CN106483211B - The method for measuring the content of NORMAX catalyst and its ligand - Google Patents
The method for measuring the content of NORMAX catalyst and its ligand Download PDFInfo
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/02—Devices for withdrawing samples
- G01N1/10—Devices for withdrawing samples in the liquid or fluent state
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Abstract
The present invention provides a kind of methods of the content of measurement NORMAX catalyst and its ligand.This method includes preparation, correction course and the sample detection analysis of sample solution.It is detected using content of the liquid chromatogram to NORMAX catalyst and its ligand, while more appropriate liquid phase chromatogram condition is obtained by inventor's creative labor, the result measured under above-mentioned specific liquid phase chromatogram condition is more accurate.This is conducive to the content for measuring NORMAX catalyst and its ligand in time in process of production, and timely adjusting process according to testing result, to be conducive to save production cost.
Description
Technical field
The present invention relates to 2- propyl enanthol production fields, in particular to a kind of measurement NORMAX catalyst and its match
The method of the content of body.
Background technique
The relatively inexpensive mixed butene of MTO device by-product, after the MTBE/ butene-1 device by pretreatment of raw material, 1-
The total content of butylene and 2- butylene is about 90wt%, this provides abundant and cheap raw material for production 2- propyl enanthol product.
It needs during 2- propyl enanthol carbongl group synthesis reaction using rhodium/NORMAX catalyst.The catalyst uses bulky ligand
Body, so that the reaction speed of alkene and the selectivity of positive structure product greatly improve.Above-mentioned reaction is stirred in three concatenated bands
It is carried out in Liquid-phase reactor, and the amount of NORMAX catalyst has vital effect to carbongl group synthesis reaction, therefore in time
Accurately the content of analysis NORMAX catalyst becomes the most important thing.Furthermore NORMAX catalyst can react production with aldehyde
Toxic phosphite, the phosphite in conjunction with rhodium catalyst and can cause its activity to reduce, while above-mentioned phosphite
It can be reacted with water and generate strong acid aldehydic acid (HPBA), therefore analyze NORMAX catalyst and NORMAX catalyst in time in production
The content of ligand is particularly important to state of arts is judged, and provides strong support to save production cost.
Summary of the invention
The main purpose of the present invention is to provide a kind of methods of the content of measurement NORMAX catalyst and its ligand, with solution
Certainly carried out using content of the existing method to NORMAX catalyst and its ligand in 2- propyl enanthol carbonylation reactor solution
The problem of result inaccuracy when detection.
To achieve the goals above, the present invention provides a kind of sides of the content of measurement NORMAX catalyst and its ligand
Method, method include: the preparation of sample solution: using the tetraethyleneglycol dimethyl ether that has deaerated as solvent, by diphenylcyclohexyl phosphine
With the tetraethyleneglycol dimethyl ether mixed preparing dilution to have deaerated；By dilution and the sample containing NORMAX catalyst and its ligand
Product are mixed, and sample solution is obtained；Correction course includes: S1, using dilution as solvent, by dilution and 3,3', and 5,5'- tetra-
The mixing of tert-butyl -2,2'- '-biphenyl diphenol standard sample is configured to calibration solution, concentration CSTD；S2 carries out the to calibration solution
One liquid-phase chromatographic analysis is measured in parallel M times, calculates wherein the 2~M times 3,3', 5,5'- tetra-tert -2,2'- biphenyl measured
The average value A of the peak area of diphenol standard sampleSTD, wherein M >=3；S3 calculates 3,3', 5,5'- tetra-terts-according to formula I
The correction factor RF of 2,2'- '-biphenyl diphenol standard samples, formula I are as follows: RF=CSTD/ASTD；S4 calculates component in sample solution
Relative correction factor: RRF (NORMAX)=RF × 0.660；RRF (monophosphate NORMAX ligand)=RF × 0.525；RRF (two
Phosphoric acid NORMAX ligand)=RF × 0.540；RRF (rhodium NORMAX ligand)=RF × 0.853；Sample detection analysis: to sample
Product solution carries out second liquid phase chromatography, obtains the peak area of each component in sample solution；According to the peak area meter of each component
The concentration of NORMAX catalyst and its ligand is calculated, wherein ligand includes monophosphate NORMAX ligand, diphosphonic acid NORMAX coordination
One of body and rhodium NORMAX ligand are a variety of；First liquid-phase chromatographic analysis and the condition of second liquid phase chromatography are to make
With ODS-SP chromatographic column, using the mixture of methanol and/or water as mobile phase, flow velocity is 0.5~1.0mL/min, is 40 in column temperature
Under conditions of DEG C, detected at wavelength 254nm using diode array detector.
Further, the collection process of sample solution includes: that nitrogen pipeline needle is passed through sample in sample detection analytical procedure
In product bottle, nitrogen valve is opened, ventilate at least 5min, displaces the air in sample bottle with bilateral needle, and wherein sample bottle uses silicon
Rubber plug sealing；Go out the air in syringe using nitrogen or inert gas replacement, takes 2mL nitrogen with syringe；2mL nitrogen will be sucked
The syringe of gas immerses in dilution, releases the nitrogen in syringe, and draw 2mL dilution；By the dilution in syringe
It is transferred to the quality W that dilution is weighed in the sample bottle filled with nitrogen1；Sample is acquired into sample bottle using bilateral needle, it is double
In the first end insertion sample of cleansing pin, second end is inserted into sample bottle, and the quality W of sample is weighed2, and dilution factor calculated DF=
(W1+W2)/W2。
Further, the step of sample detection is analyzed includes: that sample solution is carried out second liquid phase chromatography, and parallel
N times are measured, the average peak area A of each component in the calculated by peak area sample solution obtained with wherein 2~n times, wherein N >=3；
The mass percentage of each component are as follows: Wt% (NORMAX)=A (NORMAX) × RRF (NORMAX) × DF；Wt% (monophosphate
NORMAX ligand)=A (monophosphate NORMAX ligand) × RRF (monophosphate NORMAX ligand) × DF；Wt% (diphosphonic acid
NORMAX ligand)=A (diphosphonic acid NORMAX ligand) × RRF (diphosphonic acid NORMAX ligand) × DF；Wt% (rhodium
NORMAX ligand)=A (rhodium NORMAX ligand) × RRF (rhodium NORMAX ligand) × DF.
Further, the tetraethyleneglycol dimethyl ether to have deaerated is obtained by removing oxygen under nitrogen or inert atmosphere.
Further, the weight percentage of diphenylcyclohexyl phosphine is 0.1000~0.3000wt% in dilution.
Further, before the step of carrying out sample detection analysis, sample solution is filtered.
It applies the technical scheme of the present invention, is examined using content of the liquid chromatogram to NORMAX catalyst and its ligand
It surveys, while more appropriate liquid phase chromatogram condition is obtained by inventor's creative labor, in above-mentioned specific liquid chromatogram
Under the conditions of the result that measures it is more accurate.This is conducive to measure containing for NORMAX catalyst and its ligand in time in process of production
Amount, and timely adjusting process according to testing result, to be conducive to save production cost.
Detailed description of the invention
Fig. 1 shows the content in embodiment 1 using elution requirement measurement NORMAX catalyst and its ligand in table 1
Chromatography map；And
Fig. 2 shows the contents of the elution requirement measurement NORMAX catalyst and its ligand that are used in table 2 in embodiment 1
Chromatography map.
Specific embodiment
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination.Below with reference to embodiment, the present invention will be described in detail.
As described in background technique, using existing method in 2- propyl enanthol carbonylation reactor solution
Result inaccuracy when the content of NORMAX catalyst and its ligand is detected.In order to solve the above-mentioned technical problem, the present invention mentions
A kind of method for having supplied content for measuring NORMAX catalyst and its ligand, this method comprises: the preparation of sample solution: to have taken off
The tetraethyleneglycol dimethyl ether of gas is dilute by diphenylcyclohexyl phosphine and the tetraethyleneglycol dimethyl ether mixed preparing that has deaerated as solvent
Release liquid；Dilution is mixed with the sample containing NORMAX catalyst and its ligand, obtains sample solution；Correction course packet
It includes: S1, using the dilution as solvent, by the dilution and 3,3', 5,5'- tetra-tert -2,2'- '-biphenyl diphenol standard samples
Product mixing is configured to calibration solution, concentration CSTD；S2 carries out the first liquid-phase chromatographic analysis to the calibration solution, parallel to survey
Determine M times, calculates the peak area of wherein the 2~M times 3,3', 5,5'- tetra-tert -2,2'- '-biphenyl diphenol standard sample measured
Average value ASTD, wherein M >=3；S3 calculates 3,3', 5,5'- tetra-tert -2,2'- '-biphenyl diphenol standard samples according to formula I
Correction factor RF, the formula I are as follows: RF=CSTD/ASTD；S4 calculates the relative correction of other components in the calibration solution
The factor: RRF (NORMAX)=RF × 0.660；RRF (monophosphate NORMAX ligand)=RF × 0.525；RRF (diphosphonic acid
NORMAX ligand)=RF × 0.540；RRF (rhodium NORMAX ligand)=RF × 0.853；Sample detection analysis: molten to sample
Liquid carries out second liquid phase chromatography, obtains the peak area of each component in sample solution；According to the calculated by peak area of each component
The concentration of NORMAX catalyst and its ligand, wherein ligand includes monophosphate NORMAX ligand, diphosphonic acid NORMAX ligand
With one of rhodium NORMAX ligand or a variety of；First liquid-phase chromatographic analysis and the condition of second liquid phase chromatography are to use
ODS-SP chromatographic column, using the mixture of first alcohol and water as mobile phase, flow velocity is 0.5~1.0mL/min, the item for being 40 DEG C in column temperature
Under part, detected at wavelength 254nm using diode array detector.
It is detected using content of the liquid chromatogram to NORMAX catalyst and its ligand, while being created by inventor
The labour of property obtains more appropriate liquid phase chromatogram condition, and the result measured under above-mentioned specific liquid phase chromatogram condition is more quasi-
Really.Furthermore the influence that process advantageously reduces systematic error to testing result is corrected before sample detection analytical procedure,
To be conducive to further increase the accuracy of testing result.In conclusion being conducive to using measuring method provided by the present application
The content of NORMAX catalyst and its ligand is timely and accurately measured in process of production, and adjustment in time according to testing result
Technique, to be conducive to save production cost.
Preferably, elution process is pressed such as 1 institute of table during the first liquid-phase chromatographic analysis process and second liquid phase chromatography
The process shown carries out.
Table 1
During said determination, the acquisition of sample can be acquired using acquisition method commonly used in the art.In one kind
In preferred embodiment, the collection process of sample solution includes: that nitrogen pipeline needle is passed through sample in sample detection analytical procedure
In product bottle, nitrogen valve is opened, ventilate at least 5min, displaces the air in sample bottle with bilateral needle, and wherein sample bottle uses silicon
Rubber plug sealing；Go out the air in syringe using nitrogen or inert gas replacement, takes 2mL nitrogen with syringe；2mL nitrogen will be sucked
The syringe of gas immerses in dilution, releases the nitrogen in syringe, and draw 2mL dilution；By the dilution in syringe
It is transferred to the quality W that dilution is weighed in the sample bottle filled with nitrogen1；Sample is acquired into sample bottle using bilateral needle, it is double
In the first end insertion sample of cleansing pin, second end is inserted into sample bottle, and the quality W of sample is weighed2, and dilution factor calculated DF=
(W1+W2)/W2.Influence of the gases such as air to example weight in sample bottle can be removed using above-mentioned acquisition method, thus favorably
In the accuracy for improving sample weighing.
In a preferred embodiment, the step of sample detection is analyzed includes: that sample solution is carried out second liquid phase
Chromatography, and n times are measured in parallel, the average peak of each component in the calculated by peak area sample solution obtained with wherein 2~n times
Area A, wherein N >=3；The mass percentage of each component are as follows: Wt% (NORMAX)=A (NORMAX) × RRF (NORMAX) ×
DF；Wt% (monophosphate NORMAX ligand)=A (monophosphate NORMAX ligand) × RRF (monophosphate NORMAX ligand) ×
DF；Wt% (diphosphonic acid NORMAX ligand)=A (diphosphonic acid NORMAX ligand) × RRF (diphosphonic acid NORMAX ligand) ×
DF；Wt% (rhodium NORMAX ligand)=A (rhodium NORMAX ligand) × RRF (rhodium NORMAX ligand) × DF.In the first liquid
During analysis of hplc, it is measured in parallel n times, and the average peak area for the calculated by peak area each component for only 2~n times being taken to obtain
A, this is conducive to the precision for improving testing result in detection method provided by the present application.
In a preferred embodiment, the tetraethyleneglycol dimethyl ether to have deaerated under nitrogen or inert atmosphere by removing
It is obtained after oxygen.Oxygen in removing tetraethyleneglycol dimethyl ether is conducive to oxygen in suppression solution and generates to the content of measurement ingredient
It influences, and influences the accuracy of subsequent detection analysis result.
In a preferred embodiment, in dilution diphenylcyclohexyl phosphine weight percentage be 0.1000~
0.3000wt%.The concentration of diphenylcyclohexyl phosphine includes but is not limited to above range in dilution, but diphenylcyclohexyl phosphine
Concentration will affect very much the separating degree of component to be measured greatly, so that will lead to chromatographic peak cannot separate.
In a preferred embodiment, before the step of carrying out sample detection analysis, sample solution was carried out
Filter.This advantageously reduces influence of the impurity to testing result in sample solution, to be conducive to further improve testing result
Accuracy.
Below in conjunction with specific embodiment, present invention is further described in detail, these embodiments should not be understood as limitation originally
Invent range claimed.
Embodiment 1
1) preparation of dilution
Nitrogen is passed through in tetraethyleneglycol dimethyl ether and is de-gassed, the tetraethyleneglycol dimethyl ether to have been deaerated；
1.00g diphenylcyclohexyl phosphine is weighed in nitrogen glove box to be placed in the transposed 100mL vial of nitrogen, and
The tetraethyleneglycol dimethyl ether to have deaerated is added into above-mentioned vial, diphenylcyclohexyl phosphine is made to be diluted to 100.00g, it is close
Envelope, sufficiently shakes up and is allowed to dissolve, obtain required dilution.
2) preparation of standard solution
In nitrogen glove box, weighs 3,3', 5,5'- tetra-tert -2,2'- '-biphenyl diphenol of 0.1197g and be placed in nitrogen and set
In the 100mL vial changed, and dilute solution is added into above-mentioned vial, joins 3,3', 5,5'- tetra-terts -2,2'-
Benzenediol is diluted to 100.0000g, seals and sufficiently shakes up, obtains standard solution, concentration CSTD=0.1197%.
3) correction course
According to the chromatographic condition in claim 1, standard sample is carried out parallel analysis 3 times, the sample peak after taking twice
The average peak area A of area (7559923,7552506)STD=7556215, calculate 3,3', 5,5'- tetra-terts -2,2'- connection
The correction factor RF=C of benzenediolSTD/ASTD=1.584 × 10-8, and then obtain the relative correction factor of all components: RRF
(NORMAX)=RF × 0.660；RRF (monophosphate NORMAX ligand)=RF × 0.525；RRF (diphosphonic acid NORMAX coordination
Body)=RF × 0.540；RRF (rhodium NORMAX ligand)=RF × 0.853.
4) sample detection process
Sample 1.0465g is pipetted according to claim 2, gross weight 5.5290g after dilution is added, obtains dilution gfactor DF=
5.5290/1.0465=5.2833.After filtering by the sample after mixing, it a) is analyzed according to the elution program in table 1, phase
The testing result answered is shown in Fig. 1；B) it is analyzed according to the elution program in table 2, corresponding testing result is shown in Fig. 2.
Table 2
By comparing Fig. 1 and 2 it is found that rhodium NORMAX ligand non-appearance when being eluted using the elution program in table 2.
It can thus be appreciated that being conducive to improve the accuracy of measurement result using the elution requirement in claim 1.
Embodiment 2
1) preparation of dilution
Nitrogen is passed through in tetraethyleneglycol dimethyl ether and is de-gassed, the tetraethyleneglycol dimethyl ether to have been deaerated；
1.00g diphenylcyclohexyl phosphine is weighed in nitrogen glove box to be placed in the transposed 100mL vial of nitrogen, and
The tetraethyleneglycol dimethyl ether to have deaerated is added into above-mentioned vial, diphenylcyclohexyl phosphine is made to be diluted to 100.00g, it is close
Envelope, sufficiently shakes up and is allowed to dissolve, obtain required dilution.
2) preparation of standard solution
In nitrogen glove box, 0.1197g3,3', 5,5'- tetra-tert -2,2'- '-biphenyl diphenol (CAS:6390- are weighed
It 69-8) is put into the transposed vial of nitrogen, dilute solution is added and is diluted to 100.00g, seals and sufficiently shakes up, obtain
To standard solution, concentration CSTD=0.1197%.
3) correction course
According to the chromatographic condition in claim 1, standard sample is carried out parallel analysis 3 times, the sample peak after taking twice
The average value of area (7559923,7552506) obtains average peak area ASTD=7556215, calculate 3,3', 5,5'- tetra- tertiary fourths
The correction factor RF=C of base -2,2'- '-biphenyl diphenolSTD/ASTD=1.584 × 10-8, and then obtain the relative correction of all components
The factor: RRF (NORMAX)=RF × 0.660；RRF (monophosphate NORMAX ligand)=RF × 0.525；RRF (diphosphonic acid
NORMAX ligand)=RF × 0.540；RRF (rhodium NORMAX ligand)=RF × 0.853.
4) sample detection process
C) sample 1.0465g is pipetted according to method for claim 2, gross weight 5.5290g after dilution is added, is diluted
Factor D F=5.5290/1.0465=5.2833, after the sample solution filtering after mixing, according to the chromatography in claim 1
Condition carries out test sample parallel analysis 3 times, and the sample peak area after taking twice is calculated according to claim 5
The content of each component: NORMAX peak area is 1347952, concentration 745mg/kg；Monophosphate NORMAX ligand peak area is
321753, concentration 141mg/kg；Diphosphonic acid NORMAX ligand peak area is 242691, concentration 110mg/kg；Rhodium
NORMAX ligand peak area is 5200089, concentration 3712mg/kg.
D) preparation sample solution is not carried out according to claim 2, sample is exposed under air conditional, first weighs sample
1.0200g is in open sample bottle, then pipettes dilution in this sample bottle, and sample and dilution gross weight are 7.1200g, shakes
It is even, obtain dilution gfactor DF=7.1200/1.0200=6.9803.After the sample solution filtering after mixing, wanted according to right
Seek the chromatographic condition in 1, test sample carried out parallel analysis 3 times, sample peak area after taking twice according to claim 5 into
The content of each component is calculated in row: NORMAX peak area is 359154, concentration 198mg/kg；Monophosphate NORMAX ligand peak
Area is 1065924, concentration 468mg/kg；Diphosphonic acid NORMAX ligand peak area is 301140, concentration 136mg/kg；
Rhodium NORMAX ligand peak area is 2440044, concentration 1742mg/kg.
By analysis result it is found that if sample solution is not prepared according to the sample acquisition mode in claim 2, in sample
NORMAX can occur significantly to aoxidize, and concentration is reduced to 198mg/kg, monophosphate NORMAX ligand, diphosphonic acid from 745mg/kg
The content of NORMAX ligand increases, and the content of rhodium NORMAX complex reduces.It can thus be appreciated that using sample provided by the present application
The acquisition mode of solution is conducive to improve the accuracy of measurement result.
Embodiment 3
1) preparation of dilution
Nitrogen is passed through in tetraethyleneglycol dimethyl ether and is de-gassed, the tetraethyleneglycol dimethyl ether to have been deaerated；
1.00g diphenylcyclohexyl phosphine is weighed in nitrogen glove box to be placed in the transposed 100mL vial of nitrogen, and
The tetraethyleneglycol dimethyl ether to have deaerated is added into above-mentioned vial, diphenylcyclohexyl phosphine is made to be diluted to 100.00g, it is close
Envelope, sufficiently shakes up and is allowed to dissolve, obtain required dilution.
2) preparation of standard solution
In nitrogen glove box, weighs 3,3', 5,5'- tetra-tert -2,2'- '-biphenyl diphenol of 0.1065g and be placed in nitrogen and set
In the 100mL vial changed, and dilute solution is added into above-mentioned vial, joins 3,3', 5,5'- tetra-terts -2,2'-
Benzenediol is diluted to 100.00g, seals and sufficiently shakes up, obtains standard solution, concentration CSTD=0.1065wt%.
3) correction course
According to the chromatographic condition in claim 1, standard sample is carried out parallel analysis 3 times, the sample peak after taking twice
The average value of area (4461345,4102705) obtains average peak area ASTD=4102705, calculate 3,3', 5,5'- tetra- tertiary fourths
The correction factor RF=C of base -2,2'- '-biphenyl diphenolSTD/ASTD=2.487 × 10-8, and then obtain the relative correction of all components
The factor: RRF (NORMAX)=RF × 0.660；RRF (monophosphate NORMAX ligand)=RF × 0.525；RRF (diphosphonic acid
NORMAX ligand)=RF × 0.540；RRF (rhodium NORMAX ligand)=RF × 0.853.
4) sample detection process
Pipette sample 0.7400g according to method for claim 2, gross weight 4.2300g after dilution be added, obtain dilution because
Sub- DF=4.2300/0.7400=5.7162, after the sample after mixing is filtered according to claim 6, according in claim 1
Chromatographic condition, by test sample carry out parallel analysis 3 times, the sample peak area after taking twice is counted according to claim 5
Calculation obtains the content of each component, and see Table 3 for details.
Table 3
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (5)
1. a kind of method of the content of measurement NORMAX catalyst and its ligand, which is characterized in that the described method includes:
The preparation of sample solution:
Using the tetraethyleneglycol dimethyl ether that has deaerated as solvent, by diphenylcyclohexyl phosphine and the tetraethylene glycol two to have deaerated
Methyl ether mixed preparing dilution；
The dilution is mixed with the sample containing the NORMAX catalyst and its ligand, it is molten to obtain the sample
Liquid；
Correction course includes:
S1, using the dilution as solvent, by the dilution and 3,3', 5,5'- tetra-tert -2,2'- '-biphenyl diphenol standards
Sample mixing is configured to calibration solution, concentration CSTD；
S2 carries out the first liquid-phase chromatographic analysis to the calibration solution, is measured in parallel M time, what calculating wherein measured for the 2~M times
The average value A of the peak area of 3,3', 5,5'- tetra-tert -2,2'- '-biphenyl diphenol standard sampleSTD, wherein M >=3；
S3 calculates the correction factor RF of 3,3', 5,5'- tetra-tert -2,2'- '-biphenyl diphenol standard samples according to formula I, described
Formula I are as follows: RF=CSTD/ASTD；
S4 calculates the relative correction factor of component in the sample solution:
RRF (NORMAX)=RF × 0.660；
RRF (monophosphate NORMAX ligand)=RF × 0.525；
RRF (diphosphonic acid NORMAX ligand)=RF × 0.540；
RRF (rhodium NORMAX ligand)=RF × 0.853；
Sample detection analysis:
Second liquid phase chromatography is carried out to the sample solution, obtains the peak area of each component in the sample solution；
According to the concentration of NORMAX catalyst and its ligand described in the calculated by peak area of each component, wherein the ligand includes
One of monophosphate NORMAX ligand, diphosphonic acid NORMAX ligand and rhodium NORMAX ligand are a variety of；
First liquid-phase chromatographic analysis and the condition of the second liquid phase chromatography are using ODS-SP chromatographic column, with methanol
And/or the mixture of water is mobile phase, flow velocity is 0.5~1.0mL/min, under conditions of column temperature is 40 DEG C, using diode
Array detector is detected at wavelength 254nm；
The collection process of sample solution described in the sample detection analytical procedure includes:
Nitrogen pipeline needle is passed through in sample bottle, nitrogen valve is opened, ventilate at least 5min, displaces the sample bottle with bilateral needle
In air, wherein the sample bottle is sealed using silica gel plug；
Go out the air in syringe using nitrogen or inert gas replacement, takes 2mL nitrogen with the syringe；
The syringe for sucking 2mL nitrogen is immersed in the dilution, releases the nitrogen in the syringe, and draw
Dilution described in 2mL；
The dilution in the syringe is transferred in the sample bottle filled with nitrogen, the matter of the dilution is weighed
Measure W1；
The sample is acquired into the sample bottle using bilateral needle, the first end of the bilateral needle is inserted into the sample,
Second end is inserted into the sample bottle, and the quality W of sample is weighed2, and dilution factor calculated DF=(W1+W2)/W2。
2. the method according to claim 1, wherein the sample detection includes: the step of analysis
The sample solution is subjected to the second liquid phase chromatography, and is measured in parallel n times, is obtained with wherein 2~n times
The average peak area A of each component in sample solution described in calculated by peak area, wherein N >=3；
The mass percentage of each component are as follows:
Wt% (NORMAX)=A (NORMAX) × RRF (NORMAX) × DF；
Wt% (monophosphate NORMAX ligand)=A (monophosphate NORMAX ligand) × RRF (monophosphate NORMAX ligand)
×DF；
Wt% (diphosphonic acid NORMAX ligand)=A (diphosphonic acid NORMAX ligand) × RRF (diphosphonic acid NORMAX ligand)
×DF；
Wt% (rhodium NORMAX ligand)=A (rhodium NORMAX ligand) × RRF (rhodium NORMAX ligand) × DF.
3. according to the method described in claim 2, it is characterized in that, the tetraethyleneglycol dimethyl ether to have deaerated by nitrogen or
Oxygen is removed under inert atmosphere to obtain.
4. the method according to claim 1, wherein the weight of diphenylcyclohexyl phosphine described in the dilution
Percentage composition is 0.1000~0.3000wt%.
5. according to the method described in claim 4, it is characterized in that, carry out the sample detection analysis the step of before, it is right
The sample solution is filtered.
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| 1-丁烯氢甲酰化反应配体的筛选与工艺条件的优化;范曼曼;《上海师范大学硕士学位论文》;20141231;1-55 |
| 刘文星.液相色谱测定戊醛中催化剂不确定度的评定.《现代测量与实验室管理》.2015,(第4期),37-39. |
| 混合丁烯羰基合成戊醛;肖艳等;《石油化工》;20151231;第44卷(第8期);912-918 |
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