CN101614716B - Methods for indirectly determining sulfur content of oil field waste water and analyzing valence of sulfur - Google Patents
Methods for indirectly determining sulfur content of oil field waste water and analyzing valence of sulfur Download PDFInfo
- Publication number
- CN101614716B CN101614716B CN2008101114803A CN200810111480A CN101614716B CN 101614716 B CN101614716 B CN 101614716B CN 2008101114803 A CN2008101114803 A CN 2008101114803A CN 200810111480 A CN200810111480 A CN 200810111480A CN 101614716 B CN101614716 B CN 101614716B
- Authority
- CN
- China
- Prior art keywords
- content
- oilfield sewage
- solution
- oil field
- sulfur
- 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.)
- Expired - Fee Related
Links
Images
Abstract
The present invention discloses a method for indirectly determining sulfur content of oil field waste water and a method for analyzing the valence of sulfur. The method for indirectly determining sulfur content of oil field waste water comprises the following steps: 1) adding an excessive amount of Fe<2+> standard solution at a known concentration into the oil field waste water, fixing volume by using deionized water and shaking the mixture up; 2) filtering out a black precipitate from reaction solution till the reaction solution is clear; and 3) determining the content of the rest Fe<2+> in the filtrate by using an ICP-AES method and indirectly calculating the content of reducing sulfur ions in an oil field waste water sample by using a subtration method. The SO4<2-> can be obtained by subtracting the mole number of the reducing sulfur ions form the total mole number of sulfur ions, thus the analysis of different valences of S in the sample is realized. The detection method of the invention has a recovery rate of between 96.9 and 98.7 percent and a relative standard deviation up to 2.15 percent, has the advantages of high accuracy, high detection speed, wide linear range, light pollution, simple operation, low instrument and equipment requirement, low cost and the like, and is suitable to be promoted and used.
Description
Technical field
The present invention relates to sulphion Determination on content method, particularly relate to the indirect determination method of sulphion content in the oilfield sewage.
Background technology
China's freshwater resources are very deficient, and oilfield sewage emission treatment expense is very high again, and the water drive extraction sewage is joined the polymkeric substance re-injection and carried out tertiary oil recovery, begun to use at each elephant.Discover the S in some oilfield water flooding sewage
2-Content is very high, and S
2-Existence bigger to the viscosity influence of polymkeric substance, directly influence oil recovery factor.Therefore, reducing substances sulfide in each block sewage is the essential element that oxygen technology removes that exposes to the sun, also be main object (the Chen Yanling (Chen Yanling) of disposing polluted water in oil, Fan Chou (category), Yang Wenhua (Yang Wenhua), TanZhongliang (Tan Zhongliang), Fei Qi (Fei Qi), Geological Science and TechnologyInformation (geological science and technology information), 2002,21 (2): 83～86; Chen Yanling (Chen Yanling), WangHongmei (Wang Hongmei), Tan Zhongliang (Tan Zhongliang), Zhu Huaijiang (Zhu Huaijiang), Fei Qi (Fei Qi), Geological Science and Technology Information (geological science and technology information), 2002,21 (3): 61～64).S
2-Be that one of principal element of gathering performance is joined in influence, therefore, join S in the poly-preceding sewage
2-The detection problem of content is the oil field urgent problem.Along with the propelling of tertiary oil recovery, be S in the tracking and monitoring oilfield water flooding sewage
2-The situation of change of content needs a kind of S in the oilfield sewage that is applicable to
2-The quantitative determination method of content, thus theoretical foundation provided for oil field combination flooding test.At present, S
2-The Determination on content method mainly contains photometry, potential method, chromatography and fluorescence method etc., these method trivial operations, time-consuming, and because of S
2-Easily oxidation and be difficult to accurate mensuration (Zhang Xingbao (Zhang Xingbao), Tian Yingyan (Tian Yingyan), Physical Testing and ChemicalAnalysis (Part B:Chem.Anal.) (physical and chemical inspection-chemical fascicle), 2002,38 (4): 170～173; Zhao Huiju (Zhao Huiju), Acta Petrolei Sinica (Petroleum Processing Section (petroleum journal) (petrochemical complex), 2004,20 (3): 67～71; Mo Dasong (Mo Dasong), Liu Shouting (Liu Shouting), Jiang Tiancheng (Jiang Tiancheng), Xie Tao (Xie Tao), Chemical Analysis andMeterage (chemical analysis metering), 2007,16 (4): 54～55; Xu Kunming (being permitted Kunming), Si Jingyu (department Jingyu), Chinese J.Anal.Chem (analytical chemistry), 2007,35 (8): 1147～1150; SunDengming (Sun Dengming), Ruan Dawen (Ruan Dawen), Wang Lihong (Wang Lihong), Chinese J.Anal.Chem (analytical chemistry), 2004,32 (2): 179～182; Zhang Zhenxin (Zhang Zhen is new), Sun Dengming (Sun Dengming), Chen Changwu (Chen Changwu), Physical Testing and Chemical Analysis (PartB:Chem.Anal.) (physical and chemical inspection-chemical fascicle), 2005,41 (8): 604～605; Du Baozhong (Du Baozhong), Lu Guomin (the State of Lu people), Xue Li (Xue Li), Chinese Journal of AnalysisLaboratory (assay laboratory), 2002,21 (1): 49～51; Safavi A, Ramezani Z.[J] .Talanta, 1997,44 (7): 1225; Mousavi M F, Sarlack N, [J] .AnalLett, 1997,30 (8): 1567).
Summary of the invention
The invention provides the indirect determination method of reducible sulfur ion concentration in a kind of oilfield sewage accurate, quick, simple to operate.
Reducible sulfur ion (S in the oilfield sewage provided by the present invention
2-) indirect determination method of content, can may further comprise the steps:
1) to oilfield sewage V
SampleThe middle concentration known C that adds
0Excessive Fe
2+Standard solution V
0, be settled to volume V with deionized water, shake up, make S
2-With Fe
2+Reaction, the FeS that generates black precipitates;
2) black precipitate that generates in the filtering reacting liquid is to settled solution;
3) measure residual F e in the filtrate with the ICP-AES method
2+Content C
Fe, calculate Fe in the FeS precipitation according to minusing then
2+Amount, the Fe in the precipitation
2+With S
2-Molal quantity equates, calculates oilfield sewage sample V indirectly with this
SampleThe content C of middle reducible sulfur ion
S
Concrete, available formula one is calculated:
Wherein, M
SBe the molal weight of S, M
FeMolal weight for Fe.
In the indirect determination method of above-mentioned reducible sulfur ion concentration, Fe in the step 1)
2+The concentration C of standard solution
0Can be 1000mg/L, the volume V of constant volume can be 100mL.
Step 2) glass funnel that available inside is added with absorbent cotton in filters.
Can be in the step 3) according to document (Zhou Wenyong; Pay bright. measure copper, iron, lead, cadmium, calcium, content of magnesium in the cyanide silver plating solution, material protection, 2007.1 with the ICP-AES method) in the ICP-AES method of record measure residual F e in the filtrate
2+Content.If this method is used for water drive sewage S
2-During Determination on content, can adopt calibration curve method to measure the content of residual F e in the filtrate; If this method is used for measuring poly-drive extraction sewage S
2-During Determination on content,, add the shear degradation effect, thereby to the solution viscosity influence not quite, therefore can not have influence on the nebulization efficiency of sample solution, so also available method of the present invention is measured because of polymer produced concentration is low.Described residual F e
2+The Determination on content process under ICP-AES instrument best operating condition, carry out, best operating condition is: the power 1.0KW of DRE inductively coupled plasma atomic emission spectrometry instrument, argon pressure 0.6Mpa, cooling gas flow 15L/min, secondary air amount 0.2L/min, atomizer pressure 374.06Pa, lifting capacity 1.5mL/min, Fe wavelength 259.940nm.
The invention provides reducible sulfur ion (S in a kind of oilfield sewage
2-) indirect determination method of content.This method is to measure residual F e by the ICP-AES method
2+Content and reach reductibility S in the indirect determination oilfield sewage
2-The new method of content is promptly by adding excessive known Fe
2+, make the reductibility S in the oilfield sewage
2-With Fe
2+Reaction, the FeS that generates black precipitates, and filters with absorbent cotton again, measures remaining Fe in the filtrate with the ICP-AES method
2+Content is at last according to reductibility S in the minusing indirect determination oilfield sewage
2-Content.Detection method of the present invention obviously is better than the detection technique of reducible sulfur ion concentration in the existing oilfield sewage, the recovery is between 96.9%～98.7%, relative standard deviation can reach 2.15%, and have the accuracy height, detection speed is fast, the range of linearity is wide, low pollute, simple to operate, to advantages such as the instrument and equipment requirement are low and with low cost, suit large area to popularize and use.
Further, the present invention also provides the Determination of Different Valence States method of S in a kind of oilfield sewage, is to utilize the ICP-AES method to survey total quantity of S in the solution, obtains S with reducible sulfur ion concentration indirect determination method in the above-mentioned oilfield sewage
2-Amount; Utilize minusing that total quantity of S is deducted S
2-Amount obtains SO in the solution
4 2-Amount, thereby finish the different valence state analysis of S in the water sample.
Below in conjunction with specific embodiment the present invention is described in further details.
Description of drawings
Fig. 1 is that four block simulated solution prepared polymer solution (1300mg/L) viscosity are with S
2-The situation of change of concentration.
Embodiment
Method therefor is conventional method if no special instructions among the following embodiment.Described percent concentration is mass/volume (W/V) or volume/volume (V/V) percent concentration if no special instructions.
Experimental apparatus:
DRE inductively coupled plasma atomic emission spectrometry instrument: available from the U.S. graceful Leeman of profit company.
High pressure nitrating pot (the teflon high pressure melts the sample device): available from Shanghai emtallurgy research institute.
Superpure water machine (Airum611di): available from Sartorius AG.
Electronic balance (BP211D): available from Sartorius AG.
The preparation of reagent and solution:
Na
2S9H
2O, FeSO
47H
2O, NaCl and Na
2SO
4It is pure to be analysis.
Nitric acid (MOS level), perchloric acid (GR level).
The titer of standard reserving solution: Fe, S is 1000mg/L, available from national ferrous materials test center Iron and Steel Research Geueral Inst.
Standard solution: with 2% (V/V) nitric acid stepwise dilution, Fe, S concentration are respectively 0.00,5.00,10.00,20mg/L, are used for the ICP-AES method and measure with standard reserving solution.
1000mg/L Fe
2+The preparation of solution: accurately take by weighing 0.4964g FeSO
47H
2O is dissolved in the 100mL volumetric flask, with distilled water diluting to scale (matching while using).
1000mg/L S
2-Solution: accurately take by weighing 0.7500g Na
2S9H
2O is dissolved in the 100mL volumetric flask, to scale, is diluted to desired concn (matching while using) with distilled water diluting again.
The preparation of NaCl solution: accurately take by weighing a certain amount of NaCl (analyzing pure) in the 100mL volumetric flask, to scale, the time spent is diluted to desired concn (mg/L) again with distilled water diluting.
Oil field, Nanyang 4 block sewage; Nanyang oilfield polymer (homemade).
Reducible sulfur ion (S in embodiment 1, the oilfield sewage
2-) detection of content
Use indirect determination method of the present invention and known direct determination method that the reducible sulfur ion concentration in the oilfield sewage (is example with the oil field, Nanyang) is detected respectively, concrete grammar is as follows:
One, the mensuration of direct determination method-S total amount
Get Nanyang oilfield sewage sample water sample, then according to S in the oilfield sewage
2-The actual conditions of content, the different salinities of simulation preparation (represent with NaCl, see Table 1) 45,35,15, the different S of 7mg/L
2-The oilfield sewage of concentration again with oilfield sewage sample filter paper filtering, is got the 10mL water sample then and is put into the high-pressure digestion jar, shakes up behind adding 2mL nitric acid and the 0.5mL perchloric acid and tightens loam cake, places 150 ℃ of baking ovens nitrated 2 hours.Behind the nitrated antisense, take out coldly slightly, move into again in the 50mL volumetric flask, to be measured with 2% nitric acid constant volume.At ICP-AES instrument best operating condition (DRE inductively coupled plasma atomic emission spectrometry instrument: power 1.0KW, argon pressure 0.6Mpa, cooling gas flow 15L/min, secondary air amount 0.2L/min, atomizer pressure 374.06Pa, lifting capacity 1.5mL/min, S wavelength 180.669nm.The observation place Automatic Optimal.) under, first purging 2 hours is made the typical curve of S element again, according to typical curve the S total amount in each sample is measured repeated experiments 5 times then.Measurement result is as shown in table 2.
Two, indirect determination method-S
2-Determination on content
Above-mentioned different salinities 45,35,15, the different S of 7mg/L
2-The oilfield sewage of concentration is respectively got V
Sample(25mL), add V
0ML (4,3,1.5,0.6mL) concentration known is C
0Excessive Fe (1000mg/L)
2+Standard solution is settled in V (100mL) volumetric flask with deionized water, shakes up, and adds absorbent cotton filtering-depositing (the black FeS precipitation of generation) then in glass funnel, to settled solution, measures the content C of residual F e in the filtrate again with the ICP-AES method
Fe, repeated experiments 5 times is by measuring residual F e content C
Fe, reductibility S in indirect calculation (calculating) the oilfield sewage sample according to minusing
2-Content C
S(mg/L), calculating formula is referring to formula one.
Formula one
Wherein, M
SBe the molal weight of S, M
FeMolal weight for Fe.
Described mensuration process is at ICP-AES instrument best operating condition (DRE inductively coupled plasma atomic emission spectrometry instrument: power 1.0KW, argon pressure 0.6Mpa, cooling gas flow 15L/min, secondary air amount 0.2L/min, atomizer pressure 374.06Pa, lifting capacity 1.5mL/min, Fe wavelength 259.940nm.The observation place Automatic Optimal.) under carry out.Measurement result is as shown in table 1.
Three, measurement result
Above-mentioned indirect determination method and the directly measurement result demonstration of determination method, indirect method and direct method are measured the reductibility S in the oilfield sewage
2-Content, relative error satisfy the TRACE ELEMENTS ANALYSIS requirement all less than 5%, illustrate that two kinds of assay methods are all reliable; In addition, the data in table 1 and the table 2 also show, these two kinds of assay methods are all irrelevant with the solution salinity, are fit to have the S of the oilfield sewage of different salinities
2-Assay.But, directly measure S with the ICP-AES method
2-Content, the preceding necessary purging of each mensuration is more than 2 hours, thereby minute is long, and instrument operating cost height reaches indirect determination S and measure iron content by the ICP-AES method
2-The purpose of content, not only simple, quick, highly sensitive, and also accuracy is good, and the range of linearity is wide, disturbs also few.
Table 1 indirect method is measured S in the oilfield sewage
2-Concentration result (n=5)
Annotate: Fe
2+Mark liquid concentration is 1000mg/L, and sample volume is 25mL.
Table 2 direct method is measured S in the oilfield sewage sample
2-Concentration result (n=5)
Annotate:
1The mensuration sample volume be 10mL,
2The mensuration sample volume is 25mL.
In addition, also can measure iron content and reach indirect determination S by the AAS method
2-The purpose of content.Comparative experiments finds, the ICP-AES method is stronger than AAS method antijamming capability, influence factor is lacked, the range of linearity is wide and save time, and therefore, the present invention selects the ICP-AES method to survey iron, thereby reaches S in the indirect determination oilfield sewage
2-The purpose of content.
In addition, also find in the experiment, because S in the oilfield sewage
2-Content is relatively low, adds Fe
2+The precipitation that generates is also less, and is not only time saving and energy saving therefore with adding the absorbent cotton filtering-depositing in the glass funnel, and effective, is convenient to execute-in-place.
Embodiment 2, indirect method are measured reducible sulfur ion (S in the oilfield sewage
2-) interference experiment of content
In oilfield sewage, S is often with SO
4 2-And S
2-Form exist, studies show that to have only the S of ortho states
2-Bigger to the polymer viscosity influence, and directly influence oil recovery factor, as shown in Figure 1, for oil field, Nanyang four blocks (Xia Ermen, ancient city, Shuan He, rivers) simulated solution (accurately takes by weighing a certain amount of NaCl (analyzing pure) and polymkeric substance in beaker, transfer in the volumetric flask, be diluted to scale with deionized water, be made into the solution that required salinity and polymer concentration are 1300mg/L) preparation polymer solution (1300mg/L) viscosity with S
2-(horizontal ordinate is S to the situation of change of concentration
2-Concentration, ordinate are solution viscosity).Therefore, join the poly-preceding S that accurately measures in the oilfield sewage
2-Content is very necessary.
This experiment purpose is to investigate SO
4 2-To measuring reductibility S in the oilfield sewage
2-Whether content exists interference.Present embodiment is with 45mg/L S
2-Solution is example, and by different SO
4 2-And S
2-Concentration proportioning (4: 1,3: 1,2: 1,1: 1) preparation combined experiments sample, use embodiment 1 second portion indirect determination method-S respectively
2-S in the method determination experiment sample of content
2-Content.By examination SO
4 2-To S
2-The influence of assay found that SO
4 2-Indirect method is measured reductibility S in the oilfield sewage
2-Determination on content does not have influence.
Embodiment 3, indirect method are measured reducible sulfur ion (S in the oilfield sewage
2-) accuracy of content detects
One, reducible sulfur ion (S in the oilfield sewage
2-) detection limit and the precision of content indirect determination method
With embodiment 1 second portion indirect determination S
2-Content: the sample of preparation is a NaS solution, in the 100mL volumetric flask, adds the Fe of 1000mg/L 1.0mL
2+Standard solution is used the deionized water constant volume, shakes up, filter with adding absorbent cotton in the glass funnel then, with the Fe content in the ICP-AES method mensuration filtrate, repeated experiments 10 times, getting 3 times of pairing concentration of standard deviation is the detection limit of Fe element, utilizes the S in the blank water sample of minusing indirect calculation simultaneously
2-Content, basis of calculation deviation, 3 times of standard deviations are this method and measure S
2-Detection limit.Fe and S as a result
2-Detection limit be respectively 0.040mg/L, 0.023mg/L, relative standard deviation is respectively 0.14% and 2.15%, satisfies trace element analysis requirement (relative standard deviation is less than 5%).
Two, mark-on reclaims experiment
Use embodiment 1 second portion indirect method to the reducible sulfur ion (S in oil field, Nanyang four blocks (Xia Ermen, ancient city, Shuan He, rivers) the water drive sewage with the present invention
2-) content measures, and carry out mark-on and reclaim experiment, experimental data sees Table 3, repeated experiments 5 times.Testing result is as shown in table 3, and the recovery is 96.9%～98.7%, satisfies trace element analysis requirement (recovery is 90.0%～110.0%).
Table 3 indirect method is to S in the oilfield sewage of Nanyang
2-Measurement result (mg/L) (n=5)
Reducible sulfur ion (S in embodiment 4, the usefulness oilfield sewage
2-) content indirect determination method carries out the Determination of Different Valence States of S in the oilfield sewage
In oilfield sewage, S is often with SO
4 2-And S
2-Form exist, this composition with sewage is relevant.Utilizing the ICP-AES method to survey S, is total quantity of S in the solution.In embodiment 1 described indirect determination method, utilize minusing can measure S in the solution
2-Amount is again with S of the present invention
2-The mensuration of total S can calculate SO in the solution in the indirect determination method binding soln of content
4 2-Content.Thereby, utilize S of the present invention
2-The indirect determination method of content also can be finished the different valence state analysis of S in the water sample.
Embodiment 5, indirect method are measured S in the oilfield sewage
2-Content
Above-mentioned different salinities 45,35,15, the different S of 7mg/L
2-The oilfield sewage of concentration is respectively got VmL (20mL), adds V
0ML (8.0,6.0,3.0,1.2mL) concentration known is C
0Excessive Fe (500mg/L)
2+Standard solution, be settled in the 100mL volumetric flask with deionized water, shake up, in glass funnel, add absorbent cotton filtering-depositing (the black FeS precipitation of generation) then, to settled solution, measure the content of residual F e in the filtrate again with the ICP-AES method, repeated experiments 5 times, by measuring residual F e content, reductibility S in indirect calculation (calculating) the oilfield sewage sample according to minusing
2-Content (mg/L), described mensuration process is at ICP-AES instrument best operating condition (DRE inductively coupled plasma atomic emission spectrometry instrument: power 1.0KW, argon pressure 0.6Mpa, cooling gas flow 15L/min, secondary air amount 0.2L/min, atomizer pressure 374.06Pa, lifting capacity 1.5mL/min, Fe wavelength 259.940nm.The observation place Automatic Optimal.) under carry out.Measurement result is as shown in table 4.
Table 4 indirect method is measured S in the oilfield sewage
2-Concentration result (n=5)
Annotate: Fe
2+Mark liquid concentration is 500mg/L, and sample volume is 20mL.
As can be seen, with the reductibility S in the indirect method mensuration oilfield sewage of the present invention
2-Content, relative error satisfy the TRACE ELEMENTS ANALYSIS requirement all less than 5%, illustrate that this assay method is stable, reliable; In addition, the data in the table 4 also show, this assay method and solution salinity are irrelevant, thereby method of the present invention is fit to have the S of the oilfield sewage of different salinities
2-Assay.The present invention selects the ICP-AES method to survey iron, and is not only simple, quick, highly sensitive, and accuracy is good, and the range of linearity is wide, disturbs also and lacks, and can reach S in the indirect determination oilfield sewage
2-The purpose of content.
Claims (6)
1. the indirect determination method of reducible sulfur ion concentration in the oilfield sewage may further comprise the steps:
1) to oilfield sewage V
SampleThe middle concentration known C that adds
0Excessive Fe
2+Standard solution V
0, be settled to volume V with deionized water, shake up, make S
2-With Fe
2+Reaction, the FeS that generates black precipitates;
2) black precipitate that generates in the filtering reacting liquid is to settled solution;
3) measure residual F e in the filtrate
2+Content C
Fe, calculate the content C that obtains reducible sulfur ion in the oilfield sewage sample indirectly according to minusing then
S
Calculate in the described step 3) and undertaken by formula one:
Wherein, M
SBe the molal weight of S, M
FeMolal weight for Fe.
2. assay method according to claim 1 is characterized in that: Fe in the described step 1)
2+The concentration C of standard solution
0Be 1000mg/L, the volume V of constant volume is 100mL.
3. assay method according to claim 1 is characterized in that: residual F e in the described step 3)
2+Determination on content ICP-AES method.
4. assay method according to claim 1 is characterized in that: residual F e in the described step 3)
2+Determination on content AAS method.
5. according to the arbitrary described assay method of claim 1 to 4, it is characterized in that: filter with the inner glass funnel that is added with absorbent cotton described step 2).
6. the Determination of Different Valence States method of sulphur in the oilfield sewage is characterized in that: utilize the ICP-AES method to survey total quantity of S in the solution; Obtain S with reducible sulfur ion concentration indirect determination method in the arbitrary described oilfield sewage of claim 1 to 4
2-Amount; Utilize minusing that total quantity of S is deducted S
2-Amount obtains SO in the solution
4 2-Amount, thereby finish the different valence state analysis of S in the water sample.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101114803A CN101614716B (en) | 2008-06-26 | 2008-06-26 | Methods for indirectly determining sulfur content of oil field waste water and analyzing valence of sulfur |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101114803A CN101614716B (en) | 2008-06-26 | 2008-06-26 | Methods for indirectly determining sulfur content of oil field waste water and analyzing valence of sulfur |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101614716A CN101614716A (en) | 2009-12-30 |
| CN101614716B true CN101614716B (en) | 2011-09-07 |
Family
ID=41494475
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008101114803A Expired - Fee Related CN101614716B (en) | 2008-06-26 | 2008-06-26 | Methods for indirectly determining sulfur content of oil field waste water and analyzing valence of sulfur |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101614716B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105021592A (en) * | 2015-06-19 | 2015-11-04 | 上海人本集团有限公司 | Measurement method for sulfide content in bearing production sewage |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1715911A (en) * | 2004-06-29 | 2006-01-04 | 中国石油化工股份有限公司 | Method for detecting corrosive sulfur content in crude oil or fraction oil |
| CN101172726A (en) * | 2007-11-08 | 2008-05-07 | 长庆石油勘探局 | Method and technological process for treating sewage of oil recovery |
-
2008
- 2008-06-26 CN CN2008101114803A patent/CN101614716B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1715911A (en) * | 2004-06-29 | 2006-01-04 | 中国石油化工股份有限公司 | Method for detecting corrosive sulfur content in crude oil or fraction oil |
| CN101172726A (en) * | 2007-11-08 | 2008-05-07 | 长庆石油勘探局 | Method and technological process for treating sewage of oil recovery |
Non-Patent Citations (1)
| Title |
|---|
| 周风.油田污水成份分析.《胜利学刊》.1997,第11卷(第4期),43-45. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101614716A (en) | 2009-12-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Dubascoux et al. | Field-flow fractionation and inductively coupled plasma mass spectrometer coupling: History, development and applications | |
| Martinis et al. | Trace mercury determination in drinking and natural water samples by room temperature ionic liquid based-preconcentration and flow injection-cold vapor atomic absorption spectrometry | |
| Anthemidis et al. | Development of a sequential injection dispersive liquid–liquid microextraction system for electrothermal atomic absorption spectrometry by using a hydrophobic sorbent material: Determination of lead and cadmium in natural waters | |
| CN103926300A (en) | Improved method for determining free chlorine ions in cement paste or mortar | |
| CN101762653B (en) | Method for determining main phenolic compounds in main stream smoke of cigarette | |
| CN104237209A (en) | Method for synchronously detecting copper, bismuth, iron, lead, tellurium, selenium, antimony and palladium in electrolytic silver through ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectrometry) | |
| Ilander et al. | The determination of antimony and arsenic concentrations in fly ash by hydride generation inductively coupled plasma optical emission spectrometry | |
| Huang et al. | Measurement of soluble and total hexavalent chromium in the ambient airborne particles in New Jersey | |
| Park et al. | Estimation of mercury speciation in soil standard reference materials with different extraction methods by ion chromatography coupled with ICP-MS | |
| Kalyan et al. | Membrane optode for mercury (II) determination in aqueous samples | |
| CN104406943A (en) | Pretreatment method for liquid sample in laser-induced breakdown spectrum detection technology | |
| CN101732888B (en) | Method for extracting trace substances in field and portable solid-phase extractor | |
| CN101614716B (en) | Methods for indirectly determining sulfur content of oil field waste water and analyzing valence of sulfur | |
| Wen et al. | Determination of trace bismuth by using a portable spectrometer after ultrasound-assisted dispersive liquid–liquid microextraction | |
| CN103234957B (en) | Method for determining concentration of cyanides in environment | |
| CN111579510B (en) | Light sensing film and method for rapidly and quantitatively detecting Cd (II), cu (II) and Zn (II) selectively | |
| CN105445208A (en) | Determination method for trace thallium in high-salt waste water | |
| CN104655473A (en) | Method for detecting trace mercury in water | |
| CN103852509B (en) | Potentiometric titration analysis method for cyanide | |
| Boonjob et al. | Critical evaluation of novel dynamic flow-through methods for automatic sequential BCR extraction of trace metals in fly ash | |
| Adibmehr et al. | Preconcentration and speciation of chromium using dispersive liquid-liquid microextraction; application to milk and different water samples | |
| Xiao et al. | Determination of trace mercury (ii) in wastewater using on-line flow injection spectrophotometry coupled with supported liquid membrane enrichment | |
| Kalyan et al. | Membrane optode for uranium (VI) ions preconcentration and quantification based on a synergistic combination of 4-(2-thiazolylazo)-resorcinol with 8-hydroxyquinaldine | |
| Yamini et al. | Determination of trace elements in natural water using X‐ray fluorescence spectrometry after preconcentration with powdered silica gel | |
| Garoub et al. | An efficient ionic liquid-based cloud point extraction to preconcentrate mercury in environmental samples and hair of occupational workers before spectrophotometric detection |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110907 Termination date: 20210626 |