Insights into kinetic inhibition effects of MEG,PVP,and L-tyrosine aqueous solutions on natural gas hydrate formation

It is necessary to understand all the prerequisites, which result in gas hydrate formation for safe design and control of a variety of processes in petroleum industry. Thermodynamic hydrate inhibitors (THIs) are normally used to preclude gas hydrate formation by shifting hydrate stability region to lower temperatures and higher pressures. Sometimes, it is difficult to avoid hydrate formation and hydrates will form anyway. In this situation, kinetic hydrate inhibitors (KHIs) can be used to postpone formation of gas hydrates by retarding hydrate nucleation and growth rate. In this study, two kinetic parameters including natural gas hydrate formation induction time and the rate of gas consumption were experimentally investigated in the presence of monoethylene glycol (MEG), L-tyrosine, and polyvinylpyrrolidone (PVP) at various concentrations in aqueous solutions. Since hydrate formation is a stochastic phenomenon, the repeatability of each kinetic parameter was evaluated several times and the average values for the hydrate formation induction times and the rates of gas consumption are reported. The results indicate that from the view point of hydrate formation induction time, 2 wt% PVP and 20 wt% MEG aqueous solutions have the highest values and are the best choices. It is also interpreted from the results that from the view point of the rate of gas consumption, 20 wt% MEG aqueous solution yields the lowest value and is the best choice. Finally, it is concluded that the combination of PVP and MEG in an aqueous solution has a simultaneous synergistic impact on natural gas hydrate formation induction time and the rate of gas consumption. Furthermore, a semi-empirical model based on chemical kinetic theory is applied to evaluate the hydrate formation induction time data. A good agreement between the experimental and calculated hydrate formation induction time data is observed.

Application of butane geochemistry of natural gas in hydrocarbon exploration

In order to distinguish the source and migration direction of natural gas by geochemical characteristics of butane,the components and carbon isotopes of natural gas from major hydrocarbonbearing basins in China were analyzed.The results showed that：（1） Oil-type gas has i-C 4 /n-C 4 0.8,δ 13 C butane -28‰,δ 13 C i-butane -27‰,δ 13 C n-butane -28.5‰,whereas coal-type gas has i-C 4 /n-C 4 0.8,δ 13 C butane -25.5‰,δ 13 C i-butane -24‰,δ 13 C n-butane -26‰.（2） When δ 13 C i-butane-δ 13 C n-butane is greater than 0,the maturity of oil-type gas is generally more than 2.4% and that of coal-type gas is greater than 1.4%,whereas when the difference is less than 0,the maturity of oil-type gas is generally less than 1.1% and that of coal-type gas is less than 0.8%.（3） When natural gas migrates through dense cap rocks,the value of i-C 4 /n-C 4 increases,whereas when it migrates laterally along a reservoir,the value of i-C 4 /n-C 4 decreases.（4） Sapropelic transition zone gas with composition and carbon isotopic signatures similar to those of oil-type gas in the low thermal evolution stage is found to have a relatively high butane content.（5） The values of i-C 4 /n-C 4 and δ 13 C n-butane δ 13 C i-butane of gas which has suffered biological degradation are significantly higher than those obtained from thermogenic and bio-thermocatalytic transition zone gas.Thus,natural gas of different genetic types can be recognized through component analysis and carbon isotopic signatures of butane,the natural gas maturity can be estimated from the difference in carbon isotopic content between isobutane and n-butane,and the migration direction of natural gas can be determined from i-C 4 /n-C 4 ratios and transport conditions,which can also be used to thermogenic and bio-thermocatalytic transition zone gas.

Modeling of microreactor for syngas production by catalytic partial oxidation of methane

Fixed-bed reactors for the catalytic partial oxidation of methane （CPOM） to produce synthesis gas still pose hot spots problems.Microreactor is a good alternative reactor proposed to resolve these problems.In this paper,synthesis gas （hydrogen and carbon monoxide） production was investigated by a two-dimensional numerical model of single microchannel.Computational fluid dynamic （CFD） modeling with detailed chemistry was conducted to understand the CPOM on platinum （Pt） catalyst.Gas inlet velocity,microchannel pressure,and fuel to air ratio （F/A） are selected as the effective parameters on microchannel performance.Study results show that Reynolds number has considerable effect on methane conversion,hydrogen to carbon monoxide ratio （H2/CO）,and product distribution.Increasing gas inlet velocity causes all the above parameters to decrease.It is noted that increasing microchannel pressure and decreasing the ratio of fuel to air cause the decrease of the H2/CO ratio.

Multiobjective optimization scheme for industrial synthesis gas sweetening plant in GTL process

In industrial amine plants the optimized operating conditions are obtained from the conclusion of occurred events and challenges that are normal in the working units. For the sake of reducing the costs, time consuming, and preventing unsuitable accidents, the optimization could be performed by a computer program. In this paper, simulation and parameter analysis of amine plant is performed at first. The optimization of this unit is studied using Non-Dominated Sorting Genetic Algorithm-II in order to produce sweet gas with CO 2 mole percentage less than 2.0% and H 2 S concentration less than 10 ppm for application in Fischer-Tropsch synthesis. The simulation of the plant in HYSYS v.3.1 software has been linked with MATLAB code for real-parameter NSGA-II to simulate and optimize the amine process. Three scenarios are selected to cover the effect of （DEA/MDEA） mass composition percent ratio at amine solution on objective functions. Results show that sour gas temperature and pressure of 33.98 ？ C and 14.96 bar, DEA/CO 2 molar flow ratio of 12.58, regeneration gas temperature and pressure of 94.92 ？ C and 3.0 bar, regenerator pressure of 1.53 bar, and ratio of DEA/MDEA = 20%/10% are the best values for minimizing plant energy consumption, amine circulation rate, and carbon dioxide recovery.

Effect of mass transfer limitations on catalyst performance during reduction and carburization of iron based Fischer-Tropsch synthesis catalysts

Existence of intraparticle mass transfer limitations under typical Fischer-Tropsch synthesis has been reported previously,but there is no suitable study on the existence of intraparticle diffusion limitations under pretreatment steps (reduction and activation) and their effect on catalytic performance for iron based catalysts.In this study,Fe-Cu-La-SiO2 catalysts were prepared by co-precipitation method.To investigate the intraparticle mass transfer limitation under reduction,activation and reaction steps,and its effect on catalytic performance,catalyst pellets with different sizes of 6,3,1 and 0.5 mm have been prepared.All catalysts were calcined,pretreated and tested under similar conditions.The catalysts were activated in hydrogen (5%H2in N2) at 450℃ for 3 h and exposed to syngas (H2/CO=1) at 270℃ and atmospheric pressure for 40 h.Afterwards,FTS reaction tests were performed for approximately 120 h to reach steady state conditions at 290℃,17 bar and a feed flow (syngas H2/CO=1) rate of 3 L/h (STP).Using small pellets resulted in higher CO conversion,FT reaction rate and C5+ productivity as compared with larger pellets.The small pellets reached steady state conditions just 20 h after starting the reaction.Whereas for larger pellets,CO conversion,FT reaction rate and C5+ productivity increased gradually,and reached steady state and maximum values after 120 h of operation.The results illustrate that mass transfer limitations exist not only for FTS reaction but also for the reduction and carburization steps which lead to various phase formation through catalyst activation.Also the results indicate that some effects of mass transfer limitations in activation step,can be compensated in the reaction step.The results can be used for better design of iron based catalyst to improve the process economy.