Synthetic petroleum

[JebKeb]

I've been researching into making synthetic petroleum products for quite a while. I think now I should share it with the forums.

First, CO2 from the air is captured with a Linde cycle device or some other method. Next, it is mixed with H2 from electrolysis and mixed with a nickel catalyst.

CO2 + 4H2 -Ni + 350C-> CH4 + 2H2O

The methane is seperated and pumped into the natural gas grid. The other methane is taken and catalytically partially oxidised into syngas.

2CH4 + O2 -Rh + 850C-> 2CO + 4H2

This syngas is then put through a Fischer-Tropsch reactor to yield synthetic alkanes and other hydrocarbons, which can be shipped off to an oil refinery.

(2n+1)H2 + nCO -Co + 340C-> CnH(2n+2) + nH2O

Is this in any way worthwhile (money making) or is it useless?

[p1t1o]

I highly doubt it will be moneymaking (although ask again when the oil has run out...), mainly just because nobody is doing it on any kind of scale at the moment. The processes of sequestering CO2 and electrolysisng for H2 are going to eat significantly into profitability, and it will just be impossible to compete with the economies of scale that current oil production benefits from. Not useless, but not very profitable (at the moment...)

I did hear of a guy who apparently came up with a way to break down old tyres and produce a crude-oil-like derivative from that. Other synthetic fuel programs get their carbon and hydrogen from coal or biomass, these are much more dense feedstocks and require less energy to get the stuff you want from them, rather than liquefying millions of litres of air and electrolysing water.

[todofwar]

There are chemistry labs all over the world working on this very problem, some of them more successful than others. You don't need the extra step of going to CO acyually, plenty of catalysts get you there directly from CO2. But the big reason no one does it is we drill for oil for the energy it gives us. These reactions you describe are all uphill, so you will need an energy source to drive them. You're limited by where you get energy from, either nuclear or renewables. So really this is about energy storage, and while yes hydrocarbons make a great energy storage source, you're competing with hydrogen, supercapacitors, and batteries. Currently the others are easier to work with, but long term it would be nice to take advantage of all the existing petro infrustructure. 

[Kerbart]

Turning CO₂ into fuel is already done on a large scale; just not in the way the OP describes.

[kerbiloid]

As the calorific content of H₂ oxidation is much greater than CH₄'s one, this process would spend much more (external) energy to split the water than the produced methane can give.
So, you need a great external energy source. Solar/wind/hydro require large amounts of construction metals and polymers, which, in turn, require great amount of carbon and hydrocarbon-derived chemicals.
Digging deeper in the technological cycles you will soon realize that this snowball grows faster than gives a solution.

Atompunk way:
You need a powerful (thermo)nuke reactor with a carriage of ready-to-use fuel (i.e. deus ex machina) producing enormous amounts of cheap energy - at least for the first time while you are building your full-sized industrial facilities and energy plants. And you must build a nukefuel-producing industry to feed your reactor when the original fuel is over.
When this is done, you realize that you don't need as much hydrocarbon fuel as you presumed, because you can just expand your nuke and make as much pure hydrogen for rockets as you wish (or are already using hydrazine).
Also you realize that 90% of anything you can desire to build is already built.

Dieselpunk way:
You need enormous amounts of coal. It gives both energy and carbon (coke). But in this case you don't need to capture CO₂, so the original aim is to be considered as false.
You build a Dark Castle over the iron and coal mines and start building giant iron-coal smelters and coal energy plants with huge smoke pipes (Vertical Propulsion Emporium mod gives an example) making your personal mini-Mordor with rusty iron rockets flying to the sky (Rusty Rockets mod) and brutal flying aeroplanes (RetroFuture mod, but not sure if it still works in 1.1) carrying rusty iron bombs.
(Monocle in eye is optional).
Of course this means that you need a planet with rich biosphere history, so you would presume that Kerbin had prehistorical swamps and forests.

So, an atmosphere-only carbon idea looks promising until you realise that it requires an external support (machinery and chemistry traffic from Earth) or additional conditions (coal or thermonuke reactor).

Edited May 16, 2016 by kerbiloid

[Kryten]

The easiest way to think about the economics is this; you're using hydrogen to produce methane; currently, the economic method for hydrogen production is to make it out of methane.

[p1t1o]

The crux of it is, if you want cheap, clean energy, move away from hydrocarbons altogether. Before too long the only thing we will want them for is running vintage cars.

[shynung]

What about lubricants? Motor oil and the likes?

[YNM]

How much energy does that costs ? If it costs more than the energy stored in the end result then better polishing your PV-roof. Or get lots of battery.

Edited May 16, 2016 by YNM

[John JACK]

Synthetic petroleum was a thing up to the end of WWII. Middle East oil was not discovered yet and international trade was complicated due to reasons, so they had to make petroleum out of coal. Also run cars on a wood gas. It didn't work terrible well.

Nowadays best way to produce hydrocarbons and liquid fuels in general is bioengineering. People already distill ethanol and extract vegetable oil as replacement to petrol and diesel. But it's effective only in very warm climate with plenty of cheap labour. Genetic modification may create plants with greater sugar production and more spirits tolerant yeast, or even some stuff to make hydrocarbons directly from organic matter.

As for proposed reaction — hydrogen and methane are already good fuels. Hydrogen is complex to handle and utilise but methane can be easily transported and used in common IC engines.

Synthetic lubrication oils are mass produced right now. It's more expensive than cracking oil, but may give better results.

The main reason to use fossil hydrocarbons is energy return. For each joule or kilowatt-hour spent drilling and refining, you get ten times more energy back! Other ways, except nuclear energy, return much less. And synthetic fuel production returns less energy than was spent so only reason to do it is to be able to use existing hardware in desperate times.

[magnemoe]

12 minutes ago, John JACK said:

Synthetic petroleum was a thing up to the end of WWII. Middle East oil was not discovered yet and international trade was complicated due to reasons, so they had to make petroleum out of coal. Also run cars on a wood gas. It didn't work terrible well.

Nowadays best way to produce hydrocarbons and liquid fuels in general is bioengineering. People already distill ethanol and extract vegetable oil as replacement to petrol and diesel. But it's effective only in very warm climate with plenty of cheap labour. Genetic modification may create plants with greater sugar production and more spirits tolerant yeast, or even some stuff to make hydrocarbons directly from organic matter.

As for proposed reaction — hydrogen and methane are already good fuels. Hydrogen is complex to handle and utilise but methane can be easily transported and used in common IC engines.

Synthetic lubrication oils are mass produced right now. It's more expensive than cracking oil, but may give better results.

The main reason to use fossil hydrocarbons is energy return. For each joule or kilowatt-hour spent drilling and refining, you get ten times more energy back! Other ways, except nuclear energy, return much less. And synthetic fuel production returns less energy than was spent so only reason to do it is to be able to use existing hardware in desperate times.

Synthetic petroleum was mostly an thing during WW2, Germany made a lot of it, base was coal. Making petroleum from coal was looked into the the oil price spiked think break even is $120/ barrel.
Using ethanol/ metanol in diesel is another thing, diesel was not very common during ww2. Generaly an bad idea unless you use waste, as you say making metanol from cellulose would be nice as you end up with lots of waste during logging and the need of paper is down. 

[PB666]

18 minutes ago, John JACK said:

Synthetic petroleum was a thing up to the end of WWII. Middle East oil was not discovered yet and international trade was complicated due to reasons, so they had to make petroleum out of coal. Also run cars on a wood gas. It didn't work terrible well.

Nowadays best way to produce hydrocarbons and liquid fuels in general is bioengineering. People already distill ethanol and extract vegetable oil as replacement to petrol and diesel. But it's effective only in very warm climate with plenty of cheap labour. Genetic modification may create plants with greater sugar production and more spirits tolerant yeast, or even some stuff to make hydrocarbons directly from organic matter.

As for proposed reaction — hydrogen and methane are already good fuels. Hydrogen is complex to handle and utilise but methane can be easily transported and used in common IC engines.

Synthetic lubrication oils are mass produced right now. It's more expensive than cracking oil, but may give better results.

The main reason to use fossil hydrocarbons is energy return. For each joule or kilowatt-hour spent drilling and refining, you get ten times more energy back! Other ways, except nuclear energy, return much less. And synthetic fuel production returns less energy than was spent so only reason to do it is to be able to use existing hardware in desperate times.

Quote

the first commercial oil well in Saudi Arabia, struck oil on March 4, 1938. - wikipedia- history of the oil industry in Saudi Arabia.

In 1922 King Abdulaziz met a New Zealand mining engineer named Major Frank Holmes. During World War I, Holmes had been to Gallipoli and then Ethiopia, where he first heard rumours of the oil seeps of the Persian Gulf region.^[1]  - wikipedia- history of the oil industry in Saudi Arabia.

Oil production from plants is not very efficient, the most efficient are proposals to grow oil producing algae which the oil is extracted. The oil generated from plants is very different from that found in the ground, and tends to acidify with repeated exposure to heat and free radicals.

3 hours ago, kerbiloid said:

As the calorific content of H₂ oxidation is much greater than CH₄'s one, this process would spend much more (external) energy to split the water than the produced methane can give.
So, you need a great external energy source. Solar/wind/hydro require large amounts of construction metals and polymers, which, in turn, require great amount of carbon and hydrocarbon-derived chemicals.
Digging deeper in the technological cycles you will soon realize that this snowball grows faster than gives a solution.

 

The problem with hydrogen generation is simply this, its inefficient.
The problem with hydrogen usage is simply this, it does not store densely, and the dense storage schemes are expensive.

Despite its cost hydrogen does offer on real time advantage

- it can be used to lower the viscosity of tar sand oil making it a much more acceptable choice, without increasing greenhouse gases like methane.
- it can be an alternative power usage in areas with alot of wind energy when the local power output exceeds saturation and transmission lines exceed saturation.
- it can be used in areas with unusually high wind or geothermal generation capacity relative to the population size.

 

[Kerbart]

3 hours ago, kerbiloid said:

So, an atmosphere-only carbon idea looks promising until you realise that it requires an external support (machinery and chemistry traffic from Earth) or additional conditions (coal or thermonuke reactor).

While there's still external support needed, it's being done way simpler than you describe.

Method 1

• In tropical regions, sugar cane is planted.
• The sugar can plants take CO₂ from the atmosphere and turn it into complex hydrocarbons (preliminary glucose and related molecules)
• In a processing plant the sugar cane is converted into ethanol. Of course this process takes energy, but you can feed your powerplant with the ethanol output and still come out ahead (as your sugar can has already done the highly efficient CO₂ conversion)

Method 2

• In moderate climates, rapeseed is planted
• The rapeseed plants take CO₂ from the atmosphere and turn it into complex hydrocarbons (preliminary oil contained in the seeds)
• A mill can extract the rapeseed oil from the seeds
• The rapeseed oil can be converted into fuel (bio diesel and derivatives). Again, this is a process that will take a refinery, but the energey required for it can be supplied by the output

Of course you can build some kind of processing plant to convert CO₂ directly but the biological process is a lot cheaper (and knowing nature, probably more efficient). It will take large areas of land, which is why we might still need CO₂ processing plants in the future, but with the current state of affairs  it works just fine.

[wumpus]

CO2 to petroleum?  How about plant a field of canola (rapeseed) and harvest it?  I don't even want to think where you are getting the H2 from.  I can imagine a society using Thorium reactors (because there isn't enough Uranium for this level of power) doing this, but getting there is a much bigger difficulty than simply producing petroleum from even worse feedstocks.

[John JACK]

12 minutes ago, PB666 said:

The oil generated from plants is very different from that found in the ground, and tends to acidify with repeated exposure to heat and free radicals.

Right. But it's at least a renewable source that is available almost everywhere. And diesel engines can work on (processed) vegetable oils with minimal modification, like Otto engines on spirits and methane.

Biology is absolutely not efficient as chemistry, but it's cheap, self-sustaining and self-reproducing. Plant it, wait, harvest, spend a little energy on processing, repeat. You need just sun and enough place for fields. And with SCIENCE!!! it can be made much more effective.

18 minutes ago, Kerbart said:

but you can feed your powerplant with the ethanol output and still come out ahead

Even better, you can burn other parts of a plant that are not sugar. That returns most of CO2 to atmosphere, but still not produce more.

[shynung]

22 minutes ago, Kerbart said:

While there's still external support needed, it's being done way simpler than you describe.

Method 1

• In tropical regions, sugar cane is planted.
• The sugar can plants take CO₂ from the atmosphere and turn it into complex hydrocarbons (preliminary glucose and related molecules)
• In a processing plant the sugar cane is converted into ethanol. Of course this process takes energy, but you can feed your powerplant with the ethanol output and still come out ahead (as your sugar can has already done the highly efficient CO₂ conversion)

Method 2

• In moderate climates, rapeseed is planted
• The rapeseed plants take CO₂ from the atmosphere and turn it into complex hydrocarbons (preliminary oil contained in the seeds)
• A mill can extract the rapeseed oil from the seeds
• The rapeseed oil can be converted into fuel (bio diesel and derivatives). Again, this is a process that will take a refinery, but the energey required for it can be supplied by the output

Of course you can build some kind of processing plant to convert CO₂ directly but the biological process is a lot cheaper (and knowing nature, probably more efficient). It will take large areas of land, which is why we might still need CO₂ processing plants in the future, but with the current state of affairs  it works just fine.

Problems with both approaches are the energy crops competing for arable land against the food crops. Also, the machines that do the farming (tractors) drink gobs of fuel.

IMO, we should be looking for ways that turn agricultural byproducts into fuel. Cellulose, found in plants (or parts of it) that are inedible to humans, can be turned to ethanol by first breaking it down into simple sugars (glucose) by using enzymes similar to those found in ruminants.

[Kryten]

If you really need to replace fossil fuels for vehicles use, generators for wood gas can be bolted right on, meaning you need far less infrastructure. This is commonly used for trucks in the DPRK.

[shynung]

11 minutes ago, Kryten said:

If you really need to replace fossil fuels for vehicles use, generators for wood gas can be bolted right on, meaning you need far less infrastructure. This is commonly used for trucks in the DPRK.

Better yet, those wood gas generators work on any carbon-based solid fuels. Coal, coconut shells, most should work.

[John JACK]

6 minutes ago, Kryten said:

generators for wood gas can be bolted right on, meaning you need far less infrastructure

And far more very cheap but motivated labour force. And far more forests, that do not grow again overnight. Wood gas is only for really desperate, when you need to operate at least something no matter the cost.

10 minutes ago, shynung said:

IMO, we should be looking for ways that turn agricultural byproducts into fuel.

Yep. Right now humans have to process food to fuel because there are millennia of selection of edible plants, but there was no selection of combustible plants. We need bioengineering to make fuel without wasting (much) food for it.

[kerbiloid]

Wood is not a good option, as it grows slowly. Algae have a potential, but any such biological system has a puny efficiency per mass and area.
Also, hundreds of insects and sicknesses are awaing any chance to kill the harvest, As the weather also does.
And you hardly can use it outside the ideal conditions of Earth.

So, how much of total hydrocarbon fuel amount is biofuel? 3% ?

2 minutes ago, John JACK said:

We need bioengineering to make fuel without wasting (much) food for it.

There are plants 50% and more consisting of cellulose. So, bioengineering hardly could dramatically help there.

[Kryten]

7 minutes ago, John JACK said:

And far more very cheap but motivated labour force. And far more forests, that do not grow again overnight. Wood gas is only for really desperate, when you need to operate at least something no matter the cost.

It works well enough if you have a lot of hilly/mountainous terrain which which is difficult to farm, again like the DPRK. There are always going to be some areas you where you can't grow something more efficient.

[kerbiloid]

When you have a lot of wooden wastes (branches, bark, etc) it's cheap and efficient way to utilize them and produce energy. Not helpful for health, though.

[John JACK]

1 hour ago, kerbiloid said:

Wood is not a good option, as it grows slowly.

Arguably best plants for energy source now are various grass like miscanthus. It grows pretty much anywhere and gives huge amount of biomass in just one-two years. Using stems and leaves instead of seeds guarantee enough produce even despite pests or weather.

But cellulose isn't most convenient stuff if you want not just burn it outright, sugar or oils are better, and there is much to be improved.

Biofuel is not necessary yet — fossil fuels are cheap, plentiful and more effective, so it's not used widely. Only some tropical countries use it because it's cheap there.

1 hour ago, kerbiloid said:

When you have a lot of wooden wastes (branches, bark, etc) it's cheap and efficient way to utilize them and produce energy.

Nah, wood gas is nowhere near efficient. Engine give just third of it's power on it, and generator need to be restocked with dozens of kilos of wood every couple of hours. And you cannot use just some waste, gas generators need high quality dry wood, cut to cubes of certain size. Some generators may run on pellets, made of pressed ships, but pellet making consumes power and labour too. So ­— combination of good cheap workforce and of total lack of other fuels is absolutely must to use wood gas generators. And it happens only in wartime or similar conditions. You need postapocalyptic setting to justify worldwide wood gas power.

It's effective enough to burn wood and other plant matter like peat in thermal power station furnace, though you need much bigger volumes than coal. But there are no effective portable engines for it. Even running steamers on wood is only for very rich or very poor people.

[PB666]

3 hours ago, John JACK said:

Right. But it's at least a renewable source that is available almost everywhere. And diesel engines can work on (processed) vegetable oils with minimal modification, like Otto engines on spirits and methane.

Biology is absolutely not efficient as chemistry, but it's cheap, self-sustaining and self-reproducing. Plant it, wait, harvest, spend a little energy on processing, repeat. You need just sun and enough place for fields. And with SCIENCE!!! it can be made much more effective.

Even better, you can burn other parts of a plant that are not sugar. That returns most of CO2 to atmosphere, but still not produce more.

Life was not designed to make oil thats an after the fact storage compound, its primary output is aldehydes and triose sugars, which are then form acetyl Coa and acetyl CoA is then concatonated to form fatty acids. Fatty acids are then used to make the all important lipid bilayer.
Its a kind of wasteful process to say the least. If you were going to design a process to make fuel, the better choice is to genetically engineer an algae to make Hydrogen which as we know readily dissolves across thin membranes. Like is relatively good at Making NADPH all it needs is an electron acceptor and a decent enzyme and you have H. The lifeform isn't killed in the process, as occurs in oil production. You will have to have a hydrogen/oxygen separator.

[JebKeb]

Woah.

The problem seems to be, with biofuela they are not completely compatible with engines today and I don't see any great advantages switching to them over synthetic fuel apart from EROI? 

Synthetic fuel can use the multibillion dollar oil infrastructure by constructing a few basic plants. The oil industry has less stuff to worry about. It can probably be cheaper than oil.

Anyone else got methods of producing hydrogen?