G. Allan Oram

​

ABSTRACT

​

The questions of how to cost-effectively remove inefficient compounds from, and whether or

not it is feasible to charge a battery, or fuel cell with decomposition gasses is not new. Opening

the closed system will inhibit normal entropy faced in current battery technology [[i]]. It is

feasible to build and experiment with a novel open-system battery, or fuel cell that will recharge

itself through the input of decomposition gases [ii]. As an added effect this novel approach

could lead to a cost-effective refining means for removal of H2S and CO2 from mid and smallscale

decomposition gas resources, and result in an energy rich resource that will require no

combustion of fuels [[ii]].

​

HYPOTHESIS

​

The energy resources being discussed are diagrammed in the molecular model (photo) above.

The target molecule CH4, is mixed together with a number of other different compounds that

are present in natural, or released during the decomposition process in decomposition, gas.

These resources are most notably witnessed by the heated smoke column in a forest fire, but

they are also found at municipal wastewater facilities, landfills, Dairy Farms, etc. Every molecule

in natural, or decomposition gas other than CH4 limit the efficient use of natural gas. To

become a viable energy producer for human societies, the CH4 moieties must be eluted away

from all the other gases in a refining process.

​

Refining refers to the time-dependent removal of unwanted elements in a mixture. Current

research is focused on separating the valued hydrocarbons from the unwanted thiol and ketone

contaminants in energy rich gases. The intended purpose is to increase the energy content for

cost-effective conversion processes, and eventual end-use by human populations. Refining

assumes major importance in the petroleum and natural gas industries. Due to the high

importance of both water and petroleum in human activities [[iii]] refining technologies have

received a major amount of attention in recent years.

​

The technology exists to operate at cost-effective refining efficiencies on large scale application,

but current technology is incapable of replicating cost-efficiencies for overall refining processes

on mid and small-scale application. (I.E. mid-small scales are considered a refining capacity that

is not capable of processing 100-million cubic yards of unrefined natural gas per day.) In this

section focus will be placed on the mechanisms that cause mid and small-scale refining

application failures. The intended outcome is to test feasibility of novel decomposition gas

refining technologies that will not require combustion, at mid to small scales.

​

HISTORY

​

Natural gas is formed during the decomposition of organic matter [[iv]]. Over millennia the

earth sequestered this gas in underground reservoirs. The highly valued substance in natural

gas is CH4, but it contains other substances, such as: N2, He, Hg, H2S, CO2, among others [ii].

Because natural gas is a result of decomposing organic matter, contemporary technology can

capture and sequester these gasses at the point of the decomposing organic matter. Thus, these

unwanted gasses are trapped before decomposition vents more greenhouse gas to the already

taxed atmosphere. For economic purposes, the methane and other energy content therein must

then be separated from the impurities, and converted into pertinent energy sources designed

specifically for human use, and revenue generation.

​

Like ethanol in gasoline, impurities in natural, or decomposition gasses generally corrode and

deteriorate pipeline, and other metal storage components, destroy combustion engine

components, and inhibit the energy content in end use systems. These impurities must be

removed or “scrubbed” before the gas can become an economic source of energy [[v],[vi]].

Once CH4 is eluted away from the impurities, the impurities, some toxic, and most a form of

environmental pollution must as well be utilized. Absorption technology through a solution of

alkanolamines or Benfield are the most common contemporary processes used world-wide to

“scrub” natural gas of CO2 and H2S content [iv]. Once these compounds are sequestered, the

CO2 is typically vented, and the toxic H2S undergoes a sulfur reclamation process invented by

Carl Friedrich Claus [[vii]]. However, the Claus process is considered too expensive, and too

complex for mid and small scale natural, or decomposition gas refining processes [[viii]].

Therefore, utilization of most decomposition gas resources as a means for energy to power

conversion is inefficient with current technology [[ix]]. If competitive technology for

purification of methane content in decomposition gasses were available for mid, or small-scale

application, the world's forests, human dumps, wastewater facilities, and a great number of

dairy farmers, for instance, could offset greenhouse gas emissions, and operational costs by

providing electrical power, or other energy forms to the grid [vii].

​

Technically anything that decomposes overtime would then become a valuable source of energy

for human uses. Though trees would need to undergo a pyrolysis process, the show-stopper is

not at that point. The current showstopper, is the Clause Process, and its inability to "cost

effectively" remove hydrogen sulfide, H2S, gasses from a cloud of gasses smaller than a million

cubic yard. If the "Fire for Resource Benefit" process were implemented on large scale a great

many natural energy resources would then become viable, and cost competitive with the current

natural gas industry. These sources are clearly the trees burning every year in a wild fire, but

they also include city wastwater facilities, landfills, and the most notable resource for energy at

this time, Dairy Farms.

​

It is estimated that 125,000 dairy cows produce 80 million pounds of methane annually. This is

equivalent to roughly 315 thousand tons of carbon dioxide emissions [[x]]. These emissions are

becoming a concern, as it is estimated that animal agriculture emits 18 % of total anthropogenic

emissions world-wide [[xi]]. It is also estimated that utilization of anaerobic digesters could

sequester all 80 million pounds of bovine produced methane, both reducing anthropogenic

emissions, while providing energy to the growing energy network [x]. However, there are issues

involved, most political, with mid and small-scale decomposition gas refining processes that

make it cost-inefficient.

​

Identifying social, technical, and other variants in decomposition gas digestion, and innovation

to determine the path of future development in the field of science [[xii]], there are many

different forms of refining in contemporary society:

1) Polyethylene Glycol Scrubbing,

2) Chemical Absorption,

3) Pressure Swing Adsorption,

4) Bio-filtering,

5) Cryogenic Separation, and

6) Membrane separation.

​

Each refining process faces its own set of variables and obstacles. Generally, energy conversion

using Dairy Refuse feedstock increases environmental acidification and eutrophication [[xiii]].

Notably, the acidification has posed a most difficult conundrum. Eutrophication is essentially

diverted through large lagoons. In these lagoons, the high nitrogen effluents into rivers and

streams are typically averted. This aversion is apprized at a cost of venting greenhouse gasses;

emissions containing energy components that are currently wasted.

​

Development of new refining technology to capture the gasses that are currently wasted, could

improve the energy content in decomposition gas, and produce a byproduct that may become

an efficient substitute for natural gas [[xiv]]. These prospected technologies would also

contribute to a considerable anthropogenic decrease in greenhouse emissions, and

eutrophication to rivers and streams world-wide.

​

PRIOR "DAIRY" RESEARCH

​

Washington State University has conducted chemical absorption testing. The absorbents used

for the analyses were mono, and diethanolamine. Conclusions found that a 10 %

monoethanolamine solution removed 100% of the carbon dioxide in just 1 minute. However,

after the amine solution reached saturation, no further CO2 removal occurred until the

solution was regenerated. This regeneration process is lengthy, complex, and costly, and is the

part of the Claus Process that typically makes the current system cost-ineffective. The reaction

is exothermic. Hypothetical conclusions provide that large-scale removal of H2S processes are

available, but no H2S removal processes were analyzed in the study [viii].

​

Western Washington University analyzed the cost feasibility of “scrubbing” with solutions of

sodium hydroxide, and diethanolamine. Conclusions show that sodium hydroxide is not a

viable method of refining decomposition gas. A continuous need for input of sodium

hydroxide showed its initial inefficiency. Along with the continual input, the hydrogen sulfide

transport and storage facilities deteriorated rapidly and required routine replacement [viii].

Using diethanolamine [[xv]] as the absorbent a Western Washington University study

successfully eluted CH4 away from the impurities in Dairy Farm created decomposition,

greenhouse gasses, and converted it to a near pure form of biogas [viii]. However, the system

provided several operational challenges that are currently being addressed, pilot-scale, at

VanDeRHaak Dairy in Lynden, WA. These inefficient results are shown through the continual

existence of decreased pressures as the gasses elute through the system. Pressure drops that are

a result of leaks, caused by structural failures of metallic components, joints, and valve

apparatus [viii]. Though not emphatically stated in the study, the cause of the structural

degradation can be ascertained as a result of higher than norma fugacity of CO2 and H2S in the

system.

​

All of the existing biogas to energy conversion methods are intended to provide fuel for

combustion processes. Even with the multimillion dollar initiative, the current technology is

not cost effective for mid and small scale application [viii].

​

PROCESSES

​

At this point in human evolution it is theoretically inept to burn anything, if there is a process

available in which decomposition gas energy conversion to electrical power does not involve

combustion. "Fire for Resource Benefit" then becomes twofold: “sweetening” the biogas

(removing contaminants) and, “sweeting” and conversion of the available energies in a single

step through voltaic pile, or fuel cell technology [ii].

​

The most sought after component of any gas, for energy conversion purposes, is elemental

hydrogen. The laminar flame speed of pure hydrogen is 1.47 m/s faster than diesel fuel, and

1.43 m/s faster than gasoline fuel [[xvi],[xvii]]. It is 0.0145 m/s faster than methane [[xviii]].

The increased vapor pressures make hydrogen the energy sources sought. All hydrocarbons are

laden with energy potentials due to their hydrogen content. One other compound in the

mixture of decomposition gasses contains hydrogen. The thiol compound of H2S. However,

when combusting H2S, it requires the mixture of oxygen. Once the exothermic reaction occurs,

it produces sulfur dioxide, mixed with steam and given the proper catalyst (heat of formation) it

forms sulfuric acid.

​

H2S(g) + O2(g) --> SO2(g) + H2O(g)

​

2 SO2(g) + O2(g) + catalyst --> 2 SO3(g)

​

SO3(g) + H2O(l) --> H2SO4(l)

​

This acid corrodes metallic components, and provides a myriad of inefficiencies in systems

transport, and storage facilities of current technologies. Hulls Dairy, in Corvallis, Montana, has

the anaerobic capacity to digest bovine excrement, in much the same manner as

VanDeRHaack’s Dairy in Lynden, WA. The problem, as is the problem in all of the other 260

dairies nationwide that also have digester capacities [[xix]], H2S and CO2 moieties in resulting

decomposition gasses corrode and destroy combustion engines, and storage, and transport

components at an exponential rate [[xx]]. The result is constant replacement of damaged

components. Replacement expenses prove the systems to be cost-ineffective [[xxi]].

As explained earlier, refining technology in the petroleum industry is designed for large scale

application. This technology, mainly the desulfurization, or sulfur reclamation "Claus"

processes is not efficient for the mid and small scale applications that are required in these

dairy’s [viii]. Thus, the installment of retrofitted technology is needed to provide efficient

decomposition gas to energy conversion.

​

HAZARDS

​

H2S is a toxic gas, found in the Sulfide, and Inorganic reactive groups [[xxii], xx]. When put

into contact with O2 and powered Cu, or O2 and BrF5, OF2, ClF2, AgCNO, it explodes [[xxiii],

xx]. When put into contact with HgO, CaO, Tl2O3, Na2O2, AgO, AgO2, MnO2, NiO, CuO,

PbO2, BaO2, CrO3, HNO3, PbO2, Pb(ClO)2, AgBrO3, Cu2Cr2O5 and rust, it ignites [[xxiv],

xx]. It may ignite in rusty pipes [[xxv], xx]. The exothermic reaction produced when combined

with Ba(OH)2, KOH, NaOH, soda lime, and oxygen may cause ignition or explosion [xx].

Therefore, extreme caution and safety protocols must be adhered at all times when working

with, or around the substance.

​

METHODS

​

H2S has an energy component, two atoms of hydrogen. It is inefficient to waste this

component. There are myriad technologies that utilize thiol compounds. The most notable

energy conversion processes are chemical reactions in a voltaic cell. It is also noted that electric

current was the defining affect to help scientists originally isolate a number of elements [iii].

Essentially, some of the energy extracted from a lead acid battery is Gibbs energy. These “free

energies” are a result of the strong acid’s disassociation with a proton [[xxvi]].

​

H2SO4(l) --> H+(l) + HSO4-(l)

​

This reaction occurs before the acid is inserted into the voltaic cell. Because the cell is divided in

half, the anode half and the cathode half. In a lead-acid battery, when in discharge while the

anode oxidizes, reduction occurs at the cathode [[xxvii]].

​

(-)Pb(s) + HSO4-(aq) --> PbS04(s) + H+(aq) + 2e-

​

(+)PbO2(s) + 3H+ + HSO4-(aq) + 2e-(s) --> PbSO4(precipitate) + 2 H2O

​

When recharging both the anode and cathode switch polarities, while the arrows in the

identifying equation reverse directions. In essence an “ion-pump” drives the chemical reactions

at the “electrode-electrolyte interfaces” while using the electrolyte (HSO4) for internal resistance

[[xxviii]]. There are a number of possible solutions to avert the toxic effects, and volatile nature

of H2S. Because it may explode and ignite when put into contact with lead, or lead oxide, it

appears to be the show stopper to filtering for energy conversion through a lead acid battery.

Nevertheless, the technology exists [ii]. The technology also exists to strip sulfuric acid of

Hydrogen. This is the mechanism that provides electricity from a storage battery. Further

research and study for possible implication and eventual decomposition gas to energy

conversion without the use of combustion as a means for energy conversion through a voltaic

pile, or fuel cell is warranted.

​

Novel Ni anode (8 % NiO doped with Y and stabilized by ZrO2) inhibits coking (deterioration)

effect of independent catalyst layers within metal oxide fuel cells that operate on methane based

fuels. Providing a stabilized environment for voltage throughput, novel fuel cell voltage

degradation went from 0.6 V in 20 minutes, in non-doped fuel cell, to 0.03 V in 12 hours in

doped cell [[xxix]]. The interpretation of structural solid oxide fuel cell degradation due to realtime

conditions are structurally sound, and available for the lead acid version.

​

Another method involves upstream catalytic fractionation of biogas that provides high

hydrogen content syngas, and biomaterials form carbon nano-fibers in the electrolyte which can

be processesed into synthetic graphite [[xxx]]. In both methods, high methane fugacity shortens

redux time [[xxxi]], while producing high amounts of carbon deposits in dry reforming

cathode/anode recovery of hydrogen. It is also relevant to the proposed project that the biogases

used in the former and latter study, injected in the pile or fuel cell, were already “sweetened”.

Refining of H2S compounds in decomposition gas can theoretically be completed inside a

voltaic pile of sorts in a single step [ii]. If this proves inefficient, a Mobius

strip has brought this proposal back to the initial problem. Upstream catalytic fractionation of

H2S must occur in a cost-friendly manner, before mid or small-scale refining operations will

become cost-efficient.

​

Acidithiobacillia, or Thiobacillus oxidize sulfur [[xxxii]]. These bacteria convert hydrogen

sulfide into sulfuric acid [[xxxiii]]. This sulfuric acid can then be utilized as electrolyte for

battery technologies. The materials already exist to house sulfuric acid in lead acid batteries,

therefore, it could prove to be a viable means to remove H2S from decomposition gasses [ii],

and the proposed open system will improve battery technologies [i]. While H2S is toxic to

metalloproteinase, other substances are found to bind with H2S, for instance, the iron sites in

hemeproteins specifically found in sea clams [[xxxiv]], or in extracellular hemoglobin at the Cys

+ 1, and Cys + 11 of deep sea annelids [[xxxv]]. Battery and refining technologies could discover

a considerable technological advancement through the proposed novel refining processes.

This is an energy to power conversion that does not involve the combustion of fuels. If the

battery proves inefficient, once the CH4 is sufficiently “sweetened” it can be processed through a

combustion to energy process' nevertheless "Fire for Resource Benefit" is founded upon the basic

principle that in this day and age it is inept to burn anything.

​

The main purpose of "Fire for Resource Benefit" is to investigate feasible processes needed for

separation of decomposition gas components, to maximize efficiencies in energy output for

non-combustion conversion of energy content. To do this, it may not necessarily entail the

construction of a model biorefinery, as the electrochemical reaction inside the fuel cell, or

voltaic pile may provide the answer.

​

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