CN103543171A - System and method for measuring reaction velocity constant in process of producing gas by using solid fuel - Google Patents
System and method for measuring reaction velocity constant in process of producing gas by using solid fuel Download PDFInfo
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Abstract
The invention discloses a system and method for measuring a reaction velocity constant in a process of producing a gas by using a solid fuel. The system comprises a carbon dioxide bottle, an oxygen bottle, a nitrogen bottle, a gas flow meter, a water vapor generator, a reaction furnace, a gas analyzer and a temperature recorder. According to the method, velocity constants of reactions of the solid fuel with oxygen, water vapor and carbon dioxide can be determined: during the measurement of the velocity constant of reaction of the solid fuel with the oxygen, an ignition point of coal in oxygen is determined, the diffusion rate of the oxygen under an actual temperature after the solid fuel is combusted is used for characterizing the combustion rate; and during the measurement of the velocity constants of reactions of the solid fuel with the carbon dioxide and the water vapor, actual reaction velocity speeds are determined under different temperatures, and thus the velocity constants of reactions are obtained after processing. By only using little solid fuel, the velocity constants of reactions of the solid fuel with the oxygen, the carbon dioxide and the water vapor can be obtained, and basic data is provided for analog computation of a solid fuel reactor.
Description
Technical field
The present invention relates to the mensuration of solid fuel combustion gas processed and material gas process reaction reactivity parameter, in particular, the mensuration System and method for of rate constant while relating to solid fuel and oxygen, water vapour and carbon dioxide reaction.
Background technology
Solid fuel comprises the solid-state combustibles such as coal, living beings, coke.Solid fuel combustion gas processed and material gas process mainly contain reacting of carbon and oxygen in solid fuel, carbon dioxide, water vapour.Reaction equation is as follows:
Carbon reacts with oxygen: C+O
2=CO
2Δ H=-393.7kJ/mol
Carbon reacts with water vapour: C+H
2o=CO+H
2Δ H=+131.0kJ/mol
Carbon reacts with carbon dioxide: C+CO
2=2CO Δ H=+172.2kJ/mol
Determining of above-mentioned reaction velocity has important effect for solid fuel gasification engineering design and production run.Solid fuel gasification process reaction speed expression formula is:
r=kc
n
In formula: r---reaction velocity, kmol/ (m
3h);
K---rate constant, h
-1;
C---reactant concentration, kmol/m
3;
N---the order of reaction (generally can be considered 1);
Rate constant k is the important parameter that considers chemical reaction velocity and transmittance process speed, and its expression formula is:
In formula: k
g---transmission speed constant, h
-1;
K
r---microreaction velocity constant, h
-1;
The hole efficiency of η---solid fuel particle.
The Arrhenius expression formula of mi-crochemistry rate constant is:
k=k
0e
-E/RT
In formula: k
0---pre-exponential factor, h
-1;
E---energy of activation, kJ/kmol;
R---gas law constant, 8.314kJ/ (kmolK);
T---temperature of reaction, K.
The rate constant difference of differential responses is larger, for solid fuel and oxygen reaction, mainly considers the impact of transmission speed constant, need to measure solid-fuelled burning-point.For reacting of solid fuel and carbon dioxide and water vapour, mainly consider the impact of microreaction velocity constant, need to measure pre-exponential factor and energy of activation.
At present, the mensuration of solid fuel gasification rate constant adopts determination of ignition point device to measure burning-point, and the pre-exponential factor of solid fuel and carbon dioxide and steam reaction and energy of activation generally adopt weight-loss method to measure with thermobalance.Adopt the equipment of said method more, mensuration process is more complicated, and the impact of different factors is difficult to quantitative difference, and can not directly draw the rate constant of solid fuel and oxygen, carbon dioxide and water vapour.
Summary of the invention
For the problems referred to above, the invention provides a kind of mensuration System and method for of solid fuel gas-making process rate constant, for the rate constant of solid fuel and oxygen, water vapour, carbon dioxide, all can measure easily.
In order to solve the problems of the technologies described above, the present invention is achieved by following technical scheme:
A mensuration system for gas-making process reactivity parameter, this system comprises carbon dioxide cylinder, welding bottle, nitrogen cylinder, gas meter, steam generator, reacting furnace, gas analyzer and moisture recorder;
Described carbon dioxide cylinder is by being provided with the pipeline of the first valve, described welding bottle is by being provided with the pipeline of the second valve, described nitrogen cylinder is connected to described gas meter by being provided with the pipeline of the 3rd valve, described gas meter is connected in the entrance of described reacting furnace by being provided with the pipeline of the 5th valve, described gas meter is connected in described steam generator by being provided with the pipeline of the 4th valve, described steam generator is connected in the entrance of described reacting furnace by being provided with the pipeline of the 6th valve, the outlet of described reacting furnace is connected in described gas analyzer, in described reacting furnace, be provided with thermocouple thermometer, described thermocouple thermometer is for being delivered to described moisture recorder by temperature signal.
Wherein, the reaction tube of described reacting furnace adopts alundum tube, and type of heating is electrical heating.
An assay method for solid fuel gas-making process reactivity parameter, the mensuration of solid fuel and oxygen reaction velocity constant is carried out in accordance with the following steps:
(1) 5~10 grams of solid fuels are put in reacting furnace;
(2) open the second valve and the 5th valve, with the flow of 15~30L/min, oxygen is passed into reacting furnace;
(3) reacting furnace heats reaction tube with the heating rate of 10~20 ℃/min, and simultaneous temperature registering instrument records reaction tube temperature of charge, draws combustion reaction heating curve;
(4) according to combustion reaction heating curve and reacting furnace electrical heating heating curve, draw solid-fuelled burning-point;
(5) according to solid-fuelled burning-point, calculate the rate constant of solid fuel and oxygen.
An assay method for solid fuel gas-making process reactivity parameter, the mensuration of solid fuel and carbon dioxide reaction velocity constant is carried out in accordance with the following steps:
(1) prepare solid fuel coke specimen;
(2) 5~10 grams of solid fuel coke specimens are put in reacting furnace;
(3) open the first valve and the 5th valve, with the flow of 15~30L/min, carbon dioxide is passed into reacting furnace;
(4) reacting furnace is heated to 700 ℃ and constant temperature, the content of gas analyzer assaying reaction outlet of still CO with the heating rate of 10~20 ℃/min by reaction mass;
(5) reaction mass continues heat up 50 ℃ and constant temperature, the content of gas analyzer assaying reaction outlet of still CO;
(6) circulation step (5), until reaction mass reaches 1200 ℃;
(7) according to CO content at this reaction mass temperature of the each reaction mass temperature of measuring of moisture recorder and gas analysis-e/or determining, calculate solid fuel and carbon dioxide reaction velocity constant.
An assay method for solid fuel gas-making process reactivity parameter, the mensuration of solid fuel and steam reaction velocity constant is carried out in accordance with the following steps:
(1) prepare solid fuel coke specimen;
(2) 5~10 grams of solid fuel coke specimens are put in reacting furnace;
(3) distilled water in steam generator heated and be stabilized in the uniform temperature within the scope of 50~90 ℃;
(4) open the 3rd valve, the 4th valve and the 6th valve, with the flow of 15~30L/min, nitrogen is passed into steam generator, water vapour enters reacting furnace after mixing with nitrogen;
(5) reacting furnace is heated to 650 ℃ and constant temperature, gas analyzer assaying reaction outlet of still CO, CO with the heating rate of 10~20 ℃/min by reaction mass
2content;
(6) reaction mass continues heat up 50 ℃ and constant temperature, gas analyzer assaying reaction outlet of still CO, CO
2content;
(7) circulation step (6), until reaction mass reaches 1150 ℃;
(8) according to CO, CO at this reaction mass temperature of the each reaction mass temperature of measuring of moisture recorder and gas analysis-e/or determining
2content, calculates solid fuel and steam reaction velocity constant.
Wherein, in the mensuration process of the mensuration of solid fuel and carbon dioxide reaction velocity constant, solid fuel and steam reaction velocity constant, the solid fuel coke specimen of preparing of step (1) specifically carries out in accordance with the following steps:
A. feed coal is sieved into the sample that granularity is 3~6mm, sample is placed in reacting furnace after weighing;
B. open the 3rd valve and the 5th valve, the flow by the nitrogen in nitrogen cylinder with 15~30L/min passes in reacting furnace,
C. reacting furnace is heated to reaction tube after 850 ℃ with the heating rate of 10~20 ℃/min, and with the gas composition of gas analyzer analytical reactions outlet of still, the nitrogen content that records Exhaust Gas is that more than 98% rear reacting furnace stops heating;
D. reacting furnace is cooled to after normal temperature, and the coke taking out in material holder is measured the coke specimen of use as solid fuel rate constant.
The invention has the beneficial effects as follows:
Adopt mensuration System and method for of the present invention, only need with a small amount of solid fuel, can in a system, record the experimental data of solid fuel and oxygen, carbon dioxide, steam reaction, by three kinds of methods, carry out data processing respectively again, and then obtain the rate constant of aforementioned three reactions, for the analog computation of solid fuel reactor provides basic data.Because mensuration system of the present invention is the operating process of simulation real reaction device, therefore institute's determination data can react actual production process, data are comparatively reliable, for actual engineering design and production operation provide important parameter, are the simulation optimizing of the solid fuel gasification process condition of providing convenience.
Accompanying drawing explanation
Accompanying drawing is mensuration system architecture schematic diagram provided by the present invention.
In figure: 1, carbon dioxide cylinder; 2, welding bottle; 3, nitrogen cylinder; 4, gas meter; 5, steam generator; 6, reacting furnace; 7, gas analyzer; 8, moisture recorder; 9, the first valves; 10, the second valves; 11, the three valves; 12, the four valves; 13, the five valves; 14, the six valves.
Embodiment
For further understanding summary of the invention of the present invention, feature and effect, hereby exemplify following examples, and coordinate accompanying drawing to be described in detail as follows:
As shown in drawings, first the present embodiment has proposed a kind of mensuration system of solid fuel gas-making process rate constant, mainly comprises carbon dioxide cylinder 1, welding bottle 2, nitrogen cylinder 3, gas meter 4, steam generator 5, reacting furnace 6, gas analyzer 7, moisture recorder 8.The reaction tube of reacting furnace 6 adopts alundum tube, and in reaction tube, bottom is provided with material holder, can pack and draw off reaction mass into; Reacting furnace 6 use electrical heating, and be provided with temperature controller to carry out temperature programme and temperature control.Steam generator 5 is also can control the warm water storage tank of temperature with electrical heating, can make the saturated vapor of nitrogen and evaporation fully mix.Gas analyzer 7 is mainly used in analyzing the content of carbon monoxide, carbon dioxide.
In reacting furnace 6, be provided with thermocouple thermometer, thermocouple thermometer is for being delivered to moisture recorder 8 by temperature signal.
The nitrogen of the oxygen of the carbon dioxide of carbon dioxide cylinder 1, welding bottle 2, nitrogen cylinder 3 can enter separately gas meter 4 and measure.After the metering of gas meter 4, carbon dioxide and oxygen directly enters reacting furnace 6; Nitrogen can directly enter reacting furnace 6, also can enter reacting furnace 6 together with water vapour through steam generator 5.The gas of reacting furnace 6 outlets is discharged after gas analyzer 7, and the thermometric temperature of reaction in reacting furnace 6 is delivered to moisture recorder 8.
The present embodiment has also proposed the assay method of solid fuel gas-making process rate constant, and concrete steps are as follows.
(1) mensuration of solid fuel and oxygen reaction velocity constant
1. first 5~10 grams of solid fuels are put in the material holder of reaction tube in reacting furnace 6;
2. the second valve 10 and the 5th valve 13 of opening welding bottle 2, pass into 15~30L/min oxygen in the reaction tube of reacting furnace 6;
3. reacting furnace 6 heats reaction tube with the heating rate of 10~20 ℃/min, and simultaneous temperature registering instrument 8 records reaction tube temperature of charge, draws combustion reaction heating curve;
4. operating personnel, according to combustion reaction heating curve and reacting furnace 6 electrical heating heating curves, draw solid-fuelled burning-point.Before combustion reaction starts, combustion reaction heating rate is electrically heated constant heating rate; After combustion reaction starts, until before the perfect combustion of solid fuel sample, because burning heat release increases sharply combustion reaction heating rate, the residing straight line of heating curve of this combustion reaction time section and the intersection point of reacting furnace 6 electrical heating heating curves are burning-point.
5. according to solid-fuelled burning-point and related data, calculate the rate constant of solid fuel and oxygen.
During due to low temperature, the reaction velocity of solid fuel and oxygen is very low, once temperature reaches burning-point, the reaction velocity of solid fuel and oxygen is very fast, and reaction velocity depends primarily on oxygen to the rate of propagation on solid fuel particle surface.Burning-point according to the solid fuel recording in oxygen, determines the oxygen quality transfer coefficient when burning-point, can by the Physical Constants at this temperature, calculate the rate constant of solid fuel and oxygen, and calculating formula is as follows:
Sh=2+0.552Re
0.53·Sc
0.33
D---the oxygen quality transfer coefficient when burning-point, m
2/ h;
F---solid fuel particle bed specific surface area, m
2/ m
3;
D
k---solid fuel particle diameter, m;
Sh, Re, Sc---sherwood number, Reynolds number, the schmidt number of solid fuel particle flow through in solid fuel gasification process reaction agent;
U, ν---momentum coefficient of diffusion and the mass diffuse coefficient of solid fuel particle, m are flow through in solid fuel gasification process reaction agent
2/ h.
(2) mensuration of solid fuel and carbon dioxide reaction velocity constant
1. the preparation of solid fuel coke specimen.
In solid fuel, contain volatile substance, while measuring the rate constant of solid fuel and carbon dioxide, first will prepare coke specimen.Feed coal is sieved into the sample that granularity is 3~6mm, after sample is weighed, is placed in the material holder of reaction tube in reacting furnace 6.Open the 3rd valve 11 and the 5th valve 13, flow by the nitrogen in nitrogen cylinder 3 with 15~30L/min passes in the reaction tube of reacting furnace 6, reacting furnace 6 is heated to reaction tube after 850 ℃ with the heating rate of 10~20 ℃/min, gas composition with gas analyzer 7 analytical reactions stove 6 outlets, until nitrogen content of Exhaust Gas is more than 98%, reacting furnace 6 stops heating.Reacting furnace 6 is cooled to after normal temperature, and the coke taking out in material holder is measured the coke specimen of use as solid fuel rate constant.
2. carbon dioxide gasification process basic data is measured.
A. 5~10 grams of solid fuel coke specimens are put in the material holder of reaction tube in reacting furnace 6;
B. the first valve 9 and the 5th valve 13 of opening carbon dioxide cylinder 2, pass into carbon dioxide through gas meter 4 in the reaction tube of reacting furnace 6, and the flow of carbon dioxide is 15~30L/min;
D. reaction mass continues to heat up 50 ℃, and constant temperature certain hour, with the content of gas analyzer 7 assaying reaction stove 6 outlet CO, until reaction mass reaches 1200 ℃.
3. according to the each reaction mass temperature T of measuring of moisture recorder
rwith the CO content y measuring at this temperature
cO, and related data, calculate solid fuel and carbon dioxide reaction velocity constant.Calculating formula is as follows:
In formula:
---solid fuel coke specimen and carbon dioxide reaction be take the rate constant that quality is benchmark, mol/ (gh) or kmol/ (kgh);
Da---dimensionless number;
V
0---T
0cO at temperature
2measuring flow, mol/h;
T
r---reaction mass temperature, K;
T
0---atmospheric temperature, K;
Y
cO---reacting furnace 6 outlet CO content, minute subfraction;
M
c, t-1---a upper time period solid fuel coke specimen amount, g;
---the rate constant that in the upper time period, solid fuel coke specimen and carbon dioxide quality are benchmark, mol/ (gh) or kmol/ (kgh);
τ
t-1---the reaction constant temperature time in the upper time period, h.
M
c, mol---the relative molecular weight of carbon;
By the rate constant recording
k in the Arrhenius universal expression formula of instead of chemical reaction velocity, and both members is taken the logarithm:
by rate constant under the resulting different temperatures of above-mentioned experiment
logarithm and the inverse of reaction mass temperature press linear function and return, can obtain energy of activation and the pre-exponential factor of solid fuel coke specimen and carbon dioxide reaction, thereby can calculate the rate constant at any temperature by Arrhenius universal expression formula
and then calculate the rate constant of solid fuel coke specimen and carbon dioxide reaction
calculating formula is as follows:
V
mol---the volume of 1 mole of carbon dioxide, 22.4L/mol or 22.4m
3/ kmol;
The bulk density of ρ---coke specimen, kg/m
3.
(3) solid fuel and steam reaction velocity constant determination step
1. the preparation of solid fuel coke specimen.
Preparation method measures with solid fuel and carbon dioxide reaction velocity constant.
2. steam gasification process basic data is measured.
A. 5~10 grams of solid fuel coke specimens are put in the material holder of reaction tube in reacting furnace 6;
B. the steam generator 5 of fetching boiling water, heats distilled water wherein and is stabilized in uniform temperature (50~90 ℃),
C. open the 3rd valve 11, the 4th valve 12, the 6th valve 14, through gas meter 4, nitrogen is passed into water vapour
In generator 5, the flow of nitrogen is 15~30L/min; Water vapour enters in the reaction tube of reacting furnace 6 after mixing with nitrogen;
E. reaction mass continues to heat up 50 ℃, and constant temperature certain hour, with gas analyzer 7 assaying reaction stove 6 outlet CO, CO
2content, until reaction mass reaches 1250 ℃.
3. according to the each reaction mass temperature T of measuring of moisture recorder
rwith the CO measuring at this temperature, CO
2content, and related data, calculate solid fuel and steam reaction velocity constant.Calculating formula is as follows:
In formula:
---solid fuel coke specimen and steam reaction be take the rate constant that quality is benchmark, mol/ (gh) or kmol/ (kgh);
---nitrogen standard volume flow, mol/h;
C
gas, NTP---the concentration of gas under the status of criterion, 22.4L/mol or 22.4m
3/ kmol;
---the concentration (by saturation temperature calculated) of water vapour under reactiveness, mol/L or kmol/m
3;
---in the upper time period, the quality of coal and steam reaction is benchmark rate constant, mol/ (gh) or kmol/ (kgh);
τ
t-1---the reaction constant temperature time in the upper time period, h.
M
c, t-1---a upper time period coke specimen amount, g;
M
c, mol---the relative molecular weight of carbon;
M
m---the molal quantity of unit mass coke specimen, kmol/kg.
By the rate constant recording
k in the Arrhenius universal expression formula of instead of chemical reaction velocity, and both members is taken the logarithm:
by rate constant under the resulting different temperatures of above-mentioned experiment
logarithm and the inverse of reaction mass temperature press linear function and return, can obtain energy of activation and the pre-exponential factor of solid fuel coke specimen and steam reaction, thereby can calculate the rate constant at any temperature by Arrhenius universal expression formula
and then calculate the rate constant of solid fuel coke specimen and steam reaction
calculating formula is as follows:
Although the preferred embodiments of the present invention are described with preferred embodiment by reference to the accompanying drawings above; but the present invention is not limited to above-mentioned embodiment; above-mentioned embodiment is only schematic; be not restrictive; those of ordinary skill in the art is under enlightenment of the present invention; not departing from the scope situation that aim of the present invention and claim protect, can also make the concrete conversion of a lot of forms, within these all belong to protection scope of the present invention.
Claims (5)
1. a mensuration system for solid fuel gas-making process reactivity parameter, is characterized in that, this system comprises carbon dioxide cylinder, welding bottle, nitrogen cylinder, gas meter, steam generator, reacting furnace, gas analyzer and moisture recorder;
Described carbon dioxide cylinder is by being provided with the pipeline of the first valve, described welding bottle is by being provided with the pipeline of the second valve, described nitrogen cylinder is connected to described gas meter by being provided with the pipeline of the 3rd valve, described gas meter is connected in the entrance of described reacting furnace by being provided with the pipeline of the 5th valve, described gas meter is connected in described steam generator by being provided with the pipeline of the 4th valve, described steam generator is connected in the entrance of described reacting furnace by being provided with the pipeline of the 6th valve, the outlet of described reacting furnace is connected in described gas analyzer, in described reacting furnace, be provided with thermocouple thermometer, described thermocouple thermometer is for being delivered to described moisture recorder by temperature signal.
2. the mensuration system of a kind of solid fuel gas-making process reactivity parameter according to claim 1, is characterized in that, the reaction tube of described reacting furnace adopts alundum tube, and type of heating is electrical heating.
3. an assay method for solid fuel gas-making process reactivity parameter, is characterized in that, the mensuration of solid fuel and oxygen reaction velocity constant is carried out in accordance with the following steps:
(1) 5~10 grams of solid fuels are put in reacting furnace;
(2) open the second valve and the 5th valve, with the flow of 15~30L/min, oxygen is passed into reacting furnace;
(3) reacting furnace heats reaction tube with the heating rate of 10~20 ℃/min, and simultaneous temperature registering instrument records reaction tube temperature of charge, draws combustion reaction heating curve;
(4) according to combustion reaction heating curve and reacting furnace electrical heating heating curve, draw solid-fuelled burning-point;
(5) according to solid-fuelled burning-point, calculate the rate constant of solid fuel and oxygen.
3. an assay method for solid fuel gas-making process reactivity parameter, is characterized in that, the mensuration of solid fuel and carbon dioxide reaction velocity constant is carried out in accordance with the following steps:
(1) prepare solid fuel coke specimen;
(2) 5~10 grams of solid fuel coke specimens are put in reacting furnace;
(3) open the first valve and the 5th valve, with the flow of 15~30L/min, carbon dioxide is passed into reacting furnace;
(4) reacting furnace is heated to 700 ℃ and constant temperature, the content of gas analyzer assaying reaction outlet of still CO with the heating rate of 10~20 ℃/min by reaction mass;
(5) reaction mass continues heat up 50 ℃ and constant temperature, the content of gas analyzer assaying reaction outlet of still CO;
(6) circulation step (5), until reaction mass reaches 1200 ℃;
(7) according to CO content at this reaction mass temperature of the each reaction mass temperature of measuring of moisture recorder and gas analysis-e/or determining, calculate solid fuel and carbon dioxide reaction velocity constant.
4. an assay method for solid fuel gas-making process reactivity parameter, is characterized in that, the mensuration of solid fuel and steam reaction velocity constant is carried out in accordance with the following steps:
(1) prepare solid fuel coke specimen;
(2) 5~10 grams of solid fuel coke specimens are put in reacting furnace;
(3) distilled water in steam generator heated and be stabilized in the uniform temperature within the scope of 50~90 ℃;
(4) open the 3rd valve, the 4th valve and the 6th valve, with the flow of 15~30L/min, nitrogen is passed into steam generator, water vapour enters reacting furnace after mixing with nitrogen;
(5) reacting furnace is heated to 650 ℃ and constant temperature, gas analyzer assaying reaction outlet of still CO, CO with the heating rate of 10~20 ℃/min by reaction mass
2content;
(6) reaction mass continues heat up 50 ℃ and constant temperature, gas analyzer assaying reaction outlet of still CO, CO
2content;
(7) circulation step (6), until reaction mass reaches 1150 ℃;
(8) according to CO, CO at this reaction mass temperature of the each reaction mass temperature of measuring of moisture recorder and gas analysis-e/or determining
2content, calculates solid fuel and steam reaction velocity constant.
5. according to the assay method of a kind of solid fuel gas-making process reactivity parameter described in claim 3 or 4, it is characterized in that, the solid fuel coke specimen of preparing of step (1) specifically carries out in accordance with the following steps:
A. feed coal is sieved into the sample that granularity is 3~6mm, sample is placed in reacting furnace after weighing;
B. open the 3rd valve and the 5th valve, the flow by the nitrogen in nitrogen cylinder with 15~30L/min passes in reacting furnace,
C. reacting furnace is heated to reaction tube after 850 ℃ with the heating rate of 10~20 ℃/min, and with the gas composition of gas analyzer analytical reactions outlet of still, the nitrogen content that records Exhaust Gas is that more than 98% rear reacting furnace stops heating;
D. reacting furnace is cooled to after normal temperature, and the coke taking out in material holder is measured the coke specimen of use as solid fuel rate constant.
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CN108872295A (en) * | 2018-03-23 | 2018-11-23 | 中国石油天然气股份有限公司 | Method and device for determining ignition parameters of crude oil |
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