CN115248978A - Method for simplifying combustion dynamics mechanism of long-chain normal alcohol fuel - Google Patents
Method for simplifying combustion dynamics mechanism of long-chain normal alcohol fuel Download PDFInfo
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- 230000007246 mechanism Effects 0.000 title claims abstract description 101
- 238000000034 method Methods 0.000 title claims abstract description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000000446 fuel Substances 0.000 title claims abstract description 27
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- 239000000126 substance Substances 0.000 claims abstract description 23
- 238000004458 analytical method Methods 0.000 claims abstract description 13
- 230000035945 sensitivity Effects 0.000 claims abstract description 13
- 238000010168 coupling process Methods 0.000 claims abstract description 10
- 230000008878 coupling Effects 0.000 claims abstract description 9
- 238000005859 coupling reaction Methods 0.000 claims abstract description 9
- 238000010206 sensitivity analysis Methods 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 150000003384 small molecules Chemical class 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 4
- 238000010494 dissociation reaction Methods 0.000 claims description 4
- 230000005593 dissociations Effects 0.000 claims description 4
- 125000003158 alcohol group Chemical group 0.000 claims description 3
- 238000002474 experimental method Methods 0.000 claims description 2
- 239000002283 diesel fuel Substances 0.000 abstract description 6
- 238000004088 simulation Methods 0.000 abstract description 4
- 230000001502 supplementing effect Effects 0.000 abstract description 3
- 238000004364 calculation method Methods 0.000 abstract description 2
- 238000006757 chemical reactions by type Methods 0.000 abstract description 2
- 238000012216 screening Methods 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 28
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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Abstract
The invention relates to a method for simplifying a combustion dynamics mechanism of a long-chain normal alcohol fuel, and belongs to the technical field of combustion of internal combustion engines. Firstly, screening isomers in a detailed mechanism of long-chain n-alcohol by a DRGEP method; then removing unimportant substances and reactions by sensitivity and ROP analysis; then, coupling the remaining long-chain n-alcohol macromolecular skeleton mechanism with a semi-detailed C2C3 mechanism and a detailed H2/C0/C1 mechanism, and supplementing C2C3 micromolecules which are not included in the semi-detailed C2C3 mechanism; and finally, determining important reactions in the n-alcohol skeleton structure through sensitivity analysis, and adjusting the reaction rate constant of the important reactions according to the experimental data of the flame retardation period and the component concentration to obtain the finally simplified long-chain n-alcohol kinetic mechanism. The method can effectively reduce the substance types and the reaction types in the mechanism, is favorable for improving the efficiency of the long-chain normal alcohol in three-dimensional CFD simulation calculation, and can be coupled with a diesel oil simplifying mechanism and other fuel simplifying mechanisms.
Description
Technical Field
The invention relates to a method for simplifying a combustion dynamics mechanism of a long-chain normal alcohol fuel, and belongs to the technical field of combustion of internal combustion engines.
Background
Industrialization has made great progress in human society, but has also caused serious environmental damage and large amounts of carbon emissions. Therefore, diesel engines require higher efficiency and low polluting emissions to meet the carbon neutralization requirements. Oxygenated fuels are receiving increasing attention as alternative fuels to diesel. Among them, the low heating value and solubility of lower alcohols with diesel fuel limit their use as alternative fuels for diesel fuel. Compared with low-carbon alcohol, the long-chain normal alcohol has higher heat value and mixing capability, is more stable to mix, and can reduce oil consumption. Therefore, it is very important to study the influence of long-chain normal alcohol fuel on the engine and to understand the oxidation and combustion behaviors deeply.
Three-dimensional computational fluid dynamics simulation using chemical kinetics is a very useful method for understanding the oxidation and combustion characteristics of long-chain n-alcohols. The presently reported mechanisms of oxidation for detailed long-chain n-alcohols include hundreds of species and thousands of reactions, which are unacceptable for the computational resources required for three-dimensional Computational Fluid Dynamics (CFD) modeling. Therefore, there is a need for mechanistic simplification of the detailed chemical kinetic mechanism of long chain n-alcohols.
The existing mechanism simplification mostly aims at small molecular fuels such as dimethyl ether and the like, and the simplification of macromolecular fuels has the problems of incomplete simplification and relatively large mechanism quantity after simplification. In addition, due to the differences in the underlying C0-C3 mechanisms, direct coupling between the mechanisms is difficult. Therefore, a simplified method of preparing a macromolecule long-chain n-alcohol which can be directly coupled with fuel mechanisms such as diesel oil and the like is needed.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for simplifying the combustion kinetics mechanism of long-chain n-alcohol fuel.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for simplifying the combustion kinetics of a long chain n-alcohol fuel, said method steps comprising:
(1) The method adopts a Direct Relational Graph (DRGEP) method with error analysis to simplify the detailed combustion dynamics mechanism of the long-chain normal alcohol, delete isomers, unimportant substances and reactions of the long-chain normal alcohol in the detailed combustion dynamics mechanism, and reserve the long-chain normal alcohol and the mechanism;
(2) Selecting a substance with the lowest C-H bond dissociation energy in isomers formed by the long-chain n-alcohol dehydrogenation reaction, carrying out sensitivity and generation Rate (ROP) analysis on the substance, and keeping the skeleton structure and mechanism of the long-chain n-alcohol;
(3) Coupling the long chain n-alcohol backbone mechanism with a semi-detailed C2C3 mechanism, a detailed H2/C0/C1 mechanism;
(4) And determining important reactions in the long-chain normal alcohol skeleton mechanism through sensitivity analysis, and adjusting the reaction rate constant of the important reactions according to experimental data of a flame retardation period and component concentration to obtain the simplified combustion dynamics mechanism of the long-chain normal alcohol fuel.
Further, the number of carbon atoms of the long-chain n-alcohol is not less than 4.
Further, the carbon number of the long-chain n-alcohol is 4 to 8.
Further, in the step (1), the stagnation period, the fuel substance end value and the maximum OH value are used as target parameters, absolute and relative errors are set, and simplification is carried out under the working conditions of 800K-1200K, 1 bar-60 bar and 0.5-2 equivalence ratio.
Further, in step (3), the bottom C0-C3 detailed mechanism of the long-chain n-alcohol backbone mechanism is replaced with a semi-detailed C2C3 mechanism and a detailed H2/C0/C1 mechanism, supplementing the C2C3 small molecules generated by the downward reaction according to the long-chain n-alcohol backbone mechanism but not included in the semi-detailed C2C3 mechanism.
Further, in the step (4), firstly, according to the stagnation period data measured by experiments, adjusting a reaction rate constant in the mechanism to be matched with the measured stagnation period data; then optimizing a reaction rate constant to match the concentration of the experimental species; the above procedure was repeated until the simplified mechanism matched the experimentally measured stagnation data and species concentrations.
Advantageous effects
The invention provides a method for simplifying a combustion dynamics mechanism of a long-chain normal alcohol fuel, which comprises the steps of firstly, screening isomers in a detailed mechanism of the long-chain normal alcohol through a DRGEP method; then removing unimportant substances and reactions by sensitivity and ROP analysis; then, coupling the remaining long-chain n-alcohol macromolecular skeleton mechanism with a semi-detailed C2C3 mechanism and a detailed H2/C0/C1 mechanism, and supplementing C2C3 micromolecules which are not included in the semi-detailed C2C3 mechanism; and finally, determining important reactions in the n-alcohol skeleton structure through sensitivity analysis, and adjusting the reaction rate constant of the important reactions according to the experimental data of the flame retardation period and the component concentration to obtain the finally simplified long-chain n-alcohol kinetic mechanism. The method can effectively reduce the substance types and the reaction types in the mechanism, is beneficial to improving the efficiency of the long-chain normal alcohol in three-dimensional CFD simulation calculation, and can be coupled with a diesel oil simplification mechanism and other fuel simplification mechanisms.
Drawings
FIG. 1 is a flow chart of the method of the present invention.
FIG. 2 is a reaction path of the backbone mechanism of the long-chain n-alcohols described in example 1.
FIG. 3 is a reaction scheme of the skeletal mechanism of n-hexanol described in example 1.
FIG. 4 is a simplified model coupling scheme for n-hexanol as described in example 1.
FIG. 5 is a graph of simulated stagnation versus experimental data for the simplified model of n-hexanol described in example 1.
FIG. 6 is a graph of the simulated mass fraction of the simplified model of n-hexanol as described in example 1 compared to experimental data.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
As shown in fig. 1, a method for simplifying the combustion dynamics of a long-chain n-alcohol fuel, the method comprising the steps of:
(1) The method adopts a Direct Relational Graph (DRGEP) method with error analysis to simplify the detailed chemical kinetics mechanism of the long-chain normal alcohol, delete isomers, unimportant substances and reactions of the long-chain normal alcohol in the detailed combustion kinetics mechanism, and retain the long-chain normal alcohol and the mechanism.
Specifically, CHEMKIN PRO software is used for setting absolute and relative errors by taking a stagnation period, a fuel substance end value and an OH maximum value as target parameters, and simplifying under the working conditions of different temperatures (800K-1200K), different pressures (1 bar-60 bar) and different equivalence ratios (0.5-2) in order to delete long-chain n-alcohol isomers and unimportant substances and reactions in a detailed mechanism.
(2) Selecting a substance with the lowest C-H bond dissociation energy in isomers formed by the long-chain n-alcohol dehydrogenation reaction, analyzing the substance with sensitivity and generation Rate (ROP), deleting unimportant substances and reactions with smaller values of sensitivity and ROP, and keeping the skeleton structure and mechanism of the long-chain n-alcohol;
specifically, by comparing the sensitivity in the generation reaction and the consumption reaction of the long-chain n-alcohol and the numerical value in the ROP analysis under the working conditions of different temperatures, different pressures and different equivalence ratios, the unimportant reaction with smaller sensitivity and ROP numerical value is deleted, only the most important substance in the sensitivity and ROP analysis and the downward reaction thereof are reserved after simplification, and the rest isomers and the downward reactions thereof are deleted. RH is defined as long-chain n-alcohol fuel, R is hydroxyalkyl radical, and QOOH is hydroxyalkyl hydroperoxide radical. Sensitivity and ROP analysis showed that the RH down reaction has only three major reaction pathways, as shown in figure 2: 1.R → ROO → QOOH → OOQOOH → CnOHKet → C2-C3 small molecule; 2.R → "R 'CHO" → "R' CO" → "C2-C3" small molecule 3.R → alkane + alcohol or aldehyde.
Wherein, taking n-hexanol as an example, togbe et al, by adding n-hexanol macromolecules into a C1-C5 alcohol mechanism, and adopting an extended detailed chemical kinetics reaction mechanism, proposed an oxidation model of n-hexanol, including 600 species and 2977 reactions. After dehydrogenation, n-hexanol forms seven isomers (C) 6 H 12 OH-1、C 6 H 12 OH-2、C 6 H 12 OH-3、C 6 H 12 OH-4、C 6 H 12 OH-5、C 6 H 12 OH-6 and C 6 H 13 O). Selecting only the species C with the lowest dissociation energy of C-H bonds among all isomers 6 H 12 OH-1 as representative. Comparing C under different temperature (800-1200K), pressure (1-60 bar) and equivalent ratio (0.5-2) 6 H 12 The reaction in which OH-1-1 is formed and the reaction in which the reaction is consumed is sensitive and the value in the ROP analysis is small, and the reaction in which the sensitivity and the ROP value are small is not important. Only sensitivity in the simplified n-hexanol mechanism and heaviest in the ROP analysis were retainedSubstance C of interest 6 H 12 OH-1 and downward reaction thereof, and the other six isomers and downward reaction thereof are all deleted. The n-hexanol backbone mechanism path is shown in figure 3.
(3) Coupling the long chain n-alcohol backbone mechanism with a mature semi-detailed C2C3 mechanism, a detailed H2/C0/C1 mechanism;
specifically, the mature semi-detailed C2C3 mechanism and the detailed H2/C0/C1 mechanism replace the underlying C0-C3 detailed mechanism of the simplified macro-n-alcohol mechanism described above and complement the C2C3 small molecules generated by the reaction described above but not included in the semi-detailed C2C3 mechanism. Using hexanol as an example, as shown in FIG. 3, the purpose of using the semi-detailed C2C3 mechanism and the detailed H2/C0/C1 mechanism as the substrate reaction is to allow direct coupling with the use of other fuels such as diesel fuel with the substrate. The substitution coupling process can directly couple the macromolecular framework Mechanism, the semi-detailed C2C3 Mechanism and the detailed H2/C0/C1 Mechanism in a Mechanism file, and can also couple by using a Mechanism Mechanism Merge module in CHEMKIN PRO software. The n-hexanol simplified model coupling scheme is shown in FIG. 4.
(4) And determining important reactions in the long-chain normal alcohol skeleton mechanism through sensitivity analysis, and adjusting the reaction rate constant of the important reactions according to experimental data of a flame retardation period and component concentration to obtain the simplified combustion dynamics mechanism of the long-chain normal alcohol fuel.
Since a large number of isomers and reactions are deleted, only the main reaction path is retained, and the ignition delay time cannot be reproduced well by a simplified mechanism. Therefore, the rate constant of the reaction needs to be adjusted. Since the detailed H2/C0/C1 mechanism and the semi-detailed C2/C3 mechanism are relatively mature, only the reaction rate constant of the mechanism in the framework structure needs to be optimized. The detailed process is described as follows:
sensitivity and ROP analyses were performed at different temperatures using CHEMKIN PRO software to find out the key reactions. The reaction rate constants of these reactions were adjusted to determine which temperatures they would affect the burn-through period. (2) The reaction rate constant is adjusted to match the measured burn period data over a set temperature range based on experimentally measured or mechanistically detailed simulated burn period data, for example as shown in figure 5 with n-hexanol. (3) The reaction rate constants were further optimized to match the experimental species concentrations in the jet-stirred reactor (JSR) with n-hexanol as shown, for example, in fig. 6. (4) Repeating steps (2) - (3) until the simplified mechanism is able to reproduce the measured stagnation phase data and species concentrations well.
Taking n-hexanol as an example, the simplified model simulation of the flame lag phase versus experimental data is shown in fig. 5; the simplified model simulated material fraction and experimental data pair is shown in fig. 6, the symbol is experimental data, and the solid line is simplified model prediction data.
The method of the embodiment is adopted to simplify the n-alcohol with 5 and 6 carbon atoms, and the model obtained after simplification is highly consistent with experimental test data, so that the combustion dynamics mechanism of the long-chain n-alcohol can be effectively simplified by the method.
In summary, the invention includes but is not limited to the above embodiments, and any equivalent replacement or local modification made under the spirit and principle of the invention should be considered as being within the protection scope of the invention.
Claims (6)
1. A method for simplifying the combustion dynamics mechanism of long-chain normal alcohol fuel is characterized in that: the method comprises the following steps:
(1) Simplifying a detailed combustion kinetic mechanism of the long-chain normal alcohol by adopting a direct relational graph method with error analysis, deleting isomers, unimportant substances and reactions of the long-chain normal alcohol in the detailed combustion kinetic mechanism, and keeping the long-chain normal alcohol and the mechanism;
(2) Selecting a substance with the lowest C-H bond dissociation energy in isomers formed by the long-chain normal alcohol dehydrogenation reaction, carrying out sensitivity and ROP analysis on the substance, and keeping the skeleton structure and mechanism of the long-chain normal alcohol;
(3) Coupling the long-chain n-alcohol backbone mechanism with a semi-detailed C2C3 mechanism, a detailed H2/C0/C1 mechanism;
(4) And determining important reactions in the long-chain normal alcohol skeleton mechanism through sensitivity analysis, and adjusting the reaction rate constant of the important reactions according to experimental data of a flame retardation period and component concentration to obtain the simplified combustion dynamics mechanism of the long-chain normal alcohol fuel.
2. The method of claim 1, wherein the method comprises the following steps: the number of carbon atoms of the long-chain normal alcohol is more than or equal to 4.
3. The method of claim 2, wherein the method comprises the following steps: the carbon atom number of the long-chain normal alcohol is 4-6.
4. The method of claim 1, wherein the method comprises the steps of: in the step (1), absolute and relative errors are set by taking a stagnation period, a fuel substance end value and an OH maximum value as target parameters, and simplification is carried out under the working conditions of equivalent ratios of 800K-1200K, 1 bar-60 bar and 0.5-2.
5. The method of claim 1, wherein the method comprises the steps of: in step (3), a semi-detailed C2C3 mechanism and a detailed H2/C0/C1 mechanism are used for replacing the bottom layer C0-C3 detailed mechanism of the long-chain n-alcohol skeleton mechanism, and C2C3 small molecules which are generated by downward reaction according to the long-chain n-alcohol skeleton mechanism and are not included in the semi-detailed C2C3 mechanism are supplemented.
6. The method for simplifying combustion kinetics of a long-chain n-alcohol fuel according to any one of claims 1 to 5, wherein: in the step (4), firstly, according to the stagnation period data measured by experiments, a reaction rate constant in the mechanism is adjusted to be matched with the measured stagnation period data; then optimizing a reaction rate constant to match the concentration of the experimental species; the above procedure was repeated until the simplified mechanism matched the experimentally measured stagnation data and species concentrations.
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