CN106501400B - TCEP detection method in a kind of liquid chromatogram measuring water sample - Google Patents
TCEP detection method in a kind of liquid chromatogram measuring water sample Download PDFInfo
- Publication number
- CN106501400B CN106501400B CN201610919520.1A CN201610919520A CN106501400B CN 106501400 B CN106501400 B CN 106501400B CN 201610919520 A CN201610919520 A CN 201610919520A CN 106501400 B CN106501400 B CN 106501400B
- Authority
- CN
- China
- Prior art keywords
- tcep
- detection method
- sample
- water
- detection
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
TCEP detection method in a kind of liquid chromatogram measuring water sample, wherein, TCEP is tricresyl phosphate (2 chloroethyl) ester, and detection method comprises the following steps:(1) sample pre-treatments:Surface water or underground water are subjected to filter progress, filtrate is obtained as testing sample;(2) sample detection:The filtrate that step (1) is obtained carries out high performance liquid chromatography differential pulse polarograpll, and testing conditions include:Chromatographic column:Gemini C18 reversed-phase columns;Mobile phase:Mobile phase A is methanol, and Mobile phase B is water, and the volume ratio of the methanol and the water is (50~60):(40~50), two-phase contains 0.15~0.25% formic acid;Column temperature:30~40 DEG C;Detection method proposed by the present invention has detection time short, can save numerous and diverse pretreatment process, shortens sample minute, and more simple and efficient, detection sensitivity is high, and the degree of accuracy is high, and testing cost is low, high financial profit, it is easy to the advantage promoted the use of.
Description
Technical field
The present invention relates to the detection side of TCEP in technical field of analysis and detection, more particularly to liquid chromatogram measuring water sample a kind of
Method.
Background technology
TCEP is tricresyl phosphate (2- chloroethyls) ester, is a kind of alkylphosphonate, mainly as plastic products, textile, electricity
Sub- equipment and building, the flame-retardant additive of fitment material for family are widely used.The production of TCEP and its product, transport, using,
During discarded and disposal etc., TCEP easily enters environment by modes such as volatilization, product abrasion, seepages;At present in Sweden, moral
TCEP is detected in multiple national water body environments such as state, Spain, Australia's land productivity, Japan, South Korea, China.TCEP can lead in environment
Cross food chain circulation and the directly approach such as contact enters human body, be enriched with human body.TCEP belongs to 2 class carcinogens and the life of 1B classes
Grow toxicant.Intake TCEP can cause kidney, liver and brain toxicity, infringement health and induction cancer.Current European Union risk
0.2mg/m should be less than by assessing draft suggestion control TCEP suctions intake3。
Detection method the most frequently used TCEP is GC-MS (GC-MS) in existing Research Literature.Coordinate journey
Sequence heating control and selective detector, GC-MS can obtain gratifying detection limit and sensitivity, but need to be by including
The complicated pretreatment process of organic solvent extraction, consumption of organic solvent is big, can produce secondary pollution, and for the complicated sample of matrix
Product, the degree of accuracy of measure is relatively low.Compared to GC-MS, part document determines TCEP, side using liquid chromatography-mass spectrometry (LC-MS)
Method sensitivity is high, but instrument and equipment cost is higher, is difficult popularization;Not yet disclose at present and use high performance liquid chromatography-show poor folding
The method of photodetector detection tricresyl phosphate (2- chloroethyls) ester (TCEP).
The content of the invention
It is an object of the invention to propose a kind of liquid chromatogram measuring water that simple and efficient, sensitivity is high, testing cost is low
TCEP detection method in sample.
For up to this purpose, the present invention uses following technical scheme:
TCEP detection method, comprises the following steps in a kind of liquid chromatogram measuring water sample:
(1) sample pre-treatments:Surface water or underground water are subjected to filter progress, filtrate is obtained as testing sample;
(2) sample detection:The filtrate that step (1) is obtained carries out high performance liquid chromatography-differential pulse polarograpll, to phosphorus
The testing conditions of sour three (2- chloroethyls) esters include:Chromatographic column:Gemini C18 reversed-phase columns;Mobile phase:Mobile phase A is methanol,
Mobile phase B is water, and the volume ratio of the methanol and the water is (50~60):(40~50), two-phase containing 0.15~
0.25% formic acid;Column temperature:30~40 DEG C.
Further illustrate, filter progress described in step (1) is using polyethersulfone millipore filter to the surface water or underground
Water is filtered.
It is preferred that, the aperture of the polyethersulfone millipore filter is 0.45 μm.
It is preferred that, the volume ratio of the methanol and the water described in step (2) in mobile phase is 55:45, two-phase
Contain 0.2% formic acid.
It is preferred that, column temperature described in step (2) is 35 DEG C.
Further illustrate, the flow velocity of testing conditions sample introduction described in step (2) is 1.1~1.3mL/min, and sample size is 95
~105 μ L.
It is preferred that, flow velocity described in step (2) is 1.2mL/min.
It is preferred that, sample size described in step (2) is 100 μ L.
It is preferred that, the specification of the Gemini C18 reversed-phase columns is 250mm*4.60mm*5mm.
Further illustrate, it is to use efficient liquid that filtrate described in step (2), which carries out high performance liquid chromatography-differential pulse polarograpll,
Phase chromatogram-differential refraction detector is tested and analyzed, and it is qualitative to carry out TCEP with retention time, uses standard curve standard measure,
The retention time is 4.355min.
Beneficial effects of the present invention:(1) detection time is short, saves numerous and diverse pretreatment process, when shortening sample measure
Between, it is more simple and efficient.Detection method can directly detect the TCEP in water sample, without the analyte in sample is shifted
Into organic solvent, the sample pretreatment process of complexity is eliminated, reagent cost, more environmental protection is greatlyd save;Simultaneously
Each sample minute highly shortened sample minute in 8 minutes.
(2) detection sensitivity is high, and the degree of accuracy is high.Detection method is linearly closed in the range of 0.1~6.0mg/L
System, coefficient correlation is 0.9996, and method detects the rate of recovery for being limited to TCEP in 0.008mg/L, drinking water, running water, surface water
Respectively between 96~101%, 95~99%, 72~82%, relative standard deviation RSD (n=6) is 1.1%;Show to determine drink
There is the good degree of accuracy with the TCEP in water and running water, the TCEP in earth's surface water sample, rate of recovery data and other inspections are determined
Quite, correlated error can be advantageously applied to various water samples to survey method (GC-MS, LC-MS) within industry tolerance interval
Middle TCEP detection.
(3) testing cost is low, high financial profit, it is easy to promote the use of.The detection method instrument configuration cost of the present invention is low,
Equipment routine use cost is low, and need not use organic solvent, and reagent cost is low, will not cause secondary pollution;Therefore more
It is easy to promote the use of in the lab.
In summary, the range of linearity of detection method of the invention is wide, the rate of recovery is high, precision is high, and detection limit is low, economical
Efficiently and be easy to promote the use of in laboratory, the detection of TCEP in water sample can be advantageously applied to.
Brief description of the drawings
Fig. 1 is the chromatogram of tricresyl phosphate (2- chloroethyls) ester (TCEP) of one embodiment of the invention;
Fig. 2 is the canonical plotting of tricresyl phosphate (2- chloroethyls) ester (TCEP) of one embodiment of the invention.
Embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by embodiment.
TCEP detection method, comprises the following steps in a kind of liquid chromatogram measuring water sample:
(1) sample pre-treatments:Surface water or underground water are subjected to filter progress, filtrate is obtained as testing sample;
(2) sample detection:The filtrate that step (1) is obtained carries out high performance liquid chromatography-differential pulse polarograpll, to phosphorus
The testing conditions of sour three (2- chloroethyls) esters include:Chromatographic column:Gemini C18 reversed-phase columns;Mobile phase:Mobile phase A is methanol,
Mobile phase B is water, and the volume ratio of the methanol and the water is (50~60):(40~50), two-phase containing 0.15~
0.25% formic acid;Column temperature:30~40 DEG C.
The detection method of tricresyl phosphate (2- chloroethyls) ester (TCEP) in a kind of liquid chromatogram measuring water sample disclosed by the invention,
Mainly first pass through polyethersulfone millipore filter to filter water sample, and apply high performance liquid chromatography-differential pulse polarograpll
Method carries out TCEP detection to filtrate, and combines above-mentioned testing conditions, obtains a kind of effectively and rapidly TCEP analyses inspection
Survey method, the detection time of the detection method is short, simple and efficient, and sensitivity is high, and the degree of accuracy is high, and testing cost is low and applicability
Extensively, so as to provide reliable foundation to formulate corresponding standard.
The present invention is relative to prior art difference:The analytical equipment used is high performance liquid chromatography-differential refraction inspection
Survey device.
(1) detection time is short, saves numerous and diverse pretreatment process, shortens sample minute, more simple and efficient.With
The GC-MS detection methods generally used at present determine TCEP in water sample and compared, and detection method can be detected directly in water sample
TCEP, without the analyte in sample is transferred in organic solvent, eliminate complexity sample pretreatment process, save significantly
About reagent cost, more environmental protection;The each sample minute of detection method is in 8 minutes simultaneously, greatly
Shorten sample minute.
(2) detection sensitivity is high, and the degree of accuracy is high.Detection method is linearly closed in the range of 0.1~6.0mg/L
System, coefficient correlation is 0.9996, and method detects the rate of recovery for being limited to TCEP in 0.008mg/L, drinking water, running water, surface water
Respectively between 96~101%, 95~99%, 72~82%, relative standard deviation RSD (n=6) is 1.1%;These tables of data
Bright detection method of the invention determines the TCEP in drinking water and running water, with the good degree of accuracy, determines in earth's surface water sample
TCEP, rate of recovery data and other detection methods (GC-MS, LC-MS) quite, correlated error industry tolerance interval it
Interior, generally, detection method of the invention can be advantageously applied to the detection of TCEP in various water samples.
(3) testing cost is low, high financial profit, it is easy to promote the use of.Compared with existing LC-MS detection methods, this hair
Bright detection method instrument configuration cost is low, and equipment routine use cost is low, compared with GC-MS detection methods, inspection of the invention
Survey method need not use organic solvent, and reagent cost is low, will not cause secondary pollution;Therefore it is easier to promote in the lab
Use.
In summary, the range of linearity of detection method of the invention is wide, the rate of recovery is high, precision is high, and detection limit is low, economical
Efficiently and be easy to promote the use of in laboratory, the detection of TCEP in water sample can be advantageously applied to.
Further illustrate, filter progress described in step (1) is using polyethersulfone millipore filter to the surface water or underground
Water is filtered.
It is preferred that, the aperture of the polyethersulfone millipore filter is 0.45 μm.
It is preferred that, the volume ratio of the methanol and the water described in step (2) in mobile phase is 55:45, two-phase
Contain 0.2% formic acid.
It is preferred that, column temperature described in step (2) is 35 DEG C.
Further illustrate, the flow velocity of testing conditions sample introduction described in step (2) is 1.1~1.3mL/min, and sample size is 95
~105 μ L.
It is preferred that, flow velocity described in step (2) is 1.2mL/min.
It is preferred that, sample size described in step (2) is 100 μ L.
It is preferred that, the specification of the Gemini C18 reversed-phase columns is 250mm*4.60mm*5mm.
Further illustrate, it is to use efficient liquid that filtrate described in step (2), which carries out high performance liquid chromatography-differential pulse polarograpll,
Phase chromatogram-differential refraction detector is tested and analyzed, and it is qualitative to carry out TCEP with retention time, uses standard curve standard measure,
The retention time is 4.355min.
TCEP detection method in a kind of liquid chromatogram measuring water samples of embodiment 1-:
A:The preparation of laboratory apparatus
High performance liquid chromatography-differential refraction detector (Agilent company)
Gemini C18 reversed-phase columns
0.45 μm of polyethersulfone filter head
B:The preparation of reagent
Standard items:TCEP (purity 97.0%, the production of SIGMA-ALDRICH companies)
C:Specific detecting step:
Detected, comprised the following steps using high performance liquid chromatography-differential refraction detector:
(1) standard liquid is prepared:100ml volumetric flasks are taken, electronic balance is put into, removed the peel, TCEP is added with dropper, are claimed
0.1142g enters to use ultra-pure water constant volume after volumetric flask, is made into 4mmol/L stock solution;
The preparation of TCEP standard liquids:Accurately pipette appropriate Standard Reserving Solution, diluted with ultra-pure water, be made into 0,0.1,0.5,
1st, 2,3,4,6mg/L standard working solution.
(2) sample pre-treatments:Take appropriate water sample to use aperture to be filtered for 0.45 μm of polyethersulfone millipore filter, must filter
Liquid is used as testing sample;
(3) sample detection:The filtrate that step (2) is obtained uses high performance liquid chromatography-differential refraction detector pair
Tricresyl phosphate (2- chloroethyls) ester is tested and analyzed, and retention time is qualitative, and standard curve standard measure, testing conditions include:
Chromatographic column:Gemini C18 reversed-phase columns, specification is 250mm*4.60mm*5mm;
Mobile phase:Mobile phase A is methanol, and Mobile phase B is water, and the volume ratio of the methanol and the water is 55:45, two
Mutually contain 0.2% formic acid;
Column temperature:35℃;
Flow velocity:1.2mL/min;
Sample size is 100 μ L;
TCEP retention times are 4.355min.
The TCEP obtained by above-mentioned detection method chromatogram, as shown in figure 1, wherein abscissa is retention time, is indulged
Coordinate is peak area, it can be seen that the TCEP can obtain good peak shape.
Embodiment 2:Linear relationship
In above-described embodiment 1 under preferred testing conditions, TCEP is examined in 0.1~6.0mg/L concentration ranges
Survey, the TCEP of acquisition standard curve is shown in Fig. 2, as shown in Figure 2, its concentration has good linear relationship with peak area, linear side
Cheng Wei:Y=501.77X+4.9073, coefficient R 2=0.9996.
Embodiment 3:Detection limit
In above-described embodiment 1 under preferred testing conditions, to the standard specimen replication 8 times of 0.1mg/L concentration, 3 are calculated
The concentration limit that times standard deviation obtains TCEP is 0.008mg/L, as shown in table 1:
The TCEP of table 1 detection limit test
Embodiment 4:Precision
In above-described embodiment 1 under preferred testing conditions, with continuously detection 6 times of 2mg/L standard specimen, as a result (2 are shown in Table)
It has been shown that, its relative standard deviation RSD=1.1%.As can be seen here under the conditions of detection method, precision can meet analysis
The requirement of detection.
The TCEP of table 2 Precision Experiment
Embodiment 5:The rate of recovery
In above-described embodiment 1 under preferred testing conditions, added into the Different Waters sample for do not detect TCEP different
The TCEP of level, carries out sample pre-treatments as described in Example 1, detects the recovery of standard addition of object, each horizontal parallel
Determine 3 times, obtain the rate of recovery of TCEP in drinking water, running water, surface water respectively 96~101%, 95~99%, 72~
Between 82%, as shown in table 3, it can be seen that under the conditions of detection method, the degree of accuracy can meet various water body examples point
Analyse the requirement of detection.
The TCEP recovery testus of table 3
TCEP detection method is linear in a kind of embodiment 1-5, liquid chromatogram measuring water sample of present invention proposition
Scope is wide, the rate of recovery is high, precision is high, and detection limit is low, economical and efficient and is easy to promote the use of in the lab, can answer well
Detection for TCEP in water.
The technical principle of the present invention is described above in association with specific embodiment.These descriptions are intended merely to explain the present invention's
Principle, and limiting the scope of the invention can not be construed in any way.Based on explanation herein, the technology of this area
Personnel, which would not require any inventive effort, can associate other embodiments of the present invention, and these modes are fallen within
Within protection scope of the present invention.
Claims (9)
1. TCEP detection method in a kind of liquid chromatogram measuring water sample, it is characterised in that:Comprise the following steps:
(1) sample pre-treatments:Surface water or underground water are subjected to filter progress, filtrate is obtained as testing sample;
(2) sample detection:The filtrate that step (1) is obtained carries out high performance liquid chromatography-differential pulse polarograpll, testing conditions
Including:Chromatographic column:Gemini C18 reversed-phase columns;Mobile phase:Mobile phase A is methanol, and Mobile phase B is water, in the mobile phase
The volume ratio of the methanol and the water is 55:45, two-phase contains 0.2% formic acid;Column temperature:30~40 DEG C.
2. TCEP detection method in a kind of liquid chromatogram measuring water sample according to claim 1, it is characterised in that:Step
(1) filter progress described in is filtered using polyethersulfone millipore filter to the surface water or underground water.
3. TCEP detection method in a kind of liquid chromatogram measuring water sample according to claim 2, it is characterised in that:It is described
The aperture of polyethersulfone millipore filter is 0.45 μm.
4. TCEP detection method in a kind of liquid chromatogram measuring water sample according to claim 1, it is characterised in that:Step
(2) column temperature described in is 35 DEG C.
5. TCEP detection method in a kind of liquid chromatogram measuring water sample according to claim 1, it is characterised in that:Step
(2) flow velocity of testing conditions sample introduction described in is 1.1~1.3mL/min, and sample size is 95~105 μ L.
6. TCEP detection method in a kind of liquid chromatogram measuring water sample according to claim 5, it is characterised in that:Step
(2) flow velocity described in is 1.2mL/min.
7. TCEP detection method in a kind of liquid chromatogram measuring water sample according to claim 5, it is characterised in that:Step
(2) sample size described in is 100 μ L.
8. TCEP detection method in a kind of liquid chromatogram measuring water sample according to claim 1, it is characterised in that:It is described
The specification of Gemini C18 reversed-phase columns is 250mm*4.60mm*5 μm.
9. TCEP detection method in a kind of liquid chromatogram measuring water sample according to claim 1, it is characterised in that:Step
(2) filtrate described in, which carries out high performance liquid chromatography-differential pulse polarograpll, is entered using high performance liquid chromatography-differential refraction detector
Row detection and analysis, it is qualitative to carry out TCEP with retention time, uses standard curve standard measure, and the retention time is 4.355min.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610919520.1A CN106501400B (en) | 2016-10-21 | 2016-10-21 | TCEP detection method in a kind of liquid chromatogram measuring water sample |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610919520.1A CN106501400B (en) | 2016-10-21 | 2016-10-21 | TCEP detection method in a kind of liquid chromatogram measuring water sample |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106501400A CN106501400A (en) | 2017-03-15 |
CN106501400B true CN106501400B (en) | 2017-10-24 |
Family
ID=58318368
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610919520.1A Active CN106501400B (en) | 2016-10-21 | 2016-10-21 | TCEP detection method in a kind of liquid chromatogram measuring water sample |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106501400B (en) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1218905A (en) * | 1997-12-04 | 1999-06-09 | 中国科学院山西煤炭化学研究所 | Efficient liquid phase chromatographic analysis of organic fire-retardant |
CN101311721A (en) * | 2008-05-15 | 2008-11-26 | 深圳市华测检测技术股份有限公司 | Method for detecting haloalkylphosphate by liquid phase chromatograph |
CN102841132A (en) * | 2012-09-05 | 2012-12-26 | 北京工业大学 | Flexible magnetostriction and eddy integrated sensor for detecting defects of high-voltage transmission line |
-
2016
- 2016-10-21 CN CN201610919520.1A patent/CN106501400B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1218905A (en) * | 1997-12-04 | 1999-06-09 | 中国科学院山西煤炭化学研究所 | Efficient liquid phase chromatographic analysis of organic fire-retardant |
CN101311721A (en) * | 2008-05-15 | 2008-11-26 | 深圳市华测检测技术股份有限公司 | Method for detecting haloalkylphosphate by liquid phase chromatograph |
CN102841132A (en) * | 2012-09-05 | 2012-12-26 | 北京工业大学 | Flexible magnetostriction and eddy integrated sensor for detecting defects of high-voltage transmission line |
Non-Patent Citations (4)
Title |
---|
Occurrence and removal of pharmaceuticals and endocrine disruptors in South Korean surface,drinking,and waste waters;SD Kim,J Cho,IS Kim;《Water Research》;20060823;第41卷(第5期);全文 * |
北京市城市环境有机磷酸酯污染水平和分布特征研究;高立红;《中国博士论文全文数据库》;20151218;全文 * |
超高效液相色谱-串联质谱法测定污水中14种有机磷酸酯阻燃剂;梁钪,牛宇敏,刘景富;;《环境化学》;20141015;第33卷(第10期);全文 * |
高效液相色谱法分析四-2-氯乙基-乙撑二磷酸酯阻燃剂;晁国胜;《黎明化工》;19910702(第2期);全文 * |
Also Published As
Publication number | Publication date |
---|---|
CN106501400A (en) | 2017-03-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102252987B (en) | Method for detecting protein content | |
CN104833750A (en) | Method for separating and determining chromium elements with different valences in tobacco and tobacco products | |
CN106841466B (en) | A kind of liquid chromatogram pre-column derivatization detecting water glyphosate | |
CN108169385A (en) | A kind of method using six kinds of glucides in ultra performance liquid chromatography concatenation QDa simultaneously quick detection health liquor | |
CN102435703A (en) | Method for simultaneously detecting various microcystins in water | |
CN106770788A (en) | Numb-taste components content detection based on " one surveys comment more " method | |
CN102507765A (en) | Method for simultaneously detecting content of trace bromate and nitrite in drinking water | |
CN114002338A (en) | Method for measuring migration quantity of additive in food contact material | |
CN105319296A (en) | Measuring method for methyl alcohol content | |
CN105628815A (en) | Method for determining trace ethyl carbamate in fermented food | |
CN104215705A (en) | Method for detecting residual amount of organic-chlorine pesticide in grain | |
CN109991358A (en) | Measure chloroacetic method in soil | |
CN106501400B (en) | TCEP detection method in a kind of liquid chromatogram measuring water sample | |
CN103512974B (en) | Method for rapidly determining contents of aureomycin for feed and impurities of aureomycin by HPLC | |
CN105334283B (en) | Simultaneous Determination reconstituted tobacco oxalate, amber acid radical, the sample-pretreating method of sulfate radical and phosphate radical | |
CN104076032A (en) | Method for measuring ammonia nitrogen in seawater | |
CN106596765A (en) | Method for detecting addition amount of maltodextrin in food materials | |
CN101477060B (en) | Mercury ion detection test paper, its production method and use | |
CN103969319B (en) | A kind of detection method of hydrobiont metallothionein | |
CN104777139A (en) | Method for detecting total mercury, inorganic mercury and organic mercury in tobacco simultaneously and application | |
CN105301131A (en) | Use UPC2Method for measuring monoglyceride in molecular distillation glycerin monostearate by ELSD | |
CN113030339B (en) | Detection method suitable for common phosphonate in water bodies with different salinity | |
CN109100456A (en) | Method that is a kind of while measuring 3 kinds of liposoluble vitamin contents in multivitamin injection | |
CN104569251A (en) | Method for synchronously detecting water sample contaminated by mixing of trace amount of pesticide environmental hormones | |
CN109298092B (en) | HPLC method for detecting content of methylsulfonyl chloride in industrial waste liquid |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |