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Coking

Why it is necessary to maintain sulphur content to certain ppm in feed Liquid/Gas before going to furnace for cracking is it to reduce coking rate. Though we do presulfiding for passivation of coils.
Andr Vilelas That is one reason: coking rate. The other reason is to minimize the carburization effect of the radiation in the coils. With temperature, the coil material (Ni, Cr, Mo, etc..) starts to migrate and those "spaces" in the material matrix are filled with carbon. At certain point in time, the coil material no longer has its original properties (noble metals contents) and it is carburizes (or carbonized). It's now more easy to the coil to breake. In such an event, a fire inside the firebox will happen and the melting of the coils may occur. So: - always keep a certain amount of suphur (<100ppm in the feed, presulphide with TBPS, DMDS, DMS, ...) - check regularly for carbonization - design a good rule for coil replacement Chris Wallsgrove One of the most complicated issues in pyrolysis furnace technology. Andre is partly correct. If you do not have sufficient sulfur, the first thing you will notice is a VERY high CO content in the cracked gas. This is because the coking rate is high in the absence of sulfur. I have run naphttha furnaces on very sweet naphtha, but it is normally a facet of gas cracking (E, P or B) which have low sulfur content. Adding ANY sulfur compound seems to work (and I added elemental sulfur in the case of the sweet naphtha...), so it must be that sulfur compounds crack/react and form H2S. So the assumption is that the H2S is reacting with the tube metal surface and "poisoning" the catalytic effect of the metal or meta oxide surface. The problem is that laboratory measurements/investigations do not confirm this mechanism. At normal metal tube wall temperatures during cracking, the metal sulfide decomposes... And the metal wall is covered by a layer of coke anyway, after a day or so on line. But you will see increased CO and high coking rates if the sulfur content of the feed is less than 30 to 50 ppm (as S). But there is little credible evidence that the carbon (coke) layer is catalytically active - although it MUST be to explain the observed real behavior. Presulfiding freshly decoked tubes. to form a metal sulfide layer therein, appears to be a totally different mechanism. It is a good idea, but DOES NOT substitute for continuous sulfur addition. Carburization (forming metal carbides) of the tubes is MUCH MORE a function of tube wall temperature there is a carbon layer in contact with the tube wall, and it migrates into the metal at a rate as a function of temperature. Of course, if the coking rate is lower, then the tube wall temperature is lower... I have a presentation on coking mechanisms, which I can send you if you interested. Chris Chris Vikas Pawar thxs chris for elobrating this discussion.becoz now for me its third cracker plant.I worked in naphtha cracker n presently i m working in gas cracker.So as u said normally in header side we maintain above 80ppm which is normal what is found. Yea definately if you have any material related to coke mechanism plz send me.My email id is vikas.l.pawar@gmail.com.Thanks once again. Benno Ganser Hello Vikas, I just read your question and comments, especially Chris Wallsgrove explained the background very correct. from a tube manufacturers point of virew, I just want to add one comment regarding the catalytic

activity of also the cokd tube surfaces. In our own R&D program we have evidence that also the coke layer itself shows catalytic activity. The coke "strings" which grow on catalytic active tube surface spots, always hav a Nickel cluster on top of thie string tip. This Ni cluster keeps some catalytic activity. Sulphur poisons this Ni szrfaces, if you leave it out, the coking effect is much stronger. of course, Ni Suplhides decompose at cracking temperatures, but it is always an effect there. It is also correct that most Naphthas contain sufficient S to achieve this protectign effect. In a gas cracker, addition of suphur compounds is very much recommended. Chris Wallsgrove Benno You and your R&D folks are correct: As I said, the coke layer MUST be catalytically active, to some extent, to explain the observed behavior. I just pointed out that there is not much published research to confirm or explain this. The fibers or fingers of catalytic coke (less than 1 micron diameter as measured) must contain an active site. Probably metal, probably at the tip. Electron micrographs of such coke seem to confirm this, in some cases. But it is obscure, and some "experts" deny the interpretation. My personal conclusion, reached and preached since about 20 years ago, is that the coke layer has OBSERVABLE catalytic activity As proven by the sulfur effect (reducing CO make etc.) on myriad furnaces/feedstocks, repeatably. Chris Benno Ganser Hi Chris,

thanks for your comment; you are absolutely right that there is always an observable catalytic activity on coke layers, I follow your conclusion by 100%. This was the starting point for our material developments by means of a new test rig which allows us to precisely observe the surface processes and root causes for the coke string development, and which points to minimize catalytic centers on the tube surface.

Regards Fayez Al-Ofi For some of coils design in case of gas cracker and as mentioned , the sulfur content has very significant impact on the coking rate and furance runlength.Reducing sulfur content target in feed to crackers is not a good idea espcailly if occasional feed quality issues are expereinced. Andr Vilelas We only inject sulphur to LPC and ethane furnaces. Normally our naphthas have enough sulphur. As I said our rule is <100ppm. Another important issue is where you inject the sulphur: in the feedstock or in the steam. In the dilution steam it is more efective and the dispersion along the coil is better. We have excellent results in our ethane furnace: runlenghts and type of coke. Another important factor was the market itself. We used to be a high severity cracker (P/E<0.45) but now C3+ streams, mainly propylene and butadiene, are favoured and we are running a very low severities (P/E>0.50 to 0.55). This effect is important to understand the higher runlenghts of our furnaces and the amount/type of coke catched in the QO filters.

Chris: please send me the presentation to avilelas@repsol.com Andr Vilelas Samarjit Ghosh 50 to 100 ppmw sulphur in cracking feed is enough.Normally for gas cracker feed is free from sulphur and need continuous dosing whereas for liquid cracker it is off and on based on feed sulphur content.High sulphur in feed will generate lot of H2S and consume lot of Caustic in caustic tower also lower PH in quench water tower that cause emulsion and corrosion and fouling problems in this section. Sulphur helps to reduce coking rate and to control CO at Furnaces effluent.Sulphur passivates the radiant coil and help.Especially for new coil or the coil just decoked and to be taken for cracking the impact of Sulphur is obvious. We have checked and found high CO generation in absence of DMDS. In some technology they say no need to inject sulphur for new coil but my experiences say it is essential. It also helps to control the ratio of CO & CO2. Sandip Jana Chris can you please elaborate how Sulphur/H2S (from DMS, DMDS) inhibits coking once coke layer formed inside coils/tubes. Increase in CO/CO2 in understandable, but how Sulfur/H2S helps in coke inhibition during mid/end of run of furnace when there is coke layer in side coils. Also it will be great if you can send me your presentation on coking mechanism, if possible please. Mail ID sandip_jana2004@yahoo.co.in Chris Wallsgrove Sandip Good question! The sulfur addition to suppress/inhibit coking towards end-of-run is proven, but never adequately explained in published research. Look at the comment by Benno... Basically, to explain the OBSERVED behavior towards end-of-run you have to postulate that the coke layer itself has catalytic activity. This can be explained, and some research confirms, that the ends of the "whiskers" of catalytic coke have some tiny metallic inclusion (presumably lifted from the tube metal) at their tip (which is on the surface of a coke "layer")... These provide a credible catalytic site - and it is these sites that have their catalytic activity suppressed by sulfur addition throughout the run - even at end-of-run. No other explanation that I have ever seen adequately/credibly explains the known and proven behavior of sulfur into coked tubes. Chris