Abstract: Methyl hydrazine (MMH) and nitrous oxide (NTO) are commonly used liquid rocket

propellants, but the research on their reaction mechanism is still ten.

The fraction is limited. This paper first constructs a MMH/NTO reaction kinetic model
containing 23 components and 20 elementary reactions; for MMH/NTO self
The verification calculation of the ignition process shows that the mechanism can reasonably
describe the spontaneous combustion temperature rise process of MMH/NTO and accurately
predict the reactant system.
Fire delay time and equilibrium temperature, and can reasonably reflect the initial pressure of the
MMH/NTO reactant system ignition delay time and the oxygen combustion ratio
The dependence of the sensitivity analysis method on the key reactions affecting the MMH/NTO
ignition process. The simulation analysis of the different pressures and oxy-combustion
The self-ignition temperature rise process of the MMH/NTO system under different conditions
shows that as the pressure increases, the system ignition delay time becomes shorter and the
equilibrium temperature rises.
High; increase the oxygen-burning ratio within a certain range, the ignition delay time becomes
longer, and the equilibrium temperature first increases and then decreases.
Key words: methylhydrazine; dinitrogen tetroxide; reaction mechanism; ignition delay time;
equilibrium temperature; sensitivity analysis

Methyl hydrazine (MMH) and nitrous oxide (NTO) are excellent

Good physicochemical properties, widely used as a two-component small thrust liquid
Rocket engine propellant. Study the mechanism of MMH/NTO reaction
Solve the internal working process of a liquid rocket engine, especially in the combustion
chamber
The combustion process is of great significance. However, at present, MMH/
There are few studies on the mechanism of NTO reaction, the main reason is MMH/
NTO is highly toxic, and because of its high reactivity, even in
It can react quickly under extremely thin conditions, so MMH/
NTO premixed gas is very difficult, so it is studied through experimental means.
The MMH/NTO reaction kinetics are very difficult.

The MMH/NTO reaction process is different from the combustion of other fuels.
Cheng: Once MMH and NTO are in contact, they will react quickly,
The amount of heat that should be released raises the temperature of the system. 1- 8 Before the
fire,
MMH and NTO will undergo thermal decomposition reactions respectively.
Yes, unlike the ordinary decomposition reaction, the decomposition reaction of MMH will be
released.
Release a lot of heat, this part of the heat released will also promote the system
Fire.9-11 MMH/NTO reaction after spontaneous combustion
The system will react to a series of reactions at high temperatures.
There are few studies on the mechanism of MMH/NTO reaction, and most of the researchers rely
on
According to the principle of quantum chemistry, using computer simulation to discuss and
analyze
The reaction characteristics of MMH/NTO are mainly concentrated in the spontaneous
combustion stage.
Frank et al. 12 simulated the reversal of MMH/NTO before spontaneous combustion.
Methyldiazoene
(CH3N=NH) is the main stage
To produce. Ishikawa et al. 13 simulated the NO2 molecule to take away the MMH score.
The process of H atom on the child, indicating CH3NHNH, CH2NHNH,
The reactions involving H2C=NNH2 and CH3NHN should be added to
Study on the chemical reaction kinetics of the MMH/NTO system
After analyzing the structural stability of some intermediate products, pointed out the possible
Reaction path, but no specific reaction is given. Catoire et al.
Thermal tube reversal of MMH over different pressures and temperature ranges
An experimental study should be carried out to obtain a 99-step MMH pyrolysis mechanism.
And the 14-step simplification mechanism. About the MMH/NTO spontaneous combustion
process,
Catoire et al. 2 obtained MMH/NTO by quantum chemistry.
Detailed mechanism of 82 components, 403 elementary reactions, and sensitivity
The analytical method has obtained the key to affect the spontaneous combustion process of the
reactants.
Reaction, but did not give details of the mechanism. Also the scale of the mechanism
Too large to be applied to the number of flow combustion processes in the engine
Value simulation. Nie Wansheng 15,16 and Knab17 studied spontaneous combustion propellants
The MMH/NTO rocket engine uses a one-step total
Package reaction, Xu et al. 18 numerical simulation of space small thrust chamber
Do not use one-step and four-step total package reaction mechanism, these two general charter
Based on experience, it is mostly applied to natural propellant rocket engines.
In the numerical simulation of steady-state flow combustion, MMH/NTO cannot be described
The spontaneous combustion process. Therefore, build a MHK/ that can reflect
The simplified reaction kinetic model of NTO spontaneous combustion is heavy
The meaning of the meaning.
This paper builds an accurate based on existing research.
A simplified reaction kinetic model describing the MMH/NTO reaction process,
To achieve MMH/NTO chemical reaction and computational fluid dynamics coupling
Provide a valuable reaction kinetic model.
Construct
The MMH/NTO reaction history is divided into cold reverses in order of succession.
Four, thermal decomposition reaction, spontaneous combustion and high temperature reaction
Stage, 2 as the reaction progresses, these four stages each play differently
Role. In addition, this paper also considers the decomposition of fuel MMH, oxidant
Dissociation of NTO, decomposition of NO2, oxidation of intermediate CH3 and
The decomposition of HONO and other reactions.
2.1 Cold reaction
Cold reaction means after mixing from MMH/NTO to the hair
a process before spontaneous ignition, due to the reaction in the process
The temperature of the system is still low, which is generally considered to be at room
temperature (298 K).
Between 400 K, so it is called the cold reaction stage.
Once MMH is in contact with NO2, the N atom in the middle of MMH molecule
The upper H atom will be gradually removed by the strong oxidant NO2, forming the middle
Products CH3NNH2, CH3NNH, CH3N2 and HONO, this order
The activation energy of the segment reaction is very low and can be at lower temperatures (even
273 K or less) spontaneously, and emits a lot of heat, the process produces
The intermediate product HONO is unstable and will continue to decompose into small
molecules.
The important reactions in the cold reaction stage are mainly R1, R2 and R3 (see table).
1). Thermodynamic parameters and kinetic parameters of these three reactions
Available in 11, 14, 19, 20, this paper has done a numerical study on the activation energy values
of R1 and R3.
Appropriate adjustments. Thaxton et al. 21 responded to the following:
NH3+NO2→HONO+NH2 (R*)
A study was carried out and the activation energy value of the reaction was given as 104.2.
kJ·mol-1, on the basis of which Catoire et al 2 consider NH3 molecules
N-H bond (bond energy 447.7 kJ·mol-1) compared to MMH molecule
The N-H bond (368.2 kJ·mol-1) of the N atom is more stable, and the bond energy
Higher, giving the activation energy of the R1 reaction (24.7 kJ·mol-1), which is only
Considering the factor of the bond energy, the result is not reasonable enough. Since the NO2
molecule has
Unpaired electrons, high chemical activity, if NO2 is considered to be active
From the base molecule, the empirical formula for estimating the activation energy, 22 MMH+
The activation energy of NO2 reaction is taken as N-H bond on the N atom of MMH
The bond energy is about 6%, which is about 21.3 kJ·mol-1. This article considers NH3.
The molecule is a regular tetrahedral structure, which collides with the NO2 molecule.
It means that a N-H bond may break, and the MMH molecule is straight.
Chain structure, the N-H bond present in the middle N atom exists only in
Part of the MMH molecule, although it is N-H compared to the NH3 molecule
The key is more fragile, the bond can be lower, but the bond occurs with the NO2 molecule.
The probability of collision and fracture is small.
Theory, the probability of collision or the reaction activation energy and reaction
The probability of collision is related, that is, the activation energy value taken in the literature 2
should be increased.
Therefore, the value obtained by the empirical formula (21.3 kJ·mol-1)
Based on the reference to the value proposed in Document 2 (24.7 kJ·mol-1), the line
Increasing the activation energy of the reaction, taking 28 kJ·mol-1.
There is no correlation between the reactions of free radicals such as CH3NNH2 and CH3NNH.
Study, Catoire et al. 2 reacted by analogy to the following:
CH3NNH2+OH→CH3NNH+H2O (R**)
The kinetic parameters of R2 are obtained and the kinetic parameters of R3 are considered
Like R1, this paper follows this idea and gets the power of R2 and R3.
Learning parameters.
2.2 Thermal decomposition reaction
MMH is highly reactive and will be at higher temperatures
Decomposition occurs, this is the thermal decomposition reaction of MMH. In addition, cold
reverse
The HONO produced at the stage will be decomposed into small points under high temperature
conditions.
The thermal decomposition reaction of MMH will release a lot of heat,
Propellant spontaneous combustion ignition plays an important role. Thermal decomposition
reaction stage
The main reactions are R4 and R5 (see Table 1). The R4 reference
Catoire et al. 23, the reaction released a large amount in the forward direction
Heat, this part of the heat will cause the system temperature to rise sharply, resulting in
Subsequent spontaneous combustion occurs. Due to this mechanism (mechanism contains
23 components, hence the abbreviation Mech23 mechanism) lacks many intermediate
The reaction path of the components, resulting in a lower temperature when the system reaches
equilibrium.
And the ignition delay time becomes longer, in order to better reflect the fuel self-ignition
temperature
In the whole process of liter, this paper appropriately reduces the activation energy of the
reaction,
Promote the reaction to proceed, allowing the system to catch fire quickly and reach
The temperature is reasonable when it comes to equilibrium. After trying, the activation of R4 is
finally taken.
Can be about 1/3 of the value given in the literature 23. Because HONO is at high temperatures
Can not be stable, so increase the reaction R5, the reaction M is called
Trisomy, to promote the conversion of HONO to small molecule products OH and NO
Provide energy, the kinetic parameters of the reaction refer to Atkinson et al. 19
Related research, and made appropriate adjustments, on the one hand to improve HONO
Conversion rate, on the other hand, does not make R5 too fast, absorb
A lot of heat, making the system temperature rise slowly, the ignition delay time becomes
long.
The decomposition reactions involved in Mech23 are also NTO and NO2.
Decomposition (see Equation 1 for R6 and R7 for specific reaction equations).
2.3 Spontaneous combustion reaction
Spontaneous combustion is the key to the MMH/NTO reaction process.
It is also a major advantage of MMH/NTO two-component liquid fuel.
As the above two reaction stages continue to generate and accumulate heat, the reaction
The system has enough energy to stimulate the fire process, the ignition process
The time elapsed is very short, the temperature of the entire reaction system in this process
The degree and pressure suddenly rise, and the important reaction involved is R1.
R3 and R4 (see Table 1).
These three reactions are focused on the MMH/NTO spontaneous combustion
To be effective. First because the reactant molecules MMH and CH3NNH
Low stability, and there is a failure in the outer orbit of NO2 molecule
The electrons are very oxidizing, so these two reactions are very easy to occur.
Even at very low temperatures (below 0 °C) can happen quickly, positive
Because the activation energy of these two reactions is low, it will be at low temperature.
Rapidly occur under conditions and trigger a series of subsequent reactions, making
MMH/NTO can spontaneously ignite and establish high temperature, or
Said that R1 and R3 are the starting points of the entire reaction process.
For R4, because of its strong reaction, it has a strong exothermic effect.
Accumulation of heat in the system and the sudden increase in temperature during the ignition
phase
It is a crucial driving force
High temperature reaction
In the high temperature reaction phase, the MMH/NTO system mainly occurs
Lower reaction: decomposition of MMH and combustion of MMH and NTO.
The decomposition reaction of MMH has been mentioned before, the oxidation of MMH/NTO
The reactions involved in the cold reaction phase of the process are not repeated here, this
It mainly gives two important oxidation processes of CH3.
O atoms are produced by the decomposition of NO2 in the reaction system.
A series of reactions with the addition of CH3 and O atoms:
CH3→
+O
CH2O→ +O
HCO→ +O
CO2
And because of the decomposition of NO2 and HONO, it has a strong
Oxidative OH radicals and NO radicals, so consider this model
The reaction of adding OH, NO and CH3 into the type.
Added the inverse of many important small molecules (such as CH3, OH, O, NO, etc.)
Should be the path, mainly to consume the first three reaction stages generated
Inter-products, resulting in the final conversion of the entire reaction system to H2O, N2, H2
And a relatively stable small molecule such as NO, releasing the reaction intermediate
Chemical energy, the system tends to be stable. The reaction in the high temperature stage is
directly
Taken from the methane air oxidation reaction mechanism GRI Mech 2.11, select
The reaction follows the principles mentioned in the literature 24, ie for competitive reactions,
Select a reaction path with a lower reaction activation energy to reduce as much as possible
Group score, reduce the scale of the mechanism.
In summary, all the reactions of Mech23 were obtained, such as
Table 1 shows
3 verification and analysis
The Mech23 mechanism constructed above basically covers MMH/
The entire process of the NTO reaction, as there is no publicly available
Experimental study of this reaction, we aim at the theory given in the literature
Analysis and computer simulation results, using the equilibrium counter in CHEMKIN
The model of the reactor and the closed-mixed homogeneous reactor model for Mech23
The mechanism was verified and analyzed.
Ignition delay time for MMH/NTO reaction systems
Describes the delay from propellant injection into the combustion chamber to produce positive
thrust
Time, the indicator is of great significance. Adopting the simplified mechanism of construction
Calculated ignition delay time and detailed reaction mechanism and theoretical score
Analysis of the obtained data for comparative analysis.
3.1 Verification
3.1.1 Fire delay time verification
In order to verify the accuracy of the Mech23 reaction mechanism,
Self-ignition ignition process occurring in a closed full-mix homogenization reactor
Simulation, while simulating the ground test environment, select the reaction conditions
For the initial temperature T0=298 K, the initial pressure p0=2.42×104 Pa,
4. With the constant volume process, the ignition temperature rise curve is obtained.
Figure 1 shows the comparison of different mechanisms of ignition temperature rise curve. In
Figure 1,
The solid line is the temperature rise curve of the Mech23 mechanism, and the ignition delay
time is
3.2 ms; the dotted line is for Catoire et al. 2 using quantum chemistry.
The temperature rise curve of the detailed reaction mechanism, when the ignition delay is
calculated
The interval is 3.6 ms; the dotted line is Catoire et al.
(CH3N(NH2)NO2 and CH3N(NH2)ONO) action, in detail machine
Based on the rationale, the reactions related to the two components are retained, and the
The temperature rise curve of the mechanism 1 obtained by the unrelated reaction
The delay time is 1.5 ms; the dotted line is removed by Catorie et al. with CH3N
(NH2)NO2 and CH3N(NH2)ONO related components involved in the reaction
The temperature rise curve of the proposed mechanism 2 only considers the pre-ignition product
(CH3N(NH2)NO2 and CH3N(NH2)ONO)2 effects, obtained
The ignition delay time is 6.3 ms. In addition, according to Seamans et al 25
The ignition delay calculated by thermal explosion theory is 3.6 ms.
Ignition delay time and detail based on Mech23 mechanism
Reaction mechanism 2 and ignition delay obtained by thermal explosion theory 25
The agreement is good, and the simplification mechanism of Mech23 can be seen from Figure 1.
Significantly better than the simplified mechanism 1 and simplified mechanism 2 proposed by
Catorie,
Therefore, the accuracy of Mech23 mechanism is verified to some extent.
3.1.2 Pressure vs. ignition delay time impact verification
Figure 2 mainly illustrates different initial temperatures and different reactant ratios.
The effect of pressure on the ignition delay time under the condition of the condition, where the
discrete point
The value calculated for applying the Mech23 mechanism, compared to Seamans
Etc. 25 based on thermal explosion theory, the ignition delay time with pressure
Curve of variation. From Figure 2, we can see that three types of work correspond to different
line types.
Condition, as the initial pressure of the reaction decreases, the MMH/NTO fires
The late time is rapidly increasing in a negative exponential law, using Mech23 mechanism
The obtained ignition delay time varies with the initial pressure
The results obtained by Seamans et al25 are quite consistent.
3.2 Analysis
3.2.1 Effects of different pressures on the ignition process
Figure 3 shows the oxy-fuel mixture ratio (NTO/MMH ratio) as
Propellant at three different constant pressures under conditions of 1.65 (mass ratio)
Ignition temperature rise curve under force conditions. As can be seen from Figure 3, propellant
The ignition delay time of a constant pressure combustion process under standard operating
conditions
At 0.7 ms, the system quickly reaches chemical equilibrium and reaches equilibrium
The system temperature is stable at around 3000 K. In addition, with the combustion chamber
pressure
The force is reduced, the propellant ignition delay will be extended. After trial calculation,
When the pressure drops to 0.31 MPa, it advances within 2 ms of calculation time.
The agent is unable to ignite spontaneously, thus obtaining the low pressure limit of the fire.
Xiaofang et al. 26 simulates the ignition characteristics of small thrusters under low pressure.
It is pointed out that when the supply line pressure is 0.4 MPa, it corresponds to the steady-state
combustion chamber.
MMH/NTO propellant at small pulse width at a pressure of 0.3 MPa
It is difficult to ignite spontaneously within the degree, which is related to the ignition low
pressure limit calculated in this paper.
Inconsistent. Therefore, if the engine is to be produced in the minimum pulse time
Start, should ensure that the propellant supply line pressure is above 0.4 MPa
Corresponding to three different pressure conditions, the reactant system is flat
When the state is balanced, the product content is shown in Figure 4. Under steady state
conditions,
Corresponding to three different pressure values, the system exists when it reaches chemical
equilibrium
9 kinds of CH3NNH, H2, H, OH, H2O, CO2, NO, N2 and CO
The sum of the molar contents of the components is above 99%.
It can be seen that as the pressure increases, CO2, N2, H2, etc. are relatively stable.
Increasing the content of small molecules increases the equilibrium temperature of the system.
At higher temperatures, molecules such as H2O and NO are decomposed.
Decline, CH3NNH as an important reaction (R4, see Table 1)
The product should decrease as the equilibrium temperature of the system increases.
3.2.2 Influence of different oxygen-burn ratios on the ignition process
Figure 5 shows the constant steady-state combustion chamber pressure of 0.9 MPa.
Under the igniting temperature of propellant under 7 different oxy-fuel ratios
Line. At 0.9 MPa constant pressure, the propellant oxy-fuel ratio changes from 0.4
When it reaches 3.0, the ignition delay time increases monotonously, which is due to
Reduced relative fuel (MMH) content, propellant from rich to lean
The state changes, causing fire difficulties. It can also be seen that the system
The equilibrium temperature is first increased and then decreased, which can be seen from the
graph.
6 is explained.
Figure 6 shows the composition analysis of the product at different oxygen-burn ratios, when
oxygen
When the fuel ratio is raised from 0.4 to 3, the H atom content increases first and then decreases.
Trend, from the analysis of reaction mechanism, H generation is always accompanied by H2O
And the formation of complete combustion products such as CO2, so the higher the
concentration of H atoms
High, indicating that the more complete the combustion, the equilibrium temperature of the
reaction system rises
High; NO shows a trend of decreasing first and then increasing, from the reaction mechanism
Now, NO is derived from the decomposition of NO2, which has a high activation energy.
It takes a lot of heat to make it happen, which causes the reaction system to warm down.
The degree of decline is obvious, so the temperature of the reaction system is lower when the
concentration of NO is lower.
High; for very stable N2 molecules, its chemical reactivity is very low,
Higher N2 concentrations are necessarily accompanied by higher system temperatures;
At a high temperature of around 3000 K, CO fraction relative to CO2 molecules
The child is more stable, so CO also shows a first increase in concentration.
Decrease trend.
In summary, the system temperature increases with the oxy-fuel ratio from small to large
The trend of increasing and then decreasing is different from when the system reaches
equilibrium.
Balanced component concentration related.
Reaction sensitivity analysis
In order to find out which reactions are playing an important role in the fire phase
Sensitivity to the ignition delay time of the Mech23 mechanism
Analytical study, using the following conditions: The reactant ratio is MMH+2.5
NTO (1.0275 N2O4+1.4725 NO2), initial temperature T0=298
K, initial pressure p0=2.42×104 Pa, using constant volume closed full hybrid
Calculator model.
The sensitivity analysis method is to separately rate each reaction
The constant k is multiplied by 2, the other reactions are unchanged, and then in the same
calculation case
Get a new ignition delay time τ. Here, the ignition delay time
The sensitivity is defined as (τ-τ0)/τ0, where τ0 is the same mechanism as Mech23
The propellant ignition delay time obtained under the calculation conditions. Figure 7 shows
Sensitivity spectrum of ignition delay time, under which conditions
R1, R3, and R4 have higher sensitivity to ignition delay time, others
The sensitivity of the reaction to the ignition delay time is below 1%, the negative value table
Increasing the reaction rate of the reaction can shorten the ignition delay time.
Speed up the fire. R1 has the highest sensitivity to the fire delay time.
The reason is that the reaction is the beginning of the entire MMH/NTO reaction process.
The reaction provides reactants and initial energy for all subsequent reactions,
Therefore the rate and direction of the reaction occur on the ignition delay of the system
Time has a decisive role. Reaction R3 produces a large amount of CH3N2
Free radicals, and the reaction is the only source of CH3N2 radicals, from
Mech23 mechanism can be seen that CH3N2 free radical is the only CH3
Source, and can decompose to form stable small molecule N2, to the reactant system
Temperature rise has an important effect, so it is sensitive to system ignition delay time
Sense. For the reaction R4, as mentioned before, the reaction will release a large amount of
Heat, which promotes the spontaneous combustion of the propellant, the sensitivity score here.
Analysis also got the same conclusion
in conclusion
This paper constructs a 23 component and 20 primitives.
The reaction mechanism should be simplified by MMH/NTO, and it is verified.
The mechanism can accurately describe the MMH/NTO fuel spontaneous combustion
The entire process of fire. At different pressures and oxy-fuel ratios and sensitivity points
The following conclusions are obtained in the analysis.
(1) When the initial pressure of the reaction system increases from 0.5 MPa to 1.3
MPa, MMH/NTO ignition delay time is reduced, equilibrium temperature rises
High; when the pressure drops to 0.31 MPa, within 2 ms of calculation time
The propellant is unable to ignite spontaneously, resulting in a low-voltage pole that catches fire.
limit;
(2) When the oxygen-burn ratio is increased from 0.4 to 3, the MMH/NTO point
The fire delay time is prolonged, and the equilibrium temperature is raised first and then
decreased;
(3) Reactions R1, R3 and R4 have a higher ignition delay time
Figure 6 Balanced component content under different NTO/MMH ratios
Fig.6 Contents of equilibrium species under different
MMH/NTO mass ratios
Figure 7 Mech23 mechanism ignition delay time sensitivity
Fig.7 Sensitivity to ignition delay time of Mech23
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Acta Phys. -Chim. Sin. 2014 Vol.30
Sensitivity.