CN1485607A - Method for analizing cyclohexanone oxime in the cyclohexanone oxime rearrangement reaction mixture - Google Patents
Method for analizing cyclohexanone oxime in the cyclohexanone oxime rearrangement reaction mixture Download PDFInfo
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- CN1485607A CN1485607A CNA021396558A CN02139655A CN1485607A CN 1485607 A CN1485607 A CN 1485607A CN A021396558 A CNA021396558 A CN A021396558A CN 02139655 A CN02139655 A CN 02139655A CN 1485607 A CN1485607 A CN 1485607A
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Abstract
The invention relates to an analytical method for cyclohexanone oxime in cyclohexanone oxime rearrangement reaction mixture, characterized by that the rearrangement reaction mixture is first neutralized, regulating the pH value of the solution to between weak acidity to neutral, then determining the hydrolysis product of the cyclohexanone oxime, i.e. hydroxylamine, using p-aminobenzene-sulfonic acid added by chlorhydric acid as diazotization reagent, catching the nitrous acid generated by the iodine oxygenized hydroxylamine, and entering into kalium bromatum to increase reaction velocity, using sodium acetate to regulate the acidity of the solution.
Description
Technical field
The present invention relates to the mensuration of the diazotising-coupling spectrophotometric method of cyclohexanone-oxime in the rearrangement of cyclohexanone-oxime reaction mixture.
Background technology
Rearrangement of cyclohexanone-oxime reaction quality is the key reaction that influences the caprolactam product quality.Rearrangement product is complicated, contains a large amount of sulfuric acid and nicotinic acid, and viscosity is big, and corrosivity is strong, except that the principal ingredient caprolactam, also contains impurity such as cyclopentanol, cyclohexanone and aniline, acid amides, carboxylic acid.Directly the cyclohexanone-oxime of analyzing wherein almost cannot.
The domestic reported in literature of also not measuring cyclohexanone-oxime in the rearrangement product up to now.
The bibliographical information that adopts organic impurities such as caprolactam, cyclohexanone in the chromatography analysis rearrangement product is abroad arranged, do not measure the bibliographical information of cyclohexanone-oxime in the rearrangement of cyclohexanone-oxime reaction mixture
The analysis of cyclohexanone-oxime is a blank in analysis technical field in the neutralized rearrangement mixture.
Both at home and abroad the analytical approach about cyclohexanone-oxime in the caprolactam is that cyclohexanone-oxime is hydrolyzed to cyclohexanone or azanol, measures azanol again, and the method for measuring azanol has oxidimetry and acid base titration, electrochemical method, spectrophotometric method, chromatography etc.
Summary of the invention
The object of the present invention is to provide the assay method of the diazotising-coupling spectrophotometric method of cyclohexanone-oxime in the rearrangement of cyclohexanone-oxime reaction mixture
The present invention is achieved in that the rearrangement reaction potpourri is carried out neutralisation treatment earlier, the pH value of regulator solution is between 4～6, hydrolysate-the azanol of cyclohexanone-oxime is carried out diazotising-coupling reaction, form azo compound, thereby with the content of spectrophotometry azanol indirect determination cyclohexanone-oxime; With the sulfanilic acid that is added with hydrochloric acid is diazo reagent, catch the nitrous acid that generates by iodine oxidation azanol, and adding halogenide improves reaction velocity, acidity with the sodium acetate regulator solution, unnecessary iodine thiosulfuric acid sodium reduction, add the naphthalidine coupling reagent, form azo compound, measure at 520nm with spectrophotometer.
Concrete steps are as follows:
One, preparation reagent:
1, the dilute hydrochloric acid solution of sulfanilic acid preparation:
Take by weighing sulfanilic acid (analyzing pure), add the suitable quantity of water heating for dissolving, add concentrated hydrochloric acid, constant volume.
2, iodine storing solution preparation:
Take by weighing iodine (analyzing pure) and potassium iodide (analyzing pure), water dissolving and constant volume.
Iodine working fluid preparation: get above-mentioned iodine storing solution, the dilute with water constant volume.
3, sodium acetate solution preparation:
Anhydrous sodium acetate (analyzing pure) is soluble in water.
4, hypo solution preparation:
Sodium thiosulfate (analyzing pure) is soluble in water.
5, naphthalidine formulations prepared from solutions:
Naphthalidine (analyzing pure) is dissolved in the glacial acetic acid (analyzing pure), again the water constant volume.
6, ammoniacal liquor preparation:
Get strong aqua (analyzing pure) dilution constant volume.
7, citric acid solution preparation:
Citric acid (analyzing pure) constant volume soluble in water.
8, the preparation of cyclohexanone-oxime:
In 60～70 ℃ hot benzene, add cyclohexanone-oxime (analyzing pure), be stirred to saturatedly, be cooled to room temperature, separate out the cyclohexanone-oxime crystal, again the crystal of separating out is dissolved in 60～70 ℃ the hot benzene, ditto operate three times.Obtain the recrystallization crystal of cyclohexanone-oxime.
The preparation of cyclohexanone-oxime storing solution:
Take by weighing the cyclohexanone-oxime crystal of recrystallization, with sulfuric acid (analyzing pure) dissolving and constant volume.
The preparation of cyclohexanone-oxime titer:
Get above-mentioned cyclohexanone-oxime storing solution, after the suitable quantity of water dilution, with ammoniacal liquor neutralization, constant volume.
9, potassium bromide (analyzing pure)
Two, measure
1. sample preparation: take by weighing the rearrangement reaction blend sample, add citric acid solution and an amount of distilled water, stir evenly, drip with dropper while stirring.
2. blank value is measured: add sample solution respectively in several color comparison tubes, do not add iodine and naphthalidine in No. 1 color comparison tube, other reagent all adds; Do not add iodine in No. 2 color comparison tubes, other reagent all adds; Do not add naphthalidine in No. 3 color comparison tubes, other reagent all adds, and is that reference is measured absorbance in 520nm wavelength place with No. 1 color comparison tube
3. in several color comparison tubes, add sample solution respectively with ammoniacal liquor neutralization and constant volume, add the cyclohexanone-oxime titer of different volumes and an amount of sulfanilic acid solution, iodine working fluid, potassium bromide more respectively, shake up, add sodium acetate solution, hypo solution, naphthalidine solution again, shake up the back and place.No. 1 color comparison tube during with the mensuration blank value is a reference, measures absorbance in 520nm wavelength place.
4. according to determination data,, measure cyclohexanone-oxime in the neutralized rearrangement mixture with the standard addition method mapping.
Good effect of the present invention has been to provide the analytical approach of cyclohexanone-oxime in the rearrangement of cyclohexanone-oxime reaction mixture, can instruct technology to adjust sour oxime ratio, reduces raw-material consumption; Simple to operate, favorable reproducibility, highly sensitive, analysis time is short, and the coefficient of variation is less than 1%, and recovery of standard addition is greater than 90%, and minimum detectable level can reach 0.1mg/L.
Embodiment
Embodiment 1: the assay method of cyclohexanone-oxime is as follows in the rearrangement reaction potpourri:
1 preparation reagent
1. the dilute hydrochloric acid solution of 0.5% sulfanilic acid: take by weighing 0.5 gram sulfanilic acid, add the suitable quantity of water heating for dissolving, add the 10mL concentrated hydrochloric acid, be settled to 100mL.
2. 0.05mol/L iodine storing solution: take by weighing 1.27g iodine and 4g potassium iodide, the water dissolving also is settled to 100mL.
3. 0.005mol/L iodine working fluid: get 10mL iodine storing solution, be diluted with water to 100mL.
4. 2.0mol/L sodium acetate solution: the 18.2g anhydrous sodium acetate is dissolved in the 100mL water.
5. 0.1mol/L hypo solution: 2.48g sodium thiosulfate is dissolved in the 100mL water.
6. 0.3%1-naphthylamines solution: the 0.3g1-naphthylamines is dissolved in the 70mL glacial acetic acid, and water is settled to 100mL again.
7. 10% ammoniacal liquor: get strong aqua 40mL and be diluted to 100mL.
8. 20% citric acid solution: the 20g citric acid is dissolved in the 100mL water.
10. 500ppm cyclohexanone-oxime storing solution: take by weighing the 0.050g cyclohexanone-oxime with the 1+1 sulfuric acid dissolution and be settled to 100mL.
(11) 5.0ppm cyclohexanone-oxime titer: get the above-mentioned cyclohexanone-oxime storing solution of 0.5mL, after the suitable quantity of water dilution, be neutralized to about pH6.5, be settled to 50mL with 10% ammoniacal liquor.
(12) potassium bromide solid
2 measure
1. accurately take by weighing the rearrangement reaction blend sample of 2.5g, add the citric acid solution of 5mL, add the distilled water of 5～10mL, stir evenly, use 10% ammoniacal liquor about dropper Dropwise 5 mL while stirring, be neutralized to about PH4～6, be settled to 50mL.
2. add sample solution 2.5mL respectively in 3 10mL color comparison tubes, do not add I2 and naphthalidine in No. 1 color comparison tube, other reagent all adds; Do not add I2 in No. 2 color comparison tubes, other reagent all adds; Do not add naphthalidine in No. 3 color comparison tubes, other reagent all adds, and is that reference is measured absorbance in 520nm wavelength place with No. 1 color comparison tube
3. in 6 10mL color comparison tubes, add above-mentioned sample solution 2.5mL respectively, add 0 respectively again, 0.5mL, 1.0mL, 1.5mL, 2.0mL, 2.5mL 5ppm cyclohexanone-oxime titer, 1mL 0.5% sulfanilic acid solution, 1mL I2 working fluid, add the 1g potassium bromide, shake up, add the 1mL sodium acetate solution again, 0.2mL hypo solution, 0.5mL1-naphthylamines solution shakes up the back and places 10min, No. 1 color comparison tube during with the mensuration blank value is a reference, measures absorbance in 520nm wavelength place.
4. according to determination data,, measure cyclohexanone-oxime 2.7mg/L in the neutralized rearrangement mixture with the standard addition method mapping.
Claims (3)
1. the analytical approach of cyclohexanone-oxime in the rearrangement of cyclohexanone-oxime reaction mixture, it is characterized in that the rearrangement reaction potpourri is carried out neutralisation treatment earlier, the pH value of regulator solution is between 4～6, hydrolysate with cyclohexanone-oxime---azanol carries out diazotising-coupling reaction, form azo compound, thereby with the content of spectrophotometry azanol indirect determination cyclohexanone-oxime.
2. according to the analytical approach of cyclohexanone-oxime in claims 1 described a kind of rearrangement of cyclohexanone-oxime reaction mixture, the sulfanilic acid that it is characterized in that being added with hydrochloric acid is a diazo reagent, catch the nitrous acid that generates by iodine oxidation azanol, and adding halogenide improves reaction velocity, with the acidity of sodium acetate regulator solution, unnecessary iodine thiosulfuric acid sodium reduction adds the naphthalidine coupling reagent, form azo compound, measure at 520nm with spectrophotometer.
3. according to the analytical approach of cyclohexanone-oxime in claims 1 described a kind of rearrangement of cyclohexanone-oxime reaction mixture, the preparation that it is characterized in that reagent is carried out as follows, gets sulfanilic acid, adds the entry heating for dissolving, add concentrated hydrochloric acid, constant volume prepares the dilute hydrochloric acid solution of sulfanilic acid; Get iodine and potassium iodide, water dissolving and constant volume prepare the iodine storing solution, again iodine storing solution water dilution constant volume are prepared the iodine working fluid; Naphthalidine is dissolved in the glacial acetic acid, and the water constant volume prepares naphthalidine solution again; In 60～70 ℃ hot benzene, add cyclohexanone-oxime, be stirred to saturatedly, be cooled to room temperature, separate out the cyclohexanone-oxime crystal, again the crystal of separating out is dissolved in 60～70 ℃ the hot benzene, presses aforesaid operations three times, obtain the recrystallization crystal of cyclohexanone-oxime, get the cyclohexanone-oxime crystal of recrystallization again, with sulfuric acid dissolution and constant volume, preparation cyclohexanone-oxime storing solution is got the cyclohexanone-oxime storing solution again, behind the dilute with water, with preparing the cyclohexanone-oxime titer with constant volume in the ammoniacal liquor.
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| CNA021396558A CN1485607A (en) | 2002-09-29 | 2002-09-29 | Method for analizing cyclohexanone oxime in the cyclohexanone oxime rearrangement reaction mixture |
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| CNA021396558A CN1485607A (en) | 2002-09-29 | 2002-09-29 | Method for analizing cyclohexanone oxime in the cyclohexanone oxime rearrangement reaction mixture |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100494979C (en) * | 2006-06-02 | 2009-06-03 | 中国科学院沈阳应用生态研究所 | Analytical method for detecting hydroxyl amine reducing enzyme activity in soil |
| CN107089924A (en) * | 2016-09-23 | 2017-08-25 | 河北美邦工程科技股份有限公司 | A kind of azanol, hydroxylamine salt, the combined producing process of cyclohexanone oxime |
| CN108827950A (en) * | 2018-05-31 | 2018-11-16 | 成都市科隆化学品有限公司 | The detection method of micro-acetic acid acid anhydride in acetic acid |
| CN111060464A (en) * | 2019-11-28 | 2020-04-24 | 福建永荣科技有限公司 | Method for measuring chroma of caprolactam heavy discharge liquid |
-
2002
- 2002-09-29 CN CNA021396558A patent/CN1485607A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100494979C (en) * | 2006-06-02 | 2009-06-03 | 中国科学院沈阳应用生态研究所 | Analytical method for detecting hydroxyl amine reducing enzyme activity in soil |
| CN107089924A (en) * | 2016-09-23 | 2017-08-25 | 河北美邦工程科技股份有限公司 | A kind of azanol, hydroxylamine salt, the combined producing process of cyclohexanone oxime |
| 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 |
| CN108827950A (en) * | 2018-05-31 | 2018-11-16 | 成都市科隆化学品有限公司 | The detection method of micro-acetic acid acid anhydride in acetic acid |
| CN108827950B (en) * | 2018-05-31 | 2020-08-21 | 成都市科隆化学品有限公司 | Method for detecting trace acetic anhydride in acetic acid |
| CN111060464A (en) * | 2019-11-28 | 2020-04-24 | 福建永荣科技有限公司 | Method for measuring chroma of caprolactam heavy discharge liquid |
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