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Mitsui Chemicals to Build Pilot Facility to Study Process for Methanol Synthesis from CO2

Pict_0825_001
MCI’s methanol synthesis process. Click to enlarge.

Mitsui Chemicals Inc. (MCI) will begin construction of a pilot facility which will be used to continue the company’s efforts to develop a process to synthesize methanol from CO2.

MCI has been pursuing the development of a process for the synthesis of methanol (CH3OH)—later used in the production of olefins and aromatics—using the CO2 emitted from factories and hydrogen obtained from water photolysis. The effort is part of the company’s strategy to develop innovative processes to contribute to significant reductions of greenhouse gases.

The pilot plant, located at MCI’s Osaka plant, will have a production capacity of approximately 100 tonnes of methanol per year, using about 150-160 tonnes of CO2 emitted the Osaka plant. Construction of the ¥1.5 billion (US$13.7 million) plant will begin in October, and is due for completion in February 2009. The plant is projected to come online in March 2010.

From 1990 to 1999, MCI took part in “Chemical CO2 Immobilization Project (Entrusted by NEDO),” a project launched by the Research Institute of Innovative Technology for the Earth (RITE).

Two aspects of RITE’s work in this area were:

  • A single unit photoelectrocatalysis (SUPEC) system which consists of a highly efficient thin film anatase titania photocatalyst having a photon-to-current quantum efficiency of 60%; and

  • An electrocatalyst consisting of zinc oxide and copper which when operated in the SUPEC system can stably convert 82% of carbon dioxide to hydrocarbons in terms of current efficiency including 44% for methane and 24% for ethylene without deactivation of the reactions by a special operating method employing a pulsed bias.

Utilizing this joint research, MCI has already succeeded in developing the ultra-high-activity catalysts which will be upgraded and used at the new pilot facility.

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Comments

HarveyD

If CO2 conversion, into useful fuel and/or industrial products, can be done economically on a large scale, it could have a major impact on GHG control.

This could make coal fired power plants more acceptable.

Lulu

This type of idea if given enough development could go a long way to reduce CO2 emission. CO2 to plastics would be my ideal target process.

Bill Woods

What's the source of energy to drive this reaction? Coal power?

Paul F. Dietz

What's the source of energy to drive this reaction? Coal power?The energy input would largely be in the production of hydrogen, which is described as coming from water photolysis (not that I am saying that that is practical.)

ai_vin

"This could make coal fired power plants more acceptable"
Not if you're using more coal to drive the reaction.
And if you're using clean energy to drive the reaction why not use it to just replace coal?
No, this only makes sense when "using the CO2 emitted from factories" because they may not have any alternative.

Axil

@ai_vin

you are a man of rare wisdom.

ai_vin

Scary isn't it?

Axil

@ai_vin

"Scary isn't it?"

No, it's rare and very refreshing.

Henric

Man, I can tell you all stright up that this is not going to be a huge money maker for these guys.
First they have got to extract pure CO2 from rather dilute waste gases. After that they have to get hydrogen the production of which using solar energy will be low from a unit of surface area even if the photocatalyst is 100 % efficient.
The most efficient method of harnessing solar energy for making carbon containing chemicals/fuels is using biomass for that purpose. What investments do one need to get renewable carbon to a plant? A saw and an axe, and possibly a charcoal gasogene-fired tractor.

arnold

At 100% efficiency in CO2 capture and fully solar driven hydrogen production, the very best reduction in CO2 emissions will be under 50%.
new coal will always be needed.
Much the same as sequestering fluegas to algae.
Halving CO2 is not to be sneezed at.
One would think that a process of hydrogen photolysis of any note would firstly be the primary technology and world shatteringly newsworthy on its own.
Secondly the Hydrogen output would be optimum point for utilization of the novel technology.

(After making methane someone will make a newsworthy statement about turning the methane into Hydrogen)

So we have another just around the corner technology that justifies business as usual for the coal and transport industries.
But the trillions of tons CO2 currently rising in the fossil fuel industry furnaces won't even see this concept.
Will look nice on someones resume.

Darius

It seems technology quite strait forward. Hydrogen can be produced by any means - biological as well. I don't know what would be cost of shifting to methanol.
On other hand algae can be used for any fuel - diesel, ethanol, methanol. But algae plantations cost a lot themselves. Only second stage is fuel blending.

arnold

We should assume that bio from algae, like other bio's would benefit from some upgrade by added hydrogen processing for storage longevity as it would likely be subject to oxidation over a shorter time than mineral oils. Also the cold flow point could need modifying the same as mineral deisel .
This would be more important in larger supply chains and for single fuel vehicles (as opposed to multi fuel or wider tolerance) variants.
Until we know more about these aspects.

Paul F. Dietz

The most efficient method of harnessing solar energy for making carbon containing chemicals/fuels is using biomass for that purpose.

Actually, this method is horribly inefficient. It just happens to be the cheapest way at the moment.

Engineer-Poet

Quoth Henric:

First they have got to extract pure CO2 from rather dilute waste gases. After that they have to get hydrogen the production of which using solar energy will be low from a unit of surface area even if the photocatalyst is 100 % efficient.
Maybe, and then again, maybe not.  Photolysis of water yields hydrogen and oxygen, and oxyfuel combustion or oxygen-blown gasification of biomass would produce quite a bit of heat (and a product gas undiluted by nitrogen).  Synthesis of methanol from the syngas and added hydrogen would produce water and more heat as byproducts.  Co-location of the fuel operation and an industrial plant which uses the waste heat would be the most efficient option.

Feasibility of such schemes depends on the specifics.  Right now, it can't compete.

sjc

Co-location seems like a smart way to go. Future power plants may be more like energy plants. They can make fuels, chemicals, electricity, process heat and all kinds of products, so very little goes to waste.

Henry Gibson

The CO2 produced at a power plant need not be dilute. Coal can be burned with pure oxygen in a wet-air-oxidation system. The combustion can be completed with a super-critical-wet-air-oxidation system. Both water and CO2 would be produced with only small amounts of nitrogen from the waste gases. Mercury and sulphur and uranium and other ash would be trapped in the water bath.

The extra cost of purified oxygen is partially made up from the lower cost of high sulphur coal that can be burned and the process also can burn all plastics and organic wastes. The extra cost is also reduced by avoided costs of fly ash and flue gas cleaning.

Both water and CO2 can be condensed into liquid at the pressures used if the gases are cooled to room temperatures. CO2 can be stored in compact liquid form in strong tanks until needed. The additional heat from the condensing of the gases may be used for district house or factory heating.

On the other hand there is no reason that CO2 cannot be obtained from the air with chemicals, and the cost may be low enough to compete with $4.00 gasoline.

Very high temperature super critical water can produce a very high percentage of hydrogen from coal or biomass and collect the CO2. This hydrogen can be burnt in ordinary gas turbine cogeneration units or piston engines or fuel-cells with about the same efficiency.

Coal is not dirtier than petroleum industry considered as a whole including natural gas. For the same amount of energy (kilowatt-hours) delivered to the wheels of the car or the meter at the house, coal may release less CO2 than gasoline to the environment because of the 123 gallons crude to 100 gallons gasoline refinery ratio, the transportation of crude and gasoline, flaring of gases at wells and especially of the low average efficiency of large engines operating at low loads.

The cost of energy in coal delivered to the power plant is now less than one-tenth(1/10) the cost of energy in crude oil in a tanker. People who insist upon eliminating coal use with the bare mention of other fossil fuels are trading upon their relative wealth compared to people whose unemployment results in a shortened difficult existence for themselves and dependants.

Cheap energy is an absolute necessity for a funtioning and expanding economy. Just look at how the mass of people in England lived before the vast energy of coal mines relaced that of denuded forests of cellulostic wood and charcoal. The miniumum inconvenient truth is that there were far fewer of them and even those ate much less.

No energy on the face of the earth is cheaper than the heat from nuclear fission for producing electricity. The false belief, that humans have not been radio-active through out the millenia of their entire existence upon the earth, and political decisions have resulted in falsely considering nuclear materials and the power plants more dangerous than simple propane and certainly more dangerous than simple microbes. More pounds of radio-active atoms enter and exit coal fired power plants than the same sized nuclear power plants that actually destroy many pounds of radioactive atoms.

The "used" fuel rods are no more dangerous than a large pot of molten steel, but you must keep some distance away from both to avoid danger. A propane tank for a gas grill can eliminate far more people and much more property at a greater distance. Without the least modification of the "used" rods, a heavy water reactor, designed for them, could get half again or more heat out of them. Breeder-Reactors or Accelerator-Driven-Reactors could get twenty times more energy out of them.

The earth and its ocean is already naturally so radio-active that dissolving the whole reactor load of fuel rods in a few cubic miles of ocean would not measurably increase the radio-activity of that area. In spite of the remaining energy, radio-active materials that have been declared to go to disposal can be embedded a hundred feet deep, as concrete or cast iron piles, in 2000 feet deep undersea clay with known pile driver technology. The materials could also be dissolved and mixed with the binding clay and the deep subsoil of open cast mines that are being restored. The soil already has much natural radio-activity and the addition of a small percentage of more disintegrating atoms would not cause measurable danger and the materials could never be re-concentrated. The slight increase of radio-activity would be further shielded by the naturally radio-active top soil. The whole area would be far less radio-active than some towns.

Nuclear reactors can supply not only the electricity but vast amounts of heat for various processes. There are known chemical processes than can produce hydrogen from water with high temperature heat, but there are other processes that can use a great deal of heat to combine or purify fuels such as ethanol. Every nuclear power plant should be required to be able to send very hot water or hot oil to neighboring factories. Every ethanol plant and oil refinery should be built near a nuclear reactor. The additional fuel required for providing this heat costs a small fraction of a cent per kilowat-hour.

Plutonium is not the most dangerous chemical. Many people have held armament grade plutonium in their hands to feel the heat including Queen Elisabeth II as a very young queen. Plutonium from "used" fuel rods can be used to make new fuel rods at moderate cost, but its plutonium had been modified during the long period in the reactor to the point that it is contaminated with other isotopes of plutonium that would make a nuclear bomb too hard to build.

Even ten pounds of used rod plutonium in a hundred pounds of armanent plutonium makes it almost impossible to build a nuclear explosive. Even the best US technology cannot separate the materials cost effectively. It is much cheaper to process uranium to separate its isotopes. A mixture of both types of plutonium can then be used without fear of diversion as a mix with uranium in many reactors. CANDU reactors can start a thorium cycle with the mix.

Thorium is estimated to be three times as plentiful as uranium. With carefull design and fuel reprocessing, only additional natural thorium is required in small amounts. A pound of armament plutonium added to the fuel cycle of a reactor can actually produce the same heat as 3 000 000(three million) pound of coal. At todays prices, Disposing of a pound of armament plutonium is the same as throwing $150 000 away. The same is true of armament uranium. Three million pounds of coal can generate more than three million kilowatt-hours. The 145 pounds of uranium that has 1 pound of fissionable uranium in it costs about $100 a pound with speculation or $10 without, and you get $150 000 worth of coal energy for $15,000 or less. There is about 500000 pounds of unused plutonium in storage and much more U235. At $100 a ton coal costs five cents a kilowatt hours. The Peabody income three years ago indicated a price of about $20 a ton. Natural Uranium at $100 a pound is a half a cent per pound per kilowatt-hour. This ignores the cost of fabricating the fuel elements and enrichment.

There is about 35 kilowatt-hours of heat in a gallon of gasoline, so the uranium cost of producing hydrogen at 60% electrical efficiency is about 30 cents per gallon of gasoline equivalent. Chemical production can triple this efficiency. Because of the laws of physics The maximum a car engine gets out of a gallon of gasoline is nine kilowatt-hours or 45 miles. Using the electricity in a battery car could give 150 miles of range.

The used fuel rods and the depleted uranium in storage from making fuel and armaments would last the US for over a hundred years for all energy needs if used in breeder or accelerator reactors.

Although the solar energy is free, the land area and the equipment has proved costly. Electrolytic hydrogen is a waste of energy where the electricity can be used in electric cars even with fuel cells. Other hydrogen is expensive to compress or liquify and store. Hydrocarbons are the best way to store it. A hydrogen gas pipeline system may replace or parallel the natural gas system. It requires three times the volume of hydrogen for the energy of the same volume of natural gas. Hydrogen requires 360 times the volume of gasoline.

Hydrogen fuel cells with a hundred horsepower cost more than a million dollars because of the expensive catalysts in them. Fuel cells are now over a hundred years old. They have been used in space for more than 40 years. Their price has gone down a lot but not enough for cars in that time. Diesel engines may have better efficiency and certainly better well to wheel efficiency.

Plug-In-Hybrid cars are the fastest way to reduce car oil fuel consumption and CO2 release. Cogeneration is the fastest way to reduce home and business CO2 release and energy consumption. ..HG..

Axil

Hi Engineer-Poet;

Can you run your analysis using nuclear power from a micro reactor at $1000/kw installed cost that produces process heat, and electricity and hydrogen at 10% of capacity? I have done this for coal to liquids and the production when up by 400%.

Henric

Hi Axil,

Can you get heat from a nuclear reactor as a stream of inert circulating gas at no less than 2000 deg F? Because if you cannot, no CTL or XTL is possible because gasification reactions are very slow below 2000 deg F.

Henric

Henry,
Oxygen is going to be prohibitively expensive as an oxidant in a power plant. It costs about 0.25 kWh a m3 if produced by liquefaction of air. They use it for integrated gasification - combined cycle i.e. coal powder is gasified and the resulting gas is burned in a gas turbine; the exiting hot gas raises steam which drives a steam turbine; this gives about 50 - 60 % thermal to electrical. However, if C capture and sequestration is ever going to be used in a power plant, then oxygen as an oxidant is a necessity.

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