Preparation and Structure Study of Water-Blown Polyurethane/RDX Gun Propellant Foams

Water-blown polyurethane/RDX foamed propellants were prepared using polyols and isocyanate as reactive binder system, hexogen (RDX) as energetic component, triethanolamine (TEA)/Ditin butyl dilaurate (T-12) as composite catalysts, and H₂O as blowing agent. The influences of catalyst ratio, blowing agent amount, and solid filler content on the inner porous structure were studied. The results show that the balance of gel rate and cream rate that could be adjusted by catalyst ratio is a major influencing factor on porous structure of foamed propellants. When the ratio of TEA/T-12 was adjusted to 1/0.7, the morphology of the foamed propellant exhibited spherical and closed porous structure. Besides, when the water amount was increased from 0.1% to 0.5%, the pore size increased from 0.43 to 0.64 mm. The contents of RDX particles affected the cell nucleation and thus, the cell geometry. When the blowing agent amount was constant, the increased content of RDX filler led to a decreased pore size. The closed bomb test results showed that foamed propellants burned progressively in an in-depth combustion mode.     

Modeling and Simulation of Interior Ballistics Based on Actual Combustion Characteristics of Propellants

A novel interior ballistic model was established by revising actual combustion characteristics describing the relationship between burned propellants (ψ) and pressure impulse (I_t). The discrepancy between theory and experiment for gas releasing of porous propellant was investigated. Furthermore, the model was tested for multiperforated propellants, with relative errors less than 1 and 3% for the maximum pressure and velocity, respectively, indicating that this is a good model to estimate the interior ballistics performance for multiperforated propellants.     

H2S废气反应炉燃烧数值模拟

针对某炼油化工厂H_2S反应炉设计的不同结构的燃烧器进行三维数值模拟,研究了不同燃烧器结构参数、燃料气成分与分配比例、反应炉花墙结构等因素对炉内流动与燃烧的影响,并确定了合理的燃烧器结构。结果表明:原始燃烧器结构下,单烧酸性气工况时,降低内圈酸性气比例有利于H_2S的完全燃烧,炉膛出口烟温有所提高;优化后的燃烧器结构较原始结构下,增强了内圈酸性气与空气的混合,更有利于H_2S气体的燃烧;反应炉内花墙结构能造成炉膛内烟气回流,提高了烟气的停留时间,有利于H_2S气体的燃烧完全;掺烧天然气工况较单烧酸性气工况,炉内燃烧变差。     

SLAB View软件在含硫天然气井井喷泄漏扩散模拟中的应用

介绍了SLAB重气泄漏扩散模型,并运用SLAB View软件模拟了某含硫气井发生井喷事故H2S云团的扩散过程和危害区域,得出了H2S云团在指定浓度平均时间下的影响范围,以及指定浓度H2S云团出现在最远距离的时间和最远下风向扩散距离。结果表明,SLAB View软件能方便、快速地模拟平坦地形下含硫天然气井喷泄漏扩散过程,预测事故泄漏扩散后果和影响范围。     

Methane in soil gas and its transfer to the atmosphere in the Yakela condensed gas field in the Tarim Basin, Northwest China

In this study, by analyzing CH₄ concentration and δ¹³C_CH4 in soil-gas profiles, the potentials of CH₄ gas transfer from ground to atmosphere were studied at four representative sectors in the Yakela condensed gas field in the Tarim Basin, Xinjiang, China. These are: 1) the oil–gas interface sector, 2) fault sector, 3) oil–water interface sector, 4) an external area. Variation in CH₄ in soil-gas profiles showed that CH₄ microseepage resulted from the migration of subsurface hydrocarbon from deep-buried reservoirs to the earth’s surface. It was found that CH₄ from deep-buried reservoirs could migrate upwards to the surface through faults, fissures and permeable rocks, during which some CH₄ was oxidized and the unoxidized methane remained in the soil or was emitted into the atmosphere. The lowest level of CH₄ at the soil-gas profile was found at the CH₄ gas-phase equilibrium point at which the CH₄ migration upwards from deep-buried reservoirs and the CH₄ diffusion downwards from the atmosphere met. The δ¹³C_CH4 and ethane, propane in soil gas exhibited thermogenic characteristics, suggesting the occurrence of CH₄ microseepage from deep-buried reservoirs. A linear correlation analysis between CH₄ concentrations in soil gas and temperature, moisture, pH, Eh, Ec and particle size of soil indicated that both soil Eh and soil temperature could affect CH₄ concentration in soil gas while soil pH could indirectly influence soil methanotrophic oxidation via impacting soil Eh.     

Combustion of Gas-Permeable Gun Propellants

Foamed propellants prepared by supercritical fluid foaming show considerably high burning rates due to their porous structures. To further investigate combustion of foamed propellants, quenched combustion experiments and closed-vessel experiments were carried out, Scanning electron microscopy (SEM) was also used to observe their porous morphology. The SEM images show that foamed propellant grains exhibit a porous core and compact skin. The research results show that the porous core is first burned out and the compact skin is burned out at the later burning stage. The results also demonstrate that pore size exerts an important effect on the burning behaviors of foamed propellants.     

Thermal Decomposition Behaviors and Burning Characteristics of AN/RDX-Based Composite Propellants Supplemented with MnO2 and Fe2O3

Ammonium nitrate (AN)-based composite propellants have gained popularity because of the clean burning nature of AN as an oxidizer. However, such propellants have several disadvantages such as poor ignition and low burning rate. The burning characteristics of the AN propellant were improved when a portion of this propellant was replaced by an energetic material and the addition of a catalyst. In this study, RDX (1,3,5-trinitroperhydro-1,3,5-triazine) was used as the energetic material, and Fe₂O₃ and MnO₂ were used as catalysts. The burning characteristics of the AN/RDX propellants supplemented with catalysts were investigated, and the effects of the replacement of AN by RDX and the catalyst addition were evaluated.     

Visualization of CO2 and oil immiscible and miscible fl ow processes in porous media using NMR micro-imaging

CO₂ flooding is considered not only one of the most effective enhanced oil recovery（EOR） methods,but also an important alternative for geological CO₂ storage.In this paper,the visualization of CO₂ flooding was studied using a 400 MHz NMR micro-imaging system.For gaseous CO₂ immiscible displacement,it was found that CO₂ channeling or fingering occurred due to the difference of fluid viscosity and density.Thus,the sweep efficiency was small and the final residual oil saturation was 53.1%.For supercritical CO₂ miscible displacement,the results showed that piston-like displacement occurred,viscous fingering and the gravity override caused by the low viscosity and density of the gas was effectively restrained,and the velocity of CO₂ front was uniform.The sweep efficiency was so high that the final residual oil saturation was 33.9%,which indicated CO₂ miscible displacement could enhance oil recovery more than CO₂ immiscible displacement.In addition,the average velocity of CO₂ front was evaluated through analyzing the oil saturation prof ile.A special core analysis method has been applied to in-situ oil saturation data to directly evaluate the local Darcy phase velocities and capillary dispersion rate.     

Study of Different Al/Mg Powders in Hydroreactive Fuel Propellant Used for Water Ramjet

Experiments were conducted to study the effect of magnesium–aluminum alloy on the combustion performance of hydroreactive fuel propellants. The raw metal powders added to the propellants were ball-milled magnesium–50% aluminum alloy (m-AM), magnesium–50% aluminum alloy (AM), and Al and magnesium (Mg) powders, which were characterized using scanning electron microscopy, X-ray diffraction (XRD), and simultaneous thermogravimetric analysis (TGA). A high-pressure combustor and a metal/steam reactor were used to simulate the two-stage combustion of hydroreactive propellants used for a water ramjet. The combustion performance of the metal powders in propellant was studied experimentally, and the efficiency of the Al reaction in the propellants during the two-stage combustion was calculated. TGA traces in air indicated that the oxidation onset temperature of AM powders is much lower than for both Mg and Al powders. The XRD patterns for the AM and m-AM alloys exhibited Al₁₂Mg₁₇ diffraction peaks. The hydroreactive fuel propellant systems with added m-AM powder exhibited good performance in terms of burning rate, combustion heat, and the Al reaction efficiency, which was better than that for the propellants containing AM, Mg, and Al powders. At the pressure studied (3.0 MPa), the burning rate of the m-AM-containing propellant was found to be 15 mm s^?1, and the heat of primary combustion was 6,878.1 kJ kg^?1.     

Studies on energetic compounds part 15 : Transition metal salts of NTO as potential energetic ballistic modifiers for composite solid propellants

Abstract

The combustion of hydroxyl terminated polybutadiene (HTPB) - ammonium perchlorate (AP) composite solid propellants has been studied using transition metal (Mn, Fe, Co, Ni, Cu and Zn) salts of 5-nitro-2,4-dihydro-3H-1,2,4-triazole-3-one (NTO) as energetic burning rate additives. The steady burning rate (r) was considerably enhanced with Cu(NTO)₂ and Fe(NTO)₂ whereas moderately enhanced with Zn(NTO)₂ and Co(NTO)₂ at low concentration (2% by wt.). Activity of these salts has been observed during isothermal decomposition of AP at 260°C. The values of ignition delay (t_iJ), ignition temperature (T_ign.) and activation energy for ignition (E?) for AP has also been lowered when these salts are added to it at 2% wt. concentration. The processing parameters as well as mechanical properties of the propellants with Cu(NTO)₂ as additive have been studied in detail. The r of the propellants (both highly aluminized and less aluminized) with Cu(NTO)₂ as additive at various concentrations, has been determined at high pressures, also shows its activity during combustion, The condensed phase activity of Cu(NTO)₂ during propellant decomposition has also been studied using TG-DTG techniques.     

A Finite Element Computational Method for Gas Hydrate. Part II: Application

Abstract

A finite element model has been applied to the dissociation of gas hydrates in porous media by hot water injection. In the first step, it was applied to calculate the temperature and saturation profiles for a two-phase convective heat transfer case. The second step involved hydrate thawing calculations with release of water and gas. Realistic results were obtained in predicting the temperature, pressure, and water saturation profiles in the hydrate medium with respect to time, when subjected to hot water injection at high pressure in a wellbore. Furthermore, the thaw front progression calculated by this scheme exhibits stable and satisfactory behavior with respect to time.     

高含CO2天然气脱碳工艺中MDEA活化剂优选

国内高含CO_2天然气处理装置主要采用活化MDEA脱碳工艺。以DEA、MEA、PZ为活化剂,总胺物质的量浓度控制在4 mol/L。利用HYSYS软件建立运算模型,研究这3种活化MDEA溶液对CO_2的吸收性能和解吸性能,通过分析认为,高含CO_2天然气深度脱碳处理宜采用PZ为活化剂。对PZ的活化机理进行研究,发现PZ作为活化剂的效果远胜于DEA和MEA。最后,分析不同吸收温度及CO_2分压下PZ浓度变化对活化性能的影响,发现加入少量PZ即可大幅提高PZ活化MDEA溶液与CO_2反应速率,在不同CO_2分压和吸收温度的条件下均能满足高含CO_2天然气的脱碳处理要求,适应性较强,建议活化MDEA溶液中PZ的质量分数为3%~5%。     

Plasticizer migration in nitrocellulose-based propellants

Abstract

An “environmentally-friendly” technique for determining plasticizer concentration profiles in propellant sheets has been developed. The method was developed in response to a need for a quick, accurate means to study plasticizer migration in experimental gun propellents. Evidence of rapid migration between laminated sheets of nitrocellulose-based propellant containing different amounts of two nitrate ester plasticizers was obtained. An estimate of the diffusion coefficients for one of these plasticizers was also obtained.     

Combined evaluation of nitrocellulose-based propellants: toxicity,performance, and erosivity

ABSTRACT

New formulations of nitrocellulose-based propellants were evaluated aiming less-toxicity-and-less-erosivity. Three original ingredients of M-14 propellant – dinitrotoluene, dibutyl phthalate, and diphenylamine – were replaced. The new formulations, with ballistic performances similar to M-14, were based on ethylcentralite, akardite-II, RDX, diethylene glycol dinitrate, triethylene glycol dinitrate, and acetyl tributyl citrate (ATBC). The toxicities of the crude ingredients were analyzed. The H₂ content in the combustion products was a key point in the analysis. The best results were found to the compositions based on ATBC and akardite-II only. The work can be used to guide future works related to new formulations of propellants.     

Catalyst Effects of Nanometer CuCr2O4 on the Thermal Decomposition of TEGDN Propellant

The catalyst effects of nanometer CuCr₂O₄ on the thermal decomposition of triethyleneglycol dinitrate (TEGDN) propellant were investigated using thermogravimetric analysis, differential scanning calorimetry, mass spectrometry, and Fourier transform infrared spectroscopy. The Ozawa equation and step integral equation were used to calculate the activation energy. The results showed that the thermal decomposition reaction of TEGDN propellant can be seen as two reactions. Nanometer CuCr₂O₄ added in TEGDN propellant reduced the activation energy of the second reaction step; therefore, the second reaction step was sped up. Mass spectrometry, Fourier transform infrared spectrometry and the combustion residue analysis results also supported this conclusion.     

Detonation properties of ammonium nitrate/nitramine-based composite propellants

ABSTRACT

Ammonium nitrate (AN) propellants have attracted attention because of their low cost and ecofriendliness despite certain major disadvantages such as low burning rate, poor ignitability, low energy, and volume change due to phase transition of AN. The addition of nitramine to AN propellants is one of the approaches to overcome these disadvantages. However, AN/nitramine propellants are characterized by easy initiation, high sensitivity, and high detonation velocity because of the high energy of nitramine. The detonation properties of AN/nitramine propellants were investigated in this study. It was observed that the AN/nitramine propellant required a booster to detonate the propellants, as detonation did not occur while using only a commercial electric blasting cap. It was further observed that the detonation velocity (D) increased linearly as the mass of nitramine per unit propellant volume was increased, and AN had a negligible effect on the detonation properties. An approximate equation was derived from the relationship between D and the mass per unit propellant volume of nitramine. The dominant factors that can be used to estimate the detonation/no-detonation boundaries of the propellants were identified, and the experimental boundary equations were determined using these factors.     

Burning rate of artificially aged solid double-base gun propellants

ABSTRACT

Nitrocellulose (NC) and nitroglycerin (NG) are conventional energetic ingredients of solid double-base gun propellants. NC and NG are aliphatic nitrate ester compounds that are manufactured by nitrating through immersion in acid. Solid propellants are used in a wide range of both civilian and military applications, for example, as gas generators in airbags, as fuels in rocket motors or to shoot projectiles in guns. In all illustrations, the function of solid propellant is to generate gas, which is then employed to do mechanical work. The maximum pressure and the projectile velocity are important parameters of the interior ballistic process. The goal of the interior ballistic design of the gun is to attain a higher muzzle velocity under the smaller maximum chamber pressure. The burning rate of the propellant directly affects the formation rate of burning gases, which affects the ballistic parameters, either by diminishing the ballistic effectiveness or raising the safety hazard to the operator during firing. Note that the effect of the change of burning rate is not always negative; the fact is that we could change/control the burning rate to get better ballistic performances, includin ballistic efficiency as well as launching safety. Nevertheless, nitrate ester propellants are subjected to physical and chemical degradation during storage and this can modify the burning rate. Here we describe the effect of aging on the burning rate of spherical double-base propellants both qualitatively and quantitatively. We experimented unaged propellant, and propellant that was artificially aged at 71°C and 80ºC. The durations of heating at 71ºC were 10, 20, 30, 37, 48 and 62.5 days, respectively. The durations of heating at 80ºC were 1.8, 3.63, 5.41, 7.22, 9.02 and 10.83 days, respectively. The burning rate of investigating propellant was obtained by using closed-vessel experiments. The results show that towards low pressures, the burning rate increased with aging. Towards high pressure, the burning rate decreased as a function of aging. The effect of aging was quantified by the determination of defined aging sensitivity coefficients.     

大型天然气净化厂硫磺回收加氢尾气深度脱硫技术研究及工业应用

针对硫磺回收加氢尾气脱硫溶剂在低压下脱硫效果不理想导致排放尾气中SO_2质量浓度较高的问题,研究开发出了CT8-26加氢尾气深度脱硫溶剂,并在遂宁龙王庙天然气净化厂尾气处理装置上得到工业应用。应用结果表明,在天然气净化厂气质条件下,可使脱硫后加氢尾气中的H2S质量浓度20mg/m~3,能显著降低排放尾气中的SO_2质量浓度。     

The effect of wettability heterogeneity on capillary pressure and relative permeability

The effect of wettability on fluid flow properties in porous media has been extensively studied, and is still a subject of highly active investigation. Most of the work has focused on cores of homogeneous wettability. Little attention has been paid to wettability heterogeneity effects at the core or pore scale. In a previous paper, we reported on a series of centrifuge experiments performed to study the effect of wettability heterogeneity on capillary pressure. An experimental technique, named cyclic aging, was developed to create regions of different wetting in the same core sample. In this paper, the work is extended to study the effect of wettability heterogeneity on both capillary pressure and relative permeability curves using centrifuge, continuous injection and steady state techniques.The experimental procedure consists of three steps: (1) the core plug is fully saturated with brine and subsequently a drainage experiment is performed targeting an initial oil saturation S_oi, (2) after aging, oil is displaced by water to residual oil saturation S_or, and (3) oil is injected targeting higher initial oil saturation. In the secondary drainage experiment (step 3), oil first displaces water from the pores exposed to crude oil in primary drainage (step 1) and then enters fresh pores not exposed to crude oil before.In our previous study, it was found that wettability heterogeneity caused a step change in capillary pressure which correlated very well with the saturation at which wettability contrast was expected. However, the height of the step could not be explained by wettability contrast and/or water trapping alone. An experimental artifact caused by the centrifuge technique made the step higher than expected. The experimental artifact was the result of the nonuniform saturation profile developed across the core at the end of the centrifuge experiment. In this study, new techniques were used which resulted in a uniform saturation profile along the core sample during the primary drainage experiment. It was found that in this case the step in the capillary pressure is determined by wettability contrast and water trapping. It was also found that the relative permeability curve changes its characteristics when oil accesses the pores not previously exposed to crude oil.The results of this study show that (1) only the part of the pore space exposed to crude oil undergoes wettability changes on both core scale and pore scale, and (2) ignoring wettability heterogeneity can lead to large errors in the estimated two phase flow functions with important consequences with respect to fluid flow in porous media.     

An Experimental Study on the Applicability of Water-alternating-CO2 Injection in the Secondary and Tertiary Recovery in One Iranian Reservoir

Abstract

The objective of this study was to experimentally investigate the performance of water-alternating gas (WAG) injection in one of Iran's oil reservoirs that encountered a severe pressure drop in recent years. Because one of the most appropriate studies to evaluate the reservoir occurs generally on rock cores taken from the reservoir, core samples drilled out of the reservoir's rock matrix were used for alternating injection of water and gas. In the experiments, the fluid system consisted of reservoir dead oil, live oil, CO₂, and synthetic brine; the porous media were a number of carbonate cores chosen from the oilfield from which the oil samples had been taken. All coreflood experiments were conducted using live (recombined) oil at 1,700 psi and reservoir temperature of 115°F. A total of four displacement experiments were performed in the core, including two experiments on secondary WAG injection and others on the tertiary water and gas invaded zones WAG injections. Prior to each test porosity and permeability of dried cores were calculated then 100% water-saturated cores were oil-flooded to obtain connate water saturation. Therefore, all coreflooding tests started with the samples at irreducible water saturation. Parameters such as oil recovery factor, water cut, and gas-oil ratio and production pressure of the core were recorded for each test. The most similar experimental work with the main reservoir condition, indicated that approximately 64% oil were recovered after 1 pore volume of WAG process at 136,000 ppm brine salinity. Although tests show ultimate recovery of 79% and 55% for secondary and tertiary injection in gas and water invaded zones, respectively, immiscible WAG injection efficiency in the gas and water invaded zones will not be proper. In the similar test to field properties, the average pressure difference about 70 Psig was observed, which shows stable front displacement. These experiments showed that there was significant improvement in the oil recovery for alternating injection of water and CO₂, especially in the secondary recovery process. Water breakthrough time in almost all of the tests shows frontal displacement of injected fluid in cores and produced gas-oil ratio changes a little whenever the injection is miscible and increases rapidly in immiscible processes.