Archive for category Products from CO2

Production of Methanol from CO2

Posted by on Monday, 28 February, 2011

US department of energy (DOE) has got a patent to produce methanol from carbon dioxide. The process developed by DOE is for the production of methanol from natural gas containing methane.

The inventors [patents] are Meyer Steinberg, USDOE scientist at the Brookhaven, NY, National Laboratory and Yuanji Dong, EPA scientist at National Risk Management and Environmental Protection Research Laboratory in North Carolina.

The objective of this project is to provide an efficient method for the production of methanol from natural and carbon dioxide.

Process involved

A process for the production of methanol from natural gas containing methane comprising the thermal decomposition of methane and the subsequent reaction of the resulting hydrogen gas with carbon dioxide in a catalyst containing methanol synthesis reactor to produce methanol

Alternative methods include the gasification with carbon dioxide of at least a portion of the carbon produced by the decomposing step, to produce carbon monoxide, which is then reacted with hydrogen gas to produce methanol; or the reforming of a portion of the natural gas feedstock used in the decomposing step with carbon dioxide to produce carbon monoxide and hydrogen gas, which carbon monoxide and hydrogen are then combined with additional hydrogen from the natural gas decomposing step in a methanol synthesis reactor to produce methanol. The methods taught reduce the overall amount of carbon dioxide resulting from the methanol production process.

What is claimed?

A. Process for the production of methanol from methane containing natural gas comprised of:

a. Thermally decomposing said methane to produce hydrogen gas and elemental carbon; wherein this decomposing step is comprised of:

i. Bubbling the methane through a bath comprised of a molten material operating at a temperature of at least 800° C. and a pressure of 1 to 10 atm.;

ii. Cracking said methane through the use of said molten material such that elemental carbon and hydrogen gas are formed;

iii. Removing the hydrogen gas from the top of the bath; and

iv. Collecting the elemental carbon off the top of the liquid surface of the bath; and

B. Reacting said hydrogen gas with carbon dioxide in a methanol synthesis reactor in the presence of a catalyst to form a product containing methanol.

C. The process of claim A wherein the molten material is selected from the group comprising molten metal tin and molten metal iron.

Description:

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention is related to a method for the production of methanol, and more specifically, to a method for production of methanol by conversion of natural gas and carbon dioxide which method has reduced carbon dioxide emissions.

2. Description of the Prior Art

Methanol, which was first discovered in the late 1600’s, has found use as a chemical feedstock and as an efficient fuel. Its earliest and largest use to date is as a feedstock in the production of formaldehyde. While in recent years such use has decreased, methanol has found increasing use in the production of such materials as acetic acid and methyl tert-butyl ether (MTBE–a gasoline additive). In addition, methanol is being used directly (with increasing demand) as a fuel in race cars, in farm equipment and, in some areas, as a general purpose automotive fuel. Methanol is fast becoming an environmentally preferred alternative transportation fuel and can also serve as a clean stationary power plant fuel.

There are several commercially viable methods of producing methanol. These methods include:

1. The steam reforming of natural gas in accordance with the following reaction:

CH4 +H2OCO+3H2

2. The gasification of natural gas with carbon dioxide in accordance with the following reaction:

CO2 +CH4 2CO+2H2

Or a combination of these methods

As is clear to those skilled in the art the goal of each of these conventional methods is to produce or otherwise provide carbon monoxide and hydrogen in a molar ratio of 1 mole of CO to 2 moles of H2 .These reactants are then reacted in methanol synthesis reactor in the presence of a catalyst to produce methanol in accordance with the following exothermic reaction:

CO+2H2 CH3OH

The processes known in the art often produce carbon dioxide which, if fed to the methanol synthesis reactor, results in a lower methanol yielding reaction which competes with the above reaction for the valuable hydrogen as follows:

CO2+3H2 CH3OH+H2O

Therefore, carbon dioxide must be removed prior to entry into the methanol synthesis reactor. This obviously adds additional complexity, and, therefore expense to the process. In addition, the creation and/or emission of carbon dioxide by the methanol forming process creates other problems since carbon dioxide is a green house gas, the negative effects of which are only beginning to be understood. What is well understood, however, is the desire to reduce or eliminate carbon dioxide production and processes which reduce such emissions or in fact consume carbon dioxide as part of the process are desirable.

It is therefore an object of the present invention to provide an efficient method for the production of methanol from natural gas and carbon dioxide.

It is another object of the present invention to provide a method which produces a high yield of methanol per unit feedstock.

It is yet another object to the present invention to provide a method for the production of methanol having reduced carbon dioxide emissions. It is another object of the present invention to utilize waste CO2 from coal burning power plants and other sources to produce methanol to reduce overall net CO2 emissions.

It is another object of the present invention to produce carbon as a co-product to the production of methanol.

SUMMARY OF THE INVENTION

This invention relates to the production of methanol by conversion of natural gas (which is comprised mainly of methane) and carbon dioxide. The process of the present invention is comprised of two (2) basic steps, the thermal decomposition of methane (natural gas) to produce elemental carbon and hydrogen gas followed by the catalyzed reaction of the hydrogen gas produced in step one of the process with carbon dioxide in a methanol synthesis reactor to produce a gas stream containing methanol. The methanol may then be separated from the gas stream by known techniques. The carbon is separated as a co-product of the process.

As discussed above described in more detail below, the process of the  invention consumes a substantial amount of carbon dioxide.

The source of the carbon dioxide used in the present invention may be any sources. However, since as indicated above the net creation and/or emission of carbon dioxide is something to be reduced or avoided, the process of the present invention may be most advantageously operated in conjunction with a carbon dioxide producing process such as a fossil fuel fired energy producing plant (i.e., e.g., a coal fired electrical generation plant or waste incinerators).

As is well known in the art such fossil fuel fired plants produce carbon dioxide as well as other gases which, if they are not otherwise dealt with, are discharged to the air, having many negative impacts on the environment such as global warming. However, such a plant operated in conjunction with the present invention could result in reduced carbon dioxide emissions since a substantial portion of the carbon dioxide generated could be consumed in the process of the present invention.

In addition, as indicated above,  the present invention has the added feature of producing elemental carbon.

The carbon which is removed from the thermal decomposition step may be stored, sold or employed in other processes where elemental carbon is of value such as the production of carbon black.

An alternate embodiment of the present invention involves the additional step of gasification of a portion of the elemental carbon produced in step one with carbon dioxide to produce carbon monoxide and thereafter reacting the hydrogen produced in the natural gas thermal decomposition step with the carbon monoxide in a catalyzed reaction in a methanol synthesis reactor to form methanol.

A third embodiment of the present invention involves the step of reforming a portion of the natural gas feedstock with carbon dioxide to produce carbon monoxide and hydrogen which constituents are then provided to a methanol synthesis reactor along with the hydrogen gas produced in the methane decomposition step, where the carbon monoxide and hydrogen are combined in a catalyzed reaction to produce methanol.

It will be clear to those skilled in the art that the thermal energy necessary to cause the thermal decomposition of the natural gas in step one in the above described process may be provided in any of the known manners, but it is most commonly provided by the combustion of natural gas in accordance with the following reaction:

2CH4 +4O2 CO2+4H2O

As can be seen this reaction produces carbon dioxide. However, since the process of the present invention also consumes carbon dioxide and in fact does so in an amount greater than that produced by the above reaction 5, the use of the present process results in the reduction of carbon dioxide produced by the methanol producing process.

In addition, if hydrogen gas produced by methane decomposition is substituted as the fuel in the process or if an alternative non-fossil fuel method of supplying thermal energy (e.g. solar energy or nuclear energy to the methane decomposition reactor is employed, for the decomposition step, the production of carbon dioxide in the process of the present invention is further reduced.

The carbon produced in the process is either sequestered or used as a materials commodity and is not burned as fuel.
When methanol is used as an alternative transportation fuel in automotive engines or as a clean stationary power plant fuel, the methanol combustion reaction is as follows:

CH3OH+3/2O2 CO2 +2H2O

As indicated, carbon dioxide is produced. However, since carbon dioxide recovered from a fossil fuel burning power plant is used in the synthesis of methanol, the net carbon dioxide produced in the system becomes near zero when methane is used as a fuel to heat the methane decomposition reaction of step one of the process or is zero when hydrogen is used as a fuel.

Reference:

1)    http://www.wvcoal.com/201011292417/Research-Development/epa-a-doe-recycle-more-co2.html

2)  http://www.freepatentsonline.com/5767165.pdf

Fossil Fuels


Storing CO2 in products

Posted by on Thursday, 13 January, 2011

I recently came across an article where a company claims to have developed a method for producing gasoline from CO2. This seems to be interesting at a time when researchers are working on finding ways to sequester CO2 in geological formations for economic activity like enhanced oil recovery (EOR). The other option that seems to be promising is to store carbon in products like gasoline, plastics, cement etc. This post will focus on the potential of using CO2 directly as feedstock for producing carbon containing products thereby reducing the CO2 emissions into the atmosphere.

CO2 has many industrial uses. The chemical industry uses carbon dioxide to produce fertilizers, plastics, and polymers. Some of the important products that can be produced from CO2 for which research is in various stages of development are plastics, cement, and gasoline among others.

Now let’s look at how CO2 is used as feedstock for plastics production and its associated benefits. Plastics are synthetic polymers produced mainly from crude oil. Novomer, a material manufacturing company in New York is developing a process for manufacturing plastics from CO2. It is estimated that for every 1 tonne of oil burnt, 3 tonne of CO2 is released into the atmosphere and for producing 1 tonne of plastics, 2 tonne of oil is required. So for every tonne of plastics produced, 6 tonne of CO2 is released into the atmosphere. Using the process developed by Novomer, the amount of oil required can be reduced by half as it uses only 50% fossil fuel feedstock in the form of epoxides and the remaining is sourced from the captured CO2. Hence for production of 1 ton of plastics, roughly around 1 ton of CO2 is the input required which translates into 250 Mt of CO2 as input for 250 Mt of plastics produced annually (Global plastics production is 250 Mt as of 2009).

Cement

Cement Industry is considered to be one of the largest emitter of CO2 next only to power plants. Calera, a California based company has devised a method to produce cement from CO2 and estimated that for every ton of cement produced ½ ton of CO2 is used. If all the cement produced globally is produced from CO2,       1.5 billion tonnes of CO2 would be required for producing 3 billion tonnes annually. (Global cement production is approximately 3 billion tonnes in 2009).

Gasoline

Gasoline is a hydrocarbon consisting of carbon and hydrogen which is derived from crude oil. A company by name Carbon sciences is developing a technology to transform CO2 to liquid fuels like gasoline, diesel and jet fuel. According to their estimate for 3.5 tonnes of gasoline produced, 1 ton of CO2 is consumed in this process. If all the gasoline consumed globally is produced by this process (which is 4 billion tonnes annually), 1 giga tonne of CO2 would be consumed during the gasoline production process.

An estimate says that the total CO2 emitted is around 35 giga tonne, of which around 40% is contributed by power plants (which is 14 giga tonnes). Suppose all of gasoline, cement and plastics produced, use CO2 as feedstock, roughly around 2.5 giga tonnes of CO2 would be required. Hence in all, 18% of the total CO2 emitted by power plants can be used for the manufacturing of products like gasoline, cement and plastics. This technique along with algae based CO2 capture and EOR using CO2 appears to be promising techniques to sequester carbon dioxide in large amounts.

You can find elaborate description of each of these techniques of storing CO2 in products here


Carbon Dioxide for Oil Recovery Could be a $240 Billion Business

Posted by on Friday, 15 October, 2010

In what seems on the surface a little bit of a zero-sum solution, a British researcher has stated that oil recovery using carbon dioxide could be worth £150 billion (USD $240 billion) if acted upon immediately.

By using carbon dioxide to enhance the recovery from existing North Sea oil fields, the new calculation by Jon Gluyas, a Professor in CCS & Geo-Energy, Department of Earth Sciences, Durham University could yield an extra three billion barrels of oil over the next 20 years.

More from here


Calera – Using CO2 to make cement

Posted by on Thursday, 1 July, 2010

Calera, a 3 year old California-based start up, has come out with an emerging technology which represents an innovative solution to advance our energy, environmental and economic goals, by recycling carbon dioxide into beneficial building products.

One of the few weak points is that the Calera process says that it captures “86% of the flue gases which is treated”, which seems to imply that not the whole of the emitted flue gas is by them treated.

The Calera Process imitates nature

The Calera process mimics how nature grows the hard, durable materials in teeth, bone and shells. Minerals in seawater attach to CO2 molecules in the air to create a limestone-like material.

The chemical composition of Calera cement is essentially limestone, a favorite material for cement, concrete, and pavements.

Because Calera’s process removes minerals and other constituents from seawater, it also acts as a freshening system to produce fresh water, which also gives it added value for clean water projects.

Moreover, unlike traditional sequestration, where CO2 threatens to break free and escape back into the atmosphere, in the Calera process, once the CO2 is converted into cement, only temperatures hotter than 700 degrees C, or sustained exposure to concentrated acid can release it again into the atmosphere, Calera says.

Critics of the technology are concerned with an acid byproduct from the reaction that must be neutralized and disposed of. Apparently, as yet they do not have a way to neutralize the acid without creating additional environmental hazards and raising costs.

The water requirements of the process are a bit dicey – seawater is required to produce cement. The Calera process must have a plentiful source of brine, so how will they implement their idea at inland and water starved power plants? And what are the energy requirements of the process? An answer to these questions is expected soon, since Calera has announced it will open its first commercial plant next year.

An economic alternative

Calera claims that its relatively low-cost cement-making process can surpass all other CCS techniques, cutting a plant’s energy drain to less than 15 percent, instead of the 30-40% for conventional chemical scrubbing, and reducing the cost of CCS technology to zero.

A smarter economy

CO2 is an essential raw ingredient in the Calera process, so the cost of capturing and storing it in materials would be more than offset by profits from the sale of those materials.

But if the Calera process immediately replaced 100 percent of conventional cement-making in the United States, the 15.5 billion tons in current CO2 emissions from fossil fuels would not even be enough to address the demand of the aggregate market, Constantz said.

Calera recently completed a demonstration project near Moss Landing, Calif. that is capable of capturing 30,000 tons per year of a CO2, equivalent to a 10MWe natural-gas power plant. In January, Calera began drawing 1 percent of the stack gas from a Dynegy power plant across the street through a massive pipe to its cement plant. Calera was hoping to capture 80 percent of the smokestack CO2, and sequester it in its patented cement mixture using the abundant stock of magnesium hydroxide (Mg(OH)2) available on site. Calera’s plant is capturing 86 percent of the CO2 in the flue gas from the Dynegy plant per a study by R.W. Beck, a consulting firm hired by Calera.

Calera has started work on a plant in Australia, and is getting ready to announce plans to build another plant in Southern California.

Just how unclean is cement?

Pollution occurs from the use of coal, natural gas or oil as fuel in a burn of aggregates, silica and lime at 2700 degrees F, in large cylindrical steel rotating kilns. Inside, extreme heat causes a chemical change to take place. The entire process uses an enormous amount of energy – 6 million Btus for every ton of cement produced. Thus, cement uses the most energy of all industrial manufacturing processes – as much as .6% of total US energy use.

Industry taking note

In March, Peabody Energy, the world’s largest private-sector coal company, led Calera’s latest investors by purchasing a $15 million equity interest.

But skeptics not as foolhardy

The skepticism of critics like Caldeira and Romm is fueled by Calera’s evasiveness when confronted with demands for factual information about how their process actually works, and that the fact that their replies tend to come in cartoon form.

“People have been looking for ways to do this for 15 years,” said Ken Caldeira, an expert on the carbon cycle who is a senior scientist with the Carnegie Institution for Science at Stanford. “The idea that they’re going to come up with something that’s both economic and scalable? I’m highly skeptical.”

In ClimateProgress, Romm notes that Caldeira made a strong case that
* The scalability of the process is in doubt
* We won’t know if net CO2 is saved unless Calera is much more forthcoming on all of the inputs and outputs

Romm summarizes it as “I see no evidence that they have found an affordable and scalable process, but it is impossible to say anything definitive because they are not being adequately forthcoming.”

Calera’s CO2 capture technology has given us hope that CO2 capture can be economical, and produce useful byproducts, but they still have to prove that it’s actually viable, and that too at a large scale.

Sources:
ROSE RAGSDALE, Greeningfoil
Worldwideopinion
Climateprogress


CO2 into Baking Soda – Skyonic Gets $3M Stimulus Funding

Posted by on Monday, 1 March, 2010

Austin carbon capture company Skyonic will get $3 million in stimulus funding to add its technology to a San Antonio cement plant and turn carbon dioxide into baking soda.

Skyonic will wheel its CO2-to-baking-soda trailers from a Luminant coal-fired power plant, where Skyonic conducted a pilot project, to the Capitol Aggregates Ltd. cement plant, according to a spokeswoman.

The Capitol-SkyMine® plant is targeted to capture 75,000 metric-tonnes of CO2 from flue gas emitted by Capitol Aggregates’ cement plant and mineralize the carbon dioxide-emissions as baking soda, while also offsetting an additional 200,000 metric-tonnes of CO2 in the manufacture of benign chemical byproducts. The Capitol-SkyMine® plant will operate at a profit, due to the sale of these byproducts and is expected to generate over two hundred permanent jobs in Texas. The mineralized carbon dioxide (baking soda) will be used in several industrial applications and tested as feed-stock for bio-algae fuels. Capitol-SkyMine® will also neutralize acid-rain emissions, and reduce mercury and heavy metals emissions.

Source


CO2 to Carbon Monoxide and Then to Methanol and Gasoline

Posted by on Monday, 1 March, 2010

Using concentrated solar energy for power, a research team from Sandia National Laboratories is building a prototype device intended to chemically “reenergize” carbon dioxide into carbon monoxide using concentrated solar power. Carbon monoxide could then be used to serve as a building block to synthesize a liquid combustible fuel, such as methanol or even gasoline, diesel and jet fuel.

The prototype device called the Counter Rotating Ring Receiver Reactor Recuperator (CR5) is designed to break one of the carbon-oxygen bonds in the carbon dioxide molecule to form a carbon monoxide molecule and oxygen in two distinct steps. It’s a major piece of an approach to converting carbon dioxide into fuel from sunlight.
Sandia’s Solar Furnace. Click image for more info.

Rich Diver is the inventor, and explains the original idea for the device was to break down water into hydrogen and oxygen. The hydrogen could then fuel a potential hydrogen economy. Then Sandia researchers came up with the idea to use the CR5 to break down carbon dioxide, just as it would water. Over the past year they have shown proof of concept and are completing a prototype device that will use concentrated solar energy to reenergize carbon dioxide or water, the products of combustion. This will form carbon monoxide, hydrogen, and oxygen, which ultimately could be used to synthesize liquid fuels in an integrated S2P system.

The press release called it “reverse combustion.”

This invention, though probably a good 15 to 20 years away from being on the market, holds a real promise.

Source


Zero Emission Coal Power Plant Design Makes Carbon Capture Profitable

Posted by on Monday, 1 March, 2010

Power Plant Produces Hydrogen, Only Raw Materials Needed are Coal, Salt and Water

The only raw material required is coal (or natural gas), sodium chloride (salt) and water. The process locks carbon dioxide (CO2) and carbon monoxide (CO) into sodium bicarbonate and sodium carbonate.

Florida International University (FIU, Miami, Florida) FIU Center for the Study of Matter at Extreme Conditions Director Surendra Saxena developed the system of reactions for a partial sequestration of carbon (CO2 and CO) from coal burning plants and zero emission production of hydrogen and hydrides. The only raw material to be used is salt (sodium chloride, NaCl), coal and water or a metal for the hydride. Sodium hydroxide (NaOH) generated from the chloride is used for locking carbon dioxide in sodium carbonate and bicarbonate, according to Saxena in U.S. Patent Application 20100028241

Saxena process also generates hydrogen from the reaction. The reaction takes place in a closed system to achieve zero emission of carbon gases while generating hydrogen from the reaction. The process of carbonation is not a direct conversion of NaOH to Na2CO3 but is a result of a reaction with other solids and gases usually producing hydrogen in important amounts.

Source


New CO2 Fixing Catalyst Turns It into Oxalate

Posted by on Monday, 1 March, 2010

A copper-based catalyst recently developed by Elisabeth Bouwman and co-workers at Leiden University in the Netherlands represents a vast improvement over previous atmospheric carbon-dioxide-fixing processes. Most of these are poisoned by oxygen, which means that you can’t just pump air into the reactor without removing the oxygen first. Bouwman’s catalyst, however, reacts with carbon dioxide but not oxygen, producing oxalate, which is a useful feedstock for the manufacture of methyl glycolate and other organic compounds. And while Bouwman’s material is not a “true” catalyst in that it actually forms a compound with carbon dioxide and has to be regenerated in a second reaction, the regeneration step can be done electrochemically with remarkably little energy.

Source


Morphic Patent on CO2 Capture Using Carbonic Anhydrase

Posted by on Monday, 1 March, 2010

Morphic has been granted a patent on a method and system for absorbing atmospheric carbon dioxide using wind turbines, and then combining the CO2 with water and excess electricity to produce liquid biofuels. The technology for CO2 absorption has been verified in a laboratory environment, and the company is now looking for partnerships with a view to evaluating a potential commercialization of the concept.

Since 2004 Morphic has been conducting intensive research and development into energy conversion, covering processes as well as technical systems, with the aim of finding ways to convert and store renewable energy in various forms, and to adapt it for later use in fuel cells for a range of different applications.

The basic idea behind the patent is to absorb carbon dioxide using an enzyme, carbonic anhydrase, which is used to coat the blades of the wind turbine. The function is the same biochemical process that removes carbon dioxide from the blood in a human. An application for a patent on an “energy converter” for producing methanol from electricity, carbon dioxide and water was submitted as far back as 2004. The invention that has now been patented is a more advanced version of the same energy converter, where Morphic believes it has solved the problem of how to extract the CO2 from the air.

For further information, contact:

For more information, please contact:
Johannes Falk, Vice President, Corporate Strategy & IR
Morphic Technologies AB (publ)
Phone: +46 (0)706-76 73 93
E-mail: johannes.falk@morphic.com
www.morphic.com


BAET Tech Captures CO2 from Vehicles and Enriches Soil

Posted by on Monday, 1 March, 2010

As progress is made to reduce emissions from cars and trucks, the focus of scientists and regulators is turning to off-road vehicles. Now there may be a new method to capture and sequester greenhouse gas emissions from agricultural equipment – by injecting it straight into the soil.

A report from the Australian newspaper The Age on a novel home-grown carbon capture technology with unexpected benefits.
A emission-capturing, crop-boosting technology is developed and promoted by the Canadian firm N/C Quest Inc. under the label “Bio-Agtive Emissions Technology.” In short, the process works like this: exhaust from agricultural off-road equipment is captured and cooled to ambient temperature, then injected into the soil through on-board pneumatic tubes. The exhaust emissions are reported benefit the soil by increasing the uptake of phosphorus, potassium, and sulfur, while providing fixed nitrogen to the crops.

The BAET method diverges from traditional carbon sequestration techniques, in which CO2 is stored in an underground cavity such as an oil well, or bubbled through and absorbed into the ocean. In contrast, the only way that agriculture stores carbon dioxide is through the growth of biomass.

Source