CN102590437B - Method for detecting content of metal ions in methyl alcohol - Google Patents

Method for detecting content of metal ions in methyl alcohol Download PDF

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CN102590437B
CN102590437B CN201210016907.8A CN201210016907A CN102590437B CN 102590437 B CN102590437 B CN 102590437B CN 201210016907 A CN201210016907 A CN 201210016907A CN 102590437 B CN102590437 B CN 102590437B
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methyl alcohol
metallic ion
standard
concentration
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CN102590437A (en
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赵灵春
张大伟
陶英华
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China Shenhua Coal to Liquid Chemical Co Ltd
Shenhua Group Corp Ltd
Baotou Coal Chemical Branch of China Shenhua Coal To Liquid Chemical Co Ltd
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China Shenhua Coal to Liquid Chemical Co Ltd
Shenhua Group Corp Ltd
Baotou Coal Chemical Branch of China Shenhua Coal To Liquid Chemical Co Ltd
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Abstract

The invention provides a method for detecting the content of metal ions in methyl alcohol, and the method comprises the following steps: creating a standard curve on conductivity peak area and concentration of different metal ions, heating a methyl alcohol sample to be tested to volatize the methyl alcohol, mixing a metal ion mixture left when the methyl alcohol is volatized into water to form a sample to be tested, testing the sample to be tested by using an ion chromatograph to obtain corresponding peak areas of the metal ions in the to-be-tested sample, finding a concentration value corresponding to the peak area of the metal ions in the to-be-tested sample from the standard curve on conductivity peak area and concentration of the metal ions, taking the concentration value as the concentration value of the metal ions relative to water, and finally converting the content value of the metal ions according to the volumes of the to-be-tested methyl alcohol sample and the water. The analysis result of the method not only can guarantee degree of accuracy and degree of precision of analysis data, but meet the requirement on detection limit for the test; therefore, the method is suitable for the analysis of content of the metal ions in the methyl alcohol in the commercial process.

Description

The assay method of metal ion content in methyl alcohol
Technical field
The present invention relates to methanol-to-olefins field, in particular to the assay method of metal ion content in a kind of methyl alcohol.
Background technology
Methanol-to-olefins (Methanol TO Olefin, being called for short MTO) process provides one not rely on the synthesizing ethylene of oil and the approach of propylene, this synthetic method can be in regulating product in a big way the ratio of ethene and propylene, to meet the demand in market.
For cost savings, the object of waste recovery, methyl alcohol can pass through the raw material of some carbon containings, as: coal, petroleum residue, rock gas etc. can not be converted into the material of ethene and propylene and first make synthetic gas, made by synthetic gas again, in raw material due to these carbon containings, contain the impurity such as metallic ion, this just causes by pick-up metal ion in its prepared methyl alcohol.This methyl alcohol that is mixed with metallic ion is being converted in the process of alkene (MTO), and in methyl alcohol, the content of metallic ion has a significant impact catalyst reaction activity, easily makes catalyst deactivation or poisoning, and then affects the yield that MTO produces.Therefore in methanol to olefins reaction pre-test methyl alcohol, the content of metallic ion is very necessary.
At present, normally adopt the content of metallic ion in aas determination methyl alcohol.The method of metal ion content in a kind of aas determination methyl alcohol will be provided below: in order to eliminate the impact of methyl alcohol on spectral analysis, in methyl alcohol to be measured, add hydrochloric acid, and heat and remove methyl alcohol, obtain treating test sample.In this process, can in methyl alcohol to be measured, add appropriate anti-interference agent to eliminate metallic ion interference each other in methyl alcohol.Measure the corresponding spectra values of each metal ion species in test sample for the treatment of obtaining, and utilize the spectral characteristic of different metal ion to measure the content of ion.The feature of this atomic absorption spectrography (AAS) is that degree of accuracy is high, but the determination period to metallic ion in methyl alcohol to be measured is long, the polycomponent that is not suitable for batch samples detects, and be subject to the restriction of the factor such as Construction Level of Laboratory and personnel's functipnal capability, be not suitable for the determination and analysis to metal ion content in methyl alcohol in the suitability for industrialized production of methanol-to-olefins.
Summary of the invention
The present invention aims to provide the assay method of metal ion content in a kind of methyl alcohol, and to solve, in prior art, to measure the cycle long period of metal ion content in methyl alcohol long, is unfavorable for the problem that the polycomponent of batch samples detects.
The assay method that the invention provides metal ion content in a kind of methyl alcohol, comprises the following steps: a. sets up the conductivity peak area-concentration standard curve of different metal ion; B. heat methyl alcohol sample to be measured, make methyl alcohol volatilization, by soluble in water the metallic ion potpourri after methyl alcohol volatilization, form testing sample; C. adopt ion chromatograph to measure testing sample, obtain the corresponding peak area of metallic ion in testing sample, and from the conductivity peak area-concentration standard curve of metallic ion, search the concentration value of the metallic ion corresponding with the peak area of metallic ion in testing sample, the concentration value as metallic ion with respect to water; And d. is according to the volume of methyl alcohol sample to be measured and water, the content value of conversion metallic ion.
Further, the establishment step of above-mentioned metallic ion conductivity peak area-concentration standard curve comprises 1) prepare multiple metallic ion standard water solution that contains variable concentrations; 2) adopt ion chromatograph to measure each metallic ion standard water GOLD FROM PLATING SOLUTION and belong to the corresponding peak area of ion, and set up conductivity peak area-concentration standard curve according to concentration and its corresponding peak area that each metallic ion standard water GOLD FROM PLATING SOLUTION belongs to ion.
Further, above-mentioned steps 1) in metallic ion be multiple, step 2) in set up respectively the conductivity peak area-concentration standard curve of each metal ion species.
Further, above-mentioned steps 1) described in metallic ion be Na +, K +, Mg 2+and Ca 2+, the step of the metallic ion standard water solution that preparation contains variable concentrations comprises: A. preparation contains respectively Na +, K +, Mg 2+or Ca 2+standard water solution, contain respectively Na +, K +, Mg 2+or Ca 2+the ion concentration of standard water solution identical; B. get respectively the Na that contains of same volume +, K +, Mg 2+or Ca 2+standard water solution, after mixing, add high purity water constant volume 100ml to form metallic ion standard water solution; And C. repeating step B, increase successively Na +, K +, Mg 2+and Ca 2+the volume of standard water solution, form multiple metallic ion standard water solution.
Further, the Na adding in multiple metallic ion standard water solution in above-mentioned steps C +, K +, Mg 2+and Ca 2+each recruitment of volume of standard water solution be not more than 2.5ml.
Further, above-mentioned steps b comprises the following steps: get methyl alcohol sample to be measured, and water-bath, 60-90 DEG C is heated to methyl alcohol volatilization and obtains metallic ion potpourri; With high purity water dissolved metal ions potpourri, 50ml constant volume is for subsequent use, forms testing sample.
Further, above-mentioned bath temperature is 70-80 DEG C.
Further, above-mentioned steps b is further comprising the steps: in the process of methyl alcohol heating volatilization, condense with the metallic ion of methanol steam volatilization by the lid coordinating with the container that methyl alcohol sample to be measured is housed; In process with high purity water dissolved metal ions potpourri, comprise and dissolve the metallic ion that is condensed in top surface.
Further, the above-mentioned process with high purity water dissolved metal ions potpourri further comprises: adopt high purity water to splash into several times in metallic ion potpourri, each dripping quantity is 10-15ml.
Further, the HNO that the leacheate that above-mentioned ion chromatograph adopts is 3-8mmol/L 3the HNO of solution or 5-10mmol/L 3with the pyridinedicarboxylic acid mixed liquor of 10: 1 by volume.
The technique effect that the present invention reaches: utilize ion chromatograph of the present invention to analyze the method for metal ion content in methyl alcohol, the disposal route of sample is easy, safety, mensuration process is also simple, direct, save analysis cost, analysis result had both ensured to analyze accuracy and the precision of data, also meet the detectability requirement of measuring, be suitable for the analysis of commercial process methylate ion concentration.
Brief description of the drawings
Figure of description is used to provide a further understanding of the present invention, forms a part of the present invention, and schematic description and description of the present invention is used for explaining the present invention, does not form inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 shows the chromatographic background conductance value of the embodiment of the present invention 1 intermediate ion figure;
Fig. 2 shows the chromatography of ions spectrogram of testing sample in the embodiment of the present invention 1; And
Fig. 3 a shows the Na that the present invention sets up +typical curve;
Fig. 3 b shows the K that the present invention sets up +typical curve;
Fig. 3 c shows the Mg that the present invention sets up 2+typical curve; And
Fig. 3 d shows the Ca that the present invention sets up 2+typical curve.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, technical scheme in embodiments of the invention is described in detail, but following embodiment and accompanying drawing are only to understand the present invention, and can not limit the present invention, the multitude of different ways that the present invention can be defined by the claims and cover is implemented.
In the typical embodiment of one of the present invention, the assay method of metal ion content in a kind of methyl alcohol, comprises that a. sets up the conductivity peak area-concentration standard curve of metallic ion; B. heat methyl alcohol sample to be measured, make methyl alcohol volatilization, by soluble in water the metallic ion potpourri after methyl alcohol volatilization, form testing sample; C. adopt ion chromatograph to measure testing sample, obtain the corresponding peak area of metallic ion in testing sample, and from metallic ion conductivity peak area-concentration standard curve, search the concentration value of the metallic ion corresponding with the peak area of metallic ion in testing sample, the concentration value as metallic ion with respect to water; And d. is according to the volume of methyl alcohol sample to be measured and water, the content value of conversion metallic ion.
The invention provides a kind of method of utilizing metal ion content in ion-chromatographic determination methyl alcohol, this chromatography of ions is a kind of existing method in prior art, be a kind of be generally used for detecting with ionic forms exist or by the method for the material that exists with ionic forms after derivatization treatment.This method has that accuracy is good, highly sensitive, favorable reproducibility, workload is few and automaticity is high beneficial effect, and this chromatography of ions can be measured different kinds of ions simultaneously.This chromatography of ions is incorporated in methyl alcohol alkene process metal ion content in methyl alcohol is measured, not only can improve the accuracy of measurement, the impact with the content that alleviates metallic ion in methyl alcohol on catalyst reaction activity; And it can also detect the content of Determination of multiple metal elements in methyl alcohol simultaneously, simplify testing process, and the polycomponent that is applicable to methyl alcohol in enormous quantities detects.In addition, adopted in the present invention water as metallic ion standard water solution, the hydrochloric acid using with respect to atomic absorption spectrography (AAS), has not only reduced the operational risk in operation, meanwhile, has also saved cost.
The chromatography of ions of the present invention is external standard method.This external standard method is simple, is applicable to the conventional analysis in factory, and the degree of accuracy of external standard method is high, also can obtain satisfied result for the analysis of trace components.
In said determination methyl alcohol, in the actual mechanical process of the method for metal ion content, a kind of method of setting up metallic ion conductivity peak area-concentration standard curve comprises the following steps: 1) prepare multiple variable concentrations metallic ion standard water solution that contains; 2) adopt ion chromatograph to measure the corresponding peak area of metallic ion described in each described standard water solution, and set up conductivity peak area-concentration standard curve according to concentration and its corresponding peak area that each metallic ion standard water GOLD FROM PLATING SOLUTION belongs to ion.
In methanol-to-olefins process, methyl alcohol, particularly by the raw material of some carbon containings, as: coal, petroleum residue, rock gas etc. can not be converted into the material of ethene and propylene and first make synthetic gas, in the methyl alcohol being made by synthetic gas again, contain many kinds of metal ions, comprise Na +, K +, Mg 2+, Ca 2+, Fe 2+, Cu 2+, Zn 2+, Al 3+deng, in the time measuring respectively the content of each metal ion species, the mixed system of this ion can produce certain impact to the measurement result of each metal ion species.
Preferably, prepare that multiple to contain metallic ion in variable concentrations metallic ion standard water solution process be multiple, now, correspondingly need to set up respectively the conductivity peak area-concentration standard curve of each metal ion species.
Conventionally Na in methyl alcohol, +, K +, Mg 2+, Ca 2+content is more, and it easily exerts an influence to measurement result, and in order to reduce measuring error as far as possible, in a kind of relatively concrete embodiment of the present invention, in said determination methyl alcohol, in the method for metal ion content, metallic ion is Na +, K +, Mg 2+, Ca 2+, now need to set up respectively Na +, K +, Mg 2+, Ca 2+typical curve.Prepare this metallic ion standard water solution that comprises multiple hybrid ionic, can simulate the mixed system of methyl alcohol in methanol-to-olefins process, this just makes the system environment of the metallic ion standard water solution prepared by the present invention more approach the system environment of the actual methyl alcohol that will measure, strengthen the accuracy of the typical curve of being set up by the prepared metallic ion standard water solution of the present invention, and then increase the accuracy of the actual content of various metals in the methyl alcohol conversing by each typical curve.
Preferably, in a kind of concrete embodiment of the present invention, the step of the metallic ion standard water solution that preparation contains variable concentrations comprises: A, preparation contain respectively Na +, K +, Mg 2+or Ca 2+standard water solution, namely arrange and contain Na respectively +standard water solution, contain K +standard water solution, contain Mg 2+standard water solution, contain Ca 2+standard water solution.The prepared Na that contains +, K +, Mg 2+or Ca 2+the ion concentration of standard water solution identical, its ion concentration can be 10mg/L.B, respectively get same volume contain respectively Na +, K +, Mg 2+or Ca 2+standard water solution, after mixing, add high purity water constant volume 100ml to form metallic ion standard water solution; And C, repeating step B, increase successively Na +, K +, Mg 2+and Ca 2+the volume of standard water solution, form the metallic ion standard water solution that multiple concentration is different.That more preferably, in step C, in multiple metallic ion standard water solution, adds contains respectively Na +, K +, Mg 2+or Ca 2+each recruitment of volume of standard water solution be not more than 2.5ml.While preparing each metallic ion standard water solution, in close two groups of content, contain Na +, K +, Mg 2+or Ca 2+each recruitment of volume of standard water solution less, the typical curve of setting up is more accurate, each recruitment is defined as to the foundation that is not conducive to typical curve higher than 2.5ml.
The method of this metal ion species standard water solution provided by the present invention contains respectively Na by one group +, K +, Mg 2+or Ca 2+the setting of standard water solution just can make the different metallic ion standard water solution of many group concentration, can significantly reduce preparation technology's flow process of metallic ion standard water solution, and easily realize.
Preferably, in a kind of concrete embodiment of the present invention, in said determination methyl alcohol, in the method for metal ion content, step a comprises the following steps: get methyl alcohol sample to be measured, water-bath 60-90 DEG C is heated to methyl alcohol volatilization, forms metallic ion potpourri metallic ion potpourri; With high purity water dissolved metal ions potpourri, 100ml constant volume is for subsequent use, forms testing sample.In this process, the volume of got methyl alcohol sample to be measured can be controlled to 50~100ml scope, within the scope of this, can utilize better the chromatography of ions to measure the content of each metal ion species in methyl alcohol sample to be measured.In this mode, adopt heating water bath to process methyl alcohol sample to be measured, its easy and simple to handle, safety, utilizes general experiment equipment to realize, and is adapted at applying in commercial process.In this type of heating, temperature is not limited to 60-90 DEG C, can suitably improve or reduce, if but when bath temperature is too high, can cause methyl alcohol volatilization violent, in violent volatilization process, a large amount of metallic ion in methyl alcohol sample to be measured can be taken away, reduce the accuracy of measuring, if can extend the methyl alcohol volatilization time and bath temperature is too low, affect testing efficiency.From saving time and keeping data accuracy two aspects to consider, heating-up temperature is arranged in above-mentioned scope more useful.For identical reason, more preferably, bath temperature is 70-80 DEG C.
This method of preparing testing sample provided by the present invention, simple, what use is that high purity water dissolves the metallic ion potpourri staying after methyl alcohol volatilization simultaneously, has reduced operational risk, has more effectively ensured operating personnel's personal safety.
Bath temperature in the control methyl alcohol volatilization process adopting in the present invention, although can reduce to a certain extent amount of metal ion entrained in methyl alcohol volatilization process, but or some metallic ion volatilizees along with the volatilization of methanol steam, this just reduces the accuracy of measuring.Measure the accuracy of the method for metal ion content in methyl alcohol in order further to increase the present invention, preferably, in the process of methyl alcohol heating volatilization, condense with the described metallic ion of described methanol steam volatilization by the lid coordinating with the container that described methyl alcohol sample to be measured is housed.For example by lid floating head in the top of container that methyl alcohol sample to be measured is housed, in the time that methanol steam volatilizees, first touch mutually with this lid, make to produce gap between lid and container, methyl alcohol volatilizees from gap, in the process of wanting to touch in lid at methanol steam, metallic ion in methyl alcohol sticks in lid, after methyl alcohol volatilization, cooling lid, has the metallic ion with methanol steam volatilization by condensing on it; In process with high purity water dissolved metal ions potpourri, comprise and dissolve the metallic ion that is condensed in top surface.
Preferably, in the process of preparing testing sample with high purity water dissolved metal ions potpourri, adopt high purity water to splash into several times in metallic ion potpourri, each dripping quantity is 10-15ml, and high purity water impurity content is below 0.01mg/L, and conductivity is less than 0.1 μ S/cm.By repeatedly dripping and can effectively metallic ion potpourri fully be dissolved, the metallic ion evaporateing on wall can be dissolved in the lump simultaneously.
In a kind of concrete embodiment of the present invention, in said determination methyl alcohol in the method for metal ion content, the HNO that the leacheate that ion chromatograph adopts is 3-8mmol/L 3the HNO of solution or 5-10mmol/L 3with the pyridinedicarboxylic acid mixed liquor of 10: 1 by volume.Be not limited in the present invention adopt this two kinds of leacheates, as long as the leacheate of measuring for kation can use, but adopt these two kinds of leacheates chromatographic column in eluent ion chromatograph better, greatly reduce the conductivity of ion chromatograph self, to improve the accuracy of measurement.
Below with reference to embodiment 1-5 and comparative example 1, further illustrate the beneficial effect that adopts the method for metal ion content in mensuration methyl alcohol provided by the present invention.
First, preparing metal ion standard water solution is set up conductivity peak area-concentration standard curve.
1. arrange and contain respectively Na +, K +, Mg 2+or Ca 2+, and concentration is four kinds of standard water solution of 10mg/L;
2. the multiple metallic ion standard water solution that contains variable concentrations of preparation
Metallic ion standard water solution 1: pipette in each 2.5ml to the 100ml volumetric flask of above-mentioned four kinds of standard standard solution with transfer pipet, use high purity water constant volume, 4 DEG C of refrigerations are for subsequent use;
Metallic ion standard water solution 2: pipette in each 5ml to the 100ml volumetric flask of above-mentioned four kinds of standard standard solution with transfer pipet, use high purity water constant volume, 4 DEG C of refrigerations are for subsequent use;
Metallic ion standard water solution 3: pipette in each 7.5ml to the 100ml volumetric flask of above-mentioned four kinds of standard standard solution with transfer pipet, use high purity water constant volume, 4 DEG C of refrigerations are for subsequent use;
Metallic ion standard water solution 4: pipette in each 10ml to the 100ml volumetric flask of above-mentioned four kinds of standard standard solution with transfer pipet, use high purity water constant volume, 4 DEG C of refrigerations are for subsequent use.
3. the foundation of typical curve
3.1 ion chromatograph
In ion chromatograph, chromatographic column is that Metrosep C 4100/4.0, detecting device are the Measuring glass that electric conductivity detector detects, Measuring glass is 20ml.
Ion chromatograph condition determination: voltage: 220V; Flow rate pump: 0.9ml/min.
Chromatographic column in 3.2 eluent ion chromatographs, the HNO that leacheate is 3-8mmol/L 3solution.
3.3 adopt ion chromatograph to measure each metal ion species (Na in each metallic ion standard water solution +, K +, Mg 2+and Ca 2+) corresponding peak area, refer to Fig. 1 and 2, the background conductance value figure that Fig. 1 is ion chromatograph, Fig. 2 is the chromatogram spectrogram of measured testing sample.And belong to the concentration of ion and its corresponding peak area Criterion curve according to each metallic ion standard water GOLD FROM PLATING SOLUTION.Wherein Na +typical curve is referring to Fig. 3 a, K +typical curve is referring to Fig. 3 b, Mg 2+typical curve is referring to Fig. 3 c, Ca 2+typical curve is referring to Fig. 3 d.Those skilled in the art should be understood that accepted standard liquid concentration gradient is less, and titer quantity is more, and the typical curve of building is more reliable.
Embodiment 1
Raw material: MTO level methyl alcohol sample to be measured
Prepare testing sample: accurately measure 200mlMTO level methyl alcohol sample in 250ml Erlenmeyer flask, place lid at the top of Erlenmeyer flask, 80 DEG C of heating water baths 2 hours, obtain metallic ion potpourri, are cooled to room temperature.Splash in Erlenmeyer flask for 3 times with high-purity moisture, drip 10ml at every turn, metallic ion potpourri in Erlenmeyer flask, and clean on lid with the methanol steam metallic ion potpourri condensing that volatilizees, both are collected in 50ml volumetric flask, high purity water constant volume is to be measured.
Test testing sample: the HNO that adopts 3-8mmol/L 3chromatographic column in solution eluent ion chromatograph.Utilize ion chromatograph to measure the Na in testing sample +, K +, Mg 2+and Ca 2+peak area.Contrast the respective standard curve that each metallic ion is set up, obtain the respective concentration value of each metallic ion, and calculate corresponding content value according to following formula:
C=C1×50ml/200ml (1)
The content that in formula (1), C is metallic ion, C1 is the concentration value of obtained metallic ion, and 50ml is the volume of testing sample, and 200ml is the volume of methyl alcohol sample to be measured.
Duplicate measurements step 3 time, averages.
Embodiment 2
Raw material, prepare testing sample and test testing sample all with embodiment 1, wherein, leacheate is 7mmol/LHNO 3with the pyridinedicarboxylic acid potpourri of 10: 1 be by volume leacheate.
Embodiment 3
Raw material, prepare testing sample and test testing sample all with embodiment 1, wherein, preparing water bath heating temperature in testing sample process is 60 DEG C, the time is 4 hours; The dropping number of times of high purity water is 2 times, each 15ml.。
Embodiment 4
Raw material, prepare testing sample and test testing sample all with embodiment 1, wherein, preparing water bath heating temperature in testing sample process is 70 DEG C, the time is 1.5 hours.
Embodiment 5
Raw material, prepare testing sample and test testing sample all with embodiment 1, wherein, preparing water bath heating temperature in testing sample process is 90 DEG C, the time is 1.5 hours.
Comparative example
Raw material: with embodiment 1.
Prepare testing sample: in methyl alcohol sample to be measured, add hydrochloric acid, and heat and remove methyl alcohol, obtain treating test sample.
Measure testing sample: measure respectively the corresponding spectra values of each metal ion species in test sample for the treatment of obtaining, and utilize the spectral characteristic of different metal ion to measure the content of ion.
Table 1
Can be found out by data in table 1, it is basic identical that the MTO level methyl alcohol Gold Samples to be measured that embodiment 1-5 and comparative example 1 obtain belongs to ion concentration, and it is little to test by embodiment 1-5 the data relative standard deviation obtaining, measurement result is accurate, meets chemico-analytic requirement.In the mensuration methyl alcohol provided by the present invention adopting in embodiment 1-5 in addition, the method for metal ion content is easy, safety, and mensuration process is also simple, direct, has saved analysis cost, is suitable for the analysis of commercial process methylate ion concentration.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.

Claims (7)

1. an assay method for metal ion content in methyl alcohol, is characterized in that, comprises the following steps:
A. set up the conductivity peak area-concentration standard curve of different metal ion;
B. heat methyl alcohol sample to be measured, make methyl alcohol volatilization, by soluble in water the metallic ion potpourri after methyl alcohol volatilization, form testing sample;
C. adopt ion chromatograph to measure described testing sample, obtain the corresponding peak area of metallic ion in described testing sample, and from the conductivity peak area-concentration standard curve of described metallic ion, search the concentration of metal ions value corresponding with the peak area of metallic ion in described testing sample, the concentration value as described metallic ion with respect to water; And
D. according to the volume of described methyl alcohol sample to be measured and described water, the content value of the described metallic ion that converts,
Wherein, described step b comprises the following steps:
Get methyl alcohol sample to be measured, water-bath, 60-90 DEG C is heated to methyl alcohol volatilization, obtains metallic ion potpourri;
Dissolve described metallic ion potpourri with high purity water, 50ml constant volume is for subsequent use, forms described testing sample,
Described step b is further comprising the steps:
In the process of described methyl alcohol heating volatilization, condense with the described metallic ion of described methanol steam volatilization by the lid coordinating with the container that described methyl alcohol sample to be measured is housed;
In described process of dissolving described metallic ion potpourri with high purity water, comprise and dissolve the described metallic ion that is condensed in described top surface, wherein, the chromatographic column in described ion chromatograph is Metrosep C4-100/4.0 chromatographic column, and described metallic ion is Na +, K +, Mg 2+and Ca 2+,
The leacheate that described ion chromatograph adopts is: the HNO of 3-8mmol/L 3the HNO of solution or 5-10mmol/L 3with the pyridinedicarboxylic acid mixed liquor of 10:1 by volume.
2. method according to claim 1, is characterized in that, the establishment step of the conductivity peak area-concentration standard curve of described metallic ion comprises:
1) prepare multiple metallic ion standard water solution that contains variable concentrations;
2) adopt ion chromatograph to measure each described metallic ion standard water GOLD FROM PLATING SOLUTION and belong to the corresponding peak area of ion, and belong to concentration and its corresponding peak area Criterion curve of ion according to each metallic ion standard water GOLD FROM PLATING SOLUTION.
3. method according to claim 2, is characterized in that, described step 2) in set up respectively the conductivity peak area-concentration standard curve of each metal ion species.
4. method according to claim 2, is characterized in that, described step 1) in the preparation step of described metallic ion standard water solution that contains variable concentrations comprise:
A. preparation contains respectively Na +, K +, Mg 2+or Ca 2+standard water solution, the described Na that contains respectively +, K +, Mg 2+or Ca 2+the ion concentration of standard water solution identical;
B. get respectively the Na that contains of same volume +, K +, Mg 2+or Ca 2+standard water solution, after mixing, add high purity water constant volume 100ml to form described metallic ion standard water solution; And
C. repeating step B, increases Na successively +, K +, Mg 2+and Ca 2+the volume of standard water solution, form multiple described metallic ion standard water solution.
5. method according to claim 4, is characterized in that, the Na adding in multiple described metallic ion standard water solution in described step C +, K +, Mg 2+and Ca 2+each recruitment of volume of standard water solution be not more than 2.5ml.
6. method according to claim 1, is characterized in that, described bath temperature is 70-80 DEG C.
7. method according to claim 1, is characterized in that, describedly further comprises by the process that high purity water dissolves described metallic ion potpourri: adopt high purity water to splash into several times in described metallic ion potpourri, each dripping quantity is 10-15ml.
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