CN1346982A - Sensor for in-line measurement of methanol concentration in solution - Google Patents
Sensor for in-line measurement of methanol concentration in solution Download PDFInfo
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- CN1346982A CN1346982A CN 01132168 CN01132168A CN1346982A CN 1346982 A CN1346982 A CN 1346982A CN 01132168 CN01132168 CN 01132168 CN 01132168 A CN01132168 A CN 01132168A CN 1346982 A CN1346982 A CN 1346982A
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Abstract
A sensor for in-line measuring the concentration of methanol in solution is composed of a tubular casing with a gas carrying tube, a semi-permeable membrane, a gas-sensitive electronic element and a sieving plate. When its one end where said semi-permeable membrane is arranged is inserted in a fermentor, methanol in liquid phase penetrates through said membrane and is diffused in diffusing cavity. The carried gas passes through the sieving plate and is mixed with said methanol. Their mixture is led to the gas-sensitive electronic element for measuring the concentration of methanol. Its advantages are fast response speed (less than 120 seconds), and wide application range.
Description
Technical field
The present invention relates to a kind of sensor, specifically, relate to a kind of sensor that is used for the detection methyl alcohol of sweat.
Background technology
In the fermentation that with methyl alcohol is the yeast of carbon source such as Hansenula yeast (Hansenula), torulopsis (Torulopsis), Candida (Candida) and Pichia pastoris (Pichia), therefore too high methyl alcohol can suppress the growth of cell and the expression of product, need add methyl alcohol by continuing to flow the methanol concentration in the fermentation liquor is controlled in due course in the scope.It is excessive to add for fear of methyl alcohol stream, needs the methanol concentration in the online detection fermentation liquor.
The method of methanol concentration mainly contains two kinds in the online detection fermentation liquor of bibliographical information at present:
(1) silicone tube mensuration, its principle is that methyl alcohol is crossed the silica gel tube wall from the silicone tube exosmosis in the fermentation liquor, enter in the silicone tube, taken away, enter the air-sensitive electronic component by the carrier gas in managing, produce electric signal (GuarnaM.M., Lesnicki G.L., Tam B.M., et al.Biotechnol.Bioeng., 1997,56:279-286).
(2) tail gas mensuration, the tail gas that contains methyl alcohol of emitting in the fermentation tank enters the air-sensitive electronic component, produces electric signal.(Katakura?Y.，Zhang?W.，Zhuang?G.，et?al.J.Ferment.Bioeng.，1998，86：482-487)。
But above these methods have the following disadvantages:
First method is limited by silica gel tube wall rate of diffusion, and real-time is poor, and lag behind serious (the general response time was above ten minutes) can not reflect that the instantaneous methanol concentration in the fermentation tank changes, and are difficult to adapt to the robotization control of methanol concentration;
Second method is subjected to oxygen concentration, tolerance fluctuation, gas composition, moisture content etc. easily than serious disturbance, and signal stabilization is poor, and causes the sensor poison deactivation easily.
Therefore above-mentioned method is unfavorable for the industrial applications popularization.
Summary of the invention
The technical issues that need to address of the present invention are the sensors that disclose methanol concentration in a kind of online detection fermentation liquor, with overcome the response time that prior art exists slow, sensitivity is low, a little less than the anti-environmental interference ability and be not easy to the defective that industrialization promotion is used.
Technical conceive of the present invention:
(1) for the instantaneous methanol concentration in the online detection fermentation tank changes, must improve the rate of propagation of methyl alcohol, shorten the response time of sensor.Because methyl alcohol is easy to see through materials such as teflon, silica gel, tygon by molecular diffusion, the present invention selects for use these materials as semi-permeable diaphragm.Methyl alcohol in the fermentation liquor can see through semi-permeable diaphragm and be diffused into gas phase.The rate of diffusion of methyl alcohol in semi-permeable diaphragm mainly determined by the liquid phase methanol concentration.
(2) detect gas-phase methanol concentration in gas phase side with the selective gas electronic component, the resistance of this electronic component changes with the variation of methanol concentration in the gas phase, can extrapolate the methanol concentration in the liquid phase or make typical curve according to diffusion model, determine methanol concentration in the fermentation liquor by the reference standard curve with the experiment of cold mould.
(3) structural design of sensor meets industry and uses needs, can high-temperature sterilization, can be installed in easily on the general-purpose interface of fermentation tank.
Technical scheme of the present invention:
Sensor of the present invention comprises:
A middle part is provided with the tubular shell of carrier gas pipe;
A semi-permeable diaphragm that is arranged on the carrier gas tube end;
One is arranged in the carrier gas pipe and the sieve plate adjacent with semi-permeable diaphragm, and the cavity between semi-permeable diaphragm and the sieve plate is a diffusion chamber;
One be arranged in the carrier gas pipe, an end passes the wireway that sieve plate is communicated with diffusion chamber;
An air-sensitive electronic component that is connected with wireway.
Above-mentioned sensor is work like this:
An end that sensor is provided with semi-permeable diaphragm inserts fermentation tank, and the methyl alcohol penetrate semi-permeable diaphragm in the liquid phase is diffused into diffusion chamber;
Carrier gas enters diffusion chamber by the sieve aperture that the carrier gas pipe passes on the sieve plate, mix with the methyl alcohol that enters diffusion chamber by semi-permeable diaphragm, the purpose that sieve plate is set is to improve gas flow situation in the diffusion chamber, reduces back-mixing, prevents the gas in the diffusion chamber and the gas backmixing of carrier gas passage;
Carrier gas and methanol mixture import the air-sensitive electronic component by wireway, and when carrier gas flux was constant, because the rate of diffusion of methyl alcohol in semi-permeable diaphragm depends mainly on the concentration of liquid phase methyl alcohol, methanol concentration and liquid phase methanol concentration were proportional in the diffusion chamber.Therefore, the concentration that the methanol concentration in the indicated carrier gas of air-sensitive electronic component can reflect liquid phase methyl alcohol exactly can realize the concentration of methyl alcohol is measured.
The advantage of sensor of the present invention is fairly obvious: 1, the response time of this sensor is far superior to other measuring method less than 120 seconds.Can satisfy the requirement of online detection and control.2, this sensor is not subjected to throughput, the speed of agitator of fermentation tank, the influence of dissolved oxygen content.3, this sensor application is in extensive range, can be used for methyl alcohol is in the fermentation of the yeast of carbon source such as Hansenula yeast, torulopsis, Candida and Pichia pastoris etc., or is used for the online detection and the control of volatile organic gass such as other solution methyl alcohol, ethanol.
Description of drawings
Fig. 1 is the structural representation of sensor of the present invention.
Fig. 2 is the methanol concentration of sensor on-line determination in the sweat and the comparison that the sample off-line after the sampling is used the methanol concentration of gas Chromatographic Determination.
Embodiment
As seen from Figure 1, sensor of the present invention comprises:
A middle part is provided with the tubular shell 1 of carrier gas pipe 5;
A semi-permeable diaphragm 2 that is arranged on carrier gas pipe 5 ends;
One is arranged in the carrier gas pipe 5 and the sieve plate 3 adjacent with semi-permeable diaphragm 2, and the cavity between semi-permeable diaphragm 2 and the sieve plate 3 is a diffusion chamber 7;
One be arranged in the carrier gas pipe 5, an end passes the wireway 4 that sieve plate 3 is communicated with diffusion chamber 7;
An air-sensitive electronic component 6 that is connected with wireway 4.
According to the present invention, the surface area of said semi-permeable diaphragm 2 is the 3-500 square millimeter, thickness is the 0-1 millimeter, material is a teflon, silica gel, but methyl alcohol permeable materials such as tygon, diffusion chamber 7 volumes are the 1.5-2500 cubic millimeter, spacing between semi-permeable diaphragm 2 and the sieve plate 3 is 0～30mm, wireway 4 diameter range 0.1-5 millimeters, sieve plate 3 perforate apertures are the 0.1-2 millimeter, percentage of open area is 0.5%-50%, said air-sensitive electronic component 6 is a kind of organic gas sensitive resistance, and the model that can adopt Japanese Figaro company to produce is TGS822 resistance or other company's similar products.
Embodiment 1
In the recombinant yeast pichia pastoris sweat, with the methanol concentration in the online detection fermentation liquor of sensor of the present invention.Wherein:
Semipermeable membrane material is a teflon, and thickness is 0.5 millimeter, and surface area is 45 square millimeters, and the wireway diameter is 1.1 millimeters, 8 millimeters of sieve plate diameters, 0.8 millimeter in perforate aperture, percentage of open area 10%.Gas sensor is that the model that Japanese Figaro company produces is the resistance of TGS822.At first adorn water in fermentation tank, (0.1-1% v/v) makes sensor response criteria curve, dress nutrient culture media and the after fermentation of this sensor heat sterilization in fermentation tank then to add the methyl alcohol of variable concentrations.The methanol concentration in the fermentation liquor is determined in the response by sensor and the contrast of typical curve.Since the 25th hour in fermentation tank stream add methyl alcohol, Fig. 2 be sample off-line after methanol concentration and the sampling of sensor on-line determination in the sweat with the comparison of the methanol concentration of gas Chromatographic Determination, as can be seen from the figure, identical substantially between the two.Deviation wherein can be got rid of by correction.Therefore this sensor can instant preferably online detection Pichia pastoris sweat in the concentration of methyl alcohol.
Claims (10)
1. sensor that is used for online detection solution methanol concentration is characterized in that this sensor comprises:
A middle part is provided with the tubular shell (1) of carrier gas pipe (5);
A semi-permeable diaphragm (2) that is arranged on carrier gas pipe (5) end;
One is arranged in the carrier gas pipe (5) and the sieve plate (3) adjacent with semi-permeable diaphragm (2), and the cavity between semi-permeable diaphragm (2) and the sieve plate (3) is diffusion chamber (7);
One be arranged in the carrier gas pipe (5), an end passes the wireway (4) that sieve plate (3) is communicated with diffusion chamber (7);
An air-sensitive electronic component (6) that is connected with wireway (4).
2. sensor as claimed in claim 1 is characterized in that, the surface area of semi-permeable diaphragm (2) is 3～500 square millimeters, and thickness is 0～1 millimeter.
3. sensor as claimed in claim 1 is characterized in that, diffusion chamber (7) volume is 1.5～2500 cubic millimeters.
4. sensor as claimed in claim 1 is characterized in that, the spacing between semi-permeable diaphragm (2) and the sieve plate (3) is 0～30mm.
5. sensor as claimed in claim 1 is characterized in that, wireway (4) diameter is 0.1～5 millimeter.
6. sensor as claimed in claim 1 is characterized in that, sieve plate (3) perforate aperture is the 0.1-2 millimeter, and percentage of open area is 0.5%-50%.
7. as the arbitrary described sensor of claim 1～6, it is characterized in that semi-permeable diaphragm (2) material is teflon, silica gel or tygon.
8. as claim 3 or 4 described sensors, it is characterized in that the surface area of semi-permeable diaphragm (2) is 3～500 square millimeters, thickness is 0～1 millimeter.
9. sensor as claimed in claim 7 is characterized in that, the surface area of semi-permeable diaphragm (2) is 3～500 square millimeters, and thickness is 0～1 millimeter.
10. sensor as claimed in claim 1, the air-sensitive electronic component (6) of institute's condition is a kind of organic gas sensitive resistance, the model that can adopt Japanese Figaro company to produce is TGS822 resistance or other company's similar products.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011321687A CN1156691C (en) | 2001-11-09 | 2001-11-09 | Sensor for in-line measurement of methanol concentration in solution |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011321687A CN1156691C (en) | 2001-11-09 | 2001-11-09 | Sensor for in-line measurement of methanol concentration in solution |
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| CN1346982A true CN1346982A (en) | 2002-05-01 |
| CN1156691C CN1156691C (en) | 2004-07-07 |
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| CNB011321687A Expired - Fee Related CN1156691C (en) | 2001-11-09 | 2001-11-09 | Sensor for in-line measurement of methanol concentration in solution |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106093139A (en) * | 2016-06-29 | 2016-11-09 | 中国科学院长春应用化学研究所 | A kind of detection method of concentration of methanol solution |
| WO2017084064A1 (en) * | 2015-11-19 | 2017-05-26 | 江苏威凌生化科技有限公司 | Use of electronic olfactory device in on-line detection of cyclohexanecarboxylic acid concentration during dolomycin fermentation |
| CN112114004A (en) * | 2019-06-19 | 2020-12-22 | 中国石油化工股份有限公司 | Testing device for detecting gas-sensitive sensing material in simulated diffusion mode |
-
2001
- 2001-11-09 CN CNB011321687A patent/CN1156691C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017084064A1 (en) * | 2015-11-19 | 2017-05-26 | 江苏威凌生化科技有限公司 | Use of electronic olfactory device in on-line detection of cyclohexanecarboxylic acid concentration during dolomycin fermentation |
| CN106093139A (en) * | 2016-06-29 | 2016-11-09 | 中国科学院长春应用化学研究所 | A kind of detection method of concentration of methanol solution |
| CN112114004A (en) * | 2019-06-19 | 2020-12-22 | 中国石油化工股份有限公司 | Testing device for detecting gas-sensitive sensing material in simulated diffusion mode |
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| Publication number | Publication date |
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| CN1156691C (en) | 2004-07-07 |
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