concentration is 1.00molL
-1Aqueous sulfuric acid, the oxammonium hydrochloride crystal of accurate weighing joined preparation oxammonium hydrochloride concentration is 1.00molL in the aqueous sulfuric acid
-1Reaction solution.
C. be 1:1 according to the profit volume ratio, the mixed extractant that configured and reaction solution be positioned over 3L have in the reactor of whipping appts that control reaction temperature is 30 ℃, the reaction times is 20 minutes.
D. the mass concentration that records oxammonium sulfate in the mother liquor is 104.4gL
-1, the transformation efficiency of oxammonium sulfate is 80.3%.
Embodiment 8:
A. adopting tri-n-octyl amine is main extraction agent, and primary isoamyl alcohol is a thinner, and according to the method for embodiment 1, being mixed with main extraction agent volume fraction is 50%, and the diluent volume mark is 50% the organic extraction phase solution of mixing.
B. being mixed with the 1L volumetric molar concentration is 1.00molL
-1Aqueous sulfuric acid, the oxammonium hydrochloride crystal of accurate weighing joined preparation oxammonium hydrochloride concentration is 0.80molL in the aqueous sulfuric acid
-1Reaction solution.
C. be 1:1 according to the profit volume ratio, the mixed extractant that configured and reaction solution be positioned over 3L have in the reactor of whipping appts that control reaction temperature is 30 ℃, the reaction times is 20 minutes.
D. the mass concentration that records oxammonium sulfate in the mother liquor is 118.17gL
-1, the transformation efficiency of oxammonium sulfate is 90%.
Embodiment 9:
A. adopting tri-n-octyl amine is main extraction agent, and toluene is thinner, and according to the method for embodiment 1, being mixed with main extraction agent volume fraction is 27%, and the diluent volume mark is 73% the organic extraction phase solution of mixing.
B. being mixed with the 1L volumetric molar concentration is 2.00molL
-1Aqueous sulfuric acid, the oxammonium hydrochloride crystal of accurate weighing joined preparation oxammonium hydrochloride concentration is 3.00molL in the aqueous sulfuric acid
-1Reaction solution.
C. be 1:1 according to the profit volume ratio, the mixed extractant that configured and reaction solution be positioned over 3L have in the reactor of whipping appts that control reaction temperature is 25 ℃, the reaction times is 20 minutes.
D. through after three grades of cross-flow operation, the mass concentration that records oxammonium sulfate in the mother liquor is 182.34gL
-1, the transformation efficiency of oxammonium sulfate is 70.6%.
Embodiment 10:
A. with embodiment 9.
B. being mixed with the 1L volumetric molar concentration is 0.50molL
-1Aqueous nitric acid, the oxammonium hydrochloride crystal of accurate weighing joined preparation oxammonium hydrochloride concentration is 0.50molL in the aqueous nitric acid
-1Reaction solution.
C. be 1:1 according to the profit volume ratio, the mixed extractant that configured and reaction solution be positioned over 3L have in the reactor of whipping appts that control reaction temperature is 25 ℃, the reaction times is 20 minutes.
D. the mass concentration that records hydroxylamine nitriate in the mother liquor is 8.08gL
-1, the transformation efficiency of hydroxylamine nitriate is 16.48%.
Embodiment 11:
A. with embodiment 9.
B. being mixed with the 1L volumetric molar concentration is 1.00molL
-1Phosphate aqueous solution, the oxammonium hydrochloride crystal of accurate weighing joined preparation oxammonium hydrochloride concentration is 3.00molL in the phosphate aqueous solution
-1Reaction solution.
C. be 1:1 according to the profit volume ratio, the mixed extractant that configured and reaction solution be positioned over 3L have in the reactor of whipping appts that control reaction temperature is 25 ℃, the reaction times is 20 minutes.
D. the mass concentration that records phosphatic hydroxylamine in the mother liquor is 251.31gL
-1, the transformation efficiency of phosphatic hydroxylamine is 42.04%.
Claims (6)
1. hydroxylammonium salt and the hydrochloric acid that reversible chemical reaction generates strong acid M takes place according to oxammonium hydrochloride and strong acid M in a method of utilizing reaction-extraction " coupling " technology to prepare hydroxylammonium salt in the aqueous solution, and reaction equation is as follows:
nNH
2OH·HCI+M→(NH
2OH)
n·M+nHCl
M is a kind of in nitric acid, sulfuric acid or the phosphoric acid, n=1～3;
The major technique feature is to add the organic extraction phase in reaction solution, and by-product hydrochloric acid is extracted in the organic phase, makes the aqueous phase concentration of hydrochloric acid reduce, and breaks the suffered thermodynamics equilibrium limit of reaction, impels reaction to carry out towards the direction that generates product;
Concrete preparation process is as follows:
A. with the amine substance extraction agent of deciding, be positioned in the clean container, be mixed with the hybrid extraction agent solution to wherein adding thinner again, make the mixed extractant solution ratio be:
Main extraction agent volume fraction: 5%～70%
Diluent volume mark: 30%～95%
Wherein main extraction agent is any or several combination in aniline, pentanoic, xylidine, o-toluidine, N-butylaniline, tri-n-butylamine, n-octyl amine, two n-octyl amine, tri-n-octyl amine, the trialkyl tertiary amine;
Thinner is any or several combination in kerosene, primary isoamyl alcohol, toluene, trichloromethane, the tetracol phenixin;
B. be 0.2molL according to the concentration that makes oxammonium hydrochloride in the reaction solution
-1～6.0molL
-1Quantitatively, accurately taking by weighing the oxammonium hydrochloride crystal, to join volumetric molar concentration be 0.2molL
-1～5.0molL
-1Strong acid aqueous solution in prepare reaction solution; Described strong acid is a kind of in nitric acid, sulfuric acid or the phosphoric acid;
C. the volume ratio according to hybrid extraction agent solution and reaction solution is the ratio of 0.5:1～15:1, the mixed extractant and the reaction solution of steps A, B preparation are added respectively in the reactor that has whipping appts, under 15～35 ℃ of temperature, react, react while stirring, the reaction times is 15～30 minutes, keeps that temperature of reaction is constant to leave standstill about 10 minutes, make oil, the abundant layering of water two-phase, separating oil, water two-phase obtain the water of enrichment hydroxylammonium salt, collect water and obtain the hydroxylammonium salt mother liquor; Through extracting and separating, concentrated or drying treatment, obtain hydroxylammonium salt mother liquor or hydroxylammonium salt crystal again.
2. utilization reaction-extraction according to claim 1 " coupling " technology prepares the method for hydroxylammonium salt: the proportioning that it is characterized in that the hybrid extraction agent solution of steps A preparation is:
Main extraction agent volume fraction: 25%～50%
Diluent volume mark: 50%～75%
Main extraction agent is a kind of in aniline, pentanoic, tri-n-butylamine, trialkyl tertiary amine or the tri-n-octyl amine; Thinner is primary isoamyl alcohol or kerosene.
3. utilization reaction-extraction according to claim 1 " coupling " technology prepares the method for hydroxylammonium salt: it is characterized in that the used oxammonium hydrochloride crystalline of step B purity is greater than 95%, used strong acid concentration is 0.2molL
-1～3.0molL
-1, oxammonium hydrochloride concentration is 0.2molL in the reaction solution of configuration
-1～4.0molL
-1
4. utilization reaction-extraction according to claim 1 " coupling " technology prepares the method for oxammonium sulfate: it is characterized in that step C oil, water volume ratio be 1:1～5:1.
5. utilization reaction-extraction according to claim 1 " coupling " technology prepares the method for hydroxylammonium salt: it is characterized in that the separate mode that is adopted is: adopt multistage cross flow, multi-stage countercurrent, continuous cross-flow or continuous countercurrent operation mode; Concentrated, the drying mode that are adopted are low-pressure distillation, RO distillation procedure.
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| CN104925768A (en) * | 2014-03-19 | 2015-09-23 | 湖北航天化学技术研究所 | Hydroxylamine nitrate crystal preparation method |
| CN104192816B (en) * | 2014-08-26 | 2016-04-13 | 衢州巨化锦纶有限责任公司 | A kind of preparation method of high-purity solid oxammonium sulfate |
| CN105271143B (en) * | 2015-11-20 | 2017-09-22 | 山东兴辉化工有限公司 | The recovery processing technique of hydroxylamine hydrochloride mother liquor |
| CN110540177B (en) * | 2019-10-12 | 2023-05-30 | 山东省化工研究院 | Method for preparing hydroxylamine salt by continuous multistage reaction |
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