CN100368808C - Method and device for improving Karl Fischer water content determination - Google Patents
Method and device for improving Karl Fischer water content determination Download PDFInfo
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- CN100368808C CN100368808C CNB200410029958XA CN200410029958A CN100368808C CN 100368808 C CN100368808 C CN 100368808C CN B200410029958X A CNB200410029958X A CN B200410029958XA CN 200410029958 A CN200410029958 A CN 200410029958A CN 100368808 C CN100368808 C CN 100368808C
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Abstract
The present invention relates to an improved method and an improved device of a Karl Fischer water measurement device. A few factors exerting influence on Karl Fischer water measurement are illuminated in the method, and a traditional Karl Fischer water measurement device is pertinently improved according to the influence factors; the environment drying isolation of the original measuring system is carried out by a Karl Fischer electrolytic device or a device with isolation liquid. The improved Karl Fischer water measurement method reduces and stabilizes the blank value, decreases the lower limit of detection, and effectively avoids the influence caused by inverse suction during the measurement of gas dissolved in a Karl Fischer reagent; consequently, weighing accuracy is obtained, and the gas inlet speed is increased under the precondition of no influence on the absorption efficiency. The improved instrument can stably and accurately measure organic liquified samples with the water content of a few PPMs under the condition of the air humidity of 90%, and the improved instrument is also suitable for water analysis at various levels of other samples.
Description
Technical field:
The invention belongs to the technical field of coulometric analysis in the physico-chemical analysis.
Background technology:
Existing karl Fischer moisture teller has its weak point in some aspects:
1, traditional karl Fischer moisture teller all adopts silica gel or molecular sieve to make drying agent, in order to isolate soft air, as the DL-37 of Mei Tele company.But more much better than than silica gel, molecular sieve because of the water-intake capacity of karl Fischer reagent, so silica gel or molecular sieve can not isolate soft air very effectively, when working sample, and the blank value height, blank bigger with air humidity varies, causing can not the lower sample of measured moisture content.Especially under wet environment, drying tube and interface ground device can not prevent effectively that moisture from entering detection cell, often make the instrument can't operate as normal.
2, measure the organic gas dissolve in karl Fischer reagent, the sample introduction detection of end produces negative pressure in the pond sometimes, makes the air suck-back of moisture return detection cell, cause measurement result than large deviation.
3, survey organic liquefied sample, during the gravimetric method metering, near sample bottle, can condense condensate water behind the sample introduction, influence weight metering.
4, fast during the air inlet sample, the single hole pin is given vent to anger, and bubble surface area is reduced, and influences absorption efficiency.
Summary of the invention:
At above-mentioned influence factor, the karl Fischer coulometry is measured method, the device of water and is made following improvement:
Isolate the karl Fischer detection cell with the dry environment (dry pond 4) that another karl Fischer electrolysis unit is caused, emit (as Fig. 1) through spacer assembly again behind the dry environment that the gas that detected is caused by spacer assembly drying device, prevented that effectively soft air from passing back into detection cell from the gas outlet diffusion.Because the balanced degree of two cover electrolysis units may be different, the inventor places a device that is equipped with spacer pad (spacer pad requires to be the liquid hydrophobic, non-volatile, that viscosity is little) in the middle of two covering devices, to isolate two cover electrolysis systems, can make detection cell outlet aridity very high and do not influence electrolysis and measure system like this.Spacer assembly is to form with the isolation buffers that spacer pad is housed, and can isolate detection cell and dry pond, dry pond and atmosphere (detection cell and atmosphere).Guaranteed dry environment required when measuring utmost point low water content, reduced, stablized blank value effectively, made blank level off to zero, make measurement result stable more, near true value.Issuable negative pressure suck-back phenomenon when the design of spacer assembly has been considered to measure some organic gas, in the time of can making the air that advanced by suck-back through dry environment by high dry, spacer assembly also possesses the suck-back buffering and the surge capability of giving vent to anger simultaneously, can stop spacer pad effectively and be gone into detection cell and be blown into dry pond by suck-back.When using some spacer pad such as mercury, can avoid air to be gone into detection cell because of negative pressure is not enough by suck-back.
Dry environment or the isolation buffers that is caused with karl Fischer liquid wherein, its effect are to substitute silica gel, molecular sieve drying pipe, are used to isolate soft air.Can be directly installed on traditional karl Fischer moisture teller.As Fig. 3.
Wherein the dry place environment that produces with the karl Fischer electrolysis unit carries out drying to each outlet and interface ground.As Fig. 1.
Wherein directly soak each outlet and interface ground so that dry environment to be provided with karl Fischer electrolytic solution.As Fig. 2.
Wherein the dry environment that another karl Fischer liquid is caused is all put in the traditional detection pond.As Fig. 5.
A kind of scheme of the present invention is a kind of modifying device of karl Fischer determination of moisture device, and dry pond part and/or isolation buffers are arranged;
It is characterized in that:
1) said a kind of dry pond part (4) is connected on traditional karl Fischer detection cell, and the exhausr port of dry pond electrolysis electrode (10), dry pond detecting electrode (8), karl Fischer determinator and the exhausr port (9) of whole device are arranged; Electrolysis electrode (10) and dry pond detecting electrode (8) place the glass cylinder (5) of a splendid attire karl Fischer reagent, and the electrolysis electrode cathode pool has inside and outside isolation buffers (11) runs through; Be equipped with fluid partitioning (6) on the karl Fischer reagent in the electrolysis unit cathode pool; Each interface ground, outlet and the isolation buffers (11,12) of detection system all place dry system.The various circuits of the electrolysis electrode (15) of detection cell (2) and indicator electrode (16) and sample introduction needle (7) pass through by dry environment; Electrolysis electrode (10) and dry pond detecting electrode (8), the electrolysis electrode (15) of detection cell and each egress line of indicator electrode (16) and sample introduction needle (7) in dry pond are fixed on the pond body gland bonnet (18) by interface ground (13), and pond body gland bonnet (18) is fixed on the pond body (1) by the interface ground.
2) inlet of isolation buffers (12) is connected the outlet of detection cell electrolysis electrode (15); Isolation buffers (11) is through the top of dry pond electrolysis electrode, and its outlet places under the spacer pad liquid level; Isolation buffers (11) is turned back to connect by three sections conduits and is " N " shape, and outlet makes progress, and in air intake opening section and stage casing cushion chamber is set; Isolation buffers (12) is turned back to connect by four sections conduits and is " M " shape, and continuous therein three sections respectively are provided with a cushion chamber, are equipped with fluid partitioning (14) between two interludes.As Fig. 1.
Wherein a kind of easy operative installations is characterized in that it is by the karl Fischer detection cell, isolation buffers, and dry pond independently is connected in series, and adds karl Fischer reagent and spacer pad in dry pond.As Fig. 3.
Wherein a kind of easy operative installations is characterized in that it is by the karl Fischer detection cell, and isolation buffers independently is connected in series.As removing dry pond part among Fig. 3.
Wherein a kind of isolation buffers is characterized in that two sections conduits that cushion chamber is arranged of isolation buffers, is connected on second section conduit with the sleeve pipe form, makes these three sections to become one.As Fig. 4.
Wherein a kind of karl Fischer determination of moisture device, it is characterized in that adding a fixing sampling valve in sample introduction long tube stage casing, valve when sample introduction on the standard-sized sheet sample bottle, utilize the sampling valve of this adding that flow velocity is controlled, make the evaporation point of liquefaction sample away from sample bottle with adding a sampling valve, to guarantee that the sample master position of vaporizing occurs in the later part of sampling valve of adding, the condensate water that vaporization is produced does not influence weighing of sample bottle.With the increase aperture of giving vent to anger, increase the gas-liquid surface of contact.As Fig. 3.
Can be under air humidity 90% situation through improved instrument, stable organic liquefied sample of accurately measuring several PPM of water cut.
Description of drawings:
Fig. 1: installation drawing of the present invention;
Fig. 2: another kind of installation drawing of the present invention;
Fig. 3: a kind of easy operative installations figure that improves one's methods
Fig. 4: a kind of design drawing of isolation buffers;
Fig. 5: a kind of modifying device of the present invention
Embodiment:
Embodiment 1:
Shown in Figure 1, whole device mainly is made up of pond body 1, detection cell part 2, dry pond part 4 and isolation buffer device 11,12, dry pond karl Fischer reagent cup 5, electrolysis pick-up unit, pond body gland bonnet 18.It is characterized in that:
Place fluid partitioning 14 in the isolation buffers 12, two karl Fischer electrolysis systems are isolated well; Isolation buffers 11 is isolated dry system and atmosphere well.
Its dry pond part 4 is connected on traditional karl Fischer detection cell, and dry pond electrolysis electrode 10, dry pond detecting electrode 8, the exhausr port of karl Fischer determinator and the exhausr port of whole device 9 are arranged.Be equipped with karl Fischer reagent in the dry pond karl Fischer reagent cup 5, and place under dry pond electrolysis electrode 10, dry pond detecting electrode 8, isolation buffers 11 inlets, isolation buffers 12 outlets.The electrolysis electrode cathode pool has inside and outside isolation buffers 11 runs through.Be equipped with fluid partitioning 6 on the karl Fischer reagent in the electrolysis unit cathode pool.Each interface ground of detection system, outlet and isolation buffers 11,12 all place dry system.The various circuits of the electrolysis electrode 15 of detection cell and indicator electrode 16 and sample introduction needle 7 pass through by dry environment, electrolysis electrode 10 and dry pond detecting electrode 8, the electrolysis electrode 15 of detection cell and each egress line of indicator electrode 16 and sample introduction needle 7 in dry pond are fixed on the pond body gland bonnet 18 by interface ground 13, and pond body gland bonnet 18 is fixed on the pond body 1 by the interface ground.
The inlet of isolation buffers 12 is connected the outlet of detection cell electrolysis electrode 15; Isolation buffers 11 is through the electrolysis electrode top in dry pond, and its outlet places under the spacer pad liquid level.Isolation buffers 11 is turned back to connect by three sections conduits and is " N " shape, and outlet makes progress, and in air intake opening section and stage casing cushion chamber is set; Isolation buffers 12 is turned back to connect by four sections conduits and is " M " shape, and continuous therein three sections respectively are provided with a cushion chamber, are equipped with fluid partitioning 14 between two interludes.
Near sample introduction needle 7 points, be equipped with a plurality of apertures, so that the sample introduction bubble is tiny.
Embodiment 2:
Fig. 2 device is the another kind of form of embodiment 1 (Fig. 1), and the difference of it and Fig. 1 is:
Remove karl Fischer reagent cup 5 in the dry pond 4, each interface ground of detection cell directly is soaked in the karl Fischer reagent, directly it has been carried out drying.It is minimum so initial blank value to be dropped to quickly.
Embodiment 3:
Fig. 3 is a kind of easy operative installations of improving one's methods, and it is characterized in that:
It has omitted the dry environment at each interface ground place of detection cell, but reduction is also arranged, stablizes the effect of blank value, is applicable in the fast detecting of factory and enterprise to various organic and inorganic gases.Its concrete operations are as follows:
1) karl Fischer reagent is added respectively in detection cell 20 and the dry pond 22, detection cell 20 adds to the 150ml place, guarantees that male-female utmost point liquid level is equal, and dry pond 22 adds to the 100ml place.Fluid partitioning (as: paraffin) is added in isolation tank 21 and the dry pond 22, and liquid level there was not suck-back separator tube 23 and gas outlet, suck-back separator tube 24 lower end.
2) start instrument, the sampling valve 31 that is connected with sample introduction needle 29 is fixing, will be than the sample introduction needle 29 insertion detection cells 20 of growing and be equipped with a plurality of pores, the other end is connected with cylinder valve 32 with the sample introduction pipe; Make instrument to equilibrium state; Open sampling valve 31, open the valve that is connected with the sample introduction pipe on the sample steel cylinder, middling speed purges to instrument data and shows that rate of change is stable.
3) close sampling valve 31, steel cylinder 34 is positioned on the electronic balance 33, keep steel cylinder to be connected with the valve wide open of sample introduction pipe, utilize operation valve control sample introduction.
4) open sampling valve 31 sample introductions, keep constant flow rate, sample introduction is closed sampling valve 31 after finishing, and reads that dielectric value and steel cylinder are of poor quality to get water cut in the gas.
5) after mensuration finishes, close sample steel cylinder place valve 32, residual gas in the blowdown piping unloads the steel cylinder interface, and the stainless steel tube head that exposes is inserted in the rubber, and to prevent the excessive influent gas of pipeline, this helps the purging of next pipeline.
As suck-back not occurring, then only need karl Fischer detection cell and isolation buffers polyphone can be used.
As suck-back appears, and in isolation buffers 21, adding mercury, also karl Fischer detection cell and isolation buffers polyphone can be used.
Embodiment 4:
Fig. 4 is a kind of isolation buffer device, and it is connected together several sections sheathed catheters in the isolation buffers, and the isolation buffer device of formation is more convenient.It mainly is made up of an insulated chamber 42 and two suck- back surge chambers 45,47, two karl Fischer electrolytic cells is connected with ground 41,44 by wireway 43,48.Wherein, insulated chamber 42 can also prevent because of the too fast phenomenon of spacer pad being gone out insulated chamber 42 of sample introduction flow velocity.
Embodiment 5:
Fig. 5 all puts into dry environment to traditional karl Fischer detection cell integral body, carries out sample measurement.
Claims (9)
1. karl Fischer determination of moisture device improves one's methods, it is characterized in that the dry environment that caused with another karl Fischer liquid isolates the karl Fischer detection cell, or detection cell and dry pond, dry pond and atmosphere or detection cell and atmosphere are isolated with the isolation buffers that spacer pad is housed, dry environment or isolation buffers that described another karl Fischer liquid is caused are directly installed on the existing karl Fischer moisture teller, substitute silica gel, molecular sieve drying pipe on traditional karl Fischer detection cell, isolate soft air; Wherein, spacer pad is the liquid hydrophobic, non-volatile, that viscosity is little.
2. according to the improving one's methods of the described karl Fischer determination of moisture of claim 1 device, wherein said dry environment is by the dry place environment that the karl Fischer electrolysis unit produces drying to be carried out in each outlet and interface ground.
3. improving one's methods of karl Fischer determination of moisture device according to claim 1, wherein said dry environment are directly to soak each outlet and interface ground so that it is carried out drying with karl Fischer electrolytic solution.
4. improving one's methods of karl Fischer determination of moisture device according to claim 1 is characterized in that described dry environment is all put in the traditional detection pond.
5. according to the modifying device of improving one's methods and making of the described karl Fischer determination of moisture of claim 1 device, dry pond part and/or isolation buffers are arranged;
It is characterized in that:
1) dry pond part (4), be connected on traditional karl Fischer detection cell, the exhausr port of dry pond electrolysis electrode (10), dry pond detecting electrode (8), karl Fischer determinator and the exhausr port (9) of whole device are arranged, dry pond electrolysis electrode (10) and dry pond detecting electrode (8) place the glass cylinder (5) of a splendid attire karl Fischer reagent, and the electrolysis electrode cathode pool has inside and outside isolation buffers (11) runs through; Be equipped with fluid partitioning (6) on the karl Fischer reagent in the electrolysis unit cathode pool, each interface ground of detection cell system, outlet and isolation buffers (11,12) all place dry system, the various circuits of electrolysis electrode of detection cell (15) and indicator electrode (16) and sample introduction needle (7) pass through by dry environment, the electrolysis electrode (10) and the dry pond detecting electrode (8) in dry pond, each egress line of electrolysis electrode of detection cell (15) and indicator electrode (16) and sample introduction needle (7) is fixed on the pond body gland bonnet (18) by interface ground (13), and pond body gland bonnet (18) is fixed on the pond body (1) by the interface ground;
2) inlet of isolation buffers (12) is connected the outlet of detection cell electrolysis electrode (15); Isolation buffers (11) is through the electrolysis electrode top in dry pond, and its outlet places under the spacer pad liquid level, and isolation buffers (11) is turned back to connect by three sections conduits and is " N " shape, and outlet makes progress, and in air intake opening section and stage casing cushion chamber is set; Isolation buffers (12) is turned back to connect by four sections conduits and is " M " shape, and continuous therein three sections respectively are provided with a cushion chamber, are equipped with fluid partitioning (14) between two interludes.
6. modifying device according to claim 5, wherein a kind of easy operative installations are independently to be connected in series by karl Fischer detection cell, isolation buffers (21) and dry pond.
7. modifying device according to claim 5, wherein a kind of easy operative installations are independently to be connected in series by karl Fischer detection cell, isolation buffers (21).
8. modifying device according to claim 5, wherein two of isolation buffers sections conduits that cushion chamber is arranged are connected on second section conduit with the sleeve pipe form, make these three sections to become one.
9. modifying device according to claim 5 wherein adds evaporation point that a sampling valve makes the liquefaction sample away from sample bottle, or with increasing the aperture of giving vent to anger, increase gas-liquid surface of contact.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200410029958XA CN100368808C (en) | 2004-04-07 | 2004-04-07 | Method and device for improving Karl Fischer water content determination |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200410029958XA CN100368808C (en) | 2004-04-07 | 2004-04-07 | Method and device for improving Karl Fischer water content determination |
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| CN1680810A CN1680810A (en) | 2005-10-12 |
| CN100368808C true CN100368808C (en) | 2008-02-13 |
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| CNB200410029958XA Expired - Fee Related CN100368808C (en) | 2004-04-07 | 2004-04-07 | Method and device for improving Karl Fischer water content determination |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5633158B2 (en) * | 2010-03-01 | 2014-12-03 | セントラル硝子株式会社 | Method and apparatus for measuring moisture content in compounds containing hydrogen fluoride |
| CN102128945B (en) * | 2011-03-18 | 2013-08-07 | 淄博科通电气科技有限公司 | Fully-sealed trace water determination system with automatic quantitative sample feeding |
| CN102735795A (en) * | 2012-06-14 | 2012-10-17 | 清华大学 | Apparatus for analyzing electrolyte concentration under sealing condition |
| CN103852556B (en) * | 2012-12-04 | 2015-10-28 | 上海仪电科学仪器股份有限公司 | A kind of device of automatic measurement moisture |
| CN103245586B (en) * | 2013-04-15 | 2016-04-27 | 广州天赐高新材料股份有限公司 | The assay method of trace moisture content in a kind of boric acid ester compound |
| CN105223256A (en) * | 2015-10-29 | 2016-01-06 | 大庆市日上仪器制造有限公司 | A kind of Karl Fischer coulometric determination crude oil, tar water-containing measuring instrument |
| CN110850024B (en) * | 2018-08-21 | 2021-11-09 | 中国计量科学研究院 | Water detection calibration system, detection model establishing method and water detection method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5300207A (en) * | 1993-01-14 | 1994-04-05 | Harald Dahms | High current coulometric KF titrator |
| US5340541A (en) * | 1993-03-05 | 1994-08-23 | Eli Lilly And Company | Automated Karl Fischer titration apparatus and method |
| CN1161451A (en) * | 1997-01-29 | 1997-10-08 | 浙江大学 | Karl Fischer moisture determination instrument |
| CN2293072Y (en) * | 1997-01-29 | 1998-09-30 | 浙江大学 | Karl-Fischer moisture measuring apparatus |
| US6361670B1 (en) * | 1996-12-23 | 2002-03-26 | Ab Stockholms Patentyra | Device for coulometric determination of water by the Karl Fischer method |
-
2004
- 2004-04-07 CN CNB200410029958XA patent/CN100368808C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5300207A (en) * | 1993-01-14 | 1994-04-05 | Harald Dahms | High current coulometric KF titrator |
| US5340541A (en) * | 1993-03-05 | 1994-08-23 | Eli Lilly And Company | Automated Karl Fischer titration apparatus and method |
| US6361670B1 (en) * | 1996-12-23 | 2002-03-26 | Ab Stockholms Patentyra | Device for coulometric determination of water by the Karl Fischer method |
| CN1161451A (en) * | 1997-01-29 | 1997-10-08 | 浙江大学 | Karl Fischer moisture determination instrument |
| CN2293072Y (en) * | 1997-01-29 | 1998-09-30 | 浙江大学 | Karl-Fischer moisture measuring apparatus |
Non-Patent Citations (1)
| Title |
|---|
| 卡尔-费休库仑法水分测定仪的改进. 林振强等.化学分析计量，第12卷第5期. 2003 * |
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