CN101100293B - Preparation of hydroxylamine by one-step method using oxime hydrolysis reaction and infiltration gasification film separation coupling technique - Google Patents
Preparation of hydroxylamine by one-step method using oxime hydrolysis reaction and infiltration gasification film separation coupling technique Download PDFInfo
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- CN101100293B CN101100293B CN200710100329A CN200710100329A CN101100293B CN 101100293 B CN101100293 B CN 101100293B CN 200710100329 A CN200710100329 A CN 200710100329A CN 200710100329 A CN200710100329 A CN 200710100329A CN 101100293 B CN101100293 B CN 101100293B
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Abstract
In this invention, oxime is used as raw material being hydrolyzed in acid solution. Said hydrolytic process is coupled with osmotic vaporization membrane separation technique. The produced organic by-product ketone is removed by said membrane directionally and high efficiently. Thus recovers the limitation of the reaction chemical equilibrium of the hydrolysis, proceeding the reaction to the direction of production of hydroxylamine salts. This technique enhances the conversion rate greatly with high yield of hydroxylamine salts. This inventive method is better than prior art method with advantages of: simple process, less kinds of raw materials being needed, easy to operation, no side reaction, mild reaction condition and high yield of hydroxylamine salts being up to 80%.
Description
Technical field:
The present invention relates to the preparation method of hydroxylammonium salt, being specifically related to a kind of is raw material with the oxime, utilize infiltration evaporation membrane separation technique efficiently and directionally to remove the organic by-products that generates in the oxime hydrolytic process, improve the yield of reaction conversion ratio and hydroxylammonium salt, the method for single stage method synthesizing hydroxyamine salt.
Background technology:
(1) hydroxylammonium salt and production method thereof
Hydroxylammonium salt is purposes Chemicals very widely, and main azanol salt has oxammonium sulfate, oxammonium hydrochloride, hydroxylamine nitriate, phosphatic hydroxylamine etc.Oxammonium hydrochloride mainly is used as the raw material of compound probabilities such as medicine, spices, rubber chemicals, dyestuff; Oxammonium sulfate and phosphatic hydroxylamine are mainly used in the production hexanolactam, and agricultural chemicals, pharmaceutical industries; Hydroxylamine nitriate is mainly used in the extraction of radioelement, the processing and the liquid casting charge of nuclear raw material.
At present, the method for preparing oxammonium hydrochloride mainly contains Nitromethane 99Min. hydrolysis method, Sweet natural gas (methane) nitrofication process, acetoxime method, nitric oxide reduction method, disulfonic acid ammonium salt hydrolysis method etc.; The method for preparing oxammonium sulfate mainly contains nitric oxide reduction method, acetoxime method, calcium oxide method, hydrolysis method etc.; The method for preparing hydroxylamine nitriate mainly contains 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.
Above-mentioned these method ubiquity operational path complexity, technical process is long, unstable product quality, aftertreatment trouble, drawback such as yield is low.Current, the market demand of hydroxylammonium salt constantly increases, and people are also more and more higher to production safety, energy-saving and cost-reducing requirement.Thereby, need improve or develop new production route to existing technology and satisfy current production and market demand.
(2) chemical reaction and infiltration gasification film separation coupling technique
Infiltration evaporation is a kind ofly to utilize each component in the liquid mixture to dissolve in film and the difference of diffusion and make it isolating new membrane isolation technique, is mainly used in the separation of liquid mixture.This technology has the separation factor height, and sepn process is not limited by vapor-liquid equilibrium, and process is simple, does not introduce the characteristics of other reagent.Because infiltration evaporation has efficiently, orientation removes certain component in the mixed solution characteristic with itself and chemical reaction coupling, can remove certain product orientation in the reaction system, thereby break the restriction of chemical equilibrium, reinforcement reaction process, raising reaction conversion ratio.At present, chemical reaction and infiltration gasification film separation coupling technique have obtained numerous investigators' concern, but the scope of research is narrower, mainly concentrate on the coupling of esterification and infiltration evaporation membrane separation technique, promptly utilize the infiltration evaporation membrane separation technique to remove the water that generates in the esterification reaction process, improve the transformation efficiency of reaction.
Document 1: Liu Qinglin; Zhu Yushan; the Chen Hong francium. the cross-linking polyvinyl alcohol permeation evaporating film is used for esterification reaction process [J]. colleges and universities' chemical engineering journal; 1997; 11 (2): 172-176; the author adopts flat polyvinyl alcohol permeation vaporization film, and infiltration evaporation and acetate/propyl carbinol esterification coupling process are studied.90 ℃, the initial mole of charging (acetate/propyl carbinol) is that the esterification of the infiltration evaporation that is not coupled reaches balance basically under 1.599 the condition when 6hr is carried out in reaction, and its equilibrium conversion is lower than 65%; And the final transformation efficiency of esterification of coupling infiltration evaporation reaches 95%.In addition, pervaporation not only makes reaction conversion ratio improve greatly, has also accelerated the speed of reaction of esterification, and the reaction conversion ratio of band process of pervaporation reaches the molecular balance transformation efficiency and only used 2hr.
Document 2:Okamoto K, Yamamoto M, Noda S, et al.Vapor-permeation aided esterificationof oleic acid[J] .Industrial Engineering and Chemical Research, 1994,33 (4): 849-853. author adopts the infiltration evaporation process intensification oleic acid and the alcoholic acid esterification of polymkeric substance hollow-fibre membrane.85 ℃, reaction raw materials ethanol and oleic mol ratio are under 2 the condition, and after 3hr was carried out in reaction, oleic transformation efficiency surpassed 95%; And under the identical reaction conditions, not having the reaction of infiltration evaporation device to need 4hr just to reach balance substantially, transformation efficiency only is 75%.
Above-mentioned document result shows that the centrifugation of infiltration evaporation is very obvious to the strengthening effect of reaction.At present, the coupling technique of infiltration evaporation and chemical reaction is in the period of development fast, and this technology is applied in the wider scope, and improving existing manufacturing technique is the research focus in this field.
Summary of the invention:
The object of the present invention is to provide sharp the oxime hydrolysis reaction and the infiltration evaporation membrane separation technique that is coupled in acidic solution, the method of one-step synthesis hydroxylammonium salt compound, another object of the present invention provide suitable oxime hydrolysis method and prepare the used infiltration evaporation film separation reaction device of hydroxylammonium salt.
Hydrolysis reaction can take place and generate hydroxylammonium salt and by product ketone in oxime in acidic solution, react in different sour environments, can generate different hydroxylammonium salt.Reaction equation is as follows:
nR
1(C＝NOH)R
2+M+nH
2O→(NH
2OH)
n·M+nR
1(C＝O)R
2
R
1, R
2The expression carbonatoms is 1～10 alkyl, and M is a kind of in hydrochloric acid, nitric acid, sulfuric acid, the phosphoric acid, n=1～3.
Technical scheme and step are as follows:
A. according to the mol ratio that makes in the reaction solution acid with oxime be 0.5～3 quantitatively, accurately take by weighing oxime, join in the acid solution that concentration is 0.5mol/L～6.0mol/L the preparation reaction solution;
Raw materials used oxime is acetoxime, Diacetylmonoxime, cyclohexanone-oxime etc., and purity is preferably in more than 95%; Used acid is a kind of in hydrochloric acid, nitric acid, sulfuric acid, the phosphoric acid, and its concentration will be controlled between 0.5mol/L～1.0mol/L, to reduce nitric acid or the sulfuric acid corrosive nature to pipeline, membrane module and other equipment.
B. reaction solution is added in the coupling infiltration evaporation film separation reaction device, controlled temperature makes oxime generation hydrolysis reaction at 40 ℃～100 ℃, infiltrating and vaporizing membrane optionally removes byproduct of reaction ketone in the reaction process, impel oxime hydrolysis reaction to carry out to the direction that generates hydroxylammonium salt, along with the carrying out of reaction, hydroxylammonium salt concentration obtains continuing to improve; Byproduct of reaction ketone sees through infiltrating and vaporizing membrane removing by selectivity;
Because by product ketone constantly removes from reaction system, reaction process has obtained reinforcement, and reaction is carried out to generating the hydroxylammonium salt direction always.Along with the carrying out of reaction, the concentration of reaction conversion ratio and hydroxylammonium salt obtains continuing to improve.
C. collect reaction solution in clean container, according to the volume ratio of toluene and reaction solution is that 0.2: 1～10: 1 ratio adds toluene in reaction solution, after fully stirring, standing demix, upper oil phase is the toluene layer that contains unreacted oxime and micro-ketone, lower floor's water is the solution of hydroxylammonium salt, separates the profit two-phase, obtains the mother liquor of enrichment hydroxylammonium salt.
Temperature of reaction among the step B should be controlled at 40～100 ℃, and when especially preparing hydroxylamine nitriate, temperature of reaction should be strict controlled in below 100 ℃, avoids its thermolysis to set off an explosion.
The reaction unit of the coupling infiltrating and vaporizing membrane sepn process described in the step B is seen Fig. 1, comprise a material fluid bath, material fluid bath is connected with pump entry, and circulating-pump outlet is connected with calorifier inlets, heater outlet is connected with the infiltration vaporization membrane module inlet, the infiltration vaporization membrane module reaction solution exports connection material fluid bath inlet, infiltration vaporization membrane module sees through thing outlet connection condenser inlet, condensator outlet is connected with vacuum pump.
The workflow of the reaction unit of coupling infiltrating and vaporizing membrane sepn process is: reaction solution is added in the material fluid bath 1, by recycle pump 2 reaction solution is squeezed into well heater 3, by well heater 3 control reaction temperature, reaction solution after the heating enters in the infiltration vaporization membrane module 4, and circulates between membrane module 4 and material fluid bath 1.In infiltration vaporization membrane module 4, the by product ketone that generates in the reaction process is removed by selectivity, and the ketone that removes enters condenser 5 under the effect of vacuum pump 6, and condensation also reclaims.
Infiltrating and vaporizing membrane among the step B is a composite membrane, its tight zone material can be silicon rubber, poly-trimethyl silicane propine, paracril, styrene-butadiene rubber(SBR) and derivative or modifier, be good with silicon rubber and derivative thereof wherein, its thickness is at 0.1 μ m～100 μ m, and is thin more favourable; Support layer material can be that tetrafluoroethylene, polyvinylidene difluoride (PVDF) etc. have better acid proof polymer microporous film, and its thickness is between 20 μ m～500 μ m, and the micropore mean pore size should be controlled between 0.01 μ m～1 μ m.
Used infiltration vaporization membrane module can be that the flat Fig. 2 of opinion, tubular fibre formula are seen Fig. 4 or other forms in the aforesaid method, also can be the combining form of a plurality of infiltration vaporization membrane module serial or parallel connections, corresponding infiltrating and vaporizing membrane be flatly to see that accompanying drawing 3, tubular fibre formula see Fig. 5 or other forms.
The present invention and existing hydroxylammonium salt production method relatively have the following advantages:
(1) by oxime hydrolysis reaction single stage method synthesizing hydroxyamine salt, reaction process is simple, and the desired raw material kind is few, and operation does not relate to side reaction easily, and the reaction conditions gentleness.
(2) adopt infiltration evaporation membrane separation technique efficiently and directionally to remove byproduct of reaction ketone, broken the restriction of chemical equilibrium, reaction conversion ratio can reach 100% in theory, and reaction conversion ratio can reach more than 80% in the actual procedure.
Description of drawings
Fig. 1 is the reaction unit synoptic diagram of coupling infiltrating and vaporizing membrane sepn process, and wherein: 1 is material fluid bath; 2 is recycle pump; 3 is well heater; 4 is infiltration vaporization membrane module; 5 is condenser; 6 is vacuum pump.
Fig. 2 is the synoptic diagram of flat infiltration vaporization membrane module, and wherein: 1 is the reaction solution import; 2 are the reaction solution outlet; 3 is the membrane module upper body; 4 is the O V-shaped ring; 5 is infiltrating and vaporizing membrane; 6 is supporter; 7 is the membrane module lower body; 8 for seeing through the thing outlet.
Fig. 3 is the schematic cross-section of flat osmosis vaporizing compound membrane, and wherein: 1 is tight zone; 2 is micropore flat sheet membrane supporting layer; 3 is the micropore of supporting layer.
Fig. 4 is the synoptic diagram of tubular fibre formula infiltration vaporization membrane module, and wherein: 1 is the reaction solution import; 2 is end socket; 3 is the hollow-fibre membrane silk; 4 is housing; 5 is the reaction solution import; 6 for seeing through the thing outlet.
Fig. 5 is the schematic cross-section of tubular fibre formula osmosis vaporizing compound membrane, and wherein: 1 is tight zone; 2 is microporous hollow fiber film supporting layer; 3 is the micropore of supporting layer.
Embodiment:
A. by the ratio of hydrochloric acid in the reaction solution and the molar weight of cyclohexanone-oxime be 2 quantitatively, measure 2.1mol/L hydrochloric acid soln 200ml, take by weighing purity and be 95% cyclohexanone-oxime 23.73g, it is hybridly prepared into reaction solution.
B. reaction solution is added in the material fluid bath of reaction unit of coupling infiltrating and vaporizing membrane sepn process as shown in Figure 1.Used membrane module is a flat infiltration vaporization membrane module as shown in Figure 2, and wherein infiltrating and vaporizing membrane is a flat composite membrane as shown in Figure 3, and the separating layer material is a polydimethylsiloxane, membrane area 150.72cm
2, thickness 20 μ m; Supporting layer is a microporous poly tetrafluoroethylene, thickness 40 μ m, micropore size 0.2 μ m.Temperature of reaction is controlled at 50 ℃.
C. reaction is carried out collecting reaction solution behind the 4.5hr, according to toluene and the ratio of reaction solution volume than 1: 1, to wherein adding toluene 200ml, separates the profit two-phase, obtains the oxammonium hydrochloride mother liquor.
Adopt volumetry to analyze the concentration of oxammonium hydrochloride.Under identical condition, the equilibrium conversion of cyclohexanone-oxime hydrolysis reaction in hydrochloric acid soln is 6.5%, and adopts present technique, and after 4.5hr was carried out in reaction, transformation efficiency reached 72.3%, and the concentration of oxammonium hydrochloride reaches 42.58g/L in the mother liquor.
A. by the ratio of hydrochloric acid in the reaction solution and the molar weight of Diacetylmonoxime be 2 quantitatively, measure 2.1mol/L hydrochloric acid soln 200ml, take by weighing purity and be 99% Diacetylmonoxime 18.27g, it is hybridly prepared into reaction solution.
B. undertaken by the step B among the embodiment 1.
C. reaction is carried out collecting reaction solution behind the 2.5hr, according to toluene and the ratio of reaction solution volume than 0.5: 1, to wherein adding toluene 100ml, separates the profit two-phase, obtains the oxammonium hydrochloride mother liquor.
Adopt volumetry to analyze the concentration of oxammonium hydrochloride.Under identical condition, the equilibrium conversion of Diacetylmonoxime hydrolysis reaction in hydrochloric acid soln is 23.2%, and adopts present technique, and after 2.5hr was carried out in reaction, reaction conversion ratio reached 82.0%, and the concentration of oxammonium hydrochloride reaches 48.27g/L in the mother liquor.
A. by the ratio of sulfuric acid in the reaction solution and the molar weight of cyclohexanone-oxime be 0.5 quantitatively, measure 0.5mol/L sulphuric acid soln 200ml, take by weighing purity and be 95% cyclohexanone-oxime 23.73g, it is hybridly prepared into reaction solution.
B. undertaken by the step B among the embodiment 1.
C. undertaken by the step C among the embodiment 1.
Adopt volumetry to analyze the concentration of oxammonium hydrochloride.Under identical condition, the equilibrium conversion of cyclohexanone-oxime hydrolysis reaction in sulphuric acid soln is 4.2%.Adopt present technique, after 4.5hr was carried out in reaction, transformation efficiency reached 66.7%, and the concentration of oxammonium hydrochloride reaches 39.29g/L in the mother liquor.
A. by the ratio of sulfuric acid in the reaction solution and the molar weight of Diacetylmonoxime be 0.5 quantitatively, measure 0.5mol/L sulphuric acid soln 200ml, take by weighing purity and be 99% Diacetylmonoxime 18.27g, it is hybridly prepared into reaction solution.
B. undertaken by the step B among the embodiment 1.
C. undertaken by the step C among the embodiment 2.
Adopt volumetry to analyze the concentration of oxammonium hydrochloride.Under identical condition, the equilibrium conversion of Diacetylmonoxime hydrolysis reaction in sulphuric acid soln is 19.5%, and adopts present technique, and after 2.5hr was carried out in reaction, reaction conversion ratio reached 77.6%, and the concentration of oxammonium hydrochloride reaches 45.72g/L in the mother liquor.
A. undertaken by steps A among the embodiment 1.
B. reaction solution is added in the material fluid bath of reaction unit of coupling infiltrating and vaporizing membrane sepn process as shown in Figure 1.Used membrane module is a tubular fibre formula infiltration vaporization membrane module as shown in Figure 4, wherein is total to 20 of filling tubular fibre osmosis vaporizing compound membranes as shown in Figure 5, and composite membrane separating layer material is a polydimethylsiloxane, thickness 30 μ m; Supporting layer is the polyvinylidene difluoride (PVDF) hollow fiber microporous membrane, film filament length degree 20cm, thickness 40 μ m, film silk external diameter 0.886mm, micropore size 0.1 μ m, effective film area 222.56cm
2Temperature of reaction is controlled at 50 ℃.
C. undertaken by step C among the embodiment 1.
Adopt volumetry to analyze the concentration of oxammonium hydrochloride.Under identical condition, the equilibrium conversion of cyclohexanone-oxime hydrolysis reaction in hydrochloric acid soln is 6.5%, and adopts present technique, and after 4.5hr was carried out in reaction, transformation efficiency reached 70.3%, and the concentration of oxammonium hydrochloride reaches 41.39g/L in the reaction solution.
A. undertaken by steps A among the embodiment 2.
B. undertaken by step B among the embodiment 5.
C. undertaken by step C among the embodiment 2.
Adopt volumetry to analyze the concentration of oxammonium hydrochloride.Under identical condition, the equilibrium conversion of Diacetylmonoxime hydrolysis reaction in hydrochloric acid soln is 23.2%, and adopts present technique, and after 2.5hr was carried out in reaction, reaction conversion ratio reached 79.5%, and the concentration of oxammonium hydrochloride reaches 46.81g/L in the mother liquor.
Claims (1)
1. the method for oxime hydrolysis reaction and infiltration gasification film separation coupling technique preparation of hydroxylamine by one-step method, concrete steps are as follows:
A. according to the mol ratio that makes in the reaction solution acid with oxime be 0.5～3 quantitatively, accurately take by weighing oxime, join in the acid solution preparation reaction solution;
Raw materials used oxime is acetoxime, Diacetylmonoxime or cyclohexanone-oxime, and purity is more than 95%; Used acid is a kind of in hydrochloric acid, nitric acid, sulfuric acid, the phosphoric acid, and its concentration is between 0.5mol/L～1.0mol/L;
B. reaction solution is added in the coupling infiltration evaporation film separation reaction device, controlled temperature makes oxime generation hydrolysis reaction at 40 ℃～100 ℃, infiltrating and vaporizing membrane optionally removes byproduct of reaction ketone in the reaction process, impel oxime hydrolysis reaction to carry out to the direction that generates hydroxylammonium salt, along with the carrying out of reaction, hydroxylammonium salt concentration obtains continuing to improve; Byproduct of reaction ketone sees through infiltrating and vaporizing membrane removing by selectivity;
C. collect reaction solution in clean container, according to the volume ratio of toluene and reaction solution is that 0.2: 1～10: 1 ratio adds toluene in reaction solution, after fully stirring, standing demix, upper oil phase is the toluene layer that contains unreacted oxime and micro-ketone, lower floor's water is the solution of hydroxylammonium salt, separates the profit two-phase, obtains the mother liquor of enrichment hydroxylammonium salt.
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| CN103395757B (en) * | 2013-08-12 | 2015-05-06 | 河北工业大学 | Method for synthesizing hydroxylamine salt |
| CN104129765B (en) * | 2014-07-18 | 2017-02-15 | 湘潭大学 | Reaction-extraction coupling method for preparation of hydroxylamine salt / hydroxylamine |
| CN105294488B (en) * | 2015-11-20 | 2017-05-03 | 山东兴辉化工有限公司 | Pretreatment method of hydroxylammonium chloride mother solution recovery process |
| CN107522181A (en) * | 2017-03-20 | 2017-12-29 | 临沭县华盛化工有限公司 | The technique that hydroxylamine hydrochloride is prepared using oxime acid hydrolysis method |
| CN108440306B (en) * | 2018-05-24 | 2023-11-03 | 柏川新材料科技(宁波)有限公司 | Green production equipment and method of tetramethyl ammonium carbonate |
| CN112138546A (en) * | 2019-06-28 | 2020-12-29 | 岭东核电有限公司 | Radioactive strong brine processing apparatus based on pervaporation |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5281338A (en) * | 1990-08-10 | 1994-01-25 | Archaeus Technology Group Limited | Method of decolorizing water |
| CN1406929A (en) * | 2001-08-31 | 2003-04-02 | 德古萨公司 | Ammoxidation of ketone and treatment via penetrating evaporation and vapor permeation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5281338A (en) * | 1990-08-10 | 1994-01-25 | Archaeus Technology Group Limited | Method of decolorizing water |
| CN1406929A (en) * | 2001-08-31 | 2003-04-02 | 德古萨公司 | Ammoxidation of ketone and treatment via penetrating evaporation and vapor permeation |
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