Tag Archives: CO2

Upgrading landfill and digester gas for sale, methanol

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We live in a throw-away society, and the majority of it, eventually makes its way to a landfill. Books, food, grass clippings, tree-products, consumer electronics; unless it gets burnt or buried at sea, it goes to a landfill and is left to rot underground. The product of this rot is a gas, landfill gas, and it has a fairly high energy content if it could be tapped. The composition of landfill gas changes, but after the first year or so, the composition settles down to a nearly 50-50 mix of CO2 and methane. There is a fair amount of water vapor too, plus some nitrogen and hydrogen, but the basic process is shown below for wood decomposition, and the products are CO2  and methane.

System for sewage gas upgrading, uses REB membranes.

C6 H12 O6  –> 3 CO2  + 3 CH4 

This mix can not be put in the normal pipeline: there is too much CO2  and there are too many other smelly or condensible compounds (water, methanol, H2S…). This gas is sometimes used for heat on site, but there is a limited need for heat near a landfill. For the most part it is just vented or flared off. The waste of a potential energy source is an embarrassment. Besides, we are beginning to notice that methane causes global-warming with about 50 times the effect of CO2, so there is a strong incentive to capture and burn this gas, even if you have no use for the heat. I’d like to suggest a way to use the gas.

We sell small membrane modules too.

The landfill gas can be upgraded by removing the CO2. This can be done via a membrane, and REB Research sells a membranes that can do this. Other companies have other membranes that can do this too, but ours are smaller, and more suitable to small operations in my opinion. Our membrane are silicone-based. They retain CH4 and CO and hydrogen, while extracting water, CO2 and H2S, see schematic. The remainder is suited for local use in power generation, or in methanol production. It can also be used to run trucks. Also the gas can be upgraded further and added to a pipeline for shipping elsewhere. The useless parts can be separated for burial. Find these membranes on the REB web-site under silicone membranes.

Garbage trucks in New York powered by natural gas. They could use landfill gas.

There is another gas source whose composition is nearly identical to that of landfill gas; it’s digester gas, the output of sewage digesters. I’ve written about sewage treatment mostly in terms of aerobic bio treatment, for example here, but sewage can be treated anaerobically too, and the product is virtually identical to landfill gas. I think it would be great to power garbage trucks and buses with this. Gas. In New York, currently, some garbage trucks are powered by natural gas.

As a bonus, here’s how to make methanol from partially upgraded landfill or digester gas. As a first step 2/3 of the the CO2 removed. The remained will convert to methanol. by the following overall chemistry:

3 CH4 + CO2 + 2 H2O –> 4 CH3OH. 

When you removed the CO2., likely most of the water will leave with it. You add back the water as steam and heat to 800°C over Ni catalyst to make CO and H2. That’s done at about 800°C and 200 psi. Next, at lower temperature, with an appropriate catalyst you recombine the CO and H2 into methanol; with other catalysts you can make gasoline. These are not trivial processes, but they are doable on a smallish scale, and make economic sense where the methane is essentially free and there is no CNG customer. Methanol sells for $1.65/gal when sold by the tanker full, but $5 to $10/gal at the hardware store. That’s far higher than the price of methane, and methanol is far easier to ship and sell in truckload quantities.

Robert Buxbaum, June 8, 2021

China keeps building coal-fired plants so we can close ours.

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Part of the mandate to the 2020 election was to join with Europe and the rest of the western world in agreeing to stop the use of coal. It’s a low cost way to generate energy. Of course we still like to buy things, and we’ve largely turned to China, a country that still burns coal, and thus makes things cheap. The net result of this shift to Chinese goods is that China keeps building coal-fired plants while we shut ours. As it happens, China is worse than the US in terms of CO2 per output, but at least when China pollutes, we don’t see the smoke directly, and we don’t see their new coal plants at all. So we feel better buying things from China than from the US. Besides, slave labor is cheap.

From th eEconomist, December 2020.

Buying Chinese goods is good for the importers, and for the non-manufacturing consumer, at least in the short term. It has the effect of exporting jobs though, and eventually we have to support the displaced workers. It also means we don’t keep up our manufacturing technology. Long term, that affects innovation, and that starts to displace other industries. Antibiotic production has already left the US and along with it semiconductors. Still, we feel good about it since the Chinese don’t let us see the slave labor camps. We do get to see the haze of the pollution.

The Chinese expect this pattern to continue. China is building new coal-fired plants at a furious rate. Presently China has most of the world’s coal-fired power plants. Mostly these are only 4 to 12 years old, far younger than our forty year old plants China plans to build more, and keeps encouraging us to shut down ours. Even 10 years ago, China lead the world in CO2 output. And their fraction of the CO2 keeps climbing.

China is popular with the press. In part, I expect, that’s because they pay the international experts. lAlso, writers and editors are consumers industrial products, but not manufacturers. Consumers benefit from slave labor, or maybe not, but displaced American workers certainly suffer. Also, of course, the news requires pictures and personal stories to keep viewer interest. If you can’t get pictures of young protesters, like Grey Thunberg, you can get an interesting story. Our Chinese pollution is out of sight, and not in the press.

Robert Buxbaum, January 6, 2021. BTW, if we wanted preserve jobs and stop CO2 pollution, we’d go nuclear.

China worse than the US in CO2 per output

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CO2 per year, 1965-2017, China and developed world

CO2 output per year, 1965-2017, China and developed world

For the last decade at least, China has been the industrial  manufacturer to the world. If not for Chinese shoes, the US would go barefoot. if not for Chinese electronics, Americans would be without iPhones, laptops, and TVs. China still trails the US and Europe in banking, software, movies and the like, but relying on China for manufactured goods is a dangerous position for the free world economically, and it’s not much better in terms of pollution.

China is among the world’s worst polluters. It burns coal for power to an extent that the air quality of China’s major cities would be unacceptable most everywhere else. On most days, it is thick with a yellow and grey haze. By 1969 China had passed the US and the European union in terms of CO2 production. And, as 2017, they produce nearly three times as much CO2 as the USA, four times more than the entire European Union. While China claims an interest in changing, the amount of pollution China’s CO2 output is still growing while ours and the EU’s is decreasing.

Manufacturing in the US, China, EU, Japan, Korea. Source: World Bank.

Manufacturing in the US, China, Germany, Japan, Korea. Source: World Bank.

China’s pollution would not be so bad if it were an efficient manufacturer, but there is a lot to suggest that it is not. China produces 50% more industrial goods than the US, but employs far more man hours, and generates more than three times the  CO2. Even in a fairly developed industry like steel, the US uses fewer man hours per ton and generates less CO2. I’m thus drawn to conclude that US companies off-load work to China mainly to get around US labor and pollution laws. Alternately, they off-load manufacture to gain entry to the Chinese market, a market that is otherwise closed to them. When US companies do this, they benefit the corporate managers and owners, but not the US worker. 

The hope (expectation) is that president Trump’s tariffs on Chinese goods will decrease the wage advantage of manufacturing in China, and will decrease the amount of US goods manufactured there. Some of that production, I expect, will move to the US, some will remain in China, and will be imported at a higher price-point. I expect a net decrease in CO2 as the US appears to be the more efficient producer, and because fewer ships will be crossing the Pacific bringing Chinese goods to the US. I expect some increase in tax revenue to the US, and some price inflation as well, as importers pass along the increased cost of Chinese goods. Overall, I think this is an acceptable trade-off, but what do I know.

Robert Buxbaum, November 29, 2018

Global warming’s 19 year pause

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Global temperatures measured from the antarctic ice showing stable, cyclic chaos and self-similarity.

Global temperatures measured from the antarctic ice shows stable chaos and self-similarity.

The global climate is, as best I can tell, chaotic with 100,000 year ice-age cycles punctuated by smaller cycles of 1000 years, 100 years, etc. On the ice-age time scale shown at left, the temperature rise of the last century looks insignificant and very welcome; warm seems better than cold in my eyes. But the press and academic community has focused on the evils of warmth — global warming. They point out that temperatures have risen 1 1/2 °C since the little ice age of the early 1600s, and that 1/2 °C of this has occurred since 1900. Al Gore won a Nobel prize for his assertion that the rate of rise had accelerated to 4°C per century — a “hockey-stick change” caused by industrial CO2. This change was expected to bring disaster by 2015: The arctic was supposed to be ice-free, and Manhattan was expected to sink. I’ve posted a “Good Morning America” clip from 2008 highlighting this “inconvenient truth”.

Our 19 1/2 year global warming pause; plot from Andrew Watts with Al Gore's prediction shown in red. During the time shown, the atmospheric CO2 content has gone up by about 25%, but the prediction has not come to pass.

Our 19 1/2 year global warming pause; plot from Andrew Watts with Al Gore’s prediction shown in red. So far, the prediction has not come to pass.

As it happens, not only hasn’t global warming accelerated, it seems to have paused. There have been no significant temperature changes since late 1997, as shown.  The main explanations are clouds and solar variation: variations that the Obama administration claims will end any day now. The problem, as I see it, is that climate is fundamentally chaotic, and thus unpredictable except on the very long, ice-age, timescale. It will thus always make fools of those who predict.

This is not to say that pollution is good, or that CO2 is, but it suggests our models and remedies are flawed. The CO2 content of the air has increased 25% over the past 19 years. It now mostly comes from China and India, countries that enthusiastically endorse having us reduce our output. My thinking is that lowering US production will, in no way, protect us from the dire predictions below.

Despite pressure from China and India, the US pulled out of the Paris climate accord last month. It now seems several other countries will pull out as well.

Robert Buxbaum, July 27, 2017. I’ve also written about how the global warming of the mid 1800s lead us to have the president’s Resolute desk.

My latest invention: improved fuel cell reformer

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Last week, I submitted a provisional patent application for an improved fuel reformer system to allow a fuel cell to operate on ordinary, liquid fuels, e.g. alcohol, gasoline, and JP-8 (diesel). I’m attaching the complete text of the description, below, but since it is not particularly user-friendly, I’d like to add a small, explanatory preface. What I’m proposing is shown in the diagram, following. I send a hydrogen-rich stream plus ordinary fuel and steam to the fuel cell, perhaps with a pre-reformer. My expectation that the fuel cell will not completely convert this material to CO2 and water vapor, even with the pre-reformer. Following the fuel cell, I then use a water-gas shift reactor to convert product CO and H2O to H2 and CO2 to increase the hydrogen content of the stream. I then use a semi-permeable membrane to extract the waste CO2 and water. I recirculate the hydrogen and the rest of the water back to the fuel cell to generate extra power, prevent coking, and promote steam reforming. I calculate the design should be able to operate at, perhaps 0.9 Volt per cell, and should nearly double the energy per gallon of fuel compared to ordinary diesel. Though use of pure hydrogen fuel would give better mileage, this design seems better for some applications. Please find the text following.

Use of a Water-Gas shift reactor and a CO2 extraction membrane to improve fuel utilization in a solid oxide fuel cell system.

Inventor: Dr. Robert E. Buxbaum, REB Research, 12851 Capital St, Oak Park, MI 48237; Patent Pending.

Solid oxide fuel cells (SOFCs) have improved over the last 10 years to the point that they are attractive options for electric power generation in automobiles, airplanes, and auxiliary power supplies. These cells operate at high temperatures and tolerate high concentrations of CO, hydrocarbons and limited concentrations of sulfur (H2S). SOFCs can operate on reformate gas and can perform limited degrees of hydrocarbon reforming too – something that is advantageous from the stand-point of fuel logistics: it’s far easier to transport a small volume of liquid fuel that it is a large volume of H2 gas. The main problem with in-situ reforming is the danger of coking the fuel cell, a problem that gets worse when reforming is attempted with the more–desirable, heavier fuels like gasoline and JP-8. To avoid coking the fuel cell, heavier fuels are typically reforming before hand in a separate reactor, typically by partial oxidation at auto-thermal conditions, a process that typically adds nitrogen and results in the inability to use the natural heat given off by the fuel cell. Steam reforming has been suggested as an option (Chick, 2011) but there is not enough heat released by the fuel cell alone to do it with the normal fuel cycles.

Another source of inefficiency in reformate-powered SOFC systems is basic to the use of carbon-containing fuels: the carbon tends to leave the fuel cell as CO instead of CO2. CO in the exhaust is undesirable from two perspectives: CO is toxic, and quite a bit of energy is wasted when the carbon leaves in this form. Normally, carbon can not leave as CO2 though, since CO is the more stable form at the high temperatures typical of SOFC operation. This patent provides solutions to all these problems through the use of a water-gas shift reactor and a CO2-extraction membrane. Find a drawing of a version of the process following.

RE. Buxbaum invention: A suggested fuel cycle to allow improved fuel reforming with a solid oxide fuel cell

RE. Buxbaum invention: A suggested fuel cycle to allow improved fuel reforming with a solid oxide fuel cell

As depicted in Figure 1, above, the fuel enters, is mixed with steam or partially boiled water, and heated in the rectifying heat exchanger. The hot steam + fuel mix then enters a steam reformer and perhaps a sulfur removal stage. This would be typical steam reforming except for a key difference: the heat for reforming comes (at least in part) from waste heat of the SOFC. Normally speaking there would not be enough heat, but in this system we add a recycle stream of H2-rich gas to the fuel cell. This stream, produced from waste CO in a water-gas shift reactor (the WGS) shown in Figure 1. This additional H2 adds to the heat generated by the SOFC and also adds to the amount of water in the SOFC. The net effect should be to reduce coking in the fuel cell while increasing the output voltage and providing enough heat for steam reforming. At least, that is the thought.

SOFCs differ from proton conducting FCS, e.g. PEM FCs, in that the ion that moves is oxygen, not hydrogen. As a result, water produced in the fuel cell ends up in the hydrogen-rich stream and not in the oxygen stream. Having this additional water in the fuel stream of the SOFC can promote fuel reforming within the FC. This presents a difficulty in exhausting the waste water vapor in that a means must be found to separate it from un-combusted fuel. This is unlike the case with PEM FCs, where the waste water leaves with the exhaust air. Our main solution to exhausting the water is the use of a membrane and perhaps a knockout drum to extract it from un-combusted fuel gases.

Our solution to the problem of carbon leaving the SOFC as CO is to react this CO with waste H2O to convert it to CO2 and additional H2. This is done in a water gas shift reactor, the WGS above. We then extract the CO2 and remaining, unused water through a CO2- specific membrane and we recycle the H2 and unconverted CO back to the SOFC using a low temperature recycle blower. The design above was modified from one in a paper by PNNL; that paper had neither a WGS reactor nor a membrane. As a result it got much worse fuel conversion, and required a high temperature recycle blower.

Heat must be removed from the SOFC output to cool it to a temperature suitable for the WGS reactor. In the design shown, the heat is used to heat the fuel before feeding it to the SOFC – this is done in the Rectifying HX. More heat must be removed before the gas can go to the CO2 extractor membrane; this heat is used to boil water for the steam reforming reaction. Additional heat inputs and exhausts will be needed for startup and load tracking. A solution to temporary heat imbalances is to adjust the voltage at the SOFC. The lower the voltage the more heat will be available to radiate to the steam reformer. At steady state operation, a heat balance suggests we will be able to provide sufficient heat to the steam reformer if we produce electricity at between 0.9 and 1.0 Volts per cell. The WGS reactor allows us to convert virtually all the fuel to water and CO2, with hardly any CO output. This was not possible for any design in the PNNL study cited above.

The drawing above shows water recycle. This is not a necessary part of the cycle. What is necessary is some degree of cooling of the WGS output. Boiling recycle water is shown because it can be a logistic benefit in certain situations, e.g. where you can not remove the necessary CO2 without removing too much of the water in the membrane module, and in mobile military situations, where it’s a benefit to reduce the amount of material that must be carried. If water or fuel must be boiled, it is worthwhile to do so by cooling the output from the WGS reactor. Using this heat saves energy and helps protect the high-selectivity membranes. Cooling also extends the life of the recycle blower and allows the lower-temperature recycle blowers. Ideally the temperature is not lowered so much that water begins to condense. Condensed water tends to disturb gas flow through a membrane module. The gas temperatures necessary to keep water from condensing in the module is about 180°C given typical, expected operating pressures of about 10 atm. The alternative is the use of a water knockout and a pressure reducer to prevent water condensation in membranes operated at lower temperatures, about 50°C.

Extracting the water in a knockout drum separate from the CO2 extraction has the secondary advantage of making it easier to adjust the water content in the fuel-gas stream. The temperature of condensation can then be used to control the water content; alternately, a separate membrane can extract water ahead of the CO2, with water content controlled by adjusting the pressure of the liquid water in the exit stream.

Some description of the membrane is worthwhile at this point since a key aspect of this patent – perhaps the key aspect — is the use of a CO2-extraction membrane. It is this addition to the fuel cycle that allows us to use the WGS reactor effectively to reduce coking and increase efficiency. The first reasonably effective CO2 extraction membranes appeared only about 5 years ago. These are made of silicone polymers like dimethylsiloxane, e.g. the Polaris membrane from MTR Inc. We can hope that better membranes will be developed in the following years, but the Polaris membrane is a reasonably acceptable option and available today, its only major shortcoming being its low operating temperature, about 50°C. Current Polaris membranes show H2-CO2 selectivity about 30 and a CO2 permeance about 1000 Barrers; these permeances suggest that high operating pressures would be desirable, and the preferred operation pressure could be 300 psi (20 atm) or higher. To operate the membrane with a humid gas stream at high pressure and 50°C will require the removal of most of the water upstream of the membrane module. For this, I’ve included a water knockout, or steam trap, shown in Figure 1. I also include a pressure reduction valve before the membrane (shown as an X in Figure 1). The pressure reduction helps prevent water condensation in the membrane modules. Better membranes may be able to operate at higher temperatures where this type of water knockout is not needed.

It seems likely that, no matter what improvements in membrane technology, the membrane will have to operate at pressures above about 6 atm, and likely above about 10 atm (upstream pressure) exhausting CO2 and water vapor to atmosphere. These high pressures are needed because the CO2 partial pressure in the fuel gas leaving the membrane module will have to be significantly higher than the CO2 exhaust pressure. Assuming a CO2 exhaust pressure of 0.7 atm or above and a desired 15% CO2 mol fraction in the fuel gas recycle, we can expect to need a minimum operating pressure of 4.7 atm at the membrane. Higher pressures, like 10 or 20 atm could be even more attractive.

In order to reform a carbon-based fuel, I expect the fuel cell to have to operate at 800°C or higher (Chick, 2011). Most fuels require high temperatures like this for reforming –methanol being a notable exception requiring only modest temperatures. If methanol is the fuel we will still want a rectifying heat exchanger, but it will be possible to put it after the Water-Gas Shift reactor, and it may be desirable for the reformer of this fuel to follow the fuel cell. When reforming sulfur-containing fuels, it is likely that a sulfur removal reactor will be needed. Several designs are available for this; I provide references to two below.

The overall system design I suggest should produce significantly more power per gm of carbon-based feed than the PNNL system (Chick, 2011). The combination of a rectifying heat exchange, a water gas reactor and CO2 extraction membrane recovers chemical energy that would otherwise be lost with the CO and H2 bleed steam. Further, the cooling stage allows the use of a lower temperature recycle pump with a fairly low compression ratio, likely 2 or less. The net result is to lower the pump cost and power drain. The fuel stream, shown in orange, is reheated without the use of a combustion pre-heater, another big advantage. While PNNL (Chick, 2011) has suggested an alternative route to recover most of the chemical energy through the use of a turbine power generator following the fuel cell, this design should have several advantages including greater reliability, and less noise.

Claims:

1.   A power-producing, fuel cell system including a solid oxide fuel cell (SOFC) where a fuel-containing output stream from the fuel cell goes to a regenerative heat exchanger followed by a water gas shift reactor followed by a membrane means to extract waste gases including carbon dioxide (CO2) formed in said reactor. Said reactor operating a temperatures between 200 and 450°C and the extracted carbon dioxide leaving at near ambient pressure; the non-extracted gases being recycled to the fuel cell.

Main References:

The most relevant reference here is “Solid Oxide Fuel Cell and Power System Development at PNNL” by Larry Chick, Pacific Northwest National Laboratory March 29, 2011: http://www.energy.gov/sites/prod/files/2014/03/f10/apu2011_9_chick.pdf. Also see US patent  8394544. it’s from the same authors and somewhat similar, though not as good and only for methane, a high-hydrogen fuel.

Robert E. Buxbaum, REB Research, May 11, 2015.

Where does industrial CO2 come from? China mostly.

The US is in the process of imposing strict regulations on carbon dioxide as a way to stop global warming and climate change. We have also closed nearly new power plants, replacing them with cleaner options like a 2.2 billion dollar solar-electric generator in lake Ivanpah, and this January our president imposed a ban on lightbulbs of 60 W and higher. But it might help to know that China produced twice as much of the main climate change gas, carbon dioxide (CO2) as the US in 2012, and the ratio seems to be growing. One reason China produces so much CO2 is that China generates electricity from dirty coal using inefficient turbines.

Where the CO2 is coming from: a fair amount from the US and Europe, but mostly from China and India too.

From EDGAR 4.2; As of 2012 twice as much carbon dioxide, CO2 is coming from China as from the US and Europe.

It strikes me that a good approach to reducing the world’s carbon-dioxide emissions is to stop manufacturing so much in China. Our US electric plants use more efficient generating technology and burn lower carbon fuels than China does. We then add scrubbers and pollution reduction equipment that are hardly used in China. US manufacture thus produces not only less carbon dioxide than China, it also avoids other forms of air pollution, like NOx and SOx. Add to this the advantage of having fewer ships carrying products to and from China, and it’s clear that we could significantly reduce the world’s air problems by moving manufacture back to the USA.

I should also note that manufacture in the US helps the economy by keeping jobs and taxes here. A simple way to reduce purchases from China and collect some tax revenue would be to impose an import tariff on Chinese goods based, perhaps on the difference in carbon emissions or other pollution involved in Chinese manufacture and transport. While I have noted a lack of global warming, sixteen years now, that doesn’t mean I like pollution. It’s worthwhile to clean the air, and if we collect tariffs from the Chinese and help the US economy too, all the better.

Robert E. Buxbaum, February 24, 2014. Nuclear power produces no air pollution and uses a lot less land area compared to solar and wind projects.