CN103323555B - Tourmaline-containing methane activation and catalytic oxidation device - Google Patents
Tourmaline-containing methane activation and catalytic oxidation device Download PDFInfo
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- CN103323555B CN103323555B CN201310278633.4A CN201310278633A CN103323555B CN 103323555 B CN103323555 B CN 103323555B CN 201310278633 A CN201310278633 A CN 201310278633A CN 103323555 B CN103323555 B CN 103323555B
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Abstract
The invention discloses a tourmaline-containing methane activation and catalytic oxidation device. The device comprises a gas activation unit, a catalytic oxidation unit and a tail gas analysis unit, which are sequentially connected. According to the activation and catalytic oxidation device, the main point is that the activation unit is additionally arranged on basis of an original static bed quartz tube reactor and is used for activating methane and air so as to improve the conversion rate of the methane and the air; the temperature rise in the catalytic oxidation unit is procedurally controlled so that the temperature rise is stable and the conversion rates of the methane at different temperatures can be accurately measured. According to the tourmaline-containing methane activation and catalytic oxidation device, the activation unit is additionally arranged in front of the catalytic oxidation unit and is used for activating the methane, so that the catalytic combustion reaction activation energy of the methane is reduced, an ignition temperature T50 and a full conversion temperature T90 of the methane are reduced by 20-30 DEG C, and the methane converts at low temperature; thus, the conversion rate of the methane is improved.
Description
Technical field:
The present invention relates to a kind of methane activation catalytic oxidizing equipment containing tourmaline, specifically a kind of by methane gas being activated to improve the device of methane conversion efficiency, and can test for the catalytic activity of dissimilar methanation catalyst.
Background technology:
Infrared radiation can effectively promote the motion of methane molecule, reduce its energy of activation, in the radioactive wave of the far infrared of specific region, the electromagnetic wave energy that only relates to vibration or rotating certain particular wavelength region is rendered in methane molecule, make methane molecule rotation, accelerate the rotation-oscillating movement of the chemical classes alive of the conduct burning precursor of methane molecule generation.Thus, the collision energy of oxygen molecule in raising and air, and improve collision frequency, consequently can promote the decomposition reaction of methane.
Rock gas is more and more used in the various aspects of life as a kind of new forms of energy, and methane is as the principal ingredient of rock gas, preparation is a kind of efficiently, can make methane at lower temperature, start to transform and the catalyzer of conversion is completely problem anxious to be resolved aspect current rock gas utilization.The catalytic unit of methane is the covering device that the activity of prepared methanation catalyst is evaluated.
The hydrocarbon of natural gas and auto tail gas discharge is mainly the methane completely that do not burn.In the process of it gas firing, the aggregating state of methane molecule becomes disperse state, the hydrocarbon atom of methane respectively with oxygen atom in conjunction with generating carbon dioxide and water, the reason that in general methane can not perfect combustion is that the aggregating state of methane molecule has affected burning.Methane molecule belongs to a mobile equilibrium in rock gas inside, its citation form is constantly reunite and disperse.In this mobile equilibrium, the Van der Waals force in the methane molecule group associating is on the one hand interrupted, and methane molecule departs from this association group; On the other hand, there are again some methane molecules in conjunction with getting on.And the energy that this mobile equilibrium needs is to be provided by the thermal motion of methane molecule.Wavelength is that the energy that the infrared ray of 3～15 μ m has is 8～40kJmol
-1, and bond energy between methane molecule group is all at 10kJmol
-1below, so being the red line far away of 3～15 μ m, wavelength can interrupt the Van der Waals force between molecule, radiation infraredly be conducive to this mobile equilibrium and move right, so just make methane molecule become disperse state by aggregating state, the contact area of methane molecule and oxygen molecule is increased, thereby be conducive to the abundant burning of fuel oil.
Tourmaline is the ring texture silicate mineral of a kind of aluminium taking boracic as feature, sodium, iron, magnesium, lithium.Structural formula is Na (Mg, Fe, Mn, Li, Al)
3al
6[Si
6o
18] [BO
3]
3(OH, F)
4, due to its special trigonal system symmetrical structure, make it have permanent self power generation polarity, pyroelectric and and piezoelectricity.Because tourmaline has pyroelectricity and piezoelectricity, the variation meeting of the tourmaline interior molecules dipole moment being caused by the subtle change of temperature or pressure is at normal temperatures energized into high level molecule, in the time of its downward transition, unnecessary energy just can discharge with the form of infrared radiation, the far infrared wavelength of tourmaline transmitting is at 4～14 μ m, utilize its these character can carry out the activation of water, the health care of human body, and the processing of harmful gas in environment.The present invention i.e. these character of main application tourmaline.
Rock gas is more and more used in the various aspects of life as a kind of new forms of energy, and methane is as the principal ingredient of rock gas, preparation is a kind of efficiently, can make methane at lower temperature, start to transform and the catalyzer of conversion is completely problem anxious to be resolved aspect current rock gas utilization.The catalytic unit of methane is the covering device that the activity of prepared methanation catalyst is evaluated.
Patent CN2934206Y proposes a kind of methane catalyzed partial oxidation produced synthetic gas circulating fluidized bed, by separately being realized to circulation with the Lattice Oxygen reaction two parts on perovskite type catalyst surface, the oxygen in perovskite type catalyst absorbed air and methane reduces costs, this device is mainly used for synthetic other gases instead of the catalysis for methane, and the flow of methane changes in course of reaction, can not be used for measuring the reaction that methane changes.Patent CN201701920U has announced a kind of catalyst oxidation reactor that is added with catalyzer dumping device, while making the filling of catalyzer, internals need not be hung out to urceolus, make that more catalyst changeout is convenient, but its catalyzer has sieve aperture that the consumption of catalyzer can not be fixed on dump bucket, make gas follow the accurately correspondence of amount of catalyzer, easily cause the waste of catalyzer.Patent CN201932945U has introduced one and formed I and II fluidized catalytic oxidation reaction in catalytic oxidation district, fluidized-bed bottom, and catalytic oxidation carrier precipitation backflow closed circuit circulatory system; Can form the catalytic oxidation fluidization bed of forcing fluidization catalytic reaction bed, can greatly increase the contact gear ratio surface area of catalytic oxidation, but this device be only applicable to process high concentration organic sewage, not be suitable for and process gas aspect.Patent CN1865678A is a kind of evaluation system for catalytic performance of natural gas automobile tail gas being made up of vapourizing furnace, catalytic reaction stove, temperature sensor and data acquisition unit, and this system is close to practice, and with low cost.But in above-mentioned patent, all there is no activating apparatus, can not better process pollutant component in tail gas.Patent CN101120211A provides a kind of makes the methane gas before burning realize significantly activation, the far infrared generation body of the thermal efficiency while improving burning, and this device is mainly used in the high temperature flaming combustion of methane, DeGrain aspect catalytic oxidation.
The present invention has increased methane activation unit on the basis of traditional test, adopting inorganic mineral material tourmaline is main active substances, utilize tourmaline near the spectral absorption band 6.153 μ m of methane and 7.166 μ m, to there is the character of higher infrared emittance, reach the methane before catalytic oxidation is activated its reaction activity is reduced by infrared radiation, start inversion temperature thereby reduce, shorten the time that methane transforms completely, improve final conversion ratio and reach the object of processing at a lower temperature discharge of methane in natural gas and auto tail gas.
Summary of the invention:
The object of the invention is to improve for conventional art, a kind of methane activation catalytic oxidizing equipment containing tourmaline is provided.This activating catalytic oxidation unit is mainly to have increased activation unit on the basis of original fixed bed quartz tube reactor, by activation unit, methane and air are activated to improve conversion ratio, in catalytic oxidation unit, adopt programmed control to heat up, make to heat up more stable, and can measure exactly the conversion ratio of methane in different temperatures.
Technical scheme of the present invention is:
Containing a methane activation catalytic oxidizing equipment for tourmaline, this device comprises the gas activation unit connecting in turn, catalytic oxidation unit, tails assay unit;
Wherein, gas activation unit comprises gas mixer, constant temperature enclosure, secondary activation module and three grades of activation modules, its annexation is: methane and air are by passing into gas mixer, after mixing, successively by constant temperature enclosure, secondary activation module and three grades of activation modules, after activation, enter catalytic oxidation unit;
Catalytic oxidation unit is to comprise the quartz tube reactor that catalyzer is housed, and catalyst sample is contained in the flat-temperature zone in quartz ampoule sleeve pipe; Methane blended gas after catalysis enters tails assay unit;
Tails assay unit comprises gas chromatograph, tails assay workstation and computing machine.Exhaust gas component passes into chromatogram sampling, and the signal detecting is converted into methane peak area by tails assay workstation, and utilizes following formula to calculate the conversion ratio of methane:
Methane conversion=(initial methane peak area – Real-Time Monitoring methane peak area)/initial methane peak area
By Computer display result, the tail gas after is by analysis discharged by gas outlet in chromatogram.
Described secondary activation module is equipped with the activation post containing tourmaline ceramic ball in being.
Three grades of described activation modules are equipped with the activation post containing tourmaline ceramic ball in being.
Described secondary activation module is that internal diameter is the activation post of 20-25mm, and it is that 2～3mm is containing tourmaline ceramic ball, consumption 50-150g that particle diameter is housed in activation post.
Three grades of described activation modules are that internal diameter is the activation post of 25-30mm, and it is that 4～6mm is containing tourmaline ceramic ball, consumption 75-225g that particle diameter is housed in activation post.
In described catalytic oxidation unit, quartz tube reactor is connected with temperature controller, and temperature controller carries out programmed control intensification.
The invention has the beneficial effects as follows:
The present invention has increased activation unit before catalyst unit, activates reacting front methane, reduces methane catalytic combustion reaction activity, the initiation temperature T of methane gas
50and complete inversion temperature T
90reduce by 20～30 DEG C, just start at a lower temperature to transform, improved the transformation efficiency of methane.
Brief description of the drawings:
Fig. 1 is one-piece construction schematic diagram of the present invention.
Fig. 2 is the concrete schematic diagram of activation unit in the present invention.
Fig. 3 is the concrete schematic diagram of catalytic oxidation unit in the present invention.
Fig. 4 is the concrete schematic diagram of tails assay unit in the present invention.
Fig. 5 is methane activity curve comparison diagram in embodiment one in the present invention.
Fig. 6 is methane activity curve comparison diagram in embodiment two in the present invention.
Fig. 7 is methane activity curve comparison diagram in embodiment three in the present invention.
Fig. 8 is methane activity curve comparison diagram in embodiment four in the present invention.
Wherein, 1-air gas cylinder, 2-methane gas cylinder, 3-hydrogen cylinder, 4-welding bottle, 5-nitrogen cylinder; 6-suspended body flowmeter; 7-gas mixer; 8-constant temperature enclosure, 9-digital indicator; 10-secondary activation module, tri-grades of activation modules of 11-, 12-digital mass flowmeter; 13-quartz tube reactor; 14-thermopair, 15-thermocouple sheath; 16-catalyst layer; 17-is high temperature resistant silica wool; 18-temperature controller 19-gas chromatograph; 20-thermostat; 21-injector; 22-chromatographic column; 23-detecting device; 24-tails assay workstation; 25-computing machine;
Embodiment:
Known from the example shown in Fig. 1, a kind of structure containing tourmaline methane activation catalytic unit of the present invention comprises gas activation unit, catalytic oxidation unit, tails assay unit.
Shown in Fig. 1-Fig. 4 is a kind of methane activation catalytic oxidizing equipment containing tourmaline, and this device comprises the gas activation unit connecting in turn, catalytic oxidation unit, tails assay unit;
Wherein, gas activation unit comprises gas mixer 7, constant temperature enclosure 8, secondary activation module 10 and three grades of activation modules 11, its annexation is: methane and air pass into gas mixer 7 by a certain percentage, after mixing, successively by constant temperature enclosure 8, secondary activation module 10 and three grades of activation modules 11, after activation, enter catalytic oxidation unit;
Catalytic oxidation unit is mainly the quartz tube reactor 13 that catalyzer is housed, and carries out programmed control intensification by temperature controller 18, and the methane blended gas after catalysis enters tails assay unit;
Tails assay unit comprises gas chromatograph 19, tails assay workstation 24 and computing machine 25, exhaust gas component is discharged by gas outlet 26 after chromatogram sampling, the signal detecting is converted into methane peak area by tails assay workstation 24 and computing machine 25, and the overall catalytic efficiency of device is described by the variation of peak area under different temperatures.
Described secondary activation module is that 2～3mm is containing tourmaline ceramic ball, consumption 50-150g;
Three grades of described activation modules are that 4～6mm is containing tourmaline ceramic ball, consumption 75-225g;
Described tail gas workstation is the Easy-3000 analysis software that in Hangzhou, brightness science equipment company limited produces.
In above-mentioned activating catalytic oxidation unit, between each instrument and meter that gas passes through, be to be 3mm by diameter stainless steel tracheae connects, source of the gas is filled gas by commercially available gas cylinder.
The innovation part of this device is the interpolation of activation unit, and Fig. 2 further illustrates activation unit structure in the present invention.Gas from gas cylinder out flowmeter from mixer enter in gas mixer 7 and mix, the cube sealing chamber that wherein size of gas mixer is 300 × 250 × 200mm, and be installed with at 50mm place, sealing chamber positive identity distance bottom the flowmeter that two sizes are 30 × 30 × 150mm side by side, in order to the flow of adjustments of gas; Gas enters constant temperature enclosure 8 from gas mixer 7 mixes, constant temperature enclosure 8 is that size is the resistance-heated furnace of 150 × 150 × 300mm, this unit adopts Ni-Cr-Fe resistance wire to heat, inside and outside resistance wire, be all surrounded by heat-insulation layer, heat-insulation layer is that outside is surrounded by stainless high temperature cotton, and the internal diameter of heating furnace is 12mm, in the middle of stove, is that an external diameter is that 12mm internal diameter is the quartz ampoule 13 of 10mm, the O-ring seal sealing of the middle opening that has the pore of 3mm for quartz ampoule 13 two ends, so that gas passes through.Add thermal recovery D.C. regulated power supply, power is 1～3kw, and heating-up temperature is 50～200 DEG C of variations of controlling temperature by regulation voltage, for the different temperature of the pre-thermal recovery of different methane flows.It is 80 × 80 × 200 rectangular build digital indicator 9 so that temperature in real-time demonstration stove can make mixed gas in steady state (SS) by preheating that constant temperature enclosure 8 is connected with a size, makes the test result of device more stable; Then gas enters secondary activation module 10 and three grades of activation modules 11, both are the activation post of 40 × 40 × 250mm, material is plexi-glass tubular, two ends are aluminum gland, the interface that the diameter that has supplied gas turnover in the middle of gland is 3mm, nut is copper chromium plating, and both differences are that the tourmaline that the grain size of the active substance that fills in secondary activation module 10 is 4～6mm carries out heavy manual labour to gas, and three grades activate 11 li of modules is that particle size is the tourmaline of 1～3mm; The active substance two ends of filling are all stifled good to prevent having little dust to enter gas circuit in Ceramic Balls with glass wool.Adopt three grades of activation unit more stable, also can better reach activation effect.Wherein constant temperature enclosure and digital indicator, secondary activation module and three grades of activation modules be fixed on the upper end of the rectangular build that a size is 200 × 300 × 600 can the iron casing of opening in, be from left to right followed successively by heating furnace 8, digital indicator 9.Secondary activation module 10, three grades of activation modules 11.The fixing position of secondary and three grades of activators is in the place apart from bottom half 50mm.When casing upper end open for the example for different can better be changed active substance.
Concrete embodiment
Embodiment one:
Utilize the present invention to laboratory Ca-Ti ore type La processed
0.3sr
0.7mnO
3series methanation catalyst detects, first by 1mlLa
0.3sr
0.7mnO
3(particle diameter 380～550 μ m) pack in quartz tube reactor 13 methanation catalyst, fix quartz ampoule 13 and thermocouple sheath 15, access thermopair 14.In secondary activation module 10, pack the tourmaline 50g of particle size at 4～6mm into, in three grades of activation modules 11, pack the tourmaline 75g of particle size at 1～3mm into, switch on power, constant temperature enclosure 8 temperature are set are 150 DEG C, by temperature controller 18, heating schedule is set, pass into methane and air Mixture (volume ratio 1:10), and methane content is 4.5ml/min.Open welding bottle 4, nitrogen cylinder 5 and hydrogen cylinder 3, open gas chromatograph 19, regulating chromatograph 19 post case temperature is 180 DEG C, chromatographic column 22 temperature are 140 DEG C, FID23 temperature is 140 DEG C, opens the Easy-3000 analysis software of computing machine 25 the insides, and necessary parameter is set; After the temperature of question response stove arrives 200 DEG C, start sampling until 600 DEG C, sampling Easy-3000 after stratographic analysis 19 demonstrates corresponding methane peak area, record temperature and corresponding peak area, calculate the conversion ratio (methane conversion=(initial methane peak area – Real-Time Monitoring methane peak area)/initial methane peak area) of methane by the variation of peak area, and obtain the initiation temperature (T of methane
50) and complete inversion temperature (T
90).Reaction finishes chromatographic post case temperature to be transferred to 50 DEG C to be allowed to condition at carrier gas be the situation borehole cooling that nitrogen passes through afterwards, after each data ready, closes gas cylinder, reacting furnace, chromatograph 19, computing machine 25, last powered-down.The discolour silica gel that when contrast experiment, activating substance is changed to same volume, other conditions are identical with experimental group.
Experimental result, as Fig. 5, starts inversion temperature T while not adding activation unit as seen from Figure 5
50be 420 DEG C, inversion temperature T completely
90be 500 DEG C, after interpolation activation unit, start inversion temperature T
50be 400 DEG C, inversion temperature T completely
90be 475 DEG C, initiation temperature reduces by 20 DEG C, and inversion temperature reduces by 25 DEG C completely, and methane gas absorbs certain energy under the infrared radiation effect of activating apparatus, and energy of activation reduces, and is beneficial to the carrying out of catalytic reaction, and this device can improve the conversion ratio of methane.
Embodiment two:
Embodiment two is that with the difference of embodiment one ratio of institute's ventilating methane and air is 1:25, and preheat temperature is 100 DEG C.Other conditions are identical with example one.
Experimental result, as Fig. 6, starts inversion temperature T while not adding activation unit as seen from Figure 6
50be 425 DEG C, inversion temperature T completely
90be 515 DEG C, after interpolation activation unit, starting inversion temperature is T
50be 405 DEG C, inversion temperature T completely
90be 485 DEG C, initiation temperature reduces by 20 DEG C, and inversion temperature reduces by 30 DEG C completely, and methane gas absorbs certain energy under the infrared radiation effect of activating apparatus, and energy of activation reduces, and accelerates the carrying out of catalytic reaction, and this device can improve the conversion ratio of methane.
Embodiment three:
Embodiment three is that with the difference of embodiment one quality of Ceramic Balls in secondary activating chamber is 150g.In three grades of activating chamber, the quality of Ceramic Balls is 225g, and the amount of institute's ventilating methane gas is 3ml/s.Other conditions are identical with example one.
Experimental result, as Fig. 7, starts inversion temperature T while not adding activation unit as seen from Figure 7
50be 430 DEG C, inversion temperature T completely
90be 540 DEG C, after interpolation activation unit, starting inversion temperature is T
50be 420 DEG C, inversion temperature T completely
90be 520 DEG C, initiation temperature reduces by 10 DEG C, and inversion temperature reduces by 20 DEG C completely, and methane gas absorbs certain energy under the infrared radiation effect of activating apparatus, and energy of activation reduces, and is beneficial to the carrying out of catalytic reaction, and this device can improve the conversion ratio of methane.
Embodiment four:
Embodiment four is that with the difference of embodiment three ratio of institute's ventilating methane and air is 1:25, and preheat temperature is 100 DEG C.Other conditions are identical with example three.
The following Fig. 8 of experimental result, starts inversion temperature T while not adding as seen from Figure 8 activation unit blank
50be 435 DEG C, inversion temperature T completely
90be 550 DEG C, while having added activation unit, starting inversion temperature is T
50be 415 DEG C, inversion temperature T completely
90be 530 DEG C, initiation temperature reduces by 20 DEG C, and inversion temperature reduces by 20 DEG C completely, and methane gas absorbs certain energy under the infrared radiation effect of activating apparatus, and energy of activation reduces, and is beneficial to the carrying out of catalytic reaction, and this device can improve the conversion ratio of methane.
In above-mentioned activating catalytic device, the particle size of the active substance in described activation unit, consumption, the temperature of preheating and the corresponding relation of gas mixture ratio are as shown in Table 1.
The corresponding relation of the each material of table one different instances
In the specific embodiment of the invention, concrete device and step are not considered as the restriction to protection domain.
Unaccomplished matter of the present invention is known technology.
Claims (2)
1. containing a methane activation catalytic oxidizing equipment for tourmaline, it is characterized by this device and comprise the gas activation unit connecting in turn, catalytic oxidation unit, tails assay unit;
Wherein, gas activation unit comprises gas mixer, constant temperature enclosure, secondary activation module and three grades of activation modules, its annexation is: methane and air are by passing into gas mixer, after mixing, successively by constant temperature enclosure, secondary activation module and three grades of activation modules, after activation, enter catalytic oxidation unit;
Catalytic oxidation unit is to comprise the quartz tube reactor that catalyzer is housed, and catalyst sample is contained in the flat-temperature zone in quartz ampoule sleeve pipe; Methane blended gas after catalysis enters tails assay unit;
Tails assay unit comprises gas chromatograph, tails assay workstation and computing machine; Exhaust gas component is sent to tails assay workstation after passing into gas chromatograph sampling, and the signal detecting is converted into methane peak area by tails assay workstation, and by Computer display result, the tail gas after is by analysis discharged by gas outlet in chromatogram;
Described secondary activation module is equipped with the activation post containing tourmaline ceramic ball in being;
Three grades of described activation modules are equipped with the activation post containing tourmaline ceramic ball in being;
Described secondary activation module is that internal diameter is the activation post of 20-25mm, and it is that 4～6mm is containing tourmaline ceramic ball, consumption 50-150g that particle diameter is housed in activation post;
Three grades of described activation modules are that internal diameter is the activation post of 25-30mm, and it is that 1～3mm is containing tourmaline ceramic ball, consumption 75-225g that particle diameter is housed in activation post.
2. the methane activation catalytic oxidizing equipment containing tourmaline as claimed in claim 1, is characterized by quartz tube reactor in described catalytic oxidation unit and is connected with temperature controller, and temperature controller carries out programmed control intensification.
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| CN104001422B (en) * | 2014-05-23 | 2016-03-02 | 河北工业大学 | A kind of activating catalytic device of the multiple low-concentration methane pollution sources of process containing tourmaline |
| CN108037236B (en) * | 2017-11-21 | 2023-03-03 | 中国科学院西北生态环境资源研究院 | Experimental device for collecting quantitative analysis gas of methane conversion rate in torch discharge |
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| CA2404830C (en) * | 2002-10-17 | 2011-03-22 | University Of Windsor | Metallic mesoporous transition metal oxide molecular sieves, room temperature activation of dinitrogen and ammonia production |
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