CN101520393B - Measuring method of hydrogen gas and methane in ingredients of artificial fuel gas - Google Patents
Measuring method of hydrogen gas and methane in ingredients of artificial fuel gas Download PDFInfo
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- CN101520393B CN101520393B CN2009100667279A CN200910066727A CN101520393B CN 101520393 B CN101520393 B CN 101520393B CN 2009100667279 A CN2009100667279 A CN 2009100667279A CN 200910066727 A CN200910066727 A CN 200910066727A CN 101520393 B CN101520393 B CN 101520393B
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Abstract
The invention relates to a measuring method of hydrogen gas and methane in ingredients of artificial gas, which belongs to the field of chemical industry. The measuring method of hydrogen gas and methane in ingredients of artificial gas aims to reduce the cost so as to satisfy the requirements of the detection and the analysis of the fuel gas quality of the prior middle-size and small-size chemical and coal gas enterprises, and the like, and achieve measuring precision and measuring repeatability. The measuring method of hydrogen gas and methane in ingredients of artificial gas includes the following steps: the mixed gases absorbing CO2, O2, CnHm, CO and O2 are taken; the O2 is filled in a combustion flask, and the internal temperature of the combustion flask is increased to 180 DEG C to absorb H2; the temperature in the combustion flask is lowered to the normal-temperature state to absorb the generated CO2 and measure the volume after combustion. The invention provides a novel method for measuring the main ingredients of the artificial fuel gas. Compared with the prior measuring method, the measuring method of hydrogen gas and methane in ingredients of artificial gas has the characteristic of outstanding practicability, and can satisfy the requirements of the detection and the analysis of the fuel gas quality of the prior middle-size and small-size chemical and coal gas enterprises, and the like.
Description
Technical field:
The invention belongs to chemical field, it mainly is the mensuration to Main Ingredients and Appearance hydrogen and methane content in the combustion gas.
Background technology:
In the application process of the production of some coke-oven plants, chemical fertilizer factory, gasworks, biomass energy system gas and large-sized biogas and conveying; Need analyze and measure combustion gas quality and gas composition composition; Composition with the various components of understanding inflammable gas; Especially what of CO, CO2, CO+H2, O2, H2 and CH4 content, to production run and technic index control, safety in production all is very important with air feed; Can how much calculate fuel gases calorific value according to the component of CO, H2, H4 and CnHm inflammable gas, satisfy the town gas quality requirements and have great significance.The experimental technique that in the practice examining analytical work, adopts usually is a kind of gas analyzer of chemical analysis method principle, and carbon dioxide, unsaturated hydrocarbon, oxygen, carbon monoxide, hydrogen, methane and nitrogen in the gas are measured.By existing experimental technique " chemical analysis method of manufactured gas, manufactured fuel gas's major constituent " national standard code GB/T 12205-1990, recognize by the website of national authority that " GB/T 12205-1990 " analytical approach has been listed in through the computer network retrieval in the recent period and abrogate in the national standard catalogue.Recognize from 2008 the 14th phases of the up-to-date bulletin of national standard; Substitute former GB/T 10410.1-1989 by GB/T 10410-2008 " artificial coal gas and liquefied petroleum gas (LPG) major constituents gas chromatography "; GB/T 10410.3-1989 and GB/T13612-2006; But GB/T 12205-1990 " chemical analysis method of manufactured gas, manufactured fuel gas's major constituent " only made abrogate a speech explanation; Do not point out to abrogate reason, alternative method is GB/T10410-2008 " artificial coal gas and a liquefied petroleum gas (LPG) major constituents gas chromatography ".At present a lot of gasworks, chemical fertilizer factory, coke-oven plant, refinery, biogas are made in the production run; In some, still to adopt existing national standard method be the assay method of GB/T12205-1990 for the inspection department of small enterprise and laboratory; Still do not understand the time of abrogating and the reason of this method, utilize analytical approach and experimental apparatus that production run and product are carried out analytical control and control method.
Situation about understanding and grasping to GB/T 12205-199 analytical approach; Real work need with the experience of this method of long-term use and instrument; Think that this assay method exists very big artificial measuring error, method error and measuring error, during especially to hydrogen and methane blended gas burst experiment, adopt tame oxygen to light a fire with the high-frequency spark generator; Make CH4 and the H2 reaction of blasting; Calculate methane and hydrogen exists serious deviation through the volume change after the explosive reaction, hydrogen and methane explosive reaction usually take place in the experimentation accomplish back measurement cumulative volume and exceed 100%, and the volume of inert nitrogen gas to subtract poor method be zero or negative value; Twice of hydrogen and methane or experimental result repeatability repeatedly are relatively poor in addition, can not satisfy existing method standard precision and allow absolute mistake area requirement.Come into effect only to substitute GB/T 10410.1-1989 on April 1st, 2009 by latest national standards bulletin " artificial coal gas and liquefied petroleum gas (LPG) major constituents gas chromatography " GB/T 10410-2008; The method of GB/T 10410.3-1989 and GB/T13612-2006; Although the gas chromatography of artificial coal gas is a kind of than the advanced analysis method; Have higher measuring accuracy and the characteristics of analyzing polycomponent; Not only can be to manufactured gas, manufactured fuel gas's carbon dioxide, oxygen, carbon monoxide, hydrogen, methane, nitrogen assay determination, alkene CnH2n, alkynes CnH2n-2, aromatic hydrocarbon and alkanes CnHn+2 homologous series and the isomers to unsaturated hydro carbons can both carry out the multianalysis measurement simultaneously.But one can be satisfied the expensive of the common model gas chromatograph of above-mentioned experimental technique requirement; General hundreds of thousands unit even the units up to a million of wanting; And the operant level of having relatively high expectations and technical ability could satisfy the demand of work, and the cycle of measuring, and the gas chromatograph pillar is filled quite numerous and diverse; Adopt external standard method need prepare respective standard gas etc.; The cost of operation and the maintenance of experiment is higher, therefore in some, small enterprise is not only once equipment to drop into expense bigger, and need the technical skill personnel again; So high cost can not bear in enterprise, " artificial coal gas component gas chromatography " is promoted with application run into many problems and difficulty; Other some instrument analytical methods such as conductance method, enclosed pasture method, thermal conductance eudiometry, infrared gas method or the like belong to the physical and chemical experiment instrument; Being adapted to the single-component gas analysis is that on-line analysis is measured; The infrared analyzer principle of work is: when infrared light passes through gas to be measured; These gas molecules have absorption to the infrared light of specific wavelength; It absorbs relation and obeys lambert-Bill (Lambert-Beer) absorption law, and promptly some gas carries out selective absorption to infrared light, and its absorption intensity changes the concentration that depends on tested gas.Relatively the advantage of gas analyzer infrared ray gas analyzer is precision and highly sensitive, that measurement range is wide, response speed is fast, good selectivity, stability and good reliability, can not measures, especially can not analyze nonpolarity diatomics of symmetrical structure and monoatomic molecules gas to multicomponent gas simultaneously, and is inapplicable to various manufactured gas, manufactured fuel gas's classification multi component mixed gas bodies.
Existing analytical approach is that the principle of GB GB/T 12205-1990 method is the characteristic according to the component of gas to be analyzed; When utilizing combustion gas with the contact of different chemical reagent in the gas a certain component absorbed by chemical absorbing liquid; This gas is not being overflowed after absorption is fixing; Reduce the content that difference is tried to achieve out gas according to gas volume before and after absorbing; The key component analysis is with direct absorptionmetric determination carbon dioxide (CO2) unsaturated hydrocarbon (CnHm), oxygen (O2), carbon monoxide (CO), hydrogen and paraffin gas (representing) with CH4, and no matter the combustion method of hydrogen and methane is to adopt smoulder; Still the explosive combustion method is to the measurement of hydrogen and methane; Because its analytical approach and experimental procedure exist serious volumetric errors, thermometric error and artificial error, in the process of mixed gas in combustion reaction of hydrogen and methane, the duplicate measurements of methane and hydrogen is that its measurement volumes always exists deviation.The content of its methane and hydrogen then is the variation according to the chemical equation of its combustion reaction and front and back volume; Derive computing formula and try to achieve what of hydrogen and methane, the carbon dioxide, unsaturated hydrocarbon, oxygen, carbon monoxide, hydrogen, the remaining gas of methane gas content that use the overall product of taking a sample to deduct absorption at last are nitrogen.But in this method measuring process of practical application during the combustion of mixed gas of hydrogen and methane; Very big deviation often appears in the experimental result that determines, twice combustion experimental result repeated bad, and the volume number after can measuring during operation exception exceeds 100%; Caused whole analysis experimentation failure; Give normal check analysis work, brought abnormal experimental data, caused adverse influence and insecure improper factor instructing the production system technic index.
Summary of the invention:
The objective of the invention is promptly to reduce enterprise's combustion gas quality check and analysis requirements such as chemical industry that cost can satisfy existing middle and small scale, coal gas, can reach the assay method of hydrogen and methane in manufactured gas, manufactured fuel gas's component of measuring accuracy and measurement reproducibility again.
Method step of the present invention is:
A, get and absorbed CO
2, O
2, CnHm, Co mixed gas and O
2, wherein comprise H
2, CH
4And N
2Mixed gas and O
2Ratio be 1: 3～4;
B, at first with O
2Place Molotov cocktail, the Molotov cocktail internal temperature is risen to 180 ℃, kept 10～15 seconds, on the basis that keeps this temperature, put into then and contain H
2, CH
4And N
2Fuel gas mixture, to H wherein
2Absorb;
C, the temperature in the Molotov cocktail is risen to 650 ℃, to CH wherein
4Absorb;
D, reduce temperature to normal temperature state in the Molotov cocktail at last, absorb the CO that produces
2With measure volume after combustion.
The present invention absorbs H in Molotov cocktail
2And CH
4Being divided into for two steps during gas carries out, and per step absorbs 4～5 times at least repeatedly.
The Molotov cocktail of indication of the present invention comprises that on liquid level equilibrium device that firing chamber, firing chamber connect, the firing chamber gas inlet and outlet and cock, bottom, firing chamber being arranged is the combustion chamber sealing base; In the outside of firing chamber is cooling jacket; Cooling jacket bottom and combustion chamber sealing base are fixed, and gas inlet and outlet and cock place cooling jacket top, are the chilled water seals in the cooling jacket upper end; Cooling water inlet and coolant outlet are installed, chilled water thermometric thermal resistance is arranged on cooling jacket; Platinum wire protection tube and firing chamber thermometric thermal resistance pass sealed base and place the firing chamber inner, in platinum wire protection tube inside the platinum heater strip are arranged.
The present invention proposes a kind of new manufactured gas, manufactured fuel gas's major constituent measuring method; It is compared with current measuring methods; Characteristics with outstanding practicality can satisfy enterprise's combustion gas quality check and analysis requirements such as chemical industry, coal gas of existing middle and small scale, mainly are scientific and technological method and the advanced thermometrys that utilizes modern advanced person; Realized the temperature of hydrogen and methyl hydride combustion experimentation is confirmed and real-time prison hole and measurement; Through the actual exploitation of method of invention, and collect mensuration precision and the accuracy that a large amount of experimental datas have further been verified analytical approach of the present invention, satisfied assay method purpose of the present invention requirement fully.
Description of drawings:
Accompanying drawing is a Molotov cocktail structural representation of the present invention.
Embodiment:
Manufactured gas, manufactured fuel gas's major constituent assay method of the present invention; Its principle is the principle according to existing " chemical analysis method of manufactured gas, manufactured fuel gas's major constituent "; Utilize chemical absorption process at first to absorb carbon dioxide, unsaturated hydrocarbon, oxygen and carbon monoxide in the mixed gas, its main reaction equation is following:
At first absorb CO2 with 33% potassium hydroxide solution:
CO2+2KOH＝K2CO3+H2O
Aqueous slkali with pyrogallic acid (having another name called pyrogallol) absorbs oxygen
C6H3(OH)3+3KOH→C6H3(OK)3+3H
2O
4C6H3(OK)3+O2→2Cl2H4(OK)3+2H
2O
Absorb unsaturated hydrocarbon (CnHm) with saturated bromine water:
C2H4+Br2→C2H4Br2
Absorb carbon monoxide with ammonia property stannous chloride:
Cu2Cl2+2CO＝Cu2Cl2·2CO
Cu2Cl2·2CO+4NH4+2H
2O→2NH4Cl+CU2·2COONH4
The present invention is absorbing above-mentioned CO
2, O
2, carry out behind the CnHm, Co, its concrete steps are:
A, get and absorbed CO
2, O
2, CnHm, Co mixed gas and O
2, wherein comprise H
2, CH
4And N
2Mixed gas and O
2Ratio be 1: 3～4;
B, at first with O
2Place Molotov cocktail, the Molotov cocktail internal temperature is risen to 180 ℃, kept 10～15 seconds, on the basis that keeps this temperature, put into then and contain H
2, CH
4And N
2Fuel gas mixture, to H wherein
2Absorb;
2H2+O2=2H2O release heat: 2.624kj/mol
C, the temperature in the Molotov cocktail is risen to 650 ℃, to CH wherein
4Absorb;
CH4+2O2=CO2+2H2O release heat: 9.464kj/mol
D, reduce temperature to normal temperature state in the Molotov cocktail at last, absorb the CO that produces
2With measure volume after combustion.
The present invention is in order to make H
2And CH
4Gas absorption more fully thoroughly, in Molotov cocktail, absorb H
2And CH
4Being divided into for two steps during gas carries out, and per step absorbs 4～5 times at least repeatedly.
Molotov cocktail involved in the present invention; Comprise gas inlet and outlet 10 and cock 9 are arranged on liquid level equilibrium device 8 that firing chamber 12, firing chamber 12 connect, the firing chamber 12,12 bottoms, firing chamber are combustion chamber sealing bases 13; 12 outside is a cooling jacket 11 in the firing chamber; Cooling jacket 11 bottoms and combustion chamber sealing base 13 are fixing, and gas inlet and outlet 10 places cooling jacket 11 tops with cock 9, is chilled water seals 6 in cooling jacket 11 upper ends; Cooling water inlet 1 and coolant outlet 2 are installed, chilled water thermometric thermal resistance 3 is arranged on cooling jacket 11; Platinum wire protection tube 7 passes sealed base 13 with firing chamber thermometric thermal resistance 5 and places 12 inside, firing chamber, in platinum wire protection tube 7 inside platinum heater strip 4 is arranged.
The present invention is mainly to existing standard GB/T 12205-1990 analytical approach; The research and development of the combustion method of hydrogen and methane during manufactured gas, manufactured fuel gas's major constituent is measured; Satisfy according to the standard method requirement with the repeatability that guarantees hydrogen and methane blended gas measurement result in the process of smoulder; Hydrogen that proposes and methane are divided into the combustion experiment in two steps; The temperature and the oxygen use amount of strict control combustion process are eliminated issuable subsidiary reaction, are intended to approve again a kind of new manufactured gas, manufactured fuel gas's principal component analysis method.Existing experimental technique is measured manufactured gas, manufactured fuel gas's carbon dioxide, unsaturated hydrocarbon, oxygen, carbon monoxide, hydrogen, methane and nitrogen, and utilizing the absorption of the direct absorption liquid principle of absorption carbon dioxide of a certain component quilt, unsaturated hydrocarbon, oxygen, carbon monoxide in different chemical reagent and the gas and measuring accuracy is to satisfy existing method requirement.The combustion experiment of hydrogen and methane adopts the smoulder method, eliminates existing analytical approach and has measurement volumes error, temperature error and personal error with experimental procedure, make the combustion reaction of hydrogen and methane after, the deviation reduction of the repeatability of measurement methane and hydrogen.Chemical analysis method does not have a kind of suitable absorbing agent for hydrogen and methane at present, can only adopt smoulder method or explosive combustion method.The present invention proposes and in the firing chamber, must carry out sufficient preheating earlier measuring combustion-supporting oxygen; When temperature reaches 180 ℃ ± 5.0 and constant 10-15 second; Remaining gas is measured certain volume number; Combustion reaction for the first time is: the 2H2+O2=2H2O course of reaction, absorb 4-5 time repeatedly, and hydrogen has all been produced water with oxygen; Continuation heats up to platinum wire and makes chamber temperature it reaches at 650 ℃ ± 5.0 o'clock and reacts with oxygen combustion for methane for the second time: CH4+2O2=CO2+2H2O must guarantee the control of temperature of combustion and the abundance of oxygen content, otherwise other subsidiary reactions can take place; (1) oxygen is not enough, the higher CH4=C+2H2 during greater than 850 ℃ of temperature
(2) during rough burning: CH4+2O2=C+2H2O, the great amount of heat that hydrogen and methane and oxygen can discharge in combustion process simultaneously makes the gas temperature rising volumetric expansion after the burning.Therefore the Molotov cocktail external structure has been carried out design again, has increased a cyclic water jacket, is rapidly that the heat cooling is emitted in burning by the cyclic water tank feedwater is set, and makes it restore to the initial experiment temperature conditions.
In order to realize that the foregoing invention purpose realizes existing experimental technique is improved; Guarantee hydrogen and with the volume content accuracy of measurement of methane; Assay method bag of the present invention has comprised gas analysis instrument Molotov cocktail part; Experimental apparatus is the absorption bottle by a group of absorbing carbon dioxide, unsaturated hydrocarbon, oxygen and carbon monoxide, and Molotov cocktail and crossbeam, eudiometer tube, leveling bottle are formed.Molotov cocktail is the technological invention core of assay method of the present invention; It has comprised the platinum wire of a heating flame; Chamber temperature is measured the Pt-100 thermal resistance, cooling temperature of circulating water is measured the Pt-100 thermal resistance, and platinum heater strip temperature control transtat is measured the temperature secondary instrument and constituted.Said chamber temperature measurement thermal resistance and platinum heater strip are installed to the inside of Molotov cocktail by the bottom of Molotov cocktail; Outside and top is control module independently at Molotov cocktail in the measurement of the temperature of circulation; By the temperature survey thermal resistance to combustion chambers burn temperature and combustion reaction after gas temperature keep watch in real time and measure; Combustion experiment is opened the recirculated water water supply system after finishing; Make burning back gas temperature drop to the experiment original state rapidly, the temperature control part branch of platinum heater strip, the temperature control of firing chamber and recirculated water is by independently CS and secondary thermometer are formed.More than thoroughly solve in hydrogen and the methane blended gas combustion process because of rough burning or temperature of combustion uncertain; Burning time is short; It is to produce measuring error and personal error that the burning liberated heat makes the absorption volumetric expansion, has eliminated by operating personnel and has observed the empirical method that platinum ignition wire color is estimated heating-up temperature, adopts the outside thermostatical circulating water of recirculated water overcoat utilization to reduce burning gases rapidly and emits heat; The gas temperature that the burning back is produced is identical with the experiment initial temperature; Thereby eliminated the temperature variation volumetric expansion, the ignition combustion temperature is not both the rough burning of generation, has eliminated the error of analytical approach.
The order that the present invention absorbs must carry out according to above-mentioned order, the gas of interference is absorbed earlier removes.For methane and other volatile saturated hydrocarbon and hydrogen, there is not suitable absorbing agent can they be absorbed, therefore can only use firing method.Hydrogen and the 1. whole products of oxygen point combustion combustion reaction are water, generate carbon dioxide and water after 2. the combustion chemistry reaction equation of methane and oxygen burns, and the twice combustion temperature that the present invention confirms is respectively 180.0 ℃ ± 5.0 and 650 ℃ ± 5.0; Its reaction is themopositive reaction, the heat of emitting 2.624kj/mol and 9.464kj/mol respectively; The variation of gas volume in the burning, the volume of the O2 that the volume of the CO2 of production and when burning are used all and between the volume of raw-gas by certain proportionate relationship.2. volume change and generation carbon dioxide volume before and after it reacts through reaction; Can draw the methyl hydride combustion oxygen consuming amount is two times of methane volumes, and its back of burning produces the carbon dioxide with volume, so the long-pending volume number with reaction generation carbon dioxide of reacting precursor is identical; Content through the carbon dioxide methane content that converts; And generating water vapor condensation Cheng Shui behind hydrogen and the oxygen reaction, its volume is assumed to be zero, can derive the computing formula of hydrogen content.Hydrogen more of the present invention and methyl hydride combustion assay method and existing method; Under the temperature conditions of the combustion reaction temperature condition of hydrogen and oxygen and methane and oxygen combustion reaction; Temperature of combustion has been carried out monitoring and measuring; The result shows that its temperature of combustion difference is bigger to result's influence of analysis to measure; Wherein the source of error of methane is to be tried to achieve after aqueous slkali absorbs by the residue combustion gas of blast back, and the water vapor after the blast is without cooling fully, and reduction in bulk causes methane content to raise through aqueous slkali; Secondly the carbon dioxide that generates behind methyl hydride combustion reduction in bulk amount after potassium hydroxide solution absorbs is converted into methane causes the result higher.The error that carbon deposit that cracking that the high or low partially reason of hydrogen measurement result is a methane and rough burning produce and hydrogen cause; Produced rough burning less owing to get amount of oxygen during explosive combustion, the temperature of existing explosion method high-frequency spark moment is too high to have produced some subsidiary reactions.In order to reduce and to eliminate above-mentioned measuring error; The present invention is to the Molotov cocktail invention design of current measuring methods principle and apparatus; It is little to have overcome the Molotov cocktail blast area; The oxygen sampling amount mixes problem of non-uniform less, and the burning indoor temperature adopts temperature sensor that experimentation is carried out real-time supervision and measurement, with the optimal temperature conditions that guarantees that burning is lighted; While has been designed recirculated water at the Molotov cocktail skin and has fallen system, and rapid decline of gas temperature reverts to the initial temperature state after guaranteeing to satisfy the temperature of combustion condition and burning, and reduces and emits the error that heat makes gas temperature rising generation when burning.
Analytical approach of the present invention has better repeatability and method is more accurate; Its analytical approach is suitable for the component analysis with various manufactured gas, manufactured fuel gases; Adopt gas analyzer as a kind of classical chemical formula manual analyzing instrument, it is easy etc. to have simple in structure a, low price, maintenance.
Molotov cocktail structural design and improvement, in Molotov cocktail design and installation suitable for reading PT-100 temperature sensor and circulating water cooling water gateway, adopt rubber plug to be connected with the mixed gas burning bottle and seal, in order to measurement chamber temperature and cooling circulating water interface; Enlarging combustion chamber volume guarantees to burn cmpletely in the burning abundant preheating of indoor oxygen with combination gas; The sensor for measuring temperature of firing chamber is platinum wire flame tube connector from the Molotov cocktail bottom; Sensor is inserted in the firing chamber; The a large amount of heats that produce during burning make it reduce to former experimental temperature rapidly through cooling circulating water, utilize the temperature measuring gauge real time monitoring firing chamber of one two dot cycle and the temperature of recirculated water.Molotov cocktail partly is made up of appearance gas import/export, cock, float, platinum wire, PT1-100 and PT2-100 temperature sensor, cool cycles water leg, plug seal and temperature control device.Platinum is lighted silk and is snakelike ring-type tinsel, and its diameter is that 0.3 millimeter platinum is processed, and 12 millimeters of effective widths adopt resistant to elevated temperatures quartz glass tube to insert Molotov cocktail from the Molotov cocktail bottom; Temperature sensor is two PT-100 thermal resistances; Measure temperature range at 0-450 ℃; The thermal resistance diameter is 3.0 millimeters; 160/45 millimeter of effective length is measured its point for measuring temperature of chamber temperature at about 1 millimeter place, platinum wire upper end for one, and the Molotov cocktail bottom has fluid sealant consent thermal resistance and platinum wire lead to draw from the bottom; The Molotov cocktail skin is for the recirculated water chuck and establish a PT-100 temperature sensor measurement circulating water temperature, draws the chilled water gateway on Molotov cocktail top, enters the mouth to be connected with a tank that is located at the instrument upper end, and outlet enters down water or recycling,
According to experiment main points and operation steps requirement; Get a certain amount of oxygen at first accurately in the mixed gas burning bottle, the beginning preheating that reddens of energized platinum wire, two PT-100 temperature sensors are promptly measured chamber temperature and cooling water temperature; Must be when temperature rises to design temperature with oxygen preheat 3 minutes; Squeeze into slowly in the mixed gas burning bottle will analyzing appearance gas, combustion of hydrogen for the first time, then methane and alkane compound take fire when continuing to be warming up to 280 ℃ of second design temperatures; Absorb 3-5 time repeatedly; The powered-down continued absorbs 3-5 time repeatedly, at this moment opens the temperature that circulation makes it to reduce rapidly the firing chamber, can be with reading when the two dot cycle temperature that show when thermometer are close.
Molotov cocktail by appearance gas import/export 1., cock and float 2., the chilled water gateway 3., the outer water leg of Molotov cocktail 4., platinum light silk 5., the PT1-100 temperature sensor 6., the PT2-100 temperature sensor 7., 8., the sealing plug 9., 10. form; Wherein the platinum ignition wire 5. with the PT1-100 temperature sensor 6. lead draw from the Molotov cocktail bottom 9. through plug sealing, platinum is lighted silk and is snakelike ring-type tinsel, its diameter is that 0.3 millimeter platinum is processed; Open 10 millimeters of effective widths, material adopts resistant to elevated temperatures quartz glass tube, prevents that the rapid variation of temperature from bursting; The PT1-100 thermal resistance is measured temperature range at 0-450 ℃, and the thermal resistance diameter is 3.0 millimeters; Effective length is 160 millimeters; Make for anticorrosion stainless steel, prevent that the inner sulfuric acid solution of Molotov cocktail from corroding it, its point for measuring temperature is at the about 1 millimeter place of platinum wire side; One deck blow-out disc is pasted in Molotov cocktail external firing zone 8., can effectively prevent explosion accident to take place, and the Molotov cocktail outermost layer is that 4. the recirculated water chuck seals at plug of usefulness suitable for reading of Molotov cocktail; Wherein two as the cool cycles water entrance 3. to divide other to bore 3 apertures with card punch; The bottom of water jacket is inserted in water inlet, export parallelly with plug, and the outlet aperture is greater than the aperture that intakes; Water inlet is that top is provided with a tank at instrument; Its coolant-temperature gage is consistent with laboratory temperature, can water be stored certain water temperature and room temperature is close in advance before the experiment, in addition the temperature of mouth insertion PT2-100 temperature sensor measurement recirculated water; Through recirculated water it is reduced in the gas combustion process rapidly and emit a large amount of heats, the water vapor rapid condensation that guarantees burning back gas temperature and generation is to room temperature.Because stereomutation ± 0.35% of 1.0 ℃ of gases of the every variation of the temperature of gas adopts recirculated cooling water to guarantee the gas temperature after firing chamber and the burning is descended rapidly, and makes it be in the normal temperature state all the time.1. mixed gas burning bottle appearance gas import/export is connected with the gas analyzer crossbeam, is 2. controlled the height of its liquid level with instrument leveling bottle and eudiometer tube by cock and float.At first open cock in the experimentation and 2. will measure a certain amount of oxygen and make a gift to someone in the Molotov cocktail, connect heating power supply after the cut-out tap after platinum wire begin by secretly reddening, at this moment the temperature of firing chamber begins to heat up when reaching 145.0 ℃ ± 5.0 and to require abundant preheating constant 2-3 minute the time; In the Molotov cocktail of making a gift to someone with a certain amount of gas slowly to be analyzed, in Molotov cocktail, can produce blast simultaneously then, absorb 3-4 time repeatedly; Continuation strengthens electric current to platinum wire; Make chamber temperature rise at 280 ℃ ± 5.0 o'clock, absorption repeatedly 3-5 time is noted necessarily can not sulfuric acid solution being flooded platinum wire; Absorb the 2-3 powered-down repeatedly; Open cooling circulating water simultaneously, absorbing 3-5 time slowly can promote the sulfuric acid solution height until cock and float lower end slowly, when measure 2 temperature and room temperature near the time measure its volume and reading; In like manner remaining sample to be analyzed is got certain volume, carry out repeated experiments, the experimental result of twice parallel laboratory test " repeatability " must satisfy hydrogen 1.0%, and methane 2.0% requires the proof experimental duties to finish.
Be combined into a gas analysis instrument based on gas combustion bottle of the present invention and existing laboratory apparatus,
Experimental program with the our factory coke-oven gas as appearance gas; Measure hydrogen and methane content (1) in its coal gas and accurately measure the oxygen of 25-30 milliliter and squeeze in the Molotov cocktail, (2) begin that energising makes the abundant preheating of oxygen to platinum wire, when chamber temperature during at 280 ℃; Measuring 10 milliliters of left and right sides samples from 15% sulfuric acid absorption bottle slowly sends in the Molotov cocktail; Burning absorbs 6-7 time repeatedly, and 800 ℃ of absorptions 6-7 time of burning are repeatedly continued to be warming up in (3), and powered-down continues to absorb 4-5 time repeatedly; Opening cooling water system simultaneously makes burning gas be cooled to room temperature condition rapidly; (4) gas after the combustion reaction is sent in the potassium hydroxide solution to absorb remove carbon dioxide, and write down the sampling numerical value of above-mentioned experimentation and each reading, calculate the content of hydrogen and methane then according to computing formula.
The assay of experimental program () pure hydrogen
Experiment purpose: checking gaseous combustion bottle is to known hydrogen gas content measurement.
Experimentation is got a certain amount of hydrogen (purity 99.9%) and is deposited in the 7# sulfuric acid absorption bottle its assay; The oxygen of (1) accurately measuring the 25-30 milliliter is squeezed in the Molotov cocktail, and (2) energized begins to make the abundant preheating of oxygen to platinum wire energising, when about 145 ℃ of chamber temperature constant 2 minutes; Measuring a certain amount of hydrogen from 15% sulfuric acid absorption bottle replaces 2 times the transverse beam system of instrument; Measure 10 milliliters of left and right sides hydrogen accurately and slowly send in the Molotov cocktail, begin to have strong explosive reaction 2-3 time, absorb 5-6 time repeatedly rapidly; (3) ceiling temperature with thermometer is set at 150 ℃; The platinum wire power supply is then closed automatically because explosive combustion liberated heat temperature constantly rises, and continues to absorb 3-4 time repeatedly, opens cooling water system simultaneously and makes chamber temperature be cooled to room temperature condition rapidly; (4) when the temperature of the temperature of firing chamber and chilled water is close; Gas after the combustion reaction is sent in the eudiometer tube volume of measuring after its burning, and write down above-mentioned experimentation measure gas volume numerical value and accurate reading numerical value at every turn, and according to reaction principle and computing formula calculating hydrogen content.
Experimental program (two) is measured methane content in the rock gas
Experiment purpose: utilize the mixed gas burning bottle with rock gas (methane content is more than 95.0%); Measure the content of methane and alkane compound; Owing to do not contain hydrogen in the rock gas; Therefore can check the content of alkane compound, and verify the temperature of combustion condition of alkane compound through combustion experiment.(1) accurately measure 30-40 milliliter oxygen and squeeze in the Molotov cocktail, (2) begin energising makes oxygen divide preheating, when chamber temperature reaches 800 ℃; Measure 10 milliliters of left and right sides samples and slowly send into Molotov cocktail; Burning absorbs 6-7 time repeatedly, and powered-down continues to absorb 4-5 time repeatedly, opens the cooling water system cooling; (4) gas after the combustion reaction is sent in the potassium hydroxide absorption bottle to absorb remove carbon dioxide, calculate the content that can calculate methane according to computing formula.The repeatability and the reappearance of its experimental result of contrast experiment through such scheme () and (two) meet the experimental technique accuracy requirement basically.
The oxygen that experimental program (three) is accurately measured the 25-30 milliliter with coke-oven gas as hydrogen and methane content (1) in its coal gas of appearance gas mensuration is squeezed in the Molotov cocktail; (2) begin to make the abundant preheating of oxygen to platinum wire energising; When chamber temperature during at 280 ℃, measure 10 milliliters of left and right sides samples from 15% sulfuric acid absorption bottle and slowly send in the Molotov cocktail, burning absorbs 6-7 time repeatedly; (3) continue to be warming up to 800 ℃ of absorptions 6-7 time of burning repeatedly; Powered-down continues to absorb 4-5 time repeatedly, opens cooling water system simultaneously and makes burning gas be cooled to room temperature condition rapidly, and (4) are sent into the gas after the combustion reaction to absorb in the potassium hydroxide solution and removed carbon dioxide; And write down the sampling numerical value of above-mentioned experimentation and each reading, calculate the content of hydrogen and methane then according to computing formula.
In like manner adopt the experimental provision of hydrogen and methane separation; Utilizing in the Molotov cocktail mensuration coal gas methane (1) to measure 3-4 times remaining gas with to absorb hydrogen in the gas be chemical method equation: H2+CuO=Cu+H2O in cupric oxide burning absorptions side squeezes in the Molotov cocktail to the gas of sample; (2) begin to make the abundant preheating of oxygen to platinum wire energising; When chamber temperature during at 650 ℃, measure 10 milliliters of left and right sides samples from 15% sulfuric acid absorption bottle and slowly send in the Molotov cocktail, burning absorbs 6-7 time repeatedly; Continue to be warming up to 800 ℃ 2-3 time repeatedly; Powered-down continues to absorb 4-5 time repeatedly, opens cooling water system simultaneously and makes burning gas be cooled to room temperature condition rapidly, and (4) are sent into the gas after the combustion reaction to absorb in the potassium hydroxide solution and removed carbon dioxide; And write down the sampling numerical value of above-mentioned experimentation and each reading, converse methane content according to the amount of calculating carbon dioxide then.
In sum; Molotov cocktail in the analysis method for gases of the present invention; Purpose is to solve personal error and the instrument error that existing experimental technique exists in combustion process, possibly exceed unsafe factors such as explosion limits when eliminating in the binary gas mixed explosion combustion process poor repeatability and explosive combustion, reduces the systematic error and the operate miss of experimental apparatus; Improved Molotov cocktail has received effect preferably in real work is used, satisfied different combustion gas components are detected requirement.Gas analyzer is as a kind of chemical formula manual analyzing instrument of classics, has advantages such as simple in structure, low price, maintenance be easy, and this instrument widespread use under lab always, and is usually used in the assay of CO2, O2, CO, H2, hydro carbons etc.Its principle is to utilize solution absorption method to measure CO, CO2 and O2, and CH4 and H2 measure with the explosive combustion method, and residual gas is N2.Owing to look into newly through computer search rope and technology; In the laboratory, utilize the mixed gas burning bottle that the repeatability and the repeatability of experimental technique have been carried out a large amount of experiments and data statistic analysis; Whether the precision of the existing assay method of evaluation of checking property meets the requirements; Through repeatedly same sample and various sample being carried out a large amount of experimental analyses with the method; Calculated between the laboratory GRR to the contrast of gas with various, its determination data shows that the precision of this experiment meets the accuracy requirement of existing assay method, and mixed gas burning bottle of the present invention can satisfy existing experimental technique and accuracy of instrument requirement.It is reasonable that this invention mixed gas burning bottle has project organization; Experimental technique is simple and convenient; It is inhomogeneous to have overcome the narrow and small oxygen mix of former Molotov cocktail blast area; The combustion chambers burn temperature adopts the PT-100 temperature sensor that the combustion experiment process is carried out real-time supervision and measurement, guarantees to burn to light optimal temperature conditions, and skin has designed recirculating cooling water system and increased one deck safety anti-explosive film in the Molotov cocktail firing chamber; Can guarantee to satisfy experimentation temperature of combustion condition and revert to the initial temperature state with burning back rapid decline of gas temperature; The blast casualty accident has been eliminated potential safety hazard and unsafe factor that glass apparatus explosive four is split, the volumetric errors that the heat that produces when reducing explosive combustion simultaneously makes gas temperature raise and produce when effectively preventing the overbreak fried upper-bound limit of gas and oxygen blending ratio.Formulated the technical application scheme according to the foregoing invention content; Temperature monitoring and problems of measurement when burning during the first solution combination gas smoulder; The abundant preheat temperature and the time of oxygen amount and oxygen is got in assurance, and the gas mixing was inhomogeneous when control oxygen was not enough possibly produce the rough burning or the overbreak fried limit; The novel Molotov cocktail of second design increases by a cover recirculating cooling water system, and it is constant rapidly with burning back gas temperature to guarantee to satisfy experimentation temperature of combustion condition, and the volume mistake that the heat that produces when reducing explosive combustion raises gas temperature and produces makes measuring error; The 3rd skin in the firing chamber has increased one deck safety anti-explosive film, effectively prevents to reach when gas from mixing the explosion limits bound casualty accident of blasting.Guarantee that the accurately reasonable measuring repeatability of experimental result satisfies accuracy requirement, shorten the check analysis time simultaneously, reduced experimenter's working strength and safety coefficient.Formulated the technical application scheme according to the foregoing invention content; Temperature monitoring and problems of measurement when burning during the first solution combination gas smoulder; The abundant preheat temperature and the time of oxygen amount and oxygen is got in assurance, and the gas mixing was inhomogeneous when control oxygen was not enough possibly produce the rough burning or the overbreak fried limit; The novel Molotov cocktail of second design increases by a cover recirculating cooling water system, and it is constant rapidly with burning back gas temperature to guarantee to satisfy experimentation temperature of combustion condition, and the volume mistake that the heat that produces when reducing explosive combustion raises gas temperature and produces makes measuring error; The 3rd skin in the firing chamber has increased one deck safety anti-explosive film, effectively prevents to reach when gas from mixing the explosion limits bound casualty accident of blasting.Guarantee that the accurately reasonable measuring repeatability of experimental result satisfies accuracy requirement, shorten the check analysis time simultaneously, reduced experimenter's working strength and safety coefficient.
Claims (1)
1. the assay method of hydrogen and methane in manufactured gas, manufactured fuel gas's component is characterized in that:
A, utilize chemical absorption process to absorb the CO among the manufactured gas, manufactured fuel gas
2, O
2, CnHm, CO;
B, get and absorbed CO
2, O
2, CnHm, CO manufactured gas, manufactured fuel gas and O
2, wherein absorbed CO
2, O
2, CnHm, CO and comprise H
2, CH
4And N
2Manufactured gas, manufactured fuel gas and O
2Ratio be 1: 3～4;
C, at first with O
2Place Molotov cocktail, the Molotov cocktail internal temperature is risen to 180 ℃, kept 10～15 seconds, on the basis that keeps this temperature, put into the above-mentioned H of containing then
2, CH
4And N
2The manufactured gas, manufactured fuel gas, to H wherein
2Absorb;
D, the temperature in the Molotov cocktail is risen to 650 ℃, to CH wherein
4Absorb;
Wherein, in Molotov cocktail, absorb H
2And CH
4Being divided into for two steps during gas carries out, and per step absorbs 4～5 times at least repeatedly;
E, reduce temperature to normal temperature state in the Molotov cocktail at last, absorb the CO that produces
2With measure volume after combustion;
Wherein, Described Molotov cocktail structure is: comprise gas inlet and outlet (10) and cock (9) are arranged on firing chamber (12), the liquid level equilibrium device (8) that is connected with firing chamber (12), firing chamber (12), bottom, firing chamber (12) is combustion chamber sealing base (13); It is characterized in that: the outside of (12) is cooling jacket (11) in the firing chamber; Cooling jacket (11) bottom and combustion chamber sealing base (13) are fixing, and gas inlet and outlet (10) and cock (9) place cooling jacket (11) top, are chilled water seal (6) in cooling jacket (11) upper end; Cooling water inlet (1) and coolant outlet (2) are installed, chilled water thermometric thermal resistance (3) is arranged on cooling jacket (11); Platinum wire protection tube (7) and firing chamber thermometric thermal resistance (5) pass sealed base (13) and place inside, firing chamber (12), in platinum wire protection tube (7) inside platinum heater strip (4) are arranged.
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| Application Number | Priority Date | Filing Date | Title |
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| CN104897515A (en) * | 2015-06-16 | 2015-09-09 | 贵州兴化化工股份有限公司 | Orsat gas analyzer |
| CN104977394B (en) * | 2015-07-16 | 2018-10-12 | 莱芜市安诺美姿自动化仪表有限公司 | A kind of Gas Components and calorific value on-line measurement device |
| WO2018223342A1 (en) * | 2017-06-08 | 2018-12-13 | 高汴娜 | Method for detecting dimethyl ether in combustible gas |
| CN113281454A (en) * | 2021-05-28 | 2021-08-20 | 金川镍钴研究设计院有限责任公司 | Laboratory quantitative detection method for liquid nickel carbonyl raw material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6742383B2 (en) * | 2002-11-05 | 2004-06-01 | Industrial Technology Research Institute | Diluter to reduce quantity of micro particles in the air so as to facilitate calculation of concentration of the micro particles in the air |
| CN1715876A (en) * | 2005-07-12 | 2006-01-04 | 吉林大学 | Detecting method and device for methane concentration |
| CN1979172A (en) * | 2005-12-06 | 2007-06-13 | 上海神开科技工程有限公司 | Gas analyzing method and apparatus |
| CN101109685A (en) * | 2007-08-07 | 2008-01-23 | 山西大学 | Method and device for detecting concentration of methane gas |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6742383B2 (en) * | 2002-11-05 | 2004-06-01 | Industrial Technology Research Institute | Diluter to reduce quantity of micro particles in the air so as to facilitate calculation of concentration of the micro particles in the air |
| CN1715876A (en) * | 2005-07-12 | 2006-01-04 | 吉林大学 | Detecting method and device for methane concentration |
| CN1979172A (en) * | 2005-12-06 | 2007-06-13 | 上海神开科技工程有限公司 | Gas analyzing method and apparatus |
| CN101109685A (en) * | 2007-08-07 | 2008-01-23 | 山西大学 | Method and device for detecting concentration of methane gas |
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