CN103399106B - Low-pressure ion chromatography method used for simultaneously detecting contents of various aldehydes in leather - Google Patents
Low-pressure ion chromatography method used for simultaneously detecting contents of various aldehydes in leather Download PDFInfo
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Abstract
The invention relates to a low-pressure ion chromatography method used for simultaneously detecting the contents of various aldehydes in leather. The invention belongs to an extraction method of five most common aldehydes (formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, and glutaraldehyde), and a fast detection method of respective contents thereof. The method comprises the steps that: sampling and extraction are carried out; an acid and aldehyde standard data conversion program is prepared; standard curves of various acids relative to various aldehydes when a mixed standard sample SS is oxidized are determined; content determinations of various original acids relative to various aldehydes in a sample S is carried out; the sample S is oxidized; and content determination of a total content of various original acids and various reactant acids relative to various aldehydes is carried out. The principle is that: various aldehydes are oxidized into acids by using hydrogen peroxide; the acids are detected by using a low-pressure ion chromatograph; different acids are eluted by using sodium tetraborate water solutions in different time periods; amounts of different acids can be respectively determined in different time periods in one determination process; and with the acid-aldehyde conversion parameters, different aldehydes can be respectively determined. The method has the advantages that: extraction precision is high, extraction speed is high, and automatic detection can be carried out.
Description
Technical field
The invention belongs to aldehydes detection technique field, particularly the most frequently used five kinds of aldehyde (formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, glutaraldehyde) extracting method and the method for quick of content respectively thereof in leather products.
Background technology
Five kinds of aldehyde (formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, glutaraldehyde), i.e. the most frequently used five kinds of aldehyde in leather industry, the important chemical becoming in leather industry because of its unique chemical property is widely used.Aldehyde plays an important role in leather industry rawhide anticorrosion as sterilization antiseptic; Aldehyde plays unique effect as the effective constituent of tanning agent in aldehyde tannage operation and composite tanning technology; Aldehyde is the important raw and processed materials that finishing process skin material used is covered with paint, lacquer, colour wash, etc. in process hides, in use can overflow.If above aldehyde is eaten or excessive suction, people knows from experience generation intoxicating phenomenon: excited, headache, dizzy, feel sick, even lose consciousness and because respiratory failure and death; Human body contact aldehyde, skin and respiratory tract can be upset, and even cause wet lung, and long-term skin contact can cause allergic and distinctive susceptibility sunburn; Through toxicologic study, aldehydes is acknowledged as and can causes animal to produce tumour, sudden change, liver and kidney damage.Detection to aldehyde in leather-making waste water as can be seen here, has great importance to protection of the environment and health.
At present the assay method of relevant aldehyde conventional mainly contain following several: spectrophotometric method instrument condition requires low, easy and simple to handle and be widely used, but its antijamming capability is weak, measure precision not high, can not measure various aldehyde simultaneously and will survey, and be subject to certain application restric-tion.The GB diacetone spectrophotometric method of measuring aldehydes now once only can be measured a kind of aldehyde, needs the reaction of spectrophotometric method and analysis time more than 30 minutes, and only measuring a kind of aldehyde just needs more than 30 minutes; If by this GB diacetone spectrophotometric method, a spectrophotometric is surveyed above-mentioned five kinds of aldehyde to be needed more than 150 minutes; And measure these five kinds of aldehyde with low pressure ion chromatography autoanalyzer method of the present invention, need 12 minutes; Be the advantage of tool velocity determination of the present invention, thereby can carry out mobility on-site measurement, facilitate environmental protection therapy.Although high-pressure ion chromatography, vapor-phase chromatography and liquid phase chromatography can be measured various aldehydes simultaneously, instrument is expensive, and experimental situation conditional request is strict, and operating cost is high, is not suitable for the product of aldehyde-containing type to carry out in-situ automatic analyzer.
Summary of the invention
The invention provides the rapid extracting method of various aldehyde in leather, also provide this high precision containing various mixed aldehyde extracts, the quick disposable automatic analysis method that detects respectively various independent aldehydes.
High-pressure ion chromatography detects the method for various mixed aldehyde extracts, and high-pressure ion chromatogram has only been set up the detection method that detects formaldehyde and acetaldehyde according to the literature, and other aldehydes detect and have no report.High-pressure ion chromatograph is the highest with degree of recognition and the utilization rate of U.S. Dai An company, and its expensive separate unit price surpasses 400,000 yuan, 2.0 * 10
6pa～3.4 * 10
6pa operation with high pressure; chromatographic column and pipe interface conditional request are harsh; the single price of high-pressure chromatographic column, between 0.3 ten thousand yuan～20,000 yuan, needs pre-column protection in use procedure, and could be detected by electric conductivity detector after needing suppressed column to process while measuring negative ion.The technical requirement that detects aldehyde is high, and material requirements is many, and testing cost is high.
Low-voltage ion chromatography of the present invention can detect to mixed aldehyde the principle of the content of various independent aldehyde: various aldehyde analytical approachs of the present invention are to adopt low-voltage ion chromatograph 1.9 * 10
5pa～2.9 * 10
5under Pa low pressure, operate, without the external world, provide high pressure, condition simplicity and the security of operation are all high than high-pressure ion chromatography.The present invention is under alkali condition, by formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde and glutaraldehyde and peroxidating hydrogen-oxygen generation oxidation reaction, formoxy-is changed into acid: formaldehyde is only oxidized to formic acid, acetaldehyde and is only oxidized to acetic acid, propionic aldehyde and is only oxidized to propionic acid, butyraldehyde and is only oxidized to butyric acid, glutaraldehyde and is only oxidized to glutaric acid.The various acid that are oxidized to, are obtaining the content data of various acid by low-voltage ion chromatograph.In analyzing and testing stream, anion-exchange column is set, the differential migration that utilizes formic acid, acetic acid, propionic acid, butyric acid, glutaric acid to form from the different affinity of anion-exchange column, realizes the disposable content that analyzes respectively formic acid, acetic acid, propionic acid, butyric acid, glutaric acid fast.In computer processing system PC, deposit in this various acid be oxidized to the conversion program of corresponding various aldehyde, thereby can converse the content of formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde and glutaraldehyde, realize in an analysis process, obtain respectively the fast detecting object of formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde and glutaraldehyde content.
In leather, the rapid extracting method of various aldehyde, comprises the steps:
Leather is shredded, size is no more than 5mm * 5mm, after mixing, take 1g～2g sample, put into 150mL with the triangular flask of stopper, adding quality percentage composition is sodium dodecyl benzene sulfonate aqueous solution 50mL～100mL of 0.1%, after sample is completely soaked, the triangular flask that sample is housed is put into 40 ℃～45 ℃ water-bath ultrasonic extractions (20 ± 5) min, with G1 sand core funnel, filter, obtain and treat sample measuring liquid.
Various aldehyde analytical approach of the present invention is to adopt low pressure ion chromatography autoanalyzer method, and low-voltage ion chromatograph automatic analysis method is used and includes sample flow path, leacheate stream, blank solution stream, reactant liquor stream, analyzes stream, low pressure peristaltic pump P, sampling valve V, operation valve T, injection annulus C
0, reactor L, threeway mixer M1, threeway mixer M2, ion-exchange chromatography IC, conductance flow cell F, electric conductivity detector D and computer processing system PC analytical instrument.
The low-voltage ion chromatography that simultaneously detects various aldehyde difference content in leather, comprises the steps:
(1) sample preparation and extraction: leather is shredded, and size is no more than 5mm * 5mm, take 1g～2g sample after mixing, put into 150mL with the triangular flask of stopper; To holding, in the Erlenmeyer flask of sample, to add quality percentage composition be neopelex 50mL～100mL of 0.1%, after sample is completely soaked, put into 40 ℃～45 ℃ water-bath ultrasonic extractions (20 ± 5) min, with G1 sand core funnel, filter, obtain and treat that sample measuring liquid is that sample S is standby;
(2) preparation acid and aldehyde normal data converse routine: the computer program that formic acid mass concentration is scaled to formaldehyde mass concentration, quality of acetic acid concentration conversion is the computer program of acetaldehyde mass concentration, propionic acid mass concentration is scaled the computer program of propionic aldehyde mass concentration, butyric acid mass concentration is scaled the computer program of butyraldehyde mass concentration, the computer program that glutaric acid mass concentration is scaled glutaraldehyde mass concentration all deposits low-voltage ion chromatograph computer processing system PC in, as low-voltage ion chromatograph electric conductivity detector D to the formic acid recording in measured object, acetic acid, propionic acid, butyric acid, glutaric acid is distinguished the alternate program of data-switching, this alternate program in computer processing system PC makes:
The measured formic acid mass concentration of electric conductivity detector D is scaled formaldehyde mass concentration, and is formaldehyde mass concentration at Computer display;
The measured quality of acetic acid concentration conversion of electric conductivity detector D is acetaldehyde mass concentration, and is acetaldehyde mass concentration at Computer display;
The measured propionic acid mass concentration of electric conductivity detector D is scaled propionic aldehyde mass concentration, and is propionic aldehyde mass concentration at Computer display;
The measured butyric acid mass concentration of electric conductivity detector D is scaled butyraldehyde mass concentration, and is butyraldehyde mass concentration at Computer display;
The measured glutaric acid mass concentration of electric conductivity detector D is scaled glutaraldehyde mass concentration, and is glutaraldehyde mass concentration at Computer display;
(3) measure the typical curve there are the oxidized corresponding various aldehyde of various acid of various aldehyde mixed sample SS: be divided into and Ce rapid into Yang Walk and Ding Walk this Liang Walk is rapid suddenly, mixed sample SS is the mixed liquor of the formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde and the glutaraldehyde that contain concentration known;
(3-1) Jin Yang Walk is rapid: hydrogen peroxide liquid R is put into the reactant liquor R position of low pressure ion chromatography automatic analyzer V, mixed sample SS puts into the sample S position of analyser V; Operation valve T opens in hydrogen peroxide liquid R and NaOH K circulation, enters reactor L after threeway mixer M1, low-lift pump P, threeway mixer M2 simultaneously; Mixed sample SS also enters reactor L after low-lift pump P, threeway mixer M2 simultaneously; Hydrogen peroxide liquid R and mixed sample SS carry out oxidation reaction in reactor L, become acetic acid, propionic aldehyde to be oxidized to that propionic acid, butyraldehyde are oxidized to butyric acid, glutaraldehyde is oxidized to glutaric acid oxidation of formaldehyde formic acid, oxidation of acetaldehyde in mixed sample SS, mixed sample SS becomes the reaction mixture of reaction product formic acid, acetic acid, propionic acid, butyric acid, glutaric acid, is then full of injection annulus C
0, the mass concentration of the formic acid that in reaction mixture to be measured, reaction generates, acetic acid, propionic acid, butyric acid, the corresponding various aldehyde of glutaric acid;
(3-2) to Ding Walk rapid for Ce: sodium tetraborate liquid C is put into the promotion liquid C position of analyser V, analyser V is transformed into analysis state, start low-lift pump P, sodium tetraborate liquid C is injected into stream, makes injection annulus C
0in mixed sample SS and the mixed reaction solution of hydrogen peroxide liquid R under the promotion of sodium tetraborate liquid C, enter analysis stream, pass through again ion-exchange chromatography IC, enter conductance flow cell F, through electric conductivity detector D, the signal of reaction mixture feature being transferred to computer processing system PC processes, obtain the formic acid of mixed sample SS, acetic acid, propionic acid, butyric acid, glutaric acid divides other content data spectrogram, it is horizontal ordinate that computer processing system PC be take the concentration X of mixed sample SS, the peak area Y of standard specimen spectrogram of take is that ordinate draws regression equation curve, and deposit computer processing system PC in, the corresponding various aldehyde of various acid that acquisition mixed sample SS is oxidized to divide other typical curve,
(4) assay of the corresponding various aldehyde of original various acid in sample S: be divided into rapid into sample Walk and survey that determine rapid these two Walk of Walk rapid, from the sample S of rapid (1) sample preparation of Walk and extraction step, getting a part of sample S as this step (4),
(4-1) Jin Yang Walk is rapid: sample S puts into the sample S position of analyser V; Analyser V is arranged on to sample introduction state, operation valve T is opened in caustic lye of soda K circulation and the state that hydrogen peroxide liquid R closes, caustic lye of soda K enters reactor L after threeway mixer M1, low-lift pump P, threeway mixer M2; Sample S also enters reactor L after low-lift pump P, threeway mixer M2; Caustic lye of soda K and sample S mix in reactor L, are then full of injection annulus C
0, in sample to be tested S, original formic acid, acetic acid, propionic acid, butyric acid, the corresponding various aldehyde of the various acid of glutaric acid divide other mass concentration;
(4-2) to Ding Walk rapid for Ce: sodium tetraborate liquid C is put into the promotion liquid C position of low pressure ion chromatography automatic analyzer V, analyser V is transformed into analysis state, start low-lift pump P, sodium tetraborate liquid C is injected into stream, makes injection annulus C
0in sample S and the mixed liquor of caustic lye of soda K under the promotion of sodium tetraborate liquid C, enter analysis stream, pass through again ion-exchange chromatography IC, enter conductance flow cell F, through electric conductivity detector D, the signal of reaction mixture feature being transferred to computer processing system PC processes, obtaining sample S is not oxidized and original formic acid, acetic acid, propionic acid, butyric acid, glutaric acid divides other content data spectrogram, according to various acidity scale directrix curves, automatically calculate and do not have in the sample of oxidizing process S simultaneously, original formic acid, acetic acid, propionic acid, butyric acid, the various aldehyde mass concentrations that glutaric acid difference is corresponding
x 0 ,
(5) sample S is oxidized, the assay of the corresponding various aldehyde of the total content of original various acid and the various acid of reaction product: being divided into and Ce rapid into Yang Walk, to Ding rapid this Liang Walk of Walk rapid, gets a part of sample S as this step (5) from the sample S of step (2),
(5-1) Jin Yang Walk is rapid: hydrogen peroxide liquid R is put into the reactant liquor R position of low pressure ion chromatography automatic analyzer V, sample S puts into the sample S position of analyser V; Operation valve T opens in hydrogen peroxide liquid R and NaOH K circulation, enters reactor L after threeway mixer M1, low-lift pump P, threeway mixer M2 simultaneously; Sample S also enters reactor L after low-lift pump P, threeway mixer M2 simultaneously; Hydrogen peroxide liquid R and sample S carry out oxidation reaction in reactor L, become acetic acid, propionic aldehyde to be oxidized to that propionic acid, butyraldehyde are oxidized to butyric acid, glutaraldehyde is oxidized to glutaric acid oxidation of formaldehyde formic acid, oxidation of acetaldehyde in sample S, sample S becomes the reaction mixture of reaction product formic acid, acetic acid, propionic acid, butyric acid, glutaric acid, is then full of injection annulus C
0, the corresponding various aldehyde mass concentrations of various acid difference of original formic acid generating with reaction, acetic acid, propionic acid, butyric acid, glutaric acid in reaction mixture to be measured;
(5-2) to Ding Walk rapid for Ce: sodium tetraborate liquid C is put into the promotion liquid C position of low pressure ion chromatography automatic analyzer V, analyser V is transformed into analysis state, start low-lift pump P, sodium tetraborate liquid C is injected into stream, makes injection annulus C
0in sample S and the mixed reaction solution of hydrogen peroxide liquid under the promotion of sodium tetraborate liquid C, enter analysis stream, pass through again ion-exchange chromatography IC, enter conductance flow cell F, through electric conductivity detector D, the signal of reaction mixture feature being transferred to computer processing system PC processes, obtain sample S original and oxidized after formic acid, acetic acid, propionic acid, butyric acid, glutaric acid divide other content data spectrogram, simultaneously according to various acidity scale directrix curves, automatically calculate formic acid, acetic acid, propionic acid, butyric acid, glutaric acid corresponding various aldehyde mass concentrations respectively
x ;
Various aldehyde nail aldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, glutaraldehyde;
Various sour nail acid, acetic acid, propionic acid, butyric acid, glutaric acid.
The above-mentioned low-voltage ion chromatography that simultaneously detects various aldehyde difference content in leather, is characterized in that: also comprise following data processing method,
(6) calculate the corresponding various aldehyde qualitative datas of various acid difference that sample S is oxidized to:
In formula:
A
ithe mass content of aldehyde in-sample, mg/kg,
xthe mass concentration of the aldehyde that-a certain acid is corresponding, mg/L,
x 0 the corresponding aldehyde mass concentration of-a certain original acid, mg/L,
m-sample quality, mg
V-sample extracting solution volume L.
The above-mentioned low-voltage ion chromatography that simultaneously detects various aldehyde difference content in leather, it is characterized in that: the back-pressure circle Y of low pressure ion chromatography automatic analyzer V is that 10m, internal diameter are 0.5mm polyfluortetraethylene pipe by length, after coiled coil, make the spiral coil that length is 15cm, hydrogen peroxide hydraulic control valve T is stainless steel horizontal swinging arm operation valve;
Promote liquid C and select sodium tetraborate liquid C, sodium tetraborate liquid C is that concentration is the sodium tetraborate (Na of 0.002mol/L
2b
4o
7) aqueous solution;
Reactant liquor R selects hydrogen peroxide liquid R, and hydrogen peroxide liquid R is that concentration is the aqueous hydrogen peroxide solution (H of 0.6mol/L～0.8mol/L
2o
2);
Caustic lye of soda K is that concentration is the sodium hydrate aqueous solution of 0.05mol/L;
At chromatography of ions automatic analyzer V, in analysis state, the flow velocity of sodium tetraborate liquid C is: 0.6mL/min～0.8mL/min;
Low pressure anion chromatographic column column length is: 15cm～20cm.
The method of the invention has following beneficial effect:
1. precision and the speed advantage extracted: the present invention extracts various aldehyde sample errors in positive and negative 2% from leather, and extraction time is 20 minutes; And traditional water-bath succusion is extracted various aldehyde sample errors positive and negative 5% from leather, extraction time is 60 minutes.So the present invention is higher than traditional water-bath succusion extraction accuracy, efficiency is high, saves time.
2. the quick advantage of measuring: the present invention measures with low pressure ion chromatography autoanalyzer method, reaction of the present invention and analysis time only need 12 minutes, determine the normal five kinds of aldehyde (formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, glutaraldehyde) that use in leather simultaneously and only need 12 minutes altogether.The GB diacetone spectrophotometric method of measuring various aldehyde now once only can be measured a kind of aldehyde, needs the reaction of spectrophotometric method and analysis time more than 30 minutes, and only measuring a kind of aldehyde just needs more than 30 minutes; If by this GB diacetone spectrophotometric method, the above-mentioned five kinds of aldehyde of spectrophotometric determination need more than 150 minutes; And measure these five kinds of aldehyde with low pressure ion chromatography autoanalyzer method of the present invention, need 12 minutes; Be that the present invention has advantages of velocity determination, thereby can carry out mobility on-site measurement, facilitate environmental protection therapy.Although high-pressure ion chromatography, vapor-phase chromatography and liquid phase chromatography can be measured various aldehyde simultaneously, instrument is expensive, and experimental situation conditional request is strict, and operating cost is high, is not suitable for the on-line automatic analysis in scene of various aldehyde.
3. measuring can robotization: low pressure ion chromatography automatic analyzer has been designed to sample introduction and two loops of test specimens, and these two loop designs become to be simplified to as long as rotate sampling valve V just can realize two loops conversions, thereby has realized the robotization of analyzing mensuration.
4. caustic lye of soda improves sensitivity and the recovery: it is 0.05mol/L that the present invention selects caustic lye of soda K concentration, can effectively improve sensitivity and the recovery that various aldehyde detects.Sensitivity and the recovery of formaldehyde determination of take is example,
When replacing caustic lye of soda K with pure water, formaldehyde peak height is 0.41mV, and the recovery is 68.3%; When sodium hydrate aqueous solution with 0.02mol/L, formaldehyde peak height is 0.51mV, and the recovery is 85.0%;
When sodium hydrate aqueous solution with 0.10mol/L, formaldehyde peak height is 0.31mV, and the recovery of method is 57.1%, and because negative peak appears excessively by force in alkalescence.
The present invention during with the sodium hydrate aqueous solution of 0.05mol/L formaldehyde peak height be 0.58mV, the recovery is 96.6%, the inventor has also carried out more experiments, the recovery is 96.6% to be optimum efficiency, while being the present invention with the sodium hydrate aqueous solution of 0.05mol/L, measure this sample containing formaldehyde weight range (10 mg/kg～800 mg/kg) of leather, the degree of accuracy of mensuration is the highest.
5. with the different acid of wash-out at times of sodium tetraborate aqueous solution, in once measuring, different time sections is measured respectively the amount of different acid, by sour aldehyde conversion parameter, reach the object of measuring respectively different aldehyde: ion chromatogram eluate C adopts 0.002mol/L sodium tetraborate aqueous solution, coordinate low-voltage ion exchange chromatography post, can effectively carry out the reaction product formic acid of various aldehyde, acetic acid, propionic acid, butyric acid, the obviously wash-out separation respectively at times of glutaric acid, make the different acid of its different time wash-out, and the kind approximately 1 minute interval time between every kind of minimum elution amount 2% numerical value of acid, make formic acid, acetic acid, propionic acid, butyric acid, glutaric acid can not enter electric conductivity detector D with time wash-out, do not have at the same time different acid and enter electric conductivity detector D, different acid can not obscured in elution time.Just can obtain efficient, accurate various acid eluting rate and degree of separation respectively.If when leacheate C is changed into pure water, the reaction product of various aldehyde needs just to elute for 35 minutes, and glutaric acid almost can not wash-out; If adopt sodium tetraborate solution concentration to be greater than 0.002mol/L leacheate C, for example, while being 0.003mol/L, formic acid and acetic acid peak overlap, in elution time, can not completely distinguish formic acid and acetic acid, measured value is the overlapping value of formic acid and acetic acid, can not distinguish the difference content of formic acid and acetic acid, also just cannot obtain the difference content of formaldehyde and acetaldehyde.
6, with hydrogen peroxide, various aldehyde is oxidized into acid, when detecting with electric conductivity detector, there is no interfering ion and disturb bubble: the common metal class oxygenants such as potassium permanganate and potassium dichromate, in its solution, contain a large amount of ions, can produce a large amount of interfering ions, make the mensuration out of true of ion look general instrument.For preventing that foreign ion from disturbing, available oxygenant has ozone and hydrogen peroxide, but adopt ozone as oxygenant, in course of reaction, easily produce bubble, Interference Detection, can not realize on-line automatic analysis, and the present invention can overcome the shortcoming of above ozone generating bubble with hydrogen peroxide as oxygenant.In leather, various aldehyde total contents are at the sample that is no more than 800 mg/kg, it is 0.6mol/L～0.8mol/L that hydrogen peroxide R selects concentration, aldehyde is measured to degree of accuracy to be reached more than 95%, optimal, being that the aldehyde that reaches national requirements is measured degree of accuracy, is that the aldehyde that is better than present diacetone method is measured degree of accuracy.
6. the linear dependence of regression equation is good: it is sensitivity and the accuracy requirement that various mixed aldehydes are measured that the method for the invention can meet various aldehyde in leather completely, its lowest detection is limited to 0.02mg/L, the range of linearity is 0.2mg/L～6.0mg/L, obtain equation of linear regression (Y: peak area, the mV of unit;
x: aldehyde mass concentration, the mg/L of unit) and linearly dependent coefficient R
2as shown in table 1.
The various aldehyde equations of linear regression of table 1 and linearly dependent coefficient
| Title | Calibration equation | R 2 |
| Formaldehyde | Y = 24.994 X + 0.0125 | 0.9944 |
| Acetaldehyde | Y = 24.934 X + 0.1313 | 0.9976 |
| Propionic aldehyde | Y = 24.958 X + 0.0834 | 0.9963 |
| Butyraldehyde | Y = 24.977 X + 0.0469 | 0.9928 |
| Glutaraldehyde | Y = 24.987 X + 0.0251 | 0.9948 |
7. instrument is little is convenient for carrying: little 30cm * 30 of low pressure ion chromatography automatic analyzer volume cm * 40 cm, price, lower than 30,000 yuan/platform, can realize the on-line automatic analysis in scene of various aldehyde.
Accompanying drawing explanation
Fig. 1 is that the present invention is arranged on low pressure ion chromatography automatic analyzer the process chart of sample introduction state;
Fig. 2 is arranged on the low pressure ion chromatography automatic analyzer in Fig. 1 the process chart of analysis state;
Fig. 3 is the standard spectrogram of five kinds of rear relative acid of aldehydes oxidation of formaldehyde of the present invention, acetaldehyde, propionic aldehyde, butyraldehyde and glutaraldehyde.
In figure, P-low-lift pump, V-sampling valve, C
0-injection annulus, PC-computer processing system, D-electric conductivity detector, F-conductance flow cell, IC-ion-exchange chromatography, L-reactor, M1-threeway mixer, M2-threeway mixer, S-sample, C-sodium tetraborate liquid, R-hydrogen peroxide liquid, K-caustic lye of soda, T-operation valve, W-waste liquid.
Embodiment
Embodiment 1: the low-voltage ion chromatography that simultaneously detects various aldehyde difference content in ox-hide leather
In ox-hide, the preparation method of various aldehyde analytic samples, comprises the steps:
(1) sample preparation and extraction: leather is shredded, and size is no more than 5mm * 5mm, take 2g sample after mixing, put into 150mL with the triangular flask of stopper; To holding, in the Erlenmeyer flask of sample, to add quality percentage composition be 0.1% neopelex 50mL, after sample is completely soaked, puts into 40 ℃ of water-bath ultrasonic extraction 25min, with G1 sand core funnel, filters, and obtains and treat that sample measuring liquid is that ox leather sample S is standby.
(2) preparation acid and aldehyde normal data converse routine: the computer program that formic acid mass concentration is scaled to formaldehyde mass concentration, quality of acetic acid concentration conversion is the computer program of acetaldehyde mass concentration, propionic acid mass concentration is scaled the computer program of propionic aldehyde mass concentration, butyric acid mass concentration is scaled the computer program of butyraldehyde mass concentration, the computer program that glutaric acid mass concentration is scaled glutaraldehyde mass concentration all deposits computer processing system PC in, as low-voltage ion chromatograph electric conductivity detector D to the formic acid recording in measured object, acetic acid, propionic acid, butyric acid, glutaric acid is distinguished the alternate program of data-switching, this alternate program in low pressure ion chromatography computer processing system PC makes:
The measured formic acid mass concentration of low pressure ion chromatography electric conductivity detector D is scaled formaldehyde mass concentration, and is formaldehyde mass concentration at Computer display;
The measured quality of acetic acid concentration conversion of low pressure ion chromatography electric conductivity detector D is acetaldehyde mass concentration, and is acetaldehyde mass concentration at Computer display;
The measured propionic acid mass concentration of low pressure ion chromatography electric conductivity detector D is scaled propionic aldehyde mass concentration, and is propionic aldehyde mass concentration at Computer display;
The measured butyric acid mass concentration of low pressure ion chromatography electric conductivity detector D is scaled butyraldehyde mass concentration, and is butyraldehyde mass concentration at Computer display;
The measured glutaric acid mass concentration of low pressure ion chromatography electric conductivity detector D is scaled glutaraldehyde mass concentration, and is glutaraldehyde mass concentration at Computer display.
(3) measure the typical curve there are the oxidized corresponding various aldehyde of various acid of various aldehyde mixed sample SS: be divided into and Ce rapid into Yang Walk and Ding Walk this Liang Walk is rapid suddenly, mixed sample SS is the mixed liquor of the formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde and the glutaraldehyde that contain concentration known;
(3-1) Jin Yang Walk is rapid: hydrogen peroxide liquid R is put into the reactant liquor R position of low pressure ion chromatography automatic analyzer V, mixed sample SS puts into the sample S position of analyser V; Operation valve T opens in hydrogen peroxide liquid R and caustic lye of soda K circulation, enters reactor L after threeway mixer M1, low-lift pump P, threeway mixer M2 simultaneously; Mixed sample SS also enters reactor L after low-lift pump P, threeway mixer M2 simultaneously; Hydrogen peroxide liquid R and mixed sample SS carry out oxidation reaction in reactor L, become acetic acid, propionic aldehyde to be oxidized to that propionic acid, butyraldehyde are oxidized to butyric acid, glutaraldehyde is oxidized to glutaric acid oxidation of formaldehyde formic acid, oxidation of acetaldehyde in mixed sample SS, mixed sample SS becomes the reaction mixture of reaction product formic acid, acetic acid, propionic acid, butyric acid, glutaric acid, is then full of injection annulus C
0, the corresponding aldehyde mass concentration of various acid difference of the formic acid that in reaction mixture to be measured, reaction generates, acetic acid, propionic acid, butyric acid, glutaric acid;
(3-2) to Ding Walk rapid for Ce: sodium tetraborate liquid C is put into the leacheate C position of analyser V, analyser V is transformed into analysis state, start low-lift pump P, sodium tetraborate liquid C is injected into stream, makes injection annulus C
0in mixed sample SS and the mixed reaction solution of hydrogen peroxide liquid R under the promotion of sodium tetraborate liquid C, enter analysis stream, pass through again ion-exchange chromatography IC, enter conductance flow cell F, through electric conductivity detector D, the signal of reaction mixture feature being transferred to computer processing system PC processes, obtain the formic acid of mixed sample SS, acetic acid, propionic acid, butyric acid, glutaric acid divides other content data spectrogram, it is horizontal ordinate that computer processing system PC be take the concentration X of mixed sample SS, the peak area Y of standard specimen spectrogram of take is that ordinate draws regression equation curve, and deposit computer processing system PC in, obtain the typical curve of the oxidized corresponding various aldehyde of various acid of mixed sample SS, as shown in table 1.
(4) assay of the corresponding various aldehyde of original various acid in ox leather sample S: be divided into rapid into sample Walk and survey that determine rapid these two Walk of Walk rapid, from the ox leather sample S of step (2), getting a part of ox leather sample S as this step (4),
(4-1) enter sample Walk rapid: ox leather sample S puts into the sample S position of analyser V; Analyser V is arranged on to sample introduction state, operation valve T is opened in caustic lye of soda K circulation and the state that hydrogen peroxide liquid R closes, caustic lye of soda K enters reactor L after threeway mixer M1, low-lift pump P, threeway mixer M2; Ox leather sample S also enters reactor L after low-lift pump P, threeway mixer M2; Caustic lye of soda K and ox leather sample S mix in reactor L, are then full of injection annulus C
0, original formic acid, acetic acid, propionic acid, butyric acid, the corresponding aldehyde mass concentration of the various acid difference of glutaric acid in ox leather sample S to be measured;
(4-2) to Ding Walk rapid for Ce: sodium tetraborate liquid C is put into the leacheate C position of low pressure ion chromatography automatic analyzer V, analyser V is transformed into analysis state, start low-lift pump P, sodium tetraborate liquid C is injected into stream, makes injection annulus C
0in ox leather sample S and the mixed liquor of caustic lye of soda K under the promotion of sodium tetraborate liquid C, enter analysis stream, pass through again ion-exchange chromatography IC, enter conductance flow cell F, through electric conductivity detector D, the signal of reaction mixture feature being transferred to computer processing system PC processes, obtaining ox leather sample S is not oxidized and original formic acid, acetic acid, propionic acid, butyric acid, glutaric acid divides other content data spectrogram, according to various acidity scale directrix curves, automatically calculate and there is no original various acid in the ox of oxidizing process leather sample S simultaneously, contain formic acid, acetic acid, propionic acid, butyric acid, the aldehyde mass concentration that glutaric acid difference is corresponding
x 0 be respectively: formaldehyde 0.5mg/L, acetaldehyde 1.3 mg/L, propionic aldehyde 0.4mg/L, butyraldehyde 0.3mg/L, glutaraldehyde 0 mg/L.
(5) ox leather sample S oxidized after, the assay of the corresponding various aldehyde of the total content of original various acid and the various acid of reaction product: be divided into and Ce rapid into Yang Walk and Ding Walk this Liang Walk is rapid suddenly, from the ox leather sample S of step (2), get a part as the ox leather sample S of this step (5)
(5-1) enter sample Walk rapid: hydrogen peroxide liquid R is put into the reactant liquor R position of low pressure ion chromatography automatic analyzer V, ox leather sample S puts into the ox leather sample S position of analyser V; Operation valve T opens in hydrogen peroxide liquid R and caustic lye of soda K circulation, enters reactor L after threeway mixer M1, low-lift pump P, threeway mixer M2 simultaneously; Ox leather sample S also enters reactor L after low-lift pump P, threeway mixer M2 simultaneously; Hydrogen peroxide liquid R and ox leather sample S carry out oxidation reaction in reactor L, become acetic acid, propionic aldehyde to be oxidized to that propionic acid, butyraldehyde are oxidized to butyric acid, glutaraldehyde is oxidized to glutaric acid oxidation of formaldehyde formic acid, oxidation of acetaldehyde in ox leather sample S, ox leather sample S becomes the reaction mixture of reaction product formic acid, acetic acid, propionic acid, butyric acid, glutaric acid, is then full of injection annulus C
0, the corresponding aldehyde mass concentration of various acid difference of original formic acid generating with reaction, acetic acid, propionic acid, butyric acid, glutaric acid in reaction mixture to be measured;
(5-2) to Ding Walk rapid for Ce: sodium tetraborate liquid C is put into the leacheate C position of low pressure ion chromatography automatic analyzer V, analyser V is transformed into analysis state, start low-lift pump P, sodium tetraborate liquid C is injected into stream, makes injection annulus C
0in ox leather sample S and the mixed reaction solution of hydrogen peroxide liquid under the promotion of sodium tetraborate liquid C, enter analysis stream, pass through again ion-exchange chromatography IC, enter conductance flow cell F, through electric conductivity detector D, the signal of reaction mixture feature being transferred to computer processing system PC processes, obtain ox leather sample S original and oxidized after formic acid, acetic acid, propionic acid, butyric acid, glutaric acid divide other content data spectrogram, simultaneously according to various acidity scale directrix curves, automatically calculate formic acid, acetic acid, propionic acid, butyric acid, glutaric acid corresponding aldehyde mass concentration respectively
x be respectively: formaldehyde 5.3mg/L, acetaldehyde 4.3 mg/L, propionic aldehyde 0.9mg/L, butyraldehyde 0.7mg/L, glutaraldehyde 2.5mg/L.
In the above-mentioned steps of the present embodiment,
Sodium tetraborate liquid C is that concentration is 0.002mol/L sodium tetraborate (Na
2b
4o
7) aqueous solution;
Hydrogen peroxide R is that concentration is 0.8mol/L hydrogen peroxide (H
2o
2) aqueous solution;
Caustic lye of soda K is that concentration is the sodium hydrate aqueous solution of 0.05mol/L;
The flow velocity of sodium tetraborate liquid C is: 0.8mL/min;
Low pressure anion chromatographic column column length is: 20cm.
(6) calculate the corresponding aldehyde qualitative data of various acid difference that ox leather sample S is oxidized to:
By the corresponding aldehyde mass concentration of various original acid in ox leather sample S
x 0 (mg/L), original and oxidized after the corresponding aldehyde mass concentration of acid
x (mg/L), V=50 mL, m=2 g,
Computing formula below difference substitution:
In formula:
A
ithe mass content of aldehyde in-sample, mg/kg,
xthe mass concentration of the aldehyde that-a certain acid is corresponding, mg/L,
x 0 the corresponding aldehyde mass concentration of-a certain original acid, mg/L,
Draw the mass content A of various aldehyde in ox-hide leather
ibe respectively: formaldehyde 120mg/kg, acetaldehyde 75mg/kg, propionic aldehyde 12.5mg/kg, butyraldehyde 10mg/kg and glutaraldehyde 62.5mg/kg.
Embodiment 2: the low-voltage ion chromatography that simultaneously detects various aldehyde difference content in sheep
In sheep, the assay method of various aldehydes, comprises the steps:
(1) preparation of test liquid: sheep is shredded, and size is no more than 5mm * 5mm, takes 1g sample after mixing, put into 150 mL with the triangular flask of stopper; To holding, in the Erlenmeyer flask of sample, to add quality percentage composition be 0.1% neopelex 50mL, sample by complete soaking after, put into 45 ℃ of water-bath ultrasonic extraction 20min, with G1 sand core funnel, filter, obtain sheep sample S to be measured.
(2) preparation acid and aldehyde normal data converse routine: the computer program that formic acid mass concentration is scaled to formaldehyde mass concentration, quality of acetic acid concentration conversion is the computer program of acetaldehyde mass concentration, propionic acid mass concentration is scaled the computer program of propionic aldehyde mass concentration, butyric acid mass concentration is scaled the computer program of butyraldehyde mass concentration, the computer program that glutaric acid mass concentration is scaled glutaraldehyde mass concentration all deposits computer processing system PC in, as low-voltage ion chromatograph electric conductivity detector D to the formic acid recording in measured object, acetic acid, propionic acid, butyric acid, glutaric acid is distinguished the alternate program of data-switching, this alternate program in low-voltage ion chromatograph computer processing system PC makes:
The measured formic acid mass concentration of low pressure ion chromatography electric conductivity detector D is scaled formaldehyde mass concentration, and is formaldehyde mass concentration at Computer display;
The measured quality of acetic acid concentration conversion of low pressure ion chromatography electric conductivity detector D is acetaldehyde mass concentration, and is acetaldehyde mass concentration at Computer display;
The measured propionic acid mass concentration of low pressure ion chromatography electric conductivity detector D is scaled propionic aldehyde mass concentration, and is propionic aldehyde mass concentration at Computer display;
The measured butyric acid mass concentration of low pressure ion chromatography electric conductivity detector D is scaled butyraldehyde mass concentration, and is butyraldehyde mass concentration at Computer display;
The measured glutaric acid mass concentration of low pressure ion chromatography electric conductivity detector D is scaled glutaraldehyde mass concentration, and is glutaraldehyde mass concentration at Computer display.
(3) measure the typical curve there are aldehyde corresponding to the oxidized various acid of various aldehyde mixed sample SS: be divided into and Ce rapid into Yang Walk and Ding Walk this Liang Walk is rapid suddenly, mixed sample SS is the mixed liquor of the formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde and the glutaraldehyde that contain concentration known;
(3-1) Jin Yang Walk is rapid: hydrogen peroxide liquid R is put into the reactant liquor R position of low pressure ion chromatography automatic analyzer V, mixed sample SS puts into the sample S position of analyser V; Operation valve T opens in hydrogen peroxide liquid R and caustic lye of soda K circulation, enters reactor L after threeway mixer M1, low-lift pump P, threeway mixer M2 simultaneously; Mixed sample SS also enters reactor L after low-lift pump P, threeway mixer M2 simultaneously; Hydrogen peroxide liquid R and mixed sample SS carry out oxidation reaction in reactor L, become acetic acid, propionic aldehyde to be oxidized to that propionic acid, butyraldehyde are oxidized to butyric acid, glutaraldehyde is oxidized to glutaric acid oxidation of formaldehyde formic acid, oxidation of acetaldehyde in mixed sample SS, mixed sample SS becomes the reaction mixture of reaction product formic acid, acetic acid, propionic acid, butyric acid, glutaric acid, is then full of injection annulus C
0, the corresponding aldehyde mass concentration of various acid difference of the formic acid that in reaction mixture to be measured, reaction generates, acetic acid, propionic acid, butyric acid, glutaric acid;
(3-2) to Ding Walk rapid for Ce: sodium tetraborate liquid C is put into the leacheate C position of analyser V, analyser V is transformed into analysis state, start low-lift pump P, sodium tetraborate liquid C is injected into stream, makes injection annulus C
0in mixed sample SS and the mixed reaction solution of hydrogen peroxide liquid R under the promotion of sodium tetraborate liquid C, enter analysis stream, pass through again ion-exchange chromatography IC, enter conductance flow cell F, through electric conductivity detector D, the signal of reaction mixture feature being transferred to computer processing system PC processes, obtain the formic acid of mixed sample SS, acetic acid, propionic acid, butyric acid, glutaric acid divides other content data spectrogram, it is horizontal ordinate that computer processing system PC be take the concentration X of mixed sample SS, the peak area Y of standard specimen spectrogram of take is that ordinate draws regression equation curve, and deposit computer processing system PC in, obtain the typical curve of aldehyde corresponding to the oxidized various acid of mixed sample SS, as shown in table 1.
(4) assay of aldehyde corresponding to original various acid in sheep sample S: be divided into rapid into sample Walk and survey that determine rapid these two Walk of Walk rapid, from the sheep sample S of step (2), getting a part of sheep sample S as this step (4),
(4-1) Jin Yang Walk is rapid: sheep sample S puts into the sample S position of analyser V; Analyser V is arranged on to sample introduction state, operation valve T is opened in caustic lye of soda K circulation and the state that hydrogen peroxide liquid R closes, caustic lye of soda K enters reactor L after threeway mixer M1, low-lift pump P, threeway mixer M2; Ox leather sample S also enters reactor L after low-lift pump P, threeway mixer M2; Caustic lye of soda K and ox leather sample S mix in reactor L, are then full of injection annulus C
0, original formic acid, acetic acid, propionic acid, butyric acid, the corresponding aldehyde mass concentration of the various acid difference of glutaric acid in ox leather sample S to be measured;
(4-2) to Ding Walk rapid for Ce: sodium tetraborate liquid C is put into the leacheate C position of low pressure ion chromatography automatic analyzer V, analyser V is transformed into analysis state, start low-lift pump P, sodium tetraborate liquid C is injected into stream, makes injection annulus C
0in sheep sample S and the mixed liquor of caustic lye of soda K under the promotion of sodium tetraborate liquid C, enter analysis stream, pass through again ion-exchange chromatography IC, enter conductance flow cell F, through electric conductivity detector D, the signal of reaction mixture feature being transferred to computer processing system PC processes, obtaining sheep sample S is not oxidized and original formic acid, acetic acid, propionic acid, butyric acid, glutaric acid divides other content data spectrogram, according to various acidity scale directrix curves, automatically calculate and there is no original various acid in the ox of oxidizing process leather sample S simultaneously, contain formic acid, acetic acid, propionic acid, butyric acid, the aldehyde mass concentration that glutaric acid difference is corresponding
x 0 be respectively: formaldehyde 0.6mg/L, acetaldehyde 1.7 mg/L, propionic aldehyde 0.5 mg/L, butyraldehyde 0 mg/L, glutaraldehyde 0 mg/L.
(5) sheep sample S oxidized after, the aldehyde that the total content of original various acid and the various acid of reaction product is corresponding is measured: be divided into and Ce rapid into Yang Walk and Ding Walk this Liang Walk is rapid suddenly, from the sheep sample S of step (2), get a part as the sheep sample S of this step (5)
(5-1) enter sample Walk rapid: hydrogen peroxide liquid R is put into the reactant liquor R position of low pressure ion chromatography automatic analyzer V, sheep sample S puts into the ox leather sample S position of analyser V; Operation valve T opens in hydrogen peroxide liquid R and caustic lye of soda K circulation, enters reactor L after threeway mixer M1, low-lift pump P, threeway mixer M2 simultaneously; Ox leather sample S also enters reactor L after low-lift pump P, threeway mixer M2 simultaneously; Hydrogen peroxide liquid R and ox leather sample S carry out oxidation reaction in reactor L, become acetic acid, propionic aldehyde to be oxidized to that propionic acid, butyraldehyde are oxidized to butyric acid, glutaraldehyde is oxidized to glutaric acid oxidation of formaldehyde formic acid, oxidation of acetaldehyde in sheep sample S, ox leather sample S becomes the reaction mixture of reaction product formic acid, acetic acid, propionic acid, butyric acid, glutaric acid, is then full of injection annulus C
0, the corresponding aldehyde mass concentration of various acid difference of original formic acid generating with reaction, acetic acid, propionic acid, butyric acid, glutaric acid in reaction mixture to be measured;
(5-2) to Ding Walk rapid for Ce: sodium tetraborate liquid C is put into the leacheate C position of low pressure ion chromatography automatic analyzer V, analyser V is transformed into analysis state, start low-lift pump P, sodium tetraborate liquid C is injected into stream, makes injection annulus C
0in sheep sample S and the mixed reaction solution of hydrogen peroxide liquid under the promotion of sodium tetraborate liquid C, enter analysis stream, pass through again ion-exchange chromatography IC, enter conductance flow cell F, through electric conductivity detector D, the signal of reaction mixture feature being transferred to computer processing system PC processes, obtain sheep sample S original and oxidized after formic acid, acetic acid, propionic acid, butyric acid, glutaric acid divide other content data spectrogram, simultaneously according to various acidity scale directrix curves, automatically calculate formic acid, acetic acid, propionic acid, butyric acid, glutaric acid corresponding aldehyde mass concentration respectively
x be respectively: formaldehyde 1.3mg/L, acetaldehyde 2.2 mg/L, propionic aldehyde 1.0mg/L, butyraldehyde 0.9mg/L, glutaraldehyde 4.5mg/L;
In the present embodiment,
Sodium tetraborate liquid C concentration is 0.002mol/L sodium tetraborate (Na
2b
4o
7) aqueous solution;
Hydrogen peroxide R is that concentration is 0.6mol/L hydrogen peroxide (H
2o
2) aqueous solution;
Caustic lye of soda K is that concentration is the sodium hydrate aqueous solution of 0.05mol/L;
The flow velocity of sodium tetraborate liquid C is: 0.6mL/min;
Low pressure anion chromatographic column column length is: 15cm.
(6) calculate the corresponding aldehyde qualitative data of various acid difference that sheep sample S is oxidized to:
By the corresponding aldehyde mass concentration of various original acid in sheep sample S
x 0 (mg/L), original and oxidized after the corresponding aldehyde mass concentration of acid
x (mg/L), V=50 mL, m=1 g,
Computing formula below difference substitution:
In formula:
A
ithe mass content of aldehyde in-sample, mg/kg,
xthe mass concentration of the aldehyde that-a certain acid is corresponding, mg/L,
x 0 the corresponding aldehyde mass concentration of-a certain original acid, mg/L,
Draw the mass content A of various aldehyde in sheep
ibe respectively: formaldehyde 35mg/kg, acetaldehyde 25mg/kg, propionic aldehyde 25mg/kg, butyraldehyde 45mg/kg and glutaraldehyde 225mg/kg.
Claims (3)
1. the low-voltage ion chromatography that simultaneously detects various aldehyde difference content in leather, comprises the steps:
(1) sample preparation and extraction: leather is shredded, and size is no more than 5mm * 5mm, take 1g～2g sample after mixing, put into 150mL with the triangular flask of stopper; To holding, in the Erlenmeyer flask of sample, to add quality percentage composition be neopelex 50mL～100mL of 0.1%, after sample is completely soaked, put into 40 ℃～45 ℃ water-bath ultrasonic extractions (20 ± 5) min, with G1 sand core funnel, filter, obtain and treat that sample measuring liquid is that sample S is standby;
(2) preparation acid and aldehyde normal data converse routine: the computer program that formic acid mass concentration is scaled to formaldehyde mass concentration, quality of acetic acid concentration conversion is the computer program of acetaldehyde mass concentration, propionic acid mass concentration is scaled the computer program of propionic aldehyde mass concentration, butyric acid mass concentration is scaled the computer program of butyraldehyde mass concentration, the computer program that glutaric acid mass concentration is scaled glutaraldehyde mass concentration all deposits low-voltage ion chromatograph computer processing system PC in, as low-voltage ion chromatograph electric conductivity detector D to the formic acid recording in measured object, acetic acid, propionic acid, butyric acid, glutaric acid is distinguished the alternate program of data-switching, this alternate program in computer processing system PC makes:
The measured formic acid mass concentration of electric conductivity detector D is scaled formaldehyde mass concentration, and Computer display be formaldehyde mass concentration,
The measured quality of acetic acid concentration conversion of electric conductivity detector D is acetaldehyde mass concentration, and Computer display be acetaldehyde mass concentration,
The measured propionic acid mass concentration of electric conductivity detector D is scaled propionic aldehyde mass concentration, and Computer display be propionic aldehyde mass concentration,
The measured butyric acid mass concentration of electric conductivity detector D is scaled butyraldehyde mass concentration, and Computer display be butyraldehyde mass concentration,
The measured glutaric acid mass concentration of electric conductivity detector D is scaled glutaraldehyde mass concentration, and is glutaraldehyde mass concentration at Computer display;
(3) measure the typical curve there are the oxidized corresponding various aldehyde of various acid of various aldehyde mixed sample SS: be divided into and Ce rapid into Yang Walk and Ding Walk this Liang Walk is rapid suddenly, mixed sample SS is the mixed liquor of the formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde and the glutaraldehyde that contain concentration known;
(3-1) Jin Yang Walk is rapid: hydrogen peroxide liquid R is put into the reactant liquor R position of low pressure ion chromatography automatic analyzer V, mixed sample SS puts into the sample S position of analyser V; Operation valve T opens in hydrogen peroxide liquid R and NaOH K circulation, enters reactor L after threeway mixer M1, low-lift pump P, threeway mixer M2 simultaneously; Mixed sample SS also enters reactor L after low-lift pump P, threeway mixer M2 simultaneously; Hydrogen peroxide liquid R and mixed sample SS carry out oxidation reaction in reactor L, become acetic acid, propionic aldehyde to be oxidized to that propionic acid, butyraldehyde are oxidized to butyric acid, glutaraldehyde is oxidized to glutaric acid oxidation of formaldehyde formic acid, oxidation of acetaldehyde in mixed sample SS, mixed sample SS becomes the reaction mixture of reaction product formic acid, acetic acid, propionic acid, butyric acid, glutaric acid, is then full of injection annulus C
0, the mass concentration of the formic acid that in reaction mixture to be measured, reaction generates, acetic acid, propionic acid, butyric acid, the corresponding various aldehyde of glutaric acid;
(3-2) to Ding Walk rapid for Ce: sodium tetraborate liquid C is put into the promotion liquid C position of analyser V, analyser V is transformed into analysis state, start low-lift pump P, sodium tetraborate liquid C is injected into stream, makes injection annulus C
0in mixed sample SS and the mixed reaction solution of hydrogen peroxide liquid R under the promotion of sodium tetraborate liquid C, enter analysis stream, pass through again ion-exchange chromatography IC, enter conductance flow cell F, through electric conductivity detector D, the signal of reaction mixture feature being transferred to computer processing system PC processes, obtain the formic acid of mixed sample SS, acetic acid, propionic acid, butyric acid, glutaric acid divides other content data spectrogram, it is horizontal ordinate that computer processing system PC be take the concentration X of mixed sample SS, the peak area Y of standard specimen spectrogram of take is that ordinate draws regression equation curve, and deposit computer processing system PC in, the corresponding various aldehyde of various acid that acquisition mixed sample SS is oxidized to divide other typical curve,
(4) assay of the corresponding various aldehyde of original various acid in sample S: be divided into rapid into sample Walk and survey that determine rapid these two Walk of Walk rapid, from the sample S of rapid (1) sample preparation of Walk and extraction step, getting a part of sample S as this step (4),
(4-1) Jin Yang Walk is rapid: sample S puts into the sample S position of analyser V; Analyser V is arranged on to sample introduction state, operation valve T is opened in caustic lye of soda K circulation and the state that hydrogen peroxide liquid R closes, caustic lye of soda K enters reactor L after threeway mixer M1, low-lift pump P, threeway mixer M2; Sample S also enters reactor L after low-lift pump P, threeway mixer M2; Caustic lye of soda K and sample S mix in reactor L, are then full of injection annulus C
0, in sample to be tested S, original formic acid, acetic acid, propionic acid, butyric acid, the corresponding various aldehyde of the various acid of glutaric acid divide other mass concentration;
(4-2) to Ding Walk rapid for Ce: sodium tetraborate liquid C is put into the promotion liquid C position of low pressure ion chromatography automatic analyzer V, analyser V is transformed into analysis state, start low-lift pump P, sodium tetraborate liquid C is injected into stream, makes injection annulus C
0in sample S and the mixed liquor of caustic lye of soda K under the promotion of sodium tetraborate liquid C, enter analysis stream, pass through again ion-exchange chromatography IC, enter conductance flow cell F, through electric conductivity detector D, the signal of reaction mixture feature being transferred to computer processing system PC processes, obtaining sample S is not oxidized and original formic acid, acetic acid, propionic acid, butyric acid, glutaric acid divides other content data spectrogram, according to various acidity scale directrix curves, automatically calculate and do not have in the sample of oxidizing process S simultaneously, original formic acid, acetic acid, propionic acid, butyric acid, the various aldehyde mass concentrations that glutaric acid difference is corresponding
x 0 ,
(5) sample S is oxidized, the assay of the corresponding various aldehyde of the total content of original various acid and the various acid of reaction product: being divided into and Ce rapid into Yang Walk, to Ding rapid this Liang Walk of Walk rapid, gets a part of sample S as this step (5) from the sample S of step (2);
(5-1) Jin Yang Walk is rapid: hydrogen peroxide liquid R is put into the reactant liquor R position of low pressure ion chromatography automatic analyzer V, sample S puts into the sample S position of analyser V; Operation valve T opens in hydrogen peroxide liquid R and NaOH K circulation, enters reactor L after threeway mixer M1, low-lift pump P, threeway mixer M2 simultaneously; Sample S also enters reactor L after low-lift pump P, threeway mixer M2 simultaneously; Hydrogen peroxide liquid R and sample S carry out oxidation reaction in reactor L, become acetic acid, propionic aldehyde to be oxidized to that propionic acid, butyraldehyde are oxidized to butyric acid, glutaraldehyde is oxidized to glutaric acid oxidation of formaldehyde formic acid, oxidation of acetaldehyde in sample S, sample S becomes the reaction mixture of reaction product formic acid, acetic acid, propionic acid, butyric acid, glutaric acid, is then full of injection annulus C
0, the corresponding various aldehyde mass concentrations of various acid difference of original formic acid generating with reaction, acetic acid, propionic acid, butyric acid, glutaric acid in reaction mixture to be measured;
(5-2) to Ding Walk rapid for Ce: sodium tetraborate liquid C is put into the promotion liquid C position of low pressure ion chromatography automatic analyzer V, analyser V is transformed into analysis state, start low-lift pump P, sodium tetraborate liquid C is injected into stream, makes injection annulus C
0in sample S and the mixed reaction solution of hydrogen peroxide liquid under the promotion of sodium tetraborate liquid C, enter analysis stream, pass through again ion-exchange chromatography IC, enter conductance flow cell F, through electric conductivity detector D, the signal of reaction mixture feature being transferred to computer processing system PC processes, obtain sample S original and oxidized after formic acid, acetic acid, propionic acid, butyric acid, glutaric acid divide other content data spectrogram, simultaneously according to various acidity scale directrix curves, automatically calculate formic acid, acetic acid, propionic acid, butyric acid, glutaric acid corresponding various aldehyde mass concentrations respectively
x ;
Various aldehyde nail aldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, glutaraldehyde;
Various sour nail acid, acetic acid, propionic acid, butyric acid, glutaric acid.
2. the various aldehyde low-voltage ion chromatography of content respectively that simultaneously detects in leather according to claim 1, is characterized in that: also comprise following data processing method,
(6) calculate the corresponding various aldehyde qualitative datas of various acid difference that sample S is oxidized to:
In formula:
A
ithe mass content of aldehyde in-sample, mg/kg,
xthe mass concentration of the aldehyde that-a certain acid is corresponding, mg/L,
x 0 the corresponding aldehyde mass concentration of-a certain original acid, mg/L,
m-sample quality, mg,
V-sample extracting solution volume L.
3. the various aldehyde low-voltage ion chromatography of content respectively that simultaneously detects in leather according to claim 1 and 2, it is characterized in that: the back-pressure circle Y of low pressure ion chromatography automatic analyzer V is that 10m, internal diameter are 0.5mm polyfluortetraethylene pipe by length, after coiled coil, make the spiral coil that length is 15cm, hydrogen peroxide hydraulic control valve T is stainless steel horizontal swinging arm operation valve;
Promote liquid C and select sodium tetraborate liquid C, sodium tetraborate liquid C is that concentration is the sodium tetraborate (Na of 0.002mol/L
2b
4o
7) aqueous solution;
Reactant liquor R selects hydrogen peroxide liquid R, and hydrogen peroxide liquid R is that concentration is the aqueous hydrogen peroxide solution (H of 0.6mol/L～0.8mol/L
2o
2);
Caustic lye of soda K is that concentration is the sodium hydrate aqueous solution of 0.05mol/L;
At chromatography of ions automatic analyzer V, in analysis state, the flow velocity of sodium tetraborate liquid C is: 0.6mL/min～0.8mL/min;
Low pressure anion chromatographic column column length is: 15cm～20cm.
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