Chemical Forums
Chemistry Forums for Students => Organic Chemistry Forum => Topic started by: peavey_sam on August 05, 2014, 09:39:01 AM
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Hi. I have a question for you.
So, I am trying to find a way to remove sulfur (CaSO4) from the fuel chemicals that will be used in the industrial boiler. Due to the high emission level (NOx and SOx), my job is to reduce the emission level. I was able to remove the sulfur in the form of CaSO4 in the 2000 tons by weight of 0.5% but not sure how to go about this to lower down to 0.2%
My initial attempt was to add Toluene like this:
CaSO4 + Toluene --> P-Toluene surfonicacid
so that it would make P-Toluene (that is water-soluble???) and I would run the machine to extract all the water-soluble which would include the P-Toluene surfonicacid.
Would this reaction work? I am really hoping that it would. Could anyone verify this reaction for me please?
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Not unless you heavily acidify the mixture (and heat it) as well. So is CaSO4 present in the fuel or is that just a precipitate you removed the sulfur by, but sulfur is in the fuel in a different form?
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Not unless you heavily acidify the mixture (and heat it) as well. So is CaSO4 present in the fuel or is that just a precipitate you removed the sulfur by, but sulfur is in the fuel in a different form?
First of all, thank you so much for your prompt response. The reason why I am writing this is because, unlike all the other people who are running experiment in the lab with sole CaSO4 and Toluene, I am attempting to remove S out of CaSO4 from the oil that has numerous organic compounds already.
To answer your question, I have to say, the former is correct-- CaSO4 is present in the fuel.
So, this is what's happening:
The nature of the fuel that I am working is Petroleum. Thing is that it's not simple petroleum. It's a petroleum that has been used once before and our company is responsible for refining this petroleum. And one of my job description is to find a way to reduce (NOx and SOx) so that emission level is low enough to be used in the industrial boiler.
My company is so tiny that it cannot afford to purchase Hydrodesulfurization machine (which would cost about a trillion). Not to mention, if people knew that adding Toluene in the oil to get rid of Sulfur, people would already have done it.
The CaSO4 is by weight(%), 0.5%. Besides 3% of water, it's 96.5% organic chemicals that act as "Spectator ion" around CaSO4.(This is my understanding about the situation. I just started my job.) Therefore, I am not confident if acidifying and heating up would help in the situation that I am in.
I hope this was able to help you understand where I am coming from in terms of verifying the reaction.
Also, even if the reaction is possible, would P-toluenesulfornic acid be water soluble? I ask this because my final purpose of the reaction is to make the sulfur 'water soluble' so that before our company sells the "refined petroleum" to client for the boiler heater, we would extract water which I hope that it would include the SO4 in the form of P-toluenesulfornic acid in water.
What should I do from here?
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Is the sulfate the problem or the calcium? Sulfuric acid will get burned. So will residual tosic acid. I'm guessing calcium sulfate is insoluble. Convert to a soluble salt and wash it out?
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Yeah, I'd say the same - convert to water soluble sulfate and separate it out.
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CaSO4 + Toluene --> P-Toluene surfonicacid
Where did you get this reaction from? I don't believe it will even go -- I don't think you can sulfonate an aromatic with an ionic salt. This entire discussion is academic if this reaction doesn't happen. Did you just assume it would because the names are similar? Chemical reactions don't work that way.
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Is the sulfate the problem or the calcium? Sulfuric acid will get burned. So will residual tosic acid. I'm guessing calcium sulfate is insoluble. Convert to a soluble salt and wash it out?
The problem is the Sulfate. And yes, it is correct that Calcium sulfate (which is not precipitated yet) is insoluble and I am trying to make it soluble by running the reaction (by creating Tosic acid).
And would you please kindly help me understand what you mean by converting to a soluble salt and washing it out? I think that creating Tosic acid will be anion and Ca2+ is a positive which is cation. Right?
So, does this mean that I can run this reaction and make this happen by bringing it up to Tosic acid?
I am a little fuzzy with the idea of "making it water soluble and washing it out" in this context. Please forgive me for not being able to fully understand. Would you please kindly help me understand what you mean by "Making it water soluble and washing it out" and how to run the reaction with specific details?
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CaSO4 + Toluene --> P-Toluene surfonicacid
Where did you get this reaction from? I don't believe it will even go -- I don't think you can sulfonate an aromatic with an ionic salt. This entire discussion is academic if this reaction doesn't happen. Did you just assume it would because the names are similar? Chemical reactions don't work that way.
First of all, thank you for your input and helping me out answer my question.
I was looking for a way to remove SO4 and (after failing to find any kind of reaction to carry) I found it online saying that if the toluene:CaSO4 = 1:3, then it would bring it to Tosic acid(P-toluenesulfonic acid)
And if the ratio is about Toluene:CaSO4 = 3:1, then it would bring SO2 gas rather than bring it to Tosic acid. But I am guessing this reaction does not work? I am simply confused.
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CaSO4 + Toluene --> P-Toluene surfonicacid
Where did you get this reaction from? I don't believe it will even go -- I don't think you can sulfonate an aromatic with an ionic salt. This entire discussion is academic if this reaction doesn't happen. Did you just assume it would because the names are similar? Chemical reactions don't work that way.
I also heard that though, there is possibility of creating TNT from the reaction (CaSO4 +Toluene --> TNT)??
Would this be true? If yes, should I run the reaction with Benzene ring?
CaSO4 + Benezne --> ??
And I also have to inform you that I am working with putre CaSO4 and Toluene. I am working with those molecules that were added in other organic compounds (within the Petroleum fuel which makes this a bit complicated). Let's just say, simple organic reaction that I have learned in Organic chemistry does not apply here. (At least, it's the limitation of my education).
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Let's just forget about this toluene reaction please, it makes absolutely no sense.
I am very confused about this solubility think - so you are saying you have CaSO4 which is insoluble in your fuel? Obviously you just filter that out on some fine filter. Or are you saying 0.5% (w/w) percent of CaSO4 is somewhat soluble in the petroleum and you want to remove that?
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Or are you saying 0.5% (w/w) percent of CaSO4 is somewhat soluble in the petroleum and you want to remove that?
Yes sir. This is what I am saying. CaSO4 is currently soluble in the petroleum and I want to remove it by making it water soluble so that extraction of water would be equivalent to extraction of CaSO4.
I hope that I did not make you confused about this reaction equation and the states of CaSO4.
Also, people at the work keep asking how can tosic acid be water soluble when the toluene(which is organic compound) is added?
I keep saying it's water soluble per wikipedia but I feel the lack of understanding of the molecule to explain how it's water soluble even after adding toluene.
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To make it easy, I don't have to use Toluene. In a given circumstance, I have to find some sort of chemical that would react with Sulfur and make it water soluble. And as long as it's water soluble, we can extract water out so there would be a no problem. I hope I made this clear before any of you brainstorm this.
I am trying to find something to make this happen and in the process of searching everything in the ACS website but not having any luck.
Does anyone know where I should even start from? I feel stuck.
Again, thank you for your help in advance.
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I have read through this posts and the answers. Nothing is clear to me.
Please explain in simple terms what you want to do: Is it to remove sulfur as a water soluble form from the oil? Or to remove calcium sulphate?
In the first post you said "I was able to remove the sulfur in the form of CaSO4" so how did you do this?
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Does anyone know where I should even start from? I feel stuck.
To start with, you've given us limited information to work with. And you have a serious lack of expertise for us to fill in for you. Its illogical for the ionic solid calcium sulfate to be a serious contaminant in fuel. You casually mention the need to reduce SO2 and NOx in burner output. This is not trivial, and the procedures that exist, although expensive, exist for a reason. If I understand you, you've created the CaSO4 in the process of trying to remove SOx, So this should be an insoluble solid -- maybe just filter?
The CaSO4 is by weight(%), 0.5%. Besides 3% of water, it's 96.5% organic chemicals that act as "Spectator ion" around CaSO4.(This is my understanding about the situation. I just started my job.) Therefore, I am not confident if acidifying and heating up would help in the situation that I am in.
You put "spectator ion" in quotes, but that really doesn't excuse that that isn't an apt term. You're asking for something very advanced, but this isn't the correct definition. We don't know how much detail to go into.
I have to find some sort of chemical that would react with Sulfur and make it water soluble. And as long as it's water soluble, we can extract water out so there would be a no problem. I hope I made this clear before any of you brainstorm this.
What form is the sulfate present in the fuel? What compounds are there that contain sulfur? How does industrial desulfutization work, and can you copy the process in a limited fashion?
I think this may be academic. If you have dirty oil, and you've reduced pollutant causing components as much as you can, maybe you simply need a scrubber after the furnace. Unless you must sell it, and regulations require a certain level. Maybe, if you're almost at the legal level, you can dilute the end fuel with clean fuel to bring it to saleable level.
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Also, how are you quantifying contaminants? What levels of contaminants are in your source material, and how are you measuring where they are, where you've reduced them to and how will you know when you've purified enough?
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I have read through this posts and the answers. Nothing is clear to me.
Please explain in simple terms what you want to do: Is it to remove sulfur as a water soluble form from the oil? Or to remove calcium sulphate?
In the first post you said "I was able to remove the sulfur in the form of CaSO4" so how did you do this?
First of all, I truly appreciate your input and time to help me solve the problem.
To make it simple,
I am trying to remove sulfur as a water soluble form from the oil. And it does not have to react with toluene. My goal is this: To remove sulfur as a water soluble from from oil.
All I know is that the sulfur that I am trying to remove is in the form of CaSO4. I must have not proof read before submitting this: I was NOT able to remove the sulfur that is in the form of CaSO4.
Does this make sense though?
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Does anyone know where I should even start from? I feel stuck.
To start with, you've given us limited information to work with. And you have a serious lack of expertise for us to fill in for you. Its illogical for the ionic solid calcium sulfate to be a serious contaminant in fuel. You casually mention the need to reduce SO2 and NOx in burner output. This is not trivial, and the procedures that exist, although expensive, exist for a reason. If I understand you, you've created the CaSO4 in the process of trying to remove SOx, So this should be an insoluble solid -- maybe just filter?
Yes sir. You are absolutely right that I did not provide you sufficient information to fill this in. And I truly apologize for not making this problem crystal clear. So, allow me make this clear from my understanding of the situation I am in.
I am currently trying to remove Sulfur in the form of water soluble chemical. Within the fuel, the sulfur is in the form of CaSO4.
SOx and NOx is created more than usual in our clients' industrial boiler if I don't remove enough of the Sulfur before selling the fuel.
The CaSO4 is by weight(%), 0.5%. Besides 3% of water, it's 96.5% organic chemicals that act as "Spectator ion" around CaSO4.(This is my understanding about the situation. I just started my job.) Therefore, I am not confident if acidifying and heating up would help in the situation that I am in.
You put "spectator ion" in quotes, but that really doesn't excuse that that isn't an apt term. You're asking for something very advanced, but this isn't the correct definition. We don't know how much detail to go into.
As I am looking back, I am able to see that I did not use the correct term to describe the circumstance. I asked my boss and he dose not have a list of all the chemicals compounds that are in the fuel. All I do know is that it's about 96.5% of Organic compound and 3% of water and about 0.5 % of CaSO4.
I have to find some sort of chemical that would react with Sulfur and make it water soluble. And as long as it's water soluble, we can extract water out so there would be a no problem. I hope I made this clear before any of you brainstorm this.
What form is the sulfate present in the fuel? What compounds are there that contain sulfur? How does industrial desulfutization work, and can you copy the process in a limited fashion?
I think this may be academic. If you have dirty oil, and you've reduced pollutant causing components as much as you can, maybe you simply need a scrubber after the furnace. Unless you must sell it, and regulations require a certain level. Maybe, if you're almost at the legal level, you can dilute the end fuel with clean fuel to bring it to saleable level.
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The Sulfate is in the form of CaSO4. I guess I did not make it clear because a person above you also mentioned similar confusion about my comment. So, allow me to make this clear please:
CaSO4 is in the fuel. I am attempting to remove sulfur. The compounds that contain sulfur is CaSO4.
The project that I am working on is to make CaSO4 to become water soluble. I say this because when we extract all the water, (If we can make Sulfur from CaSO4 water soluble), we would lower the sulfur level. So that way, we can sell this product (processed oil) to the client and the regulation requires our company to lower the Sulfur.
And yes sir, it is quite close to the salelevel/legal level but simply diluting would not decrease much sulfur and the boss hired me to remove the sulfur so that the 'processed oil' would be in safe zone of the sulfur level.
I am truly grateful for your input and time. I really want to keep this job so bad. I just simply realizing that undergrad chemistry is a lot more different and simpler than industrial chemistry. I am very humbled today.
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Also, how are you quantifying contaminants? What levels of contaminants are in your source material, and how are you measuring where they are, where you've reduced them to and how will you know when you've purified enough?
So, yeah, as far as I understand, after processing the oil, they send an sample of the 'processed oil' to the lab and measure the contaminants level which I have not seen how they do it. Would you like to me quantify the contaminants? All I do know is that they offer me that it has to be lower than now since it's at the boarder line of being qualified for the legal level (not quite boarder line but if I do something about it, it would be on the boarder line.)
I feel like it's so close yet so far away. Did you go into grad school for chemistry? My knowledge is limited up to undergrad level as a chemistry major.
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Perhaps an ion exchange resin would help here?
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How come CaSO4 is dissolved in a fuel? The only way I can imagine fuel being contaminated by CaSO4 is in a form of suspension.
Or am I wrong? Am I missing something?
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There is 3% water and 0.5% by weight calcium sulphate. According to Wikipedia the water solubility of the hydrated form is 0.24 w%as a dihydrate. So they are just about on the solubility limits.
I also suppose that there are large quantities involved. Passing the fuel through a column of dry neutral alumina will remove water and any sulphate that precipitates out will stick to the alumina, maybe!
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How come CaSO4 is dissolved in a fuel? The only way I can imagine fuel being contaminated by CaSO4 is in a form of suspension.
Or am I wrong? Am I missing something?
Again, I did not make this clear. The reason why CaSO4 is dissolved in the fuel is that this oil used to be used as a lubrication in an engine. After overly used, our company purchase those('dirty oil') to refine it. And the part of refinement of the oil is to reduce Sulfur because we will resell the oil as industrial boiler which will create industrial emission mainly SOx. To decrease, I have been trying to figure out what would be necessary to make this sulfur water soluble? I came up with the equation which I am not sure if it would work.
What do you think?
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There is 3% water and 0.5% by weight calcium sulphate. According to Wikipedia the water solubility of the hydrated form is 0.24 w%as a dihydrate. So they are just about on the solubility limits.
I also suppose that there are large quantities involved. Passing the fuel through a column of dry neutral alumina will remove water and any sulphate that precipitates out will stick to the alumina, maybe!
As large as 1%, and it appears that it varies from which used engine oil the company purchases it.
As I was researching some of ideas, I brought this:
http://www.google.com/patents/US20030014911
In the paragraph 28, it also mentioned that using the alumina would reduce the sulfur like you mentioned. Could this also be possible? And if yes, how feasible is it? I guess I never thought of this but it seems like a brilliant idea.
(Or, I am desperate enough that any idea looks feasible and doable.)
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There is 3% water and 0.5% by weight calcium sulphate. According to Wikipedia the water solubility of the hydrated form is 0.24 w%as a dihydrate.
0.24 g/100 mL in water, not in oil. That's when CaSO4 is dissociated, which is definitely not the case here. Having just 3% of water in the oil is not enough, besides, even 0.5% in water would be twice the solubility, well above the limit.
The reason why CaSO4 is dissolved in the fuel is that this oil used to be used as a lubrication in an engine.
What was the engine made of, plaster of Paris?
Some quick googling:
The U.S. Department of Health and Human Services reports that used motor oil can contain toxic chemicals and contaminants such as benzene, lead, zinc, and cadmium;
Motor oil picks up a variety of hazardous contaminants when used in engines and transmissions. These contaminants include lead, cadmium, chromium, arsenic, dioxins, benzene and polycyclic aromatics.
No CaSO4 listed. I can imagine some sulfates being present if the fuel used in the engine had a high sulfur content, but I can't imagine source of calcium in such place. Unless the oil was used also/later for something else.
Sorry if I sound blunt, but things you post don't add, and I hate it when we try to help solve the problem only to learn something important (and ruining all what we suggested) after everyone tried to think about the problem.
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Some grease is based on calcium (calcium soap mixed with mineral oil) but I thought most modern lubricants were based on lithium.
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There is 3% water and 0.5% by weight calcium sulphate. According to Wikipedia the water solubility of the hydrated form is 0.24 w%as a dihydrate.
0.24 g/100 mL in water, not in oil. That's when CaSO4 is dissociated, which is definitely not the case here. Having just 3% of water in the oil is not enough, besides, even 0.5% in water would be twice the solubility, well above the limit.
I attempted to work with the alumina. I learned that being dissociated in water is different than in oil. Unfortunately, it did not help.
The reason why CaSO4 is dissolved in the fuel is that this oil used to be used as a lubrication in an engine.
What was the engine made of, plaster of Paris?
Some quick googling:
The U.S. Department of Health and Human Services reports that used motor oil can contain toxic chemicals and contaminants such as benzene, lead, zinc, and cadmium;
Motor oil picks up a variety of hazardous contaminants when used in engines and transmissions. These contaminants include lead, cadmium, chromium, arsenic, dioxins, benzene and polycyclic aromatics.
No CaSO4 listed. I can imagine some sulfates being present if the fuel used in the engine had a high sulfur content, but I can't imagine source of calcium in such place. Unless the oil was used also/later for something else.
And yes, this is not the case here. My company is not in U.S. It is in Korea. What exactly do you mean by "what is engine made of?". Do you mean what kind of vehicles/machine is the original oil used for?
Sorry if I sound blunt, but things you post don't add, and I hate it when we try to help solve the problem only to learn something important (and ruining all what we suggested) after everyone tried to think about the problem.
I totally understand your concern. I am just hoping to help you help me to get through this. In the end, I am simply grateful for your help. I really do.
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Some grease is based on calcium (calcium soap mixed with mineral oil) but I thought most modern lubricants were based on lithium.
Thank you for your input. And yes, you are right that some grease is based on calcium but modern lubricants were based on lithium. As a matter of fact, that some other lubricants contains MgSO4, MoSO4. It happened because we were adding all kinds of used lubricants from various different kinds of vehicles.(hoping to refine this to sell to the other companies with the need in the boiler)
Before selling refined lubricant as a fuel, my company is looking for a way to reduce CaSO4, MoSO4, LiSO4 and MgSO4 since sulfate causes emission (air pollutants).
A few other things that I am responsible is to reduce is as follows:
- Sulfur (CaSO4, MoSO4, LiSO4, MgSO4.. and metal will precipitate but since a form of Metal-SO4 was artificially added, we think we can extract it and yes, as I posted earlier, simple extraction using Alumina did not work since it's in oil as Borek said).
- Ash
- Water
- Heavy metal (Cr, Cd, Pd, Bi....) and taking out those heavy metal has been just as big problem as taking out sulfur at this moment.
Please let me know if there is any other thing that I can clarify pelase. B
And Borek-- is this sufficient information for you? I just out of meeting and let me just say,
I am learning a lot here in terms of the process and the problems that company is facing.
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What exactly do you mean by "what is engine made of?".
That was rather a sarcastic comment. Engine parts are made of steel, some of aluminum. Steel can contain other metals - like Co, Mo, Cr - and that's why you will see these between contaminants. But I fail to see source of calcium, as calcium is not used in these alloys.
You know what the plaster of Paris is?
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What exactly do you mean by "what is engine made of?".
That was rather a sarcastic comment. Engine parts are made of steel, some of aluminum. Steel can contain other metals - like Co, Mo, Cr - and that's why you will see these between contaminants. But I fail to see source of calcium, as calcium is not used in these alloys.
You know what the plaster of Paris is?
I do not know what the plaster of paris is. Do you mean CaSO4 that used to be Gypsum and is heated up to 300 degree celcius and mainly used for coating walls and ceiling like a plaster? Well, I think that is how I understood from the Wikipedia (I would like to admit that I don't know much about it because humbling is what makes a person more diligent and proactive in learning) :D
Yes, the source of CaSO4 is from the low level grade of Sulfate. I believe the car engine lubricant has a different kind of level grade (from high end to low end) and when low end lubricant contains CaSO4 and the point of having metal-SO4 in the lubricant oil is to help the engine sustain within the high pressure.So, that is where Ca is coming from.
Now, someone at my work also suggested me if PEA (Polyetheramine) would possibly has to do with the bringing SO4 to dissolve in water side rather than being dissolved in oil side. I mean within the PEA, there are so many different kind of PEA. Would this work?
Or, colleagues also heard that some website like:
http://www.dow.com/amines/apps/index.htm
indicates that
Ethylenediamine (EDA), Diethylenetriamine (DETA) and/or Aminoethylethanolamine (AEEA) could work toward removing SO4 and Ash (without really knowing the mechanism behind.).
Do you(Borek) know anything about Poly--Amines chemistry? Or Does any know anything about this at all?
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How do you know that the alumina did not work?
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How do you know that the alumina did not work?
Thank you for your replay.
Before I attempted to run an experiment, I talked to my boss about running this experiment and they already have run it and told me that the company already has run the experiment before I came in. I assumed they were looking for a different way to go about this problem. (I am kind of glad that I did not mention about CaSO4 + Toluene reaction as a suggestion. :D)