CN104792725B - Monoethanolamine dehydration prepares the rapid analysis method of aziridine product stream - Google Patents

Monoethanolamine dehydration prepares the rapid analysis method of aziridine product stream Download PDF

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Publication number
CN104792725B
CN104792725B CN201510217035.5A CN201510217035A CN104792725B CN 104792725 B CN104792725 B CN 104792725B CN 201510217035 A CN201510217035 A CN 201510217035A CN 104792725 B CN104792725 B CN 104792725B
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process products
aziridine
monoethanolamine
stream
near infrared
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CN104792725A (en
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温晓燕
杨建明
涂健
吕剑
胡岚
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Hubei Xianlin Chemical Co ltd
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Xian Modern Chemistry Research Institute
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Abstract

The invention discloses the rapid analysis method that a kind of monoethanolamine dehydration prepares aziridine product stream, this method is analyzed for monoethanolamine dewatering process product stream, one material is extracted from process products stream as tributary, near infrared spectrum of the near infrared spectrum of tributary material as process products stream is gathered, is analyzed using near infrared spectroscopy;The corresponding chemical score of the near infrared spectrum of process products stream is associated using PLS, establishes quantitative calibration models, using institute's established model, passes through the mass fraction that obtained near infrared spectrum directly determines various ingredients in process products stream.Present invention is mainly used for the quick analysis that monoethanolamine dehydration prepares aziridine product stream.

Description

Monoethanolamine dehydration prepares the rapid analysis method of aziridine product stream
Technical field
The invention belongs to the analysis and testing technology field of chemical process, is related to a kind of monoethanolamine dehydration and prepares aziridine product The rapid analysis method of stream.
Background technology
Aziridine, also known as Ethylenimine, in fields such as medicine, agricultural chemicals, high-energy fuel, bonding agent, photosensitive material, crosslinking agents There is extensive purposes.Aziridine belongs to ternary azepine ring structure, and ring strain is big, low boiling point, and easily decomposes polymerization, unstable It is fixed.
Using monoethanolamine as raw material, aziridine can be obtained through molecule inner dewatering reaction.In aziridine technique is synthesized, run into A problem be how quickly to analyze the species and mass fraction that judge aziridine and accessory substance, thus instruct technical process Control, and the method for obtaining each product separating-purifying one by one.It is more difficult that the general product, which is chemically analyzed,.
Near-infrared (NIR) spectral technique can be used for being characterized in the molecule absorbed in the near infrared region of spectrum, NIR light spectrometry Allow qualitative and quantitative analysis.Since the nineties in last century, laser, optical fiber, microelectronics, computer and Chemical Measurement etc. with Under the drive that spectrum new technology related to wave spectrometer continues to develop, On-line NIR analytical technology (NIR), because of its instrument Compared with the features such as simple, analyze speed is fast, non-destructive and sample preparation amount are small, turn into the new technology in on-line analysis.
Through retrieval, the report that monoethanolamine dehydration prepares the near-infrared rapid analysis method of aziridine product stream is not retrieved Data.
The content of the invention
It is an object of the invention to provide a kind of rapid analysis method of aminating reaction process-stream, has operating procedure letter Singly, the advantages of analysis time is short, and it is capable of the growing amount of Rapid Simultaneous Determination aminating reaction liquid reclaimed water.
According to the present invention, there is provided a kind of monoethanolamine dehydration prepares the rapid analysis method of aziridine product stream, technique production Logistics is the reaction output stream of aminating reaction device, and the process products stream has at least 125 DEG C of temperature, the component of process products stream In vapor phase, this method includes:
(1) one material is extracted from process products stream as tributary;
(2) tributary temperature of charge is higher than the temperature of its dew point;
(3) tributary material is analyzed using near infrared spectroscopy, the near infrared spectrum for gathering tributary material produces as technique The near infrared spectrum of logistics;
(4) it is that calibration set and checking collect by the process products flow point with chemical score, calibration set is used to establish model, verifies Collect the accuracy for verifying model, using PLS, by correction light harvesting spectrum by the pretreated data of selectivity With corresponding chemical score linear correlation, calibration model is established, checking collection is predicted using above-mentioned calibration model, by predicted value With chemical score contrast verification model;
(5) institute's established model is used, is directly obtained from the near infrared spectrum of collection technology product stream a variety of in process products stream The mass fraction of component;
The process products stream includes monoethanolamine, water, aziridine, ethoxy aziridine, vinylamine, pyrazine;
Monoethanolamine, aziridine, ethoxy aziridine, vinylamine, the mass fraction of pyrazine in the process products stream Method analysis is used in conjunction using gas chromatography-mass spectrum in value, and moisture content chemical score is determined using Karl_Fischer method;
The process products stream is 9710~9515cm by quantitative SPECTRAL REGION-1, 8914~7740cm-1With 7453~ 5326cm-1
Advantages of the present invention:
(1) present invention analyzes tributary material using near infrared spectroscopy, the near infrared spectrum letter of collection technology product stream Breath, compared with gas chromatography, titration, eliminates sample pre-treatments step, operating procedure is simple.
(2) present invention uses institute's established model, can be straight in 1 minute according to the near infrared spectrum of collection technology product stream Connect to obtain the mass fraction of one or more components in reacting product stream, analysis time is short, has the advantages of succinct, quick.
(3) present invention, according to the mass fraction determined, can realize monoethanolamine dehydration according to the demand of aminating reaction On-line analysis, be advantageously implemented automation, be easy to industrial processes control.
Brief description of the drawings
Fig. 1 monoethanolamine dehydrations prepare the quick analysis schematic diagram of aziridine product stream
Embodiment
The present invention is described in further detail for the embodiment provided below in conjunction with inventor.
Fig. 1 is the quick analysis schematic diagram that monoethanolamine dehydration prepares aziridine product stream.Circulated including reactor (3), NIR Pond (2), NIR light spectrometer (1), optical fiber cable (110) and (109), adjuster (5);101st, 102,103,104,105,106, For pipeline.
As shown in figure 1, using NIR analyzers, the NIR spectra of process products stream component is quickly analyzed.Technique inputs thing Stream monoethanolamine is inputted to reactor (3) by pipeline 101, and progress amination is anti-in the presence of amination catalysis in reactor (3) Should, the product stream of reactor (3) generation passes through pipeline 104, and into liquid separator (4), gas passes through control through pipeline 106 Pressure regulator (10) discharge of system pressure, liquid are discharged by pipeline 105.
The process products stream of reactor (3) generation, is led under 125 DEG C and 1.8MPa gross pressures by branch line 102 NIR flow cells (2), NIR flow cells (2) are connected to NIR light spectrometer (1), NIR flow cells by optical fiber cable (110) and (109) (2) steam mixture in is analyzed by NIR light spectrometer (1).Spectrometer scanning wavelength scope is 12500 to 4000cm-1, resolution ratio 8cm-1, using optical cable and optical fibres loop as reference.
In the present invention, NIR analyzers are available commercially near infrared spectrometers, and main element includes light source, optics System and detector.NIR light spectrometer (1), for the Fourier transformation type spectrometer of Brooker company manufacture.
NIR light spectrometer (1) is connected by optical cable and optical fibres with NIR flow cells (2), flow cell and vapor line be electrically heated to Higher than the dew point of steam mixture.The NIR flow cells used are low hydroxyl quartz material, optical path length 7.5cm, and resolution ratio is 8cm-1
It is that calibration set and checking collect by process products flow point, calibration set is used to establish model, and checking collection is used to verify model Accuracy, using PLS, by correction light harvesting spectrum by the pretreated data of selectivity and corresponding chemical score Linear correlation, establish the calibration model of process products stream;Using above-mentioned calibration model to checking collection be predicted, by predicted value with Above-mentioned chemical score contrast verification model.
Process products stream includes monoethanolamine, water, aziridine, ethoxy aziridine, vinylamine, wherein pyrazine, moisture chemical Value is determined using Karl_Fischer method, and remaining component chemical value is used in conjunction analysis method using gas chromatography-mass spectrum and determined.
It is direct according to the near infrared spectrum of collection technology product stream using the model of above-mentioned built process products stream each component Obtain monoethanolamine in process products stream, water, aziridine, ethoxy aziridine, vinylamine, the mass fraction of pyrazine.
Embodiment 1:
As shown in figure 1, using NIR analyzers, the NIR spectra of process products stream component is quickly analyzed.Technique inputs thing Stream monoethanolamine is inputted to reactor (3) by pipeline 101, and progress amination is anti-in the presence of amination catalysis in reactor (3) Should, the product stream of reactor (3) generation passes through pipeline 104, and into liquid separator (4), gas passes through control through pipeline 106 Pressure regulator (10) discharge of system pressure, liquid are discharged by pipeline 105.
The process products stream of reactor (3) generation, inputted by branch line 102 under 125 DEG C and 1.8MPa gross pressures NIR flow cells (2), NIR flow cells (2) are connected to NIR light spectrometer (1), NIR flow cells by optical fiber cable (110) and (109) (2) steam mixture in is analyzed using NIR light spectrometer (1).Spectrometer scanning wavelength scope is 12500 to 4000cm-1, light path 7.5cm, resolution ratio 8cm-1, scan 32 times, using optical cable and optical fibres loop as reference.
The spectrum 158 of reaction process process product stream is gathered, is divided into calibration set and checking collects.In collection spectrum Sample simultaneously and carry out chemical score analysis, process products stream includes monoethanolamine, water, aziridine, ethoxy aziridine, vinylamine, pyrrole Six kinds of components of piperazine, the mass fraction for generating water are determined using Karl_Fischer method, and remaining constituent mass fraction uses gas-chromatography-matter Spectrum analysis.
Using PLS, by correction light harvesting spectrum by the pretreated data of selectivity and corresponding mass fraction Linear correlation, establish process products stream monoethanolamine, water, aziridine, ethoxy aziridine, vinylamine, the school of six kinds of components of pyrazine Positive model.
Calibration model verified, evaluated with checking collection sample, optimize monoethanolamine in reaction process product stream, water, Six kinds of aziridine, ethoxy aziridine, vinylamine, pyrazine optimal calibration models of constituent mass fraction.The main ginseng of model optimization Number is optimal spectrum quantification range, preprocessing procedures, the coefficient of determination (R of model of every kind of measured portions2), model intersect Verify root-mean-square-deviation (RMSECV) and checking collection root-mean-square-deviation (RMSEP).Calibration model is examined with checking collection sample Test, evaluate, the parameter of optimization gained best model is shown in Table 1.
Process products stream is 9710~9515cm by quantitative SPECTRAL REGION-1, 8914~7740cm-1With 7453~ 5326cm-1
The preprocess method of use has:Without Pretreated spectra, multiplicative scatter correction, vector normalization method, min-max normalizing Change, first derivative, first derivative+vector normalization method, first derivative+MSC (multiplicative scatter correction), second dervative etc..Using not Model is established with optimization the methods of pretreatment, different dimensions, different spectral bands, selectable rejecting abnormalities sample.Using institute Positive model for school building is predicted to checking collection, and by predicted value and above-mentioned chemical score contrast verification, optimization determines model.
Using above-mentioned institute's established model, the near infrared spectrum of collection technology product stream directly obtains ethanol in process products stream Amine, water, aziridine, ethoxy aziridine, vinylamine, the mass fraction of pyrazine, and acquire 18 samples and entered using chemical method Analysis is gone, the standard value of near infrared spectroscopy predicted value and chemical determination is shown in Table 2.
Table 1 exports the parameter of logistics each component model
Table 2 is using near infrared spectroscopy predicted value and the standard value using chemical determination

Claims (1)

1. a kind of monoethanolamine dehydration prepares the rapid analysis method of aziridine product stream, the analysis method is used for monoethanolamine dehydration work Skill product stream is analyzed, and this method includes:
(1) one material is extracted from process products stream as tributary;
(2) tributary temperature of charge is higher than the temperature of its dew point;
(3) tributary material is analyzed using near infrared spectroscopy, gathers the near infrared spectrum of tributary material as process products stream Near infrared spectrum;
(4) it is that calibration set and checking collect by the process products flow point with chemical score, calibration set is used to establish model, and checking collection is used In the accuracy of checking model, using PLS, will correction light harvesting spectrum by the pretreated data of selectivity with it is right The chemical score linear correlation answered, establishes calibration model, checking collection is predicted using above-mentioned calibration model, by predicted value with changing Value contrast verification model;
(5) institute's established model is used, a variety of groups are directly obtained in process products stream according to the near infrared spectrum of collection technology product stream The mass fraction divided;
The process products stream has at least 125 DEG C of temperature, and the component of process products stream is in vapor phase;
The process products stream includes monoethanolamine, water, aziridine, ethoxy aziridine, vinylamine, pyrazine;
Monoethanolamine, aziridine, ethoxy aziridine, vinylamine, the mass fraction chemical score of pyrazine in the process products stream Method analysis is used in conjunction using gas chromatography-mass spectrum, moisture content chemical score is determined using Karl_Fischer method;
The process products stream can be 9710~9515cm by quantitative SPECTRAL REGION-1, 8914~7740cm-1With 7453~ 5326cm-1
CN201510217035.5A 2015-04-30 2015-04-30 Monoethanolamine dehydration prepares the rapid analysis method of aziridine product stream Active CN104792725B (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101707919A (en) * 2007-06-15 2010-05-12 英国石油化学品有限公司 A method for the online analysis of a vapour phase process stream

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FR2631957B1 (en) * 1988-05-30 1990-08-31 Bp Chimie Sa PROCESS AND APPARATUS FOR MANUFACTURING OLEFINS AND DIOLEFINS BY CONTROLLED HYDROCARBON SPRAYING REACTION USING A SYSTEM COMPRISING AN INFRARED SPECTROPHOTOMETER
EP0706049A1 (en) * 1994-10-07 1996-04-10 Bp Chemicals S.N.C. Cracking property determination
US6072576A (en) * 1996-12-31 2000-06-06 Exxon Chemical Patents Inc. On-line control of a chemical process plant
US6294764B1 (en) * 1998-10-07 2001-09-25 Mississippi State University Multi-component process analysis and control
KR20100003400A (en) * 2008-07-01 2010-01-11 주식회사 티모넷 System for paymenting the electronic payment amount of money using mobile and method therefor
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Publication number Priority date Publication date Assignee Title
CN101707919A (en) * 2007-06-15 2010-05-12 英国石油化学品有限公司 A method for the online analysis of a vapour phase process stream

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