CN100390535C - Liquid-phase colour-spectrum quantitative analysis method for cyclohexane carboxylic-acid sulfoacid in process system for producing caprolactam by methylbenzene method - Google Patents
Liquid-phase colour-spectrum quantitative analysis method for cyclohexane carboxylic-acid sulfoacid in process system for producing caprolactam by methylbenzene method Download PDFInfo
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Abstract
The invention discloses a toluene-cyclohexane carboxylic acid-acid liquid chromatography system quantitative analysis method in process of caprolactam production. Its technical features are: (1)Do toluene-cyclohexane carboxylic acid-acid extraction and preparation in cyclohexane carboxylic acid containing sulfonate system by the way of extraction and adsorption, elution, extraction and the crystalline means. The purity of samples from the cyclohexane carboxylic acid-acid >= 98%, absorbents and extract the raw materials are easy to get, adsorption and elution process is simple and easy to operate; (2)Using of the 1H and 13C NMR spectral analysis. FT-IR, UV and LC AAS analysis for Cyclohexane carboxylic acid acid qualitative and quantitative analysis, and the analysis is reliable qualitative and quantitative analysis; (3)Adapting to a complex system of cyclohexane carboxylic acid-acid liquid chromatography quantitative analysis method, the analysis method can separate cyclohexane carboxylic acid-acid from various other components, and have an appropriate response signal, and analyze the harsh conditions, the results of the analysis accuracy and reproducibility, analysis is quick, sample handling is simple.
Description
Technical field
The present invention relates to a kind of chromatogram quantitative analysis of the liquid phase method of cyclohexane-carboxylic acid sulfonic acid.
Background technology
It is that Italian Si Niya (SNIA Viscosa) company is the method that raw material is produced caprolactam with toluene in the nineteen sixty exploitation that toluene method is produced caprolactam, the advantage of toluene method is that flow process is short, handling safety, preceding current cost is lower, is suitable for the abundant country of toluene.But come with some shortcomings simultaneously, many and atmospheric environment had the pollution except by-product sulfuric acid, also have selectivity and yield by cyclohexane-carboxylic acid production caprolactam to be not so good as to produce the caprolactam height by methods such as cyclohexanone-oximes, main cause is that there is sulfonation subsidiary reaction etc. in the premixing reaction of cyclohexane-carboxylic acid.Subsidiary reaction mainly is the sulfonating reaction on the cyclohexane-carboxylic acid alpha-position, and accessory substance mainly is cyclohexane-carboxylic acid sulfonic acid and acid by-product and other a small amount of gaseous product such as CO, NO, SO
2And N
2Deng.In 13% accessory substance,, wherein contain the cyclohexane-carboxylic acid sulfonated acid by-product of 6-8%, the acid by-product of 4-5% according to preresearch estimates.Caprolactam yield meter with 50,000 tons/year, the annual cyclohexane-carboxylic acid sulfonic acid that the 3000-4000 ton will be arranged, and this by-product is handled with the form of burning or discharging, and not only environment is polluted, and is to influence the main cause that SNIA produces the caprolactam market competitiveness.From producing actual and scientific research, influence SNIA and produce caprolactam selectivity and yield, be each reaction mechanism and influence factor shortage are fully realized, and present analysis condition, not to generating the qualitative and quantitative analysis of instrument accurately of by-product such as many a spot of cyclohexane-carboxylic acid sulfonic acid, the process conditions that the premixing reaction of cyclohexane-carboxylic acid has been generated many a spot of cyclohexane-carboxylic acid sulfonic acid and influence main side effect proportion of products relation do not have quantitative test and are familiar with unclear, how to set up the chromatogram quantitative analysis of the liquid phase method of a cover cyclohexane-carboxylic acid sulfonic acid, qualitative and quantitative analysis result according to accessory substances such as cyclohexane-carboxylic acid sulfonic acid, find the situation of change of cyclohexane-carboxylic acid sulfonic acid in the premixing reaction main side effect products distribution of cyclohexane-carboxylic acid and the subsequent technique process, for optimizing the premixing reaction process conditions, the growing amount of reduction by-product cyclic cyclohexane carboxylic-acid sulfonic acid etc. improves toluene method production caprolactam reaction yield and has very important significance.Produce the advantage and the deficiency of caprolactam at toluene method, National Natural Science Foundation of China was in project verification (bullets 20233040 in 2003, country is from section's fund primary study project), carry out the emphasis tackling of key scientific and technical problems with regard to " environmental friendliness is produced innovation of caprolactam gordian technique and fundamental research ", what tackling key problem was mainly studied is eco-friendly production technology, the analytical approach that does not relate to cyclohexane-carboxylic acid sulfonic acid in the system is set up, simultaneously, in existing patent and document, the report that does not have in each system of SNIA technological process the instrumental quantitative analysis method of relevant cyclohexane-carboxylic acid sulfonic acid and acid by-product, chemical analysis method to cyclohexane-carboxylic acid sulfonic acid in neutral and the alkaline system is only arranged, and the chemical analysis of cyclohexane-carboxylic acid sulfonic acid is the neutralization titration that adopts two equivalent points, this method shows through producing reality and scientific research application, have limitation and wretched insufficiency: analysis condition is quite harsh, need repeatedly extraction, treatment step is loaded down with trivial details, the consumption of reagent is big, the judgement of equivalent point is very difficult, analysis time is long, analysis result do not repeat and analysis deviation big, incompatible more to acid system, can not satisfy the needs of production and scientific research, set up the liquid chromatography instrument quantitative analysis method that is adapted to component such as cyclohexane-carboxylic acid sulfonic acid in the various systems of SNIA technological process quickly and accurately, toluene method is produced caprolactam technology, instruct in suitability for industrialized production and the scientific research all very necessary.
Summary of the invention
The method that the purpose of this invention is to provide a kind of extraction cyclohexane-carboxylic acid sulfonic acid from contain cyclohexane-carboxylic acid sulfonic acid system, and the cyclohexane carboxylic acid sulfonic acid that extraction obtains carried out chromatogram quantitative analysis of the liquid phase, thereby set up the chromatogram quantitative analysis of the liquid phase method that toluene method is produced cyclohexane-carboxylic acid sulfonic acid in the caprolactam technology system, instruct and optimize the process conditions that toluene method is produced caprolactam, improve the yield that toluene method is produced caprolactam.
Toluene method is produced the chromatogram quantitative analysis of the liquid phase method of cyclohexane-carboxylic acid sulfonic acid in the caprolactam technology system, and the present invention realizes in the following way:
1), analyze the extraction of quantitatively using cyclohexane-carboxylic acid sulfonic acid standard model:
A) produce in the neutrality of the cyclohexane-carboxylic acid sulfonic acid composition that the caprolactam technology process contains 5%-10% or the alkaline solution at toluene method and extract sample, regulating the pH value is 3-4, and be mixed with the sample solution of 2%-3% concentration, evenly flowing through length is 40cm, internal diameter 20mm, the adsorption column of interior dress large aperture strong-basicity styrene series anion exchange resin, absorption is wherein with the material of acidic-group, after treating that adsorption column is saturated, stop the conveying of sample solution, effluent is an A liquid;
B) with the acid solution of 5%-10% as desorbing agent, wash-out has adsorbed the styrene series anion exchange resin of acidic materials, acidic materials be eluted in 5%-10% acid solution in, B liquid;
C) B liquid evenly being flow through length is 40cm, internal diameter 20mm, and interior dress large hole strong acid styrene system cation exchange resin's adsorption column, with the absorption impurity that contains basic group wherein, effluent is a C liquid;
D) C liquid is concentrated, with dichloromethane solvent extraction three times, raffinate is a D liquid;
E) D liquid is concentrated once more, hydro-oxidation potassium or NaOH make the pH value be 7-8 in ice-water bath, crystallisation by cooling, and with dissolving of crystal water and adjust pH to 2.0, recrystallization obtains cyclohexane-carboxylic acid sulfonic acid analytical standard sample again;
2) chromatogram quantitative analysis of the liquid phase of cyclohexane-carboxylic acid sulfonic acid;
Chromatographic condition:
A) instrument: the high performance liquid chromatograph of band UV, visible light spectrophotometric detector UV and chromatographic work station;
B) chromatographic column: the UP-ODS or the C that adorn 5 μ m granularity fillers in 15cm-25cm length and the 4.6mm internal diameter
18The CBPC post;
C) moving phase: moving phase is prepared by 37.5: 62.5 volume ratio by solution A and solution B; Solution A is made up of chromatographically pure methyl alcohol or acetonitrile single solvent, and solution B is by adding 0.4% ion-pairing agent and the phosphoric acid of 5mmol and the phosphate dressing agent of 75mmol in the experiment one-level water, and ion-pairing agent is a quaternary amine;
D) analytical wavelengths: 220nm;
Analytic process:
A) get cyclohexane-carboxylic acid sulfonic acid standard analysis sample is prepared one group of 3mg/ml-9mg/ml concentration with experiment one-level water standard model solution;
B) getting testing sample, is the testing sample solution of 1mg/ml-15mg/ml with experiment one-level water compound concentration;
C) under above-mentioned chromatographic condition, above-mentioned standard model solution of quantitative sample injection and testing sample solution sample introduction, get analysis of spectra, each sample feeding three times, being not more than 1.5% with its peak area relative error of three sample introductions of each sample is effective sample introduction, and the mean value of three sample introduction peak areas of a sample is used data for calculating;
Quantivative approach: adopt external standard method.
Send out beneficial effect of the present invention: 1. in containing cyclohexane-carboxylic acid sulfonic acid system, carry out the extraction of cyclohexane-carboxylic acid sulfonic acid, cyclohexane-carboxylic acid sulfonic acid standard model purity 〉=98% of quantitative usefulness is analyzed in the conduct that extraction obtains, adsorbent and eluant, eluent raw material are easy to get, absorb-elute flow process and equipment are simple, and is easy to operate; 2. extract the cyclohexane-carboxylic acid sulfonic acid standard model qualitative and quantitative analysis reliable results that obtains; 3. set up the chromatogram quantitative analysis of the liquid phase method that is adapted to cyclohexane-carboxylic acid sulfonic acid in the various complex systems of SINA technology, this analytical approach can make the various components of cyclohexane-carboxylic acid sulfonic acid and other separate fully, and suitable response signal arranged all, and analysis condition is not harsh, analysis result accurate and reproduction, standard deviation≤± 5%, analysis speed is fast, analysis time＜40 minute; Sample preparation is simple, does not need special processing, directly water preparation.
Description of drawings;
Fig. 1 is the UV spectrogram of cyclohexane-carboxylic acid sulfonic acid analysis with standard model;
Fig. 2 is the FT-IR spectrogram of cyclohexane-carboxylic acid sulfonic acid analysis with standard model;
Fig. 3 is a cyclohexane-carboxylic acid sulfonic acid analysis standard model
13C composes spectrogram;
Fig. 4 is a cyclohexane-carboxylic acid sulfonic acid analysis standard model
1H composes spectrogram;
Fig. 5 is the HPLC analysis of spectra of cyclohexane-carboxylic acid sulfonic acid analysis with standard model;
Fig. 6 is the HPLC analysis of spectra that contains the sample of cyclohexane-carboxylic acid sulfonic acid;
Embodiment
The present invention will be further described below in conjunction with embodiment:
Embodiment:
1) analyze the extraction of using cyclohexane-carboxylic acid sulfonic acid standard model:
Prepare No. 1 adsorption column, No. 1 adsorption column length is 40cm, internal diameter 20mm, and interior dress large aperture strong-basicity styrene series anion exchange resin, as D201, the performance of D201 resin is as follows:
| Name of product | The large aperture strong-basicity styrene series anion exchange resin |
| Resin structure | Styrene-DVB |
| Functional group | -N +(CH 3) 3 |
| Full exchange capacity | (a)≥3.3，(b)≥0.8 |
| Outward appearance | The opaque spherical particle of milky |
| Granularity (0.315-1.25mm) | ≥95 |
| Moisture (%) | 60-70 |
| Wet true density (g/ml) | 1.05-1.10 |
| Wet pseudodensity (g/ml) | 0.65-0.70 |
| Mill back rate of small round spheres (%) | ≥80 |
| Expansivity (%) makes the transition | CI→OH 15-18 |
| Maximum operation (service) temperature (℃) | |
| The pH usable range | 1-14 |
Full exchange capacity: (a) (b) mM/gram (wetting) of mM/gram (doing)
A) in the process of toluene method production caprolactam technology, extract sample, get not causticization acid amides oil (chemical analysis wherein contains the cyclohexane-carboxylic acid sulfonic acid of 5%-7%) of 100ml,, make its pH value between 3.5-4.0, get sample solution with the dilution of 100ml water; Sample solution is slowly passed through No. 1 adsorption column, with absorption acidic components wherein; After treating that adsorption column is saturated, stop the conveying of sample solution, acidic materials are adsorbed on the adsorbent, and neutrality and alkaline matter are in the solution that flows out, and effluent is an A liquid;
B) adsorbed No. 1 adsorption column of acidic components with 5% hydrochloric acid solution wash-out, eluent B solution, adsorption column 1 recycles.
Prepare No. 2 adsorption column, No. 2 adsorption column length are 40cm, internal diameter 20mm, and interior dress large hole strong acid styrene system cation exchange resin, as D072, the performance of D072 resin is as follows:
| Name of product | Large aperture strongly acidic styrene's series anion exchange resin |
| Resin structure | Styrene-DVB |
| Functional group | -SO 3- |
| Full exchange capacity mmol/ml | ≥4.2 |
| Outward appearance | Light yellow spherical particle |
| Granularity (0.3-1.2mm) | ≥95 |
| Moisture (%) | 50-55 |
| Wet true density ((20 ℃) g/ml) | 1.20-1.30 |
| Wet pseudodensity (g/ml) | 0.70-0.80 |
| Mill back rate of small round spheres (%) | ≥80 |
| Expansivity (%) makes the transition | (Na +→H +)≤8％ |
| Maximum operation (service) temperature (℃) | 100 |
| The pH usable range | 1-14 |
C) B solution is slowly passed through No. 2 adsorption columns,, collect effluent, claim C solution with absorption other impurity that contains basic group wherein;
D) with the C solution concentration to 150ml, with washed with dichloromethane extraction 3 times, each methylene chloride consumption 50ml, with extraction components such as cyclohexane-carboxylic acid wherein, raffinate is a D solution;
E) with the D solution concentration to 50ml, hydro-oxidation potassium is neutralized to the pH value between 7-8 in ice-water bath, crystallisation by cooling, filtration drying get cyclohexane-carboxylic acid sulfonic acid potassium salt first product; Cyclohexane-carboxylic acid sulfonic acid potassium salt first product is dissolved with low amounts of water, carefully transfer pH to 2.0 with hydrochloric acid solution, recrystallization gets content greater than 98% cyclohexane-carboxylic acid sulfonic acid standard analysis sample.
2) the cyclohexane-carboxylic acid sulfonic acid analysis that extraction the is obtained qualitative analysis of standard model
To use the qualitative analysis of standard model by the cyclohexane-carboxylic acid sulfonic acid analysis of said method extraction, adopt following method:
Whether a) as shown in Figure 1, ultraviolet-visible pectrophotometer analysis (UV) detects its maximum absorption wavelength, differentiate consistent with the theoretical maximum absorption wavelength of inferring of cyclohexane-carboxylic acid sulfonic acid; Analyze through UV, absorption maximum is arranged, with matching that theory is inferred at the 214nm place.
B) as shown in Figure 2, FFIR analysis (FT-IR), infrared spectrogram, the absorption peak position of judging its characteristic group whether absorption peak position of the theory characteristic group of cyclohexane-carboxylic acid sulfonic acid is consistent; Analyze through FT-IR,, can find the absorption peak of the theory characteristic group that absorbs cyclohexane-carboxylic acid sulfonic acid, with matching that theory is inferred at different wave number sections.
C) as shown in Figure 3, Figure 4, nuclear magnetic resonance
13The C spectrum,
1The analysis of H spectrum is used
13The C analysis of spectrum is measured the chemical shift of the carbon skeleton of cyclohexane-carboxylic acid sulfonic acid reference material, measure the influence of chemical environment to the chemical shift of different C atoms, the chemical shift of differentiate extracting the cyclohexane-carboxylic acid sulfonic acid reference material for preparing whether with matching that theory is inferred, use
1The H analysis of spectrum is measured the chemical shift of the H atom of cyclohexane-carboxylic acid sulfonic acid reference material, measure the influence of chemical environment to the chemical shift of different H atoms, differentiate extract the cyclohexane-carboxylic acid sulfonic acid reference material for preparing chemical shift whether with matching that theory is inferred.Warp
13The C spectrum,
1The H analysis of spectrum, the chemical shift of the carbon skeleton of cyclohexane-carboxylic acid sulfonic acid reference material and the chemical shift of H atom and theoretical matching of inferring.
The sample of preparation is from reality and all can obtain reasonable dismissal in theory.
3) quantitative test:
As shown in Figure 5, liquid-phase chromatographic analysis (HPLC) is analyzed cyclohexane-carboxylic acid sulfonic acid analysis standard model, change the analytical wavelengths (210nm-230nm) of UV-detector (UV), whether the area normalization method percentage composition is more than 98%, and whether the content of metallic ion potassium and sodium is below 1% in employing atomic absorption (AAS) the analysis analytic sample.
4) the chromatogram quantitative analysis of the liquid phase method of cyclohexane-carboxylic acid sulfonic acid in each system of SINA technology
A) preparation of instrument: the high performance liquid chromatograph of band uv-spectrophotometric detecting device (UV) and chromatographic work station.
B) preparation of chemical reagent: methyl alcohol or acetonitrile (chromatographically pure), tetraethyl amine bromide or other quaternary amine, phosphoric acid, sodium hydrogen phosphate (potassium), sodium dihydrogen phosphate (potassium), (it is pure that above reagent is analysis), one-level water.
C) preparation of moving phase: example CH
3OH/H
20=37.5/62.5 (V/V), include 0.4% tetraethyl amine bromide ion-pairing agent, the potassium dihydrogen phosphate of the phosphoric acid of 5mmol concentration and 75mmol concentration is as dressing agent and buffering agent.
D) UP-ODS or the C of chromatographic column: 15cm-25cm * Ф 4.6mm 5 μ m
18The CBPC post of chromatographic column or other type.
E) absorbing wavelength and flow rate of mobile phase: 220nm, 0.7-1.0ml/min.
F) preparation of sample solution: accurately take by weighing the sample about 0.1000g, be settled to one-level water in the volumetric flask of 10ml.
G) preparation of standard model solution: to adopting the standard model of method for preparing, under 105-110 ℃, (under above-mentioned analysis condition, adopted area normalization method in dry 2 hours, its relative percentage composition 〉=98%), is mixed with the standard solution of 3mg/ml, 6mg/ml and 9mg/ml respectively.
H) under above-mentioned chromatographiccondition, advance standard model solution 10 μ l, quantitative sample injection, get analysis of spectra, each sample feeding three times, being not more than 1.5% with its peak area relative error of three sample introductions of each sample is effective sample introduction, and the mean value of three sample introduction peak areas of a sample is used data for calculating.Make external standard curve (peak area-weight).
I) under above-mentioned identical chromatographiccondition, sample introduction product solution 10 μ l, it is effective sample introduction that same its peak area relative error of three sample introductions with each sample is not more than 1.5%, the mean value of three sample introduction peak areas of a sample is used data for calculating, qualitative with retention time, get the peak area of determinand cyclohexane-carboxylic acid sulfonic acid, with external standard method quantitative Analysis content.Contain cyclohexane-carboxylic acid sulfonic acid sample the HPLC analysis of spectra as shown in Figure 6, the peak of 10.858min is a cyclohexane-carboxylic acid sulfonic acid.
Claims (1)
1. a toluene method is produced the chromatogram quantitative analysis of the liquid phase method of cyclohexane-carboxylic acid sulfonic acid in the caprolactam technology system, it is characterized in that:
1), analyze the extraction of quantitatively using cyclohexane-carboxylic acid sulfonic acid standard model:
A) produce in the neutrality of the cyclohexane-carboxylic acid sulfonic acid composition that the caprolactam technology process contains 5%-10% or the alkaline solution at toluene method and extract sample, regulating the pH value is 3-4, and be mixed with the sample solution of 2%-3% concentration, evenly flowing through length is 40cm, internal diameter 20mm, the adsorption column of interior dress large aperture strong-basicity styrene series anion exchange resin, absorption is wherein with the material of acidic-group, after treating that adsorption column is saturated, stop the conveying of sample solution, effluent is an A liquid;
B) with the acid solution of 5%-10% as desorbing agent, wash-out has adsorbed the styrene series anion exchange resin of acidic materials, acidic materials be eluted in 5%-10% acid solution in, B liquid;
C) B liquid evenly being flow through length is 40cm, internal diameter 20mm, and interior dress large hole strong acid styrene system cation exchange resin's adsorption column, with the absorption impurity that contains basic group wherein, effluent is a C liquid;
D) C liquid is concentrated, with dichloromethane solvent extraction three times, raffinate is a D liquid;
E) D liquid is concentrated once more, hydro-oxidation potassium or NaOH make the pH value be 7-8 in ice-water bath, crystallisation by cooling, and with dissolving of crystal water and adjust pH to 2.0, recrystallization obtains cyclohexane-carboxylic acid sulfonic acid analytical standard sample again;
2) chromatogram quantitative analysis of the liquid phase of cyclohexane-carboxylic acid sulfonic acid;
Chromatographic condition:
A) instrument: the high performance liquid chromatograph of band UV, visible light spectrophotometric detector UV and chromatographic work station;
B) chromatographic column: the UP-ODS or the C that adorn 5 μ m granularity fillers in 15cm-25cm length and the 4.6mm internal diameter
18The CBPC post;
C) moving phase: moving phase is prepared by 37.5: 62.5 volume ratio by solution A and solution B; Solution A is made up of chromatographically pure methyl alcohol or acetonitrile single solvent, and solution B is by adding 0.4% ion-pairing agent and the phosphoric acid of 5mmol and the phosphate dressing agent of 75mmol in the experiment one-level water, and ion-pairing agent is a quaternary amine;
D) analytical wavelengths: 220nm;
Analytic process:
A) get cyclohexane-carboxylic acid sulfonic acid standard analysis sample is prepared one group of 3mg/ml-9mg/ml concentration with experiment one-level water standard model solution;
B) getting testing sample, is the testing sample solution of 1mg/ml-15mg/ml with experiment one-level water compound concentration;
C) under above-mentioned chromatographic condition, above-mentioned standard model solution of quantitative sample injection and testing sample solution sample introduction, get analysis of spectra, each sample feeding three times, being not more than 1.5% with its peak area relative error of three sample introductions of each sample is effective sample introduction, and the mean value of three sample introduction peak areas of a sample is used data for calculating;
Quantivative approach: adopt external standard method.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0899954A (en) * | 1994-08-04 | 1996-04-16 | Toray Ind Inc | Lactam and its purification |
| CN1629143A (en) * | 2004-09-24 | 2005-06-22 | 中国石油化工股份有限公司 | Process for extracting and separating caprolactam from amide oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0899954A (en) * | 1994-08-04 | 1996-04-16 | Toray Ind Inc | Lactam and its purification |
| CN1629143A (en) * | 2004-09-24 | 2005-06-22 | 中国石油化工股份有限公司 | Process for extracting and separating caprolactam from amide oil |
Non-Patent Citations (2)
| Title |
|---|
| SINA法生产己内酰胺工艺中杂质分析. 于广欣等.分析测试学报，第23卷第5期. 2004 |
| SINA法生产己内酰胺工艺中杂质分析. 于广欣等.分析测试学报，第23卷第5期. 2004 * |
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