A kind of fiber gas sensor
Technical field:
The invention belongs to the technical field that harmful gas detects, particularly detect the fiber gas sensor of phosgene and volatile organic matter gas.
Background technology:
Phosgene and volatile organic matter (VOCs) gas, as: benzene,toluene,xylene, acetaldehyde, propionic aldehyde, methyl alcohol, ethanol, ethane, triethylamine etc. are in environment for human survival and the commercial production, as ubiquitous organic contaminant in chemistry and chemicals, oil and coal product, press, footwear and garment products and the rubber, need check and analysis.VOCs gas easily enters human body by respiratory tract, alimentary canal and skin and produces murder by poisoning, can cause that human body stimulates and other many malaise symptoms, VOCs gas long term exposure has teratogenesis, mutagenesis and harm such as carcinogenic to human body, also is the one of the main reasons that produces sick Building syndrome (SBS).Phosgene is a kind of special commercial production raw material, and it has great toxicity, and very micro-phosgene just is enough to make an adult to get killed.Therefore develop a kind of highly sensitive, simple in structure, the detection phosgene of practical safe ready and the fiber gas sensor of VOCs gas and pollute administering, the protection environment has actual important meaning.
The existing method that detects phosgene and volatile organic matter (VOCs) gas mainly contains vapor-phase chromatography, chromatograph-mas spectrometer and sensor technology.But the direct-reading chromatograph-mass spectrometer coupling costs an arm and a leg, and be difficult for applying, and the detection error of direct-reading instrument is bigger, can not be accurately quantitative.Thermal desorption-vapor-phase chromatography finds that in this method of enforcement the thermal desorption rate is lower, the accuracy that does not reach defined.The sensor of detected gas generally has piezoelectric sensor and absorbing light spectral pattern sensor.Piezoelectric sensor is difficult to realize that the one matter selectivity detects, but with after chromatographic separation technology combine, is expected to overcome this defective, realizes the selectivity detection of material, the working temperature height, and power consumption is big, device making technics complexity, shortcomings such as poor selectivity; Absorbing light spectral pattern sensor utilizes the absorbing light wavelength difference of different material, adopt the light incident of different wave length, can measure different materials, behind the light of this wavelength and other matter interaction, wavelength can be moved, thereby calculates the concentration of determining this material by signals collecting and disposal system.Fibre Optical Sensor has unique advantage again in the absorption-type sensor: highly sensitive, and light weight, loss is few, but the bandwidth of transmission signals, electrical insulation capability is good, fire-resistant, water-tolerant, anti-electromagnetic interference (EMI) is strong, can detour, and can realize advantages such as uncharged full fibre-optical probe.
It as application number " a kind of fiber gas sensor " patent of 200510012344.5, disclosed fiber gas sensor comprises: the light source, coupling mechanism, gas absorption cell, contrast optical fiber, photodetector, signals collecting and the disposal system that have common solid core fibres to connect.This patent is that gas directly contacts with the solid sensitive materials of Fibre Optical Sensor, and it is limited to exist the gas absorption amount, and gaseous matter can not fully contact with sensitive materials and fully reaction, thereby sensitivity is reduced; Sensitive materials are disposable use, because sensitive materials can not fully contact with gas and fully reaction, can cause the wasting of resources; Optical fiber adopts the form singly advance singly to go out, detection be certain information of target substance, exist shortcoming such as selectivity recognition capability difference and influence the promotion and application of this type of sensor.
Summary of the invention:
The objective of the invention is weak point, a kind of fiber gas sensor is provided at the existing fiber gas sensor.This sensor has that gas sensitization is good, stable performance, the selectivity recognition capability is strong, highly sensitive, the response time is short, safe and convenient to use and can detect the characteristics such as organic compound of phosgene and multiple effumability.By making up metalloporphyrin solution fiber gas sensor, overcome existing fiber sensor sensing material and can not fully contact with gas and fully react, cause wasting of resources selectivity recognition capability poor, shortcoming such as sensitivity is low.
Principle of the present invention is: porphyrin for can connect multiple substituting group on big ring pi-electron delocalization system, the outer shroud, central metal can change, be that molecule has modifiability, and very strong extinction characteristic is arranged, especially with transition metal complex after.Because porphyrin contains a big conjugated system, have chromophore, so utilize spectral techniques such as ultraviolet, infrared, fluorescence, phosphorescence, Raman can detect its subtle change.When running into phosgene and volatile organic matter, wavelength is moved, and runs into different volatile organic matters, and the distance that wavelength moves is different, thereby determines concrete material.For example, existing discovering: the cobalt porphyrin has alkanes such as class materials such as methyl alcohol and ethanol and hexanes sensitivity is arranged, zinc protoporphyrin has amine substances such as aromatics such as phosgene, benzene,toluene,xylene and trimethylamines sensitivity is arranged, manganoporphyrin has susceptibility to aldehyde materials such as acetaldehyde, propionic aldehyde and amine substance, the rhodium porphyrin has alkanes such as hexanes sensitivity is arranged, plumbous porphyrin has sensitivity to ammonia and amine substance, and iron porphyrin has sensitivity to aromatics, amine and alkanes substance.Therefore the sensitive element made from cobalt, zinc, manganese, rhodium, lead and iron porphyrin and some other metalloporphyrins can successfully detect gases such as phosgene, triethylamine, hexane, ethanol, methyl alcohol, benzene.
The object of the present invention is achieved like this: a kind of fiber gas sensor mainly comprises incident optical and outgoing optical fiber, reaction tank and metalloporphyrin solution etc.Incident optical and outgoing optical fiber are respectively 2~4, and symmetry and be fixedly connected on the both sides of reaction tank equably respectively, the other end of 2~4 incident opticals is connected with light-source system, as importing light signal into, the other end of 2~4 outgoing optical fiber is connected with micro spectrometer and signal processing system, so that the light signal behind the reaction tank internal reaction spread out of carry out analyzing and processing, thereby realize object gas is discerned.Reaction tank is rectangle or symmetric double taper or oval-shaped glass housing, its strong point is that 10~15mm, the widest part are 4~12mm, evenly be divided into 2~4 little reaction tanks in it, different metalloporphyrin solution is housed respectively in each little reaction tank, reacts as sensitive materials and target substance to be measured.On an end of the upper end of each little reaction tank housing, an exhausr port is set respectively, an affixed gas outlet on exhausr port, installing one retaining valve in gas outlet is so that control gas, hydraulic coupling in the little reaction tank automatically.When the pressure of gas to be measured in the little reaction tank during greater than the hydraulic pressure of metalloporphyrin solution, retaining valve is closed automatically, thereby guarantees the contact reaction of gas to be measured and metalloporphyrin solution.On the other end of each little reaction tank lower end housing, one blow vent is set respectively, an affixed snorkel on blow vent, in snorkel, be equiped with and add air pump and retaining valve, so that in each little reaction tank, send into object gas to be measured, and gas is fully contacted with metalloporphyrin solution, to improve the sensitivity that detects.On the other end of each little reaction tank upper end housing corresponding to exhausr port, one charge door is set respectively, an affixed charge pipe on charge door, install an elastic plug on the top of charge pipe, in order in reaction tank, to add different metalloporphyrin solution sensitive materials easily and to clean the cleaning fluid of each little reaction tank.On the other end of each little reaction tank lower end housing, a leakage fluid dram is set corresponding to snorkel, an affixed discharging tube on leakage fluid dram, installing one retaining valve in discharging tube is so that give off each little reaction tank interior metalloporphyrin solution and cleaning fluid.Discharge opeing has just been finished the function of cleaning little reaction tank easily and changing the metalloporphyrin solution in each little reaction tank with reinforced cooperating, and guarantees the precision that each little reaction tank detects.Be positioned over the interior metalloporphyrin solution of each little reaction tank for to be dissolved in 2~4 kinds of metalloporphyrins in cobalt porphyrin, zinc protoporphyrin, manganoporphyrin, rhodium porphyrin, plumbous porphyrin and the iron porphyrin etc. in the organic solvent respectively, its organic solvent is chloroform or chlorobenzene or dimethyl formamide, and solution concentration is 3 * 10
-8~8 * 10
-8Mol/L, the concrete kind of metalloporphyrin and quantity are determined according to the object gas that need detect.Because the cobalt porphyrin has alkanes such as alcohols material such as methyl alcohol and ethanol and hexanes sensitivity is arranged, zinc protoporphyrin has amine substances such as aromatics such as phosgene, benzene,toluene,xylene and trimethylamines sensitivity is arranged, manganoporphyrin has susceptibility to aldehyde materials such as acetaldehyde, propionic aldehyde and amine substance, the rhodium porphyrin has alkanes such as hexanes sensitivity is arranged, plumbous porphyrin has sensitivity to ammonia and amine substance, and iron porphyrin has sensitivity to aromatics, amine and alkanes substance.Therefore the sensitive element made with cobalt, zinc, manganese, rhodium, lead and iron porphyrin and some other metalloporphyrins of sensor of the present invention detects gases such as phosgene, triethylamine, hexane, ethanol, methyl alcohol, benzene.
After the present invention adopted technique scheme, principal feature was: sensor of the present invention has simple in structure, with low cost; The sensitive materials metalloporphyrin is dissolved in organic solvent and forms metalloporphyrin solution and adds in the reaction tank, and the length of reaction tank is 10~15mm, wide 4~12mm, and promptly the total amount of each porphyrin solution that adds is seldom; Gas to be measured adds from the blow vent of reaction tank below, is soluble in organic solvent because of phosgene and VOCs gas again, thereby phosgene and VOCs gas and metalloporphyrin solution sensitive materials are fully reacted, and significantly improves the sensitivity of detection; One reaction pool can effectively detect simultaneously to plurality of target gas; Add different metalloporphyrin solution from the charge door of reaction tank, just can different object gas effectively be detected, sensing range is wide etc.The present invention can be widely used in the detection of phosgene and volatile organic matter gas in the industries such as factory building finishing, interior decoration, commercial production and fine chemistry industry, helps environmental protection and people's physical and mental health.
Description of drawings
Fig. 1: be the structural drawing of present embodiment 1;
Fig. 2: be the vertical view of Fig. 1;
Fig. 3: be schematic diagram with the sensor gas of present embodiment 1.
Among the figure: 1 incident optical, 2 reaction tanks, 3 discharging tubes, 4 retaining valves, 5 snorkels, 6 retaining valves, 7 add air pump, 8 outgoing optical fiber, 9 metalloporphyrin solution, 10 charge pipes, 11 elastic plugs, 12 retaining valves, 13 gas outlets, 14 light-source systems, 15 micro spectrometers, 16 signal acquiring processing systems.
Embodiment
Further specify the present invention below in conjunction with embodiment.
Embodiment 1
Shown in Fig. 1~2, a kind of fiber gas sensor mainly comprises incident optical 1 and outgoing optical fiber 8, reaction tank 2 and metalloporphyrin solution 9 etc.Incident optical 1 and outgoing optical fiber 8 are respectively 4, and respectively symmetry and equably glue bond in the both sides of reaction tank 2, the other end of 4 incident opticals 1 is connected with light-source system 14, as importing light signal into, the other end of 4 outgoing optical fiber 8 is connected with micro spectrometer 15 and signal processing system 16, so that the light signal behind reaction tank 2 internal reactions spread out of carry out analyzing and processing, thereby realize object gas is discerned.Reaction tank 2 is rectangular glass housing, and its length is 10mm, wide 12mm, evenly is divided into 4 little reaction tanks in it, and different metalloporphyrin solution 9 is housed respectively in each little reaction tank, reacts as sensitive materials and target substance to be measured.On an end of the upper end of each little reaction tank housing, an exhausr port is set respectively, on exhausr port, stick with glue knot one gas outlet 13, installing one retaining valve 12 in gas outlet 13 is so that control gas, hydraulic coupling in the little reaction tank automatically.When the pressure of gas to be measured in the little reaction tank during greater than the hydraulic pressure of metalloporphyrin solution 9, retaining valve 12 is closed automatically, thereby guarantees the contact reaction of gas to be measured and metalloporphyrin solution 9.On the other end of each little reaction tank lower end housing, one blow vent is set respectively, on blow vent, stick with glue knot one snorkel 5, in snorkel 5, be equiped with and add air pump 7 and retaining valve 6, so that in each little reaction tank, send into object gas to be measured, and gas is fully contacted with metalloporphyrin solution 9, to improve the sensitivity that detects.On the other end of each little reaction tank upper end housing corresponding to exhausr port, one charge door is set respectively, on charge door, stick with glue knot one charge pipe 10, install an elastic plug 11 on the top of charge pipe 10, in order in reaction tank 2, to add different metalloporphyrin solution 9 sensitive materials and the chloroform of each little reaction tank of cleaning easily.On the other end of each little reaction tank lower end housing corresponding to snorkel a leakage fluid dram is set, sticks with glue knot one discharging tube 3 on leakage fluid dram, installing one retaining valve 4 in discharging tube 3 is so that give off each little reaction tank interior metalloporphyrin solution 9 and chloroform cleaning fluid.Discharge opeing has just been finished the function of cleaning little reaction tank easily and changing the metalloporphyrin solution 9 in each little reaction tank with reinforced cooperating, and guarantees the precision that each little reaction tank detects, and detectability reaches the ppm level.Be positioned over the interior metalloporphyrin solution 9 of each little reaction tank for cobalt porphyrin, zinc protoporphyrin, manganoporphyrin, 4 kinds of metalloporphyrins of rhodium porphyrin are dissolved in respectively in the organic solvent chloroform, the concentration of solution is 3 * 10
-8Mol/L.Gases such as phosgene, ethanol, methyl alcohol, benzene,toluene,xylene, acetaldehyde, propionic aldehyde are detected.
Embodiment 2
A kind of fiber gas sensor mainly comprises incident optical 1 and outgoing optical fiber 8, reaction tank 2 and metalloporphyrin solution 9 etc.Incident optical 1 and outgoing optical fiber 8 are respectively 2, and respectively symmetry and equably glue bond in the both sides of reaction tank 2, the other end of 2 incident opticals 1 is connected with light-source system 14, as importing light signal into, the other end of 2 outgoing optical fiber 8 is connected with micro spectrometer 15 and signal processing system 16, so that the light signal behind reaction tank 2 internal reactions spread out of carry out analyzing and processing, thereby realize object gas is discerned.Reaction tank 2 is symmetrical diconical glass housing, its strong point is that 15mm, the widest part are 4mm, evenly be divided into 2 little reaction tanks in it, different metalloporphyrin solution 9 is housed respectively in each little reaction tank, react as sensitive materials and target substance to be measured.On an end of the upper end of each little reaction tank housing, an exhausr port is set respectively, on exhausr port, stick with glue knot one gas outlet 13, installing one retaining valve 12 in gas outlet 13 is so that control gas, hydraulic coupling in the little reaction tank automatically.When the pressure of gas to be measured in the little reaction tank during greater than the hydraulic pressure of metalloporphyrin solution 9, retaining valve 12 is closed automatically, thereby guarantees the contact reaction of gas to be measured and metalloporphyrin solution 9.On the other end of each little reaction tank lower end housing, one blow vent is set respectively, on blow vent, stick with glue knot one snorkel 5, in snorkel 5, be equiped with and add air pump 7 and retaining valve 6, so that in each little reaction tank, send into object gas to be measured, and gas is fully contacted with metalloporphyrin solution 9, to improve the sensitivity that detects.On the other end of each little reaction tank upper end housing corresponding to exhausr port, one charge door is set respectively, on charge door, stick with glue knot one charge pipe 10, install an elastic plug 11 on the top of charge pipe 10, in order in reaction tank 2, to add different metalloporphyrin solution 9 sensitive materials easily and to clean the chlorobenzene of each little reaction tank.On the other end of each little reaction tank lower end housing corresponding to snorkel a leakage fluid dram is set, sticks with glue knot one discharging tube 3 on leakage fluid dram, installing one retaining valve 4 in discharging tube 3 is so that give off each little reaction tank interior metalloporphyrin solution 9 and chlorobenzene cleaning fluid.Discharge opeing has just been finished the function of cleaning little reaction tank easily and changing the metalloporphyrin solution 9 in each little reaction tank with reinforced cooperating, and guarantees the precision that each little reaction tank detects, and detectability reaches the ppm level.Be positioned over the interior metalloporphyrin solution 9 of each little reaction tank for plumbous porphyrin and 2 kinds of metalloporphyrins of iron porphyrin are dissolved in respectively in the organic solvent chlorobenzene, the concentration of solution is 8 * 10
-8Mol/L.To triethylamine, hexane, benzene,toluene,xylene, etc. volatile organic matter gas detect.
Embodiment 3
A kind of fiber gas sensor mainly comprises incident optical 1 and outgoing optical fiber 8, reaction tank 2 and metalloporphyrin solution 9 etc.Incident optical 1 and outgoing optical fiber 8 are respectively 3, and respectively symmetry and equably glue bond in the both sides of reaction tank 2, the other end of 3 incident opticals 1 is connected with light-source system 14, as importing light signal into, the other end of 3 outgoing optical fiber 8 is connected with micro spectrometer 15 and signal processing system 16, so that the light signal behind reaction tank 2 internal reactions spread out of carry out analyzing and processing, thereby realize object gas is discerned.Reaction tank 2 is oval-shaped glass housing, and its length is 13mm, wide 9mm, evenly is divided into 3 little reaction tanks in it, and different metalloporphyrin solution 9 is housed respectively in each little reaction tank, reacts as sensitive materials and target substance to be measured.On an end of the upper end of each little reaction tank housing, an exhausr port is set respectively, on exhausr port, stick with glue knot one gas outlet 13, installing one retaining valve 12 in gas outlet 13 is so that control gas, hydraulic coupling in the little reaction tank automatically.When the pressure of gas to be measured in the little reaction tank during greater than the hydraulic pressure of metalloporphyrin solution 9, retaining valve 12 is closed automatically, thereby guarantees the contact reaction of gas to be measured and metalloporphyrin solution 9.On the other end of each little reaction tank lower end housing, one blow vent is set respectively, on blow vent, stick with glue knot one snorkel 5, in snorkel 5, be equiped with and add air pump 7 and retaining valve 6, so that in each little reaction tank, send into object gas to be measured, and gas is fully contacted with metalloporphyrin solution 9, to improve the sensitivity that detects.On the other end of each little reaction tank upper end housing corresponding to exhausr port, one charge door is set respectively, on charge door, stick with glue knot one charge pipe 10, install an elastic plug 11 on the top of charge pipe 10, in order in reaction tank 2, to add different metalloporphyrin solution 9 sensitive materials easily and to clean the dimethyl formamide of each little reaction tank.On the other end of each little reaction tank lower end housing, a leakage fluid dram is set corresponding to snorkel, on leakage fluid dram, stick with glue knot one discharging tube 3, installing one retaining valve 4 in discharging tube 3 is so that give off each little reaction tank interior metalloporphyrin solution 9 and dimethyl formamide cleaning fluid.Discharge opeing has just been finished the function of cleaning little reaction tank easily and changing the metalloporphyrin solution 9 in each little reaction tank with reinforced cooperating, and guarantees the precision that each little reaction tank detects, and detectability reaches the ppm level.Be positioned over the interior metalloporphyrin solution 9 of each little reaction tank for cobalt porphyrin, rhodium porphyrin and 3 kinds of metalloporphyrins of iron porphyrin are dissolved in respectively in the organic solvent dimethyl formamide, the concentration of solution is 5 * 10
-8Mol/L.Volatile organic matter gases such as ethanol, methyl alcohol, benzene are detected.
The course of work of detected gas of the present invention: as shown in Figure 3, the intact device of utilizing sensor gas of the present invention is by light-source system, fiber gas sensor, micro spectral negotiation signals collecting and disposal system.Add metalloporphyrin solution from charge door, make the reaction tank top that certain space be arranged, when the aerating pump work, gas to be measured adds reaction tank under the promotion that adds air pump, make its fully reaction in reaction tank, when pressure surpassed the pressure of vapor liquid equilibrium, gas was discharged through retaining valve by evacuated tube, when gas-liquid reached balance again, retaining valve was closed automatically.After reacting completely, light-source system is started working, and forms the incident light part of sensor.When incident light is mapped on the metalloporphyrin solution, can be with the reacted metalloporphyrin solution of object gas to some fixed wave length light signal generating absorption in the light signal.After this section wavelength energy was absorbed, the incident light after the change reached micro spectrometer by outgoing optical fiber, arrived signals collecting and disposal system again.Metalloporphyrin solution has the certain absorption wavelength, and with phosgene and volatile organic compounds effect, wavelength is moved, when gas not simultaneously, the distance that wavelength moves is different, gas is again by signals collecting with handle and calculate, pattern-recognition, and to the end recognition result.At last, metalloporphyrin solution is discharged by discharging tube.