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Steam Reforming - Science topic

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A typical reforming section in a large-scale Haber-Bosch process (Figure 1) comprises two reactors. A mixture of methane (CH4) and steam (H2O) is fed into a primary reformer to produce syngas via steam reforming (SMR). The gas product is then fed into a secondary reformer where it is mixed with air before going through a second steam reforming process. The air introduced into the secondary reformer (ATR) provides not only a suitable amount of nitrogen for ammonia synthesis but also some oxygen to exothermally oxidize part of the feed stream, thus decreasing the energy requirements of the steam reforming section of this reformer.
An alternative reforming process is proposed in Figure 2. Unlike the conventional approach, the first reactor is used to catalytically oxidize the methane feedstock at low temperatures using a sub-stoichiometric amount of air (CPOX) and consuming 100% of the oxygen. In the secondary reformer, a steam reforming process is performed to increase the amount of H2 produced.
Based on thermodynamic grounds, these two processes are expected to produce the same reformate; however, the use of low-temperature catalytic partial oxidation in the first reformer may lead to smaller reactor sizes as well as the reduction of potential fire hazards as flammable mixtures will not be exposed to high temperatures.
Is there any other foreseeable advantage of the alternative reforming approach?
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Ok, I salute your thinking keep it up with good ideas, The great work because the primary reformer is the main contributor of GHG.
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I need a PET + Solvent mixture to feed it to a fixed bed reactor for steam reforming.
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PET is insoluble in water, diethyl ether, and many common organic solvents. However, it is soluble in DMSO, nitrobenzene, phenol, and o-chlorophenol. The reforming can be done with fixed bed reactor using Ni over La2O3-Al2O3 support with temperature 700 degree C to 800 degree Cent. PET can be efficiently converted to hydrogen and valuable fuels at optimized condition. Production of hydrogen from plastic waste could be a prospective key to the ecological problems resulted from waste.the steam reforming of Polyethylene terephthalate (PET) dissolved in phenol can be conducted in a fixed bed reactor using above mentioned catalyst.
The following five factors studied be maintained
1. Temperature of the furnace
2. Feed flow rate
3. Mass flow
4. Phenol((C6H5OH))concentration and
5. Concentration of PET solution (E),
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I would like your expertise and guidance regarding a challenging Computational Fluid Dynamics (CFD) problem I currently have. The project involves species transport in Ansys Fluent, focusing on simulating a steam methane reforming process.
The issue I am encountering pertains to the Chemkin files that I have uploaded into the Ansys Fluent software. Unfortunately, I am encountering persistent errors, and it seems the software is not properly considering the uploaded Chemkin files. I have thoroughly reviewed the inputs, but the problem persists. Despite my best efforts, I have been unable to resolve this issue.
Furthermore, in this simulation, a key aspect involves maintaining a wall at an elevated temperature of 2000 degrees Celsius. The objective is to facilitate heat transfer to the methane and steam feed mixture to initiate the steam methane reforming reaction.
Regrettably, I have observed that the heat is not effectively transferring to the feed mixture, resulting in the absence of the desired chemical reaction. This poses a significant setback to the project, as the core objective is to study the reaction kinetics and product distribution in this specific environment.
Your support in this matter would be immensely important to my research progress.
Thank you in advance for considering my request. I am eager to learn from your expertise and am open to any suggestions or instructions you may have.
Sincerely,
Sudeep N S
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Hi Anurag Sharma,
Thanks for showing interest in my problem.
Could you please review the attached files and guide me in understanding the concept of the core?
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Hi all,
To set things clearly: I am a PhD student working on the process implications of electryfing the ammonia production by replacing conventional SMR with Water Electrolysis. A part of my preliminary work is to assess the difference in theoretical minimum energy consumption. To do so, I have calculated a first approximation by summing up the reactions (SMR, Water gas shift, Haber-Bosch,...) and calculating the enthalpy of the resulting "total" reaction. I have done this for the "Water Electrolysis + Haber-Bosch scenario" and validated the minimum with values from the literature.
However, for the conventional "SMR + Haber-Bosch scenario", values from the literature are different. To be more specific, here is the energy minimum calculated in the following conference paper:
(...) the theoretical minimum of energy consumption for the process itself (represented by LHV of methane) is 22.2 GJ/t NH3 (...)
So here is my question: Why use the LHV of methane (instead the enthalpy of reactions) to calculate the energy minimum ? I feel like this is incorrect as I do not take into account the synthesis of methane.
Thanks in advance for any answers,
Antoine
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The paper you cited also includes the combustion of methane to provide the energy needed to account for the endothermic reaction as well as bringing the reaction temperature to that where the reaction occurs (850 C). For the combustion reaction, the LHV of methane is appropriate, where as for the SMR reaction, the heat of formation is appropriate. The reactor(s) consist of tubes packed with catalyst where the SMR, WGS, and HB reactions occur. On the outside of the tubes, CH4 is burned using either air or pure O2 to provide the energy needed for the process.
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How to solve x, y, and z on Matlab or excel?
I have tried many times but all times get negative values for x and y (using equation 7-13). If you have any idea or MATLAB code to solve these equations, then please let me know.
fuel composition is CH4=97%; CO2=1.5%; N2=1.5%
Air Composition is O2 =32%; N2=79%.
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Dear all,
I have planned to do kinetic studies of Dry (CO2) Reforming of Methane experimentally and theoretically for my developed Ni/CeX-Zr1-XO2. I went through some published papers, and they have shown the final kinetics equation based on different kinetic models, which is very difficult for me to understand and perform for my experiment. May I get help from any one of you in this regard or anybody willing to research collaboration with me in these regard?
Thank you in advance for your kind consideration and any valuable supports!
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Okay, thank you Sudesh Kumar !
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I've been tasked to design a PSA to produce 99.9% pure hydrogen via steam reforming. The inlet feed into the PSA consists of hydrogen, carbon monoxide, carbon dioxide and nitrogen. Can anyone please help me on how i would go about designing a PSA.
Thanks
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The World leader for H2 plants design and construction is a TechnipFMC. You can Google this company and get a lot of answers to your question about PCA design
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I want to convert flow rate unit Cubic centimeters per minute to KPa. What would be the conversion for 60 SCCM of H2 in KPa.?
Thank you
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I recommend you use PV=znRT.
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In general, syngas from gasification or steam reforming, etc, can generate H2, CO, CO2, and/or CH4.
However, many papers compared only H2/CO.
Therefore, I want to know the reason why H2/CO2 is not used.
Is there a characteristic or importance of H2/CO?
Thank you so much!
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Colleaque ,more informations in the attached ref:Sciencedirect.Com.topics/en
Best regards
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Hi,
We all know that the catalysts provide an alternative (lower energy) pathway for a reaction to occur. For example, the gas reforming reactions (say steam reforming of methane) are highly endothermic and the use of catalysts economize the reaction. But how does all this actually take place? I just want an explanation that can help me realize this phenomenon.
In absence of catalyst the gas molecules can collide at very high temperatures (>1000 oC) to form the products, but in presence of catalyst the same reaction is taking place at 600 oC. How this happens?
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i agree with
Mohammad Yusuf
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Dear all ,
I want to use Rapidox 7100 Multigas Analyser to analyze the reactants and products of the dry CH4 reforming reaction . But the instrument is not responding, I am working at a total flow rate of 60ml/min( CO2:CH4:N2, 5:5 :50 ml/min), can there be a flow rate problem? If not, if a colleague works with the same instrument, please clarify especially the connection of the gas inlet.
thanks
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Hydrogen plant has a turndown ratio of 40% and after reaching this stage, extra H2 is being produced than the required. So it is being vented.
Is there any way to stop this venting and use it as a fuel somewhere like boilers by mixing it with current fuel-natural gas?
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Yes you can use H2 as fuel but there may be some problems related to the low volumetric heating value of H2 (valves wide open to produce required heat).
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Im currently designing an adiabatic pre reformer? I cant find any reference regarding the rate of reactions and also kinetics for the pre reformer design.
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This presentation should help. Reactions approach equilibrium. The Prereformer cracks all of the heavier Hydrocarbon to methane (exothermic) and does a small amount of reformiing (exothermic) there is typically a small net temperature rise across a pre-refomer for heavy feed and net decrease for natural gas feed
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In order to simulate one process of SOFC with internal methane reforming, in the Reformer some reaction take a place like: CO+H2O = CO2+H2, C+CO2 = 2 CO, C+H2O = CO+H2, CO+3 H2 = CH4+H2O, C+2 H2 = CH4 and each of this reactions have an equilibrium temperature, which tells me the direction of the reaction.
I need to know, what is the relationship between the equilibrium temperature and the mass flux of the fuel, which enter the reformer. In my case, I use the exhaust gases generated in the Anode to supply the Reformer with energy after mixing with the natural gas. It will be very helpful if there is a Formel or scientific paper which gives the relationship between the equilibrium temperature in the reformer and the mass flux of the fuel entering the reformer.
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Here is a spreadsheet that does the calcs you need based on a fired heater H2 plant design. You should be able to modify it to match or extract the thermodynamic that you need.
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The most current research focused on hydrogen production, storage, and use, considers the following distribution of commercial hydrogen production technologies as the standard for the global hydrogen production matrix:
48% methane steam reforming
30% oil/naphtha reforming
18% coal gasification
4% water electrolysis
However, this information is more than 30 years old and comes from the statistics of the world hydrogen production from 1988 presented by (Roesler, R. and Zittel, W. 1994). I have tried, unsuccessfully, to update these numbers to today's reality.
Finally, I would like to know your opinion on this topic. Do you consider it to be worthwhile to update this information, and if so, do you have any information on where these data could be found?
Attached you may find a paper by Gaudernack from 1998 where Roesler is cited.
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I would recommend you to read the report "The Future of Hydrogen" by the International Energy Agency, which I identified earlier in my previous comments to this post.
Best Regards.
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In ethanol steam reforming , how to calculate the heat of the different unit operation in aspen plus, provided with different NIO/ethanol molar ratios and the carbon yield?
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Why would anyone want to turn ethanol - a valuable trasportation fuel in syngas - CO + H2 waiting t be turned into something more valueable - like ethanol.
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Hydrogen is an eco-friendly fuel in part because when it burns, the result is water. However, there are no convenient suitable natural sources for pure hydrogen. Today, hydrogen is obtained by steam reforming (or "cracking") hydrocarbons, such as natural gas. This process, though, requires fossil fuels and creates carbon byproducts, which makes it less suited for sustainable production.
Steam electrolysis, by contrast, needs only water and electricity to split water molecules, thereby generating hydrogen and oxygen. The electricity can come from any source, including wind, solar, nuclear and other emission-free sources. Being able to do electrolysis efficiently at as low a temperature as possible minimizes the energy needed.
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Dear Lala,
There is also the H2 generation by water electrolyzer driven by the PV generated power. Every device is efficiency optimized to realize the maximum yield of the system. There is also the direct water analysis by using photoelectrochemical electrodes., which can derive autonomously the analysis process without assistance from an electrical source. This effort was within the scope of a project called Hysolar at King Saud University.
Best wishes
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I have both the mass and energy balances from Aspen plus; I was thinking of specifying the residence time and then calculating the volume from that but I can't find the typical values for residence time in industrial reformers.
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hi anybody, what is circular variable dependency in comsol and how can i overcome it? im working on modeling and simulating of methane steam reforming in membrane reactor and i use a kinetic that its expressions are circularly depended to each other , this is a 2-D steady model. i wonder if you help me thanks
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Circular variable dependence happens a lot in simulation models. It usually requires one stream to be identified as a recycle in order to converge. I don't know if a similar approach is possible in the comsol environment.
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I'm designing a primary reformer(tubular top fired methane steam reformer) for a ammonia production plant. I have issue in deciding the mounting method of tubes and standard gaps between tubes and furnace wall. It will be great if you can help me with resources
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Chathura,
Optimizing Steam Methane Reformingfurnace design is a complex and diffiicult issue. It is importand to arrange the tubes and the burners in a way that makes the heat flux at each tube as uniform as possible. There is some flexibility to adust indivisual burners to help even out heat flux and make tube metal temperatures as uniform as possible.
Inside of the furnace most of the heat transfer is radiant including flame to tube, flame to wall, wall to tube and tube to tube radiation. An ideal design would spreadout heat flux ubiformally across all tubes and vertically in a way that matches the heat of reaction required for the steam refoming reaction aong the tube.
Some H2 plants have offset convection sections to prevent the loss of radiant heat to the convection section, some have terraced walls, Some have extremely large numbers of side fired burners whil others have larger bottom fired or top fired burners. It is a complex optimization that ttempts to trade of efficiency, reliabilty and cost in an optimal way. Halder-Topsoe tends to publish information about their desing more frelly than other licensors. I have attached two public domain articles on H2 plant design. I have a lot more. Hopefully these will give you a feel for how different licensors approach H2 plant design. It is a trade off between Investment cost and efficiency that must also maintain safety and reliability
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How can we overcome the sintering of nanoparticles, happens at the surface, in the synthesis of Pd-based intermetallic compound as a catalyst on Methanol Steam Reforming process? In face, the most challenging part of synthesizing an intermetallic compound is the annealing section where the mixture should go through a comparably moderate heating so that we could reach the ordered compound known as intermetallic, not an unordered alloy (solid solution).
You may want to consider ZnPd (intermetallic) as the case study. Recommending some applicable papers is profoundly appreciated.
Thank you in advance.
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Sure. Thanks for your help. I thought there is a special technique.
All the best.
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Main Liquid products are Glycerol water acetic acid acrolein acetone methanol and ethanol.
Is there any way to avoid ion exchange column for such components detection ?
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Dear Mustapha,
You should be able to analyze the samples on HP-5.
I have performed glycerol etherification and analyzed the products on GC with BPX-5 type capillary column. Please see my article for details. I hope this would be helpful.
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I have run preliminary reaction for Methane dry reforming at 1:1 ratio of CH4:CO2 at 500 oC and 600 oC, the conversion was as following:
500 oC  CH4= 14% CO2= 20%
600 oC   CH4= 36% CO2= 46%.
For the Design of Experiments (DOE) Shall I start from 500 oC.
Thank you
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How about  the stoichiometric relations. Just define one conversion degree.
Regards,
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In oxidation growth processes, parabolic kinetics occurs when the mass gain or oxide growth on a sample is proportional to the square root of time.
In my case I only have experimental data correlating the average thickness of the oxide growth with square root of time and as a result, I am trying to convert it from [m2/s] to [g2cm-4s-1] in order to compare with other studies wherein their focus was mass gain.
Thank you
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Film thickness w and film mass m are related by material density \rho and film area A as
    m = w A \rho
You are after rmA = (dm/dt)/A = (dw/dt) \rho, the rate of mass per area per time. You must obtain dw/dt, the rate of change of film thickness per time. You have the constant k in the equation
    w2 - wo2 = k t
You can determine from this that
     2 w dw = k dt
This leads to the following expressions 
     rmA =  (k \rho) / (2 w)
The growth rate depends on the thickness of the film. It is not just one value for the entire film growth process.
Suppose that you have a spreadsheet with three columns: t, w, and w2. You have determined k and you know the film density \rho. Create a fourth column to calculate rmA according to the above equation.
To summarize, to obtain rmA, you must
  • know the density \rho of the deposited film
  • report the value as a function of t, w, or m
As a further recommendation, when you have determined k by non-linear regression, you will also have \Delta k, the standard uncertainty of the fit constant. Linear propagation of uncertainty will show you that 
    \Deltar2 rmA = \Deltar2 k + \Deltar2 w
This rigorous analysis of the confidence in you final report should be included.
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I am running dry reforming on Ni-based catalyst. During the reaction Huge amount of carbon formed below the quarts, However, this coke formation doesn't deactivate the catalyst. If I want to quantify the carbon shall I consider the carbon on the catalyst or both (below the quartz wool. I could easily separate the layer of carbon formed below the catalyst bed.
Thank you
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Dry reforming usually makes a lot of carbon in and around the catalyst. Many patents and articles offer ways to decrease the carbon. One of my first technical jobs was to enter the vessels during shut down and take measurements for evaluating different ways of adding value and decreasing cost.  
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Carbon formed on the catalyst used for dry reforming. From the attached SEM image can I know the type of carbon. Thank you
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It looks like thin graphite flakes. XRD and/or Raman will tell you more about the nature of the carbon.
Alain
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I have a Two Stage Coal Gasifier. The Oxidation and Reduction zones are in the Annular Boiler. We would like to measure the bed temperature at difference heights of the annular boiler. we have concerns about drilling through the annular boiler plates as that might compromise the strength on the plates. What other options can I consider as means of measuring the temperatures at different zones.
Regards
Lawrence
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as said by Eslam.. infra red thermometer will solve the purpose.
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What would be the most accurate method to calculate the LHV of a fuel (heterogeneity of IW and MSW)  in a incineration power plant. If hydrocarbon contents, and other relevant elements are unknown (question of a real-life practice) 
For instance, could the property of a steam, boiler efficiency, etc.  be used in a reversed calculation. And how could it be done?
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The difference between the values of HHV and LHV is the heat required to evaporate the water content in the fuel.
The best way to measure the LHV is to perform elemental analysis on a fuel sample to know the content of carbon, H2, S, etc.
You can write down the combustion equation of each element and sum up the oxidation energy (heat of reaction) to calculate the required heating value. For example:
C + O2 ==> CO2 + heat
H2 + 1/2O2 ==> H2O + heat
S + O2 ==> SO2 + heat
Hope this helps answer your question
Professor Yehia Khalil, Yale University, USA
Fellow of the University of Oxford, UK
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Does anybody have experience with the online detection of carbon formation in a reforming process? We would like to determine if any carbon is formed during operation. One of the ideas is to use mass balance over the reactor. Does anybody have experience with this, may it be accurate enough?
Can anybody reccomend literature on this? So far all literature I know discusses the analysis of the catalyst itself outside the reactor via XRD or similar techniques.
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Actually, I am working on steam reforming of hydrocarbons field. As we know, lots of carbon generate over catalyst surface during reaction time. Before the reaction, I used binder such as bentonite to make catalyst extrude. So, the bentonite surface area will include with actual catalyst surface area. I want to know that how can I know the surface area of the catalyst after reaction.    
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Dear Sujoy Bepari,
Specific surface area (SSA) is a property of solids defined as the total surface area of a material per unit of mass (with units of m²/kg or m²/g) or solid or bulk volume (units of m²/m³ or m−1).
It is a derived scientific value that can be used to determine the type and properties of a material (e.g. soil or snow. It has a particular importance for adsorption, heterogeneous catalysis, and reactions on surfaces.The SSA can be simply calculated from a particle size distribution, making some assumption about the particle shape. This method, however, fails to account for surface associated with the surface texture of the particles.The SSA can be measured by adsorption using the BET isotherm. This has the advantage of measuring the surface of fine structures and deep texture on the particles. However, the results can differ markedly depending on the substance adsorbed.
Regards,
Prem Baboo
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Considering an initial mixture of steam and methane with steam to carbon ratio of 2, based on the methane steam reforming and water gas shift reactions, how can I compute the mixture composition after 10% pre-reforming, where the shift reaction is at equilibrium?
Actually, I know the procedure for determining the mole fractions at equilibrium considering the two reactions, but I don't understand the role of the word ''10%'' pre-reforming in the problem !!
Thanks in advance.
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please refer to one of my articles [J. of Natural Gas Science & Engineering, 21 (2014)275-282 or Energy Conversion and Management, 88 (2014)1011-1019], as you see, in the pre-reformer we assume that all heavier hydrocarbons
are converted to methane and CO in this section. So the question is that what is your feed composition?if your feed contains heavier hydrocarbons, pre-reformer is mandatory and you should consider converting of thus components to CO and methane.
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it is possible to minimize coke formation by using non acidic catalyst
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Yes.
-Use some additives, as : calcium, barium, lanthanum, potassium;
- Improve the metal dispersion on support;
- Use high V/C relations and a bigger temperature.
There are a lot of literature about this issue. Look for Rostrup-Nielsen articles.
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We performed a Raman-TPO (up to 600 ºC) experiment with a spent catalyst, deactivated by coke in a bio-oil steam reforming process, and the Raman spectra were recorded during the combustion process. However, we see an increasing G band width and D/G ratio and a decrease in G band position during the process, which is not in line with Robertson ('Diamond-like amorphous carbon', 2002). Do our results have any sense? I will fully appreciate any provided help, thanks a lot.
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Many thanks to both.
Cédric, in my case the parameters show the opposite trend of yours, as it is a combustion and not a 'reorganization'/aromatization of the structure, but both cases are in line with Robertson 2002. We did not observe that reversible shift you mentioned.
Julien, we have been deconvoluting the bands into lorentzians from the first moment, but thank you for the bibliographic support.
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I would appreciate it if  there are any appropriate scientific references paper in which the authors are working on a small scale anaerobic digester  combined with steam reforming followed by Fischer Tropsch reactor.
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Go to this website may please may can help you 
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A set of experiment for steam reforming were carried out using NiO at 800C varying the time, after reforming experiment the NiO reduced to Ni with adsorbed C.
Hence, I want to evaluate the amount of Carbon deposited in the NiO catalyst.
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Low Z elements like Carbon are difficult quantify by XRD, I  suggest you use for example XPS spectroscopy it is surface sensitive tecnique.
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The goal of gasification/ steam reformation is the complete transformation of feedstock carbon content into gases (syngas) with high heating values. The Boudouard reaction is a very important process to achieve this goal by transforming solid residue carbon content and non-combustible carbon dioxide into a usable gas - carbon monoxide and increasing the heating value of the produced syngas.
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It seems to me that the generation of the intercalation compound include the modication of the graphite structure. If it is so, how the intercalation compounds are created should also be considered.
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i working for methane steam reforming simulation.
i want calculate the heat transfer coefficient in catalyst bed.
and i want compare to some one's coefficient.
Currently I am studying 'Methane Steam Limitations and Reforming II. Diffusional Reactor Simulation'
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There is no simple answer to your question. You may use Schlünder's Heat Transfer Atlas" for resolving your problem. You will get thje heat Transfer coefficient between wall and porous media and in the porous media. The last depends heavily on the heat transfer of the fluid and less of the solid and of course of the flow.
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What is the optimum steam to carbon ratio for steam reforming of naptha C11H24, and how do you get the balance in the desulfurizer for removing 22 ppm by weight of sulphur contained in the liquid naptha? I used a ratio of 6.5 and my balancing gets off tune in the primary reformer.
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Hi Masih
Yes,please find attached.
Best Regards
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The pipe is horizontal and is rotating about its central axis. The pipe resistivity is very low (range 10^8 ohms). A very high current will be required in general to generate heat fluxes in the range of 2kw at least.
Is it feasible to go ahead with this kind of a set up.
Conventional heaters will restrict the access to various sections of the pipe and I would like to access all the parts of the outer pipe surface in order to measure local temperatures.
The flow rate will be in laminar range and the pipe is partially filled with water.
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I return to my original question. Do you know that you can get a power supply big enough to handle the current and voltage requirements that you have calculated? Aside from asking whether anyone else has done this kind of set up, you absolutely need to look (on line for example) to see if you can find a power supply to handle your requirements.
As for heating hollow tubes with current flow, I have done this on a smaller scale in the past. High currents (up to about 10 amps) were required, and I found a power supply for what I needed. I had gas flowing through my tube. With water flowing through your tube, you will probably also have to consider how best to insulate your system electrically.