CN108982588B - System and method for determining fuel chemistry by using oxygen bomb calorimeter - Google Patents

System and method for determining fuel chemistry by using oxygen bomb calorimeter Download PDF

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CN108982588B
CN108982588B CN201810503045.9A CN201810503045A CN108982588B CN 108982588 B CN108982588 B CN 108982588B CN 201810503045 A CN201810503045 A CN 201810503045A CN 108982588 B CN108982588 B CN 108982588B
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oxygen
reaction
bomb calorimeter
fuel
oxygen bomb
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CN108982588A (en
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张亚宁
李炳熙
刘丙旭
姜宝成
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Harbin Institute of Technology
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Abstract

Determination of fuel chemistry using oxygen bomb calorimeter
Figure DDA0001670458530000011
The invention relates to determining fuel chemistry using an oxygen bomb calorimeter
Figure DDA0001670458530000012
Systems and methods of (1). The invention aims to solve the problem that the fuel chemistry can not be determined for the fuel with unknown element components
Figure DDA0001670458530000013
Estimating fuel chemistry based on empirical formula
Figure DDA0001670458530000014
Usually with large errors. Determination of fuel chemistry using oxygen bomb calorimeter
Figure DDA0001670458530000015
The system comprises an oxygen cylinder, an oxygen bomb calorimeter, a temperature sensor, a first pressure sensor, a first valve, a second valve, a filter, a dryer, a vacuum pump, a gas analyzer and a second pressure sensor; the outlet of the oxygen cylinder is connected with the inlet of the oxygen bomb calorimeter through a first valve, the outlet of the oxygen bomb calorimeter is connected with the inlet of the filter through a second valve, the outlet of the filter is connected with the inlet of the dryer, the outlet of the dryer is connected with the inlet of the vacuum pump, and the outlet of the vacuum pump is connected with the gas analyzer. The invention is used for determining fuel chemistry
Figure DDA0001670458530000016
The field of (1).

Description

System and method for determining fuel chemistry by using oxygen bomb calorimeter
Technical Field
The invention relates to the determination of fuel chemistry using an oxygen bomb calorimeter
Figure GDA0002595868850000012
Systems and methods of (1).
Background
Figure GDA0002595868850000013
Is the maximum work theoretically done by a material reversibly changing to a silent state in equilibrium with the environment, and the maximum work done due to imbalance of heat and force is physical
Figure GDA0002595868850000014
The maximum work that can be done due to compositional and concentration imbalances is chemical
Figure GDA0002595868850000015
Of fuel
Figure GDA0002595868850000016
Mainly chemical
Figure GDA0002595868850000017
Chemistry in the analysis and evaluation of energy quality, economics, environmental effects, ecological impact, reaction apparatus, conversion processes and utilization systems of fuels
Figure GDA0002595868850000018
The determination of (a) is a precondition, and is also a first step.
Fuel chemistry
Figure GDA0002595868850000019
The determination method mainly comprises a theoretical deduction method and an empirical formula correction method, and the two methods are used for determining the fuel chemistry
Figure GDA00025958688500000110
The invention provides a novel method which is based on chemistry and has no universality, and an empirical formula correction method is easy to cause larger errors
Figure GDA00025958688500000111
By definition of (1), a method for determining fuel chemistry using an oxygen bomb calorimeter is proposed
Figure GDA00025958688500000112
Method of fuel chemistry
Figure GDA00025958688500000113
The new method and formula of accurate determination provide theoretical basis and data reference.
And (3) theoretical deduction:
theoretical extrapolation algorithm to determine chemistry
Figure GDA00025958688500000114
It is premised on the elemental composition that makes up the fuel. To determine the chemistry of the various elements
Figure GDA00025958688500000115
Firstly, a reasonable and convenient environment model is established, namely, besides the reference state (pressure and temperature) of the specified environment, reference substances of various elements and the concentration of the elements in the environment are selected. The actual ambient pressure and temperature are usually off the reference state, and the reference state is still adopted
Figure GDA00025958688500000116
Calculation will result in errors, and therefore temperature correction coefficients are often introduced for correction.
Empirical formula correction:
the fuels used in practice are usually complex substances containing many components whose composition is difficult to determine with precision, and in particular solid fuels are often composed of an undefined molecular geometry, so that a plurality of different computational chemistries have been proposed
Figure GDA00025958688500000117
The approximate expression of (c). Such as Rant, Xinze, Xichuan and Fanquilian formulas, but these estimation formulas are relatively coarse and have large errors, which affect the quality of analysis, such as Rant and Xichuan Fanquili formulas which do not consider fuel component pairs
Figure GDA00025958688500000118
The value impact, the formal political formulation, requires knowledge of the detailed elemental analysis data of the fuel, which is often not readily available and less applicable in engineering.
In summary, fuel chemistry
Figure GDA00025958688500000119
The determination method mainly comprises the following steps: (1) for fuel with known element components, a reasonable and convenient environment model is established to obtain element reference
Figure GDA00025958688500000120
And the temperature correction coefficient is adopted for correction. (2) Estimating fuel by empirical formula
Figure GDA00025958688500000121
The value is obtained.
Disclosure of Invention
The invention aims to solve the problem that the existing method for determining fuel chemistry based on the known element composition of a theoretical deduction algorithm is adopted
Figure GDA00025958688500000122
While fuel chemistry cannot be determined for fuels of unknown elemental composition
Figure GDA0002595868850000021
Estimating fuel chemistry based on empirical formula
Figure GDA0002595868850000022
Usually with large errors, an oxygen bomb calorimeter is proposed to determine fuel chemistry
Figure GDA0002595868850000023
Systems and methods of (1).
Determination of fuel chemistry using oxygen bomb calorimeter
Figure GDA0002595868850000024
Is a system ofThe system comprises an oxygen cylinder, an oxygen bomb calorimeter, a temperature sensor, a first pressure sensor, a first valve, a second valve, a filter, a dryer, a vacuum pump, a gas analyzer and a second pressure sensor;
an outlet of the oxygen cylinder is connected with an inlet of the oxygen bomb calorimeter through a first valve, an outlet of the oxygen bomb calorimeter is connected with an inlet of a filter through a second valve, an outlet of the filter is connected with an inlet of a dryer, an outlet of the dryer is connected with an inlet of a vacuum pump, and an outlet of the vacuum pump is connected with a gas analyzer;
a first pressure sensor is arranged between the oxygen cylinder and the first valve and used for measuring the pressure of oxygen in the oxygen cylinder; a temperature sensor and a second pressure sensor are arranged in the oxygen bomb calorimeter and are used for measuring the temperature and the pressure in the oxygen bomb calorimeter.
Determination of fuel chemistry using oxygen bomb calorimeter
Figure GDA0002595868850000025
The method comprises the following specific processes:
step one, build fuel chemistry
Figure GDA0002595868850000026
Reversible separation-reversible reference reaction-reversible diffusion multi-process thermodynamic model;
step two, based on fuel chemistry
Figure GDA0002595868850000027
Reversible separation-reversible reference reaction-reversible diffusion multi-process thermodynamic model for respectively establishing fuel separation
Figure GDA0002595868850000028
Reaction of
Figure GDA0002595868850000029
Diffusion
Figure GDA00025958688500000210
The expression of (1);
based on fuel separation
Figure GDA00025958688500000211
Reaction of
Figure GDA00025958688500000212
Diffusion
Figure GDA00025958688500000213
Expression of (2) establishing fuel chemistry
Figure GDA00025958688500000214
The expression of (1);
step three, multiple processes of oxygen and calibration substances in fuel
Figure GDA00025958688500000215
Reacting in the characteristic measurement system, obtaining the mass change of the filter and the dryer through the filter and the dryer, and obtaining the gas components after the reaction through a gas analyzer; measuring the reaction heat of oxygen and a calibration substance by an oxygen bomb calorimeter;
step four, based on mass change of the filter and the dryer, gas composition after reaction, oxygen and calibration material reaction heat correction separation in step two
Figure GDA00025958688500000216
Reaction of
Figure GDA00025958688500000217
Diffusion
Figure GDA00025958688500000218
And chemistry
Figure GDA00025958688500000219
To obtain a corrected fuel separation
Figure GDA00025958688500000220
Reaction of
Figure GDA00025958688500000221
Diffusion
Figure GDA00025958688500000222
And chemistry
Figure GDA00025958688500000223
The invention has the beneficial effects that:
a: the main innovation of the project is that the fuel chemistry is determined based on the traditional methods such as theoretical calculation, empirical correction and the like
Figure GDA00025958688500000224
Further proposes to determine the fuel chemistry by using an oxygen bomb calorimeter in combination with theory and experiment
Figure GDA00025958688500000225
Of fuel chemistry
Figure GDA00025958688500000226
Provides a new idea for experimental determination and instrument development.
B: the second innovation of the project is that the experimental measurable quantity of the fuel combustion thermal effect is taken as a bridge, and a global multi-process thermodynamic model of oxygen reversible separation, fuel reversible reference reaction and product reversible diffusion is constructed. The second process (fuel reversible reference reaction) of the model establishes the incidence relation with the heat effect, and lays a foundation for the development of experimental work. The third process (reversible diffusion of products) builds a correlation with ash, a fuel chemistry
Figure GDA00025958688500000227
The accurate determination of (a) provides a safeguard. Solving the existing method for determining fuel chemistry based on the known element components of a theoretical deduction algorithm
Figure GDA0002595868850000031
While fuel chemistry cannot be determined for fuels of unknown elemental composition
Figure GDA0002595868850000032
To a problem of (a).
C: the invention has another main innovation point that a multifunctional experimental system of fuel combustion-state determination-substance determination-reaction heat determination is constructed based on the Hess law, and the system has two functions of: providing a site for a complete combustion reaction, and measuring the thermal effect of the complete combustion reaction; there are also two functions that oxygen bomb calorimeters do not have: the state (pressure and temperature) before and after the reaction was measured, and the substances (components and amounts) before and after the reaction were measured. At the same time, the fuel chemistry will also be modified on the basis of this experiment
Figure GDA0002595868850000033
Reduced fuel chemistry
Figure GDA0002595868850000034
Improved fuel chemistry
Figure GDA0002595868850000035
The accuracy of the estimation. Solving the existing fuel chemistry estimation based on empirical formula
Figure GDA0002595868850000036
Usually with large errors.
Fuel chemistry of the invention
Figure GDA0002595868850000037
The calculation error is within 1%.
Drawings
FIG. 1 is a graph of fuel chemistry determination using an oxygen bomb calorimeter according to the present invention
Figure GDA0002595868850000038
A general study plan of (1);
FIG. 2 is a fuel multi-process of the present invention
Figure GDA0002595868850000039
A thermodynamic model schematic of the property;
FIG. 3 shows an embodiment of the present inventionDetermination of fuel chemistry with oxygen bomb calorimeter
Figure GDA00025958688500000310
Experimental system diagram (2).
Detailed Description
The first embodiment is as follows: the present embodiment will be described with reference to fig. 3, and the present embodiment is a method for determining fuel chemistry using an oxygen bomb calorimeter
Figure GDA00025958688500000311
The system comprises a multifunctional experimental device for establishing fuel combustion-state measurement-substance measurement-reaction heat measurement, and comprises an oxygen cylinder 1, an oxygen bomb calorimeter 2, a temperature sensor 3, a first pressure sensor 4, a first valve 5, a second valve 6, a filter 7, a dryer 8, a vacuum pump 9, a gas analyzer 10, a second pressure sensor 11, a gas pipeline and the like;
an outlet of the oxygen cylinder 1 is connected with an inlet of an oxygen bomb calorimeter 2 through a first valve 5, an outlet of the oxygen bomb calorimeter 2 is connected with an inlet of a filter 7 through a second valve 6, an outlet of the filter 7 is connected with an inlet of a dryer 8, an outlet of the dryer 8 is connected with an inlet of a vacuum pump 9, and an outlet of the vacuum pump 9 is connected with a gas analyzer 10;
a first pressure sensor 4 is arranged between the oxygen cylinder 1 and the first valve 5, and the first pressure sensor 4 is used for measuring the pressure of oxygen in the oxygen cylinder 1; the oxygen bomb calorimeter 2 is internally provided with a temperature sensor 3 and a second pressure sensor 11 for measuring the temperature and the pressure in the oxygen bomb calorimeter 2.
The second embodiment is as follows: the present embodiment will be described with reference to fig. 1, 2 and 3, and the present embodiment is one of determining fuel chemistry using an oxygen bomb calorimeter
Figure GDA00025958688500000312
The method comprises the following specific processes:
fuel chemistry
Figure GDA00025958688500000313
The conventional determination methods suggest: chemistry of fuels
Figure GDA00025958688500000314
The heat of reaction (higher heating value and lower heating value) is highly correlated, and therefore is estimated mainly by the heat of reaction. Based on this, the assumptions made are: chemistry of fuels
Figure GDA00025958688500000315
Highly correlated with the heat of reaction, which can be determined experimentally, so that the chemistry of the fuel can be determined by a combination of theory and experiment
Figure GDA0002595868850000041
Step one, according to the chemistry
Figure GDA0002595868850000042
(complete combustion reaction based on fuel), build fuel chemistry
Figure GDA0002595868850000043
Reversible separation-reversible reference reaction-reversible diffusion multi-process thermodynamic model;
step two, based on fuel chemistry
Figure GDA0002595868850000044
Reversible separation-reversible reference reaction-reversible diffusion multi-process thermodynamic model for respectively establishing fuel separation
Figure GDA0002595868850000045
Reaction of
Figure GDA0002595868850000046
Diffusion
Figure GDA0002595868850000047
The expression of (1);
based on fuel separation
Figure GDA0002595868850000048
Reaction of
Figure GDA0002595868850000049
Diffusion
Figure GDA00025958688500000410
Expression of (2) establishing fuel chemistry
Figure GDA00025958688500000411
The expression of (1);
step three, building a multifunctional experimental device for fuel combustion-state measurement-substance measurement-reaction heat measurement, and carrying out multi-process of oxygen and calibration substances in fuel
Figure GDA00025958688500000412
Reacting in a characteristic measurement system (a multifunctional experimental device for fuel combustion-state measurement-substance measurement-reaction heat measurement), obtaining mass changes of a filter and a dryer through the filter and the dryer, and obtaining gas components after reaction through a gas analyzer; measuring the reaction heat of oxygen and a calibration substance by an oxygen bomb calorimeter;
step four, based on mass change of the filter and the dryer, gas composition after reaction, oxygen and calibration material reaction heat correction separation in step two
Figure GDA00025958688500000413
Reaction of
Figure GDA00025958688500000414
Diffusion
Figure GDA00025958688500000415
And chemistry
Figure GDA00025958688500000416
To obtain a corrected fuel separation
Figure GDA00025958688500000417
Reaction of
Figure GDA00025958688500000418
Diffusion
Figure GDA00025958688500000419
And chemistry
Figure GDA00025958688500000420
(accurate value).
Survey separation
Figure GDA00025958688500000421
Reaction of
Figure GDA00025958688500000422
And diffusion
Figure GDA00025958688500000423
Size and ratio of (a) to (b), revealing multiple processes of the fuel
Figure GDA00025958688500000424
And (4) characteristics.
The third concrete implementation mode: the second embodiment is different from the first embodiment in that: in the step one, the chemical basis is
Figure GDA00025958688500000430
(complete combustion reaction based on fuel), build fuel chemistry
Figure GDA00025958688500000425
Reversible separation-reversible reference reaction-reversible diffusion multi-process thermodynamic model; the specific process is as follows:
fuel chemistry
Figure GDA00025958688500000426
The multi-process thermodynamic model of reversible separation-reversible reference reaction-reversible diffusion comprises three processes: as shown in figure 2 of the drawings, in which,
a first process of reacting oxygen with the fuel from an ambient reference pressure P0And temperature T0Is separated out from the environment of the reactor to obtain an oxygen separation
Figure GDA00025958688500000427
Second, fuel and oxygen are at ambient reference pressure P0And temperature T0Enters an oxygen bomb calorimeter to perform reversible reference reaction, the product is pure substances in an environmental reference substance, and the pure substances and oxygen gas are subjected to environmental reference pressure P0And temperature T0The oxygen bomb calorimeter is separated to obtain the maximum useful work of the second process, namely chemical reaction
Figure GDA00025958688500000428
The pure substances are mixed;
third, the product (pure material on an environmental basis) is at an environmental reference pressure P0And temperature T0Down diffusion to ambient reference pressure P0And temperature T0To obtain product diffusion
Figure GDA00025958688500000429
The pure substances are separated;
the multiple processes are a first process, a second process and a third process;
other steps and parameters are the same as those in the second embodiment.
The fourth concrete implementation mode: the second or third embodiment is different from the first or second embodiment in that: based on fuel chemistry in step two
Figure GDA0002595868850000054
Reversible separation-reversible reference reaction-reversible diffusion multi-process thermodynamic model for respectively establishing fuel separation
Figure GDA0002595868850000055
Reaction of
Figure GDA0002595868850000056
Diffusion
Figure GDA0002595868850000057
The expression of (1);
based on fuel separation
Figure GDA0002595868850000058
Reaction of
Figure GDA0002595868850000059
Diffusion
Figure GDA00025958688500000510
Expression of (2) establishing fuel chemistry
Figure GDA00025958688500000511
The expression of (1);
the specific process is as follows:
separation of the first Process
Figure GDA00025958688500000512
Can be diffused by oxygen
Figure GDA00025958688500000513
To determine, the formula is:
Figure GDA0002595868850000051
in the formula: exSTo separate
Figure GDA00025958688500000514
R is a molar gas constant, and R is a molar gas constant,
Figure GDA00025958688500000523
is O2The amount of substance(s) in mol;
Figure GDA00025958688500000524
is O2Partial pressure, P0The reference pressure is 1.01 × 105pa，T0The temperature is taken as the environmental reference temperature, and the value is 25 ℃;
the most useful work of the second process is the reaction
Figure GDA00025958688500000515
Is also standard (ambient reference pressure P)0And temperature T0Below) negative value of reaction free enthalpy:
ExR＝-ΔG0＝-ΔH0+T0ΔS0(2)
in the formula, ExRTo react
Figure GDA00025958688500000516
ΔG0Is the standard free enthalpy of reaction,. DELTA.H0Is a standard (ambient reference pressure P)0And temperature T0Lower) heat of reaction (i.e., the standard calorific value of the fuel, with negative exotherm), Δ S0Is taken as a reference (environmental reference pressure P)0And temperature T0Under) entropy difference under the condition;
third process diffusion
Figure GDA00025958688500000517
Figure GDA0002595868850000052
In the formula, ExDTo diffuse
Figure GDA00025958688500000518
i is a gas component (for example, the gas in the reaction is oxygen, nitrogen or carbon dioxide, i represents 3 gas components, and each gas can be measured by an instrument); m isiIs the amount of gas component substances, in mol,
Figure GDA00025958688500000525
is in a standard condition (ambient reference pressure P)0And temperature T0) The gas component ratio (the volume ratio of each gas to the total gas);
chemistry of fuels
Figure GDA00025958688500000519
To separate
Figure GDA00025958688500000520
Reaction of
Figure GDA00025958688500000521
And diffusion
Figure GDA00025958688500000522
And (3) the sum:
Figure GDA0002595868850000053
other steps and parameters are the same as those in the second or third embodiment.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: in the third step, a multifunctional experimental device for fuel combustion-state measurement-substance measurement-reaction heat measurement is established, and oxygen and calibration substances are used in multiple processes of fuel
Figure GDA0002595868850000063
Reacting in a characteristic measurement system (a multifunctional experimental device for fuel combustion-state measurement-substance measurement-reaction heat measurement), obtaining mass changes of a filter and a dryer through the filter and the dryer, and obtaining gas components after reaction through a gas analyzer; measuring the reaction heat of oxygen and a calibration substance by an oxygen bomb calorimeter; the specific process is as follows:
aiming at the core and the key of the reversible reference reaction in the multi-process thermodynamic model, the heat effect of the reversible reference reaction is transferred to the heat effect of the actual complete combustion process according to the Hess law;
multiple process of shutting down fuel
Figure GDA0002595868850000064
The characteristic measurement system comprises a first valve 5 and a second valve 6, the first valve 5 is opened, oxygen in an oxygen cylinder 1 enters an oxygen bomb calorimeter 2 through the first valve 5, the oxygen amount entering the oxygen bomb calorimeter is controlled through a first pressure sensor 4, when the oxygen amount entering the oxygen bomb calorimeter 2 reaches a threshold value, the first valve 5 is closed, a calibration substance (graphite or benzoic acid) is put into the oxygen bomb calorimeter 2, the oxygen reacts with the calibration substance, and when a temperature sensor 3 and a second pressure sensor 2 in the oxygen bomb calorimeter are detected, the oxygen bomb calorimeter is heated, and the oxygen bomb calorimeter is heated to a temperature higher than the first pressure sensor 3 and the second pressure sensor 6Sensor 11 reaches P at the same time0And T0When the second valve 6 is opened, the gas flow after the reaction of the oxygen and the calibration substance passes through the filter 7, the dryer 8, the vacuum pump 9 and the gas analyzer 10 in sequence, the mass changes of the filter 7 and the dryer 8 are obtained through the filter 7 and the dryer 8, and the gas components after the reaction are obtained through the gas analyzer 10; measuring the reaction heat of the oxygen and the calibration substance by an oxygen bomb calorimeter 2;
P0the reference pressure is 1.01 × 105pa，T0The temperature is taken as the environmental reference temperature, and the value is 25 ℃;
the threshold value was set artificially (when the calibration substance in the oxygen bomb calorimeter was 12g of graphite, the amount of oxygen charged in the standard case was 22.4L).
Other steps and parameters are the same as in one of the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is: in the fourth step, based on the mass change of the filter and the dryer, the separation in the second step of reaction heat correction of the gas components, oxygen and calibration substances after the reaction
Figure GDA0002595868850000065
And reaction of the mixture
Figure GDA0002595868850000066
Diffusion
Figure GDA0002595868850000067
And chemistry
Figure GDA0002595868850000068
To obtain a corrected fuel separation
Figure GDA0002595868850000066
Reaction of
Figure GDA00025958688500000610
Diffusion
Figure GDA0002595868850000067
And chemistry
Figure GDA00025958688500000612
(accurate value); the specific process is as follows:
in the third step, the oxygen bomb calorimeter (2) is a closed system, and the measured reaction heat is the reaction heat of the closed system (the gas volume of the oxygen bomb calorimeter (2) is constant along with the change of pressure when the mouth is closed); - Δ H in the formula (4)0The standard reaction heat of the open system, the standard reaction heat of the open system and the closed system can be converted by the following formula:
Figure GDA0002595868850000061
in the formula (I), the compound is shown in the specification,
Figure GDA0002595868850000062
Δ m, the standard heat of reaction under constant volume conditionsiIs the amount of change in the amount of gas component substances in mol;
in addition, the pressure (P) in the bomb is significantly higher than the ambient reference pressure (P)0) Therefore, further reaction is required
Figure GDA00025958688500000613
And (3) correcting the pressure, wherein a pressure correction term is expressed as:
Figure GDA0002595868850000071
wherein p is the oxygen nitrogen internal pressure; v is the volume of the oxygen bomb calorimeter;
thus, fuel chemistry
Figure GDA0002595868850000073
The expression of (c) is modified to:
Figure GDA0002595868850000072
other steps and parameters are the same as those in one of the first to fifth embodiments.
Fuel chemistry
Figure GDA0002595868850000074
Inspection of
According to the chemistry of graphite (C) or benzoic acid (calibration material for the heat of reaction of the fuel)
Figure GDA0002595868850000075
Verification of the accuracy of equation 7, its heat of reaction and chemistry
Figure GDA0002595868850000076
The test material can be used as the test material of the method because the test material has a definite theoretical value.

Claims (3)

1. Determination of fuel chemistry using oxygen bomb calorimeter
Figure FDA0002595868840000012
The system of (a), characterized by: the system comprises an oxygen cylinder (1), an oxygen bomb calorimeter (2), a temperature sensor (3), a first pressure sensor (4), a first valve (5), a second valve (6), a filter (7), a dryer (8), a vacuum pump (9), a gas analyzer (10) and a second pressure sensor (11);
an outlet of the oxygen bottle (1) is connected with an inlet of an oxygen bomb calorimeter (2) through a first valve (5), an outlet of the oxygen bomb calorimeter (2) is connected with an inlet of a filter (7) through a second valve (6), an outlet of the filter (7) is connected with an inlet of a dryer (8), an outlet of the dryer (8) is connected with an inlet of a vacuum pump (9), and an outlet of the vacuum pump (9) is connected with a gas analyzer (10);
a first pressure sensor (4) is arranged between the oxygen cylinder (1) and the first valve (5), and the first pressure sensor (4) is used for measuring the pressure of oxygen in the oxygen cylinder (1); a temperature sensor (3) and a second pressure sensor (11) are arranged in the oxygen bomb calorimeter (2) and are used for measuring the temperature and the pressure in the oxygen bomb calorimeter (2).
2. Determination of fuel chemistry using oxygen bomb calorimeter
Figure FDA0002595868840000013
The method of (2), characterized by: the method comprises the following specific processes:
step one, build fuel chemistry
Figure FDA0002595868840000014
Reversible separation-reversible reference reaction-reversible diffusion multi-process thermodynamic model;
build fuel chemistry
Figure FDA0002595868840000015
The multi-process thermodynamic model of reversible separation-reversible reference reaction-reversible diffusion comprises three processes:
a first process of reacting oxygen with the fuel from an ambient reference pressure P0And temperature T0Is separated out from the environment of the reactor to obtain an oxygen separation
Figure FDA0002595868840000016
Second, fuel and oxygen are at ambient reference pressure P0And temperature T0Enters an oxygen bomb calorimeter to perform reversible reference reaction, the product is pure substances in an environmental reference substance, and the pure substances and oxygen gas are subjected to environmental reference pressure P0And temperature T0The oxygen bomb calorimeter is separated to obtain the maximum useful work of the second process, namely chemical reaction
Figure FDA0002595868840000017
Third process, the product is at ambient reference pressure P0And temperature T0Down diffusion to ambient reference pressure P0And temperature T0To obtain product diffusion
Figure FDA0002595868840000018
The multiple processes are a first process, a second process and a third process; step two, based on fuel chemistry
Figure FDA0002595868840000019
Reversible separation-reversible reference reaction-reversible diffusion multi-process thermodynamic model for respectively establishing fuel separation
Figure FDA00025958688400000112
Reaction of
Figure FDA00025958688400000110
Diffusion
Figure FDA00025958688400000111
The expression of (1);
based on fuel separation
Figure FDA00025958688400000113
Reaction of
Figure FDA00025958688400000114
Diffusion
Figure FDA00025958688400000115
Expression of (2) establishing fuel chemistry
Figure FDA00025958688400000116
The specific process of the expression (2) is as follows:
separation of the first Process
Figure FDA00025958688400000117
By diffusion of oxygen
Figure FDA00025958688400000118
To determine, the formula is:
Figure FDA0002595868840000011
in the formula: exSTo separate
Figure FDA0002595868840000025
R is a molar gas constant, and R is a molar gas constant,
Figure FDA00025958688400000225
is O2The amount of substance(s) in mol;
Figure FDA00025958688400000226
is O2Partial pressure, P0The reference pressure is 1.01 × 105pa，T0The temperature is taken as the environmental reference temperature, and the value is 25 ℃;
the most useful work of the second process is the reaction
Figure FDA0002595868840000026
Also negative for the standard reaction free enthalpy:
ExR＝-ΔG0＝-ΔH0+T0ΔS0(2)
in the formula, ExRTo react
Figure FDA0002595868840000027
ΔG0Is the standard free enthalpy of reaction,. DELTA.H0As standard heat of reaction,. DELTA.S0The entropy difference under the reference condition;
third process diffusion
Figure FDA0002595868840000028
Figure FDA0002595868840000021
In the formula, ExDTo diffuse
Figure FDA0002595868840000029
i is a gas component; m isiIs the amount of gas component substance in mol, yi 0The gas component proportion under the standard condition;
chemistry of fuels
Figure FDA00025958688400000210
To separate
Figure FDA00025958688400000211
Reaction of
Figure FDA00025958688400000216
And diffusion
Figure FDA00025958688400000215
And (3) the sum:
Figure FDA0002595868840000022
step three, multiple processes of oxygen and calibration substances in fuel
Figure FDA00025958688400000214
Reacting in the characteristic measurement system, obtaining the mass change of the filter and the dryer through the filter and the dryer, and obtaining the gas components after the reaction through a gas analyzer; measuring the reaction heat of oxygen and a calibration substance by an oxygen bomb calorimeter; wherein the outlet of the oxygen cylinder is connected with the inlet of the oxygen bomb calorimeter through a first valve, the outlet of the oxygen bomb calorimeter is connected with the inlet of a filter through a second valve, the outlet of the filter is connected with the inlet of a dryer, the outlet of the dryer is connected with the inlet of a vacuum pump, and the outlet of the vacuum pump is connected with a gas analyzer;
step four, based on mass change of the filter and the dryer, gas composition after reaction, oxygen and calibration material reaction heat correction separation in step two
Figure FDA00025958688400000219
Reaction of
Figure FDA00025958688400000218
Diffusion
Figure FDA00025958688400000217
And chemistry
Figure FDA00025958688400000220
To obtain a corrected fuel separation
Figure FDA00025958688400000219
Reaction of
Figure FDA00025958688400000222
Diffusion
Figure FDA00025958688400000219
And chemistry
Figure FDA00025958688400000224
The specific process comprises the following steps:
the oxygen bomb calorimeter (2) in the step three is a closed system, and the measured reaction heat is the reaction heat of the closed system; - Δ H in the formula (4)0The standard reaction heat of the open system, the standard reaction heat of the open system and the closed system can be converted by the following formula:
Figure FDA0002595868840000023
in the formula (I), the compound is shown in the specification,
Figure FDA0002595868840000024
Δ m, the standard heat of reaction under constant volume conditionsiIs the amount of change in the amount of gas component substances in mol;
for reaction
Figure FDA0002595868840000033
And (3) correcting the pressure, wherein a pressure correction term is expressed as:
Figure FDA0002595868840000031
wherein p is the oxygen nitrogen internal pressure; v is the volume of the oxygen bomb calorimeter;
thus, fuel chemistry
Figure FDA0002595868840000034
The expression of (c) is modified to:
Figure FDA0002595868840000032
3. the method of claim 2 wherein fuel chemistry is determined using an oxygen bomb calorimeter
Figure FDA0002595868840000035
The method of (2), characterized by: in the third step, oxygen and calibration substances are in multiple processes of fuel
Figure FDA0002595868840000036
Reacting in the characteristic measurement system, obtaining the mass change of the filter and the dryer through the filter and the dryer, and obtaining the gas components after the reaction through a gas analyzer; measuring the reaction heat of oxygen and a calibration substance by an oxygen bomb calorimeter; the specific process is as follows:
multiple process of shutting down fuel
Figure FDA0002595868840000037
The characteristic measurement system comprises a first valve (5) and a second valve (6), the first valve (5) is opened, oxygen in an oxygen bottle (1) enters an oxygen bomb calorimeter (2) through the first valve (5), the oxygen amount entering the oxygen bomb calorimeter is controlled through a first pressure sensor (4), when the oxygen amount entering the oxygen bomb calorimeter (2) reaches a threshold value, the first valve (5) is closed, a calibration substance is put into the oxygen bomb calorimeter (2), the oxygen reacts with the calibration substance, and when a temperature sensor (3) and a second pressure sensor (11) in the oxygen bomb calorimeter (2) reach P simultaneously0And T0When the second valve (6) is opened, the gas after the reaction of oxygen and the calibration materialThe flow sequentially passes through a filter (7), a dryer (8), a vacuum pump (9) and a gas analyzer (10), the mass changes of the filter (7) and the dryer (8) are obtained through the filter (7) and the dryer (8), and the gas components after reaction are obtained through the gas analyzer (10); measuring the reaction heat of oxygen and a calibration substance by an oxygen bomb calorimeter (2); a first pressure sensor is arranged between the oxygen cylinder and the first valve and used for measuring the pressure of oxygen in the oxygen cylinder; a temperature sensor and a second pressure sensor are arranged in the oxygen bomb calorimeter and are used for measuring the temperature and the pressure in the oxygen bomb calorimeter;
P0the reference pressure is 1.01 × 105pa，T0The temperature is taken as the environmental reference temperature, and the value is 25 ℃;
the threshold is set manually.
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