Title: Modeling equations of state with special emphasis on CO2 capture and storage.

Abstract:
The purpose of this paper is to develop a base model(hereby referred to as RPnet) for
equations of state using artificial neural networks with special emphasis on CO2 capture and
storage. The base model is akin to a VGG-16 utilized in CNNs albeit a lot less computationally
expensive. This was done keeping in mind the rising industrial need to predict CO2 states for
sequestration and the difficulties faced in doing so at the moment due to lack of data and highly
expensive test experiments that needs to be conducted for the same.
Different equations of state was compared in terms of accuracy to predict the volume of CO2
especially in conditions encountered during CO2 sequestration. Then the RPnet was checked
for similar conditions. It was found that for basic conditions the error percentage of RPnet was
<1% but as the conditions fed became critical, the error percentage hovered around 10%
seemingly due to lack of data to train on.
An attempt has been made to explain the accuracy levels of RPnet in terms of mathematical
analysis incorporating basic thermodyamic principles and inclinations have been established as
to how much more of data would be required to increase the accuracy levels to make it
conducive for industrial use.

Introduction:

Emissions of greenhouse gasses (GHG) will increase the average global temperature by 1.1 to
6.4 degree Celsius by the end of the 21st century according to the Intergovernmental Panel on
Climate Change (IPCC). A global warming of more than 2 degree Celsius increase in global
average temperature will lead to serious consequences, and IPCC have therefore stated that
global GHG emissions should be reduced by 50 to 80 percent by 2050.

One of the major strategies is to focus on CO2 carbon and storage from major industries so as
to reduce the amount of CO2 released in the atmosphere. Very recently, a company named
Climatix came out with a industry-use level model of CO2 sequestration. However, one problem
was constantly outlined and it referred to the lack of a rapid and accurate method to predict CO2
properties in subcritical conditions encountered in CO2 sequestration.
This can be largely attributed to the expense it takes to conduct experiments for checking on
CO2 properties in subcritical pressure regimes and the potential environmental catastrophes,
such as the 1986 incident in the Lake Nyos.

At the moment, most of the EOS fail to predict CO2 properties from PVT data at pressures as
low as 80 bars and even the Spycher EOS, which is thought to be pretty accurate, starts to
deviate from actual properties at pressures beyond 600 bars.
Most of the new EOS are being made by computer template fitting of observed data and
theoretical explanations of observed properties of CO2 are still evolving.

This paper, hence, tries to achieve what VGG16 did for CNN, i.e making a base model(RPnet)
for existing data and making certain fine-tuning features' provisions to accommodate for new
data being continuously generated. Thermodynamic explanation for the base model is
attempted so as to make it conducive for industry use.
(somewhere insert picture of VGG16)
Theory:

Let us start by examining the current problems faced in predicting CO2 data for sequestration:-
(you chuts come up with bulleted stuffs)
• Lack of a robust theoretical model capable of calculating density of carbon dioxide ,especially
that of liquid or supercritical carbon dioxide , at all potential process conditions.
• A possible reason for the lack of such a model is said to be due to huge dependence of liquid
and supercritical phase co2 on mixture composition and process conditions.
• Using theoretical methods ,on the short range of conditions where applicable , can be too
cumbersome to implement in actual industrial practice.
•

(Then Explain ann in general)

(take pictures sent by Akhauri. Also ask him to send his graphic stuffs on vgg/matmul in short.
Remember to expedite Wolfram stuff as a favor.)

Now, lets first make a small overview of the RPnet being developed.
It consists of three layers with the final layer being the finetuning layer.
It has been trained keeping the greedy layer-by-layer principle in mind.

Hence, the first layer is supposed to deal with co2 properties in normal conditions.
(snapshot of base layer)

The second layer is supposed to deal with co2 properties in a wider range keeping in mind that
during the CO2 transportation in pipelines, certain degree of extremes and error have to be
taken in account.
(snapshot of wider layer)

The third layer is the fine-tuning layer. It has been trained on co2 data in the subcritical
pressure regime, with data gathered from (mention links)
(snapshot of larger model)

So now we try to mathematically analyse how the RPnet is able to account for the non ideality of
CO2 at subcritical pressures.
(write in peace after discussion with everyone.)

Analysis and Comparison clubbed together~(Think of a single word and inform Banasri first):
(Sit with those along with Himanshu and Kanav and write stuffs.)

PR EOS
In 1976 the Chemical Engineers Donald B. Robinson and Ding-Yu Peng presented a new cubic
equation of state ,a result of a trial to improve the predictive capability of the 1972 Soave
modified Redlich-Kwong (SRK).The PR eos was able to increase the reliability of cubic eos in
the critical region and along the saturated liquid line.The work towards modifying the srk eos
was started due to its inaccuracy in calculating liquid densities and for predicting critical
properties.

Advantages over other eos

1. It is more accurate for predicting properties near critical state for mixtures.Following are
some of the experimental values of Zc .Though they are not equal they are pretty close and
thus can be said to be following the law of corresponding states.

CO2 = 0.2744

CH4 = 0.2862

C2H6 = 0.2793

nC5 = 0.2693

nC6 = 0.2659

Now these are the Z c values predicted by various eos vdW EOS = 0.375

RK EOS = 0.333

SRK EOS = 0.333

PR EOS = 0.301

As we can see no eos is able to predict the Z c value close to as low as .27 .PR eos comes
the closest to predicting the Z c value and thus this illustrates that the PR eos performs better
near critical conditions.

2. Gives more accurate prediction of properties along saturated liquid line.this can be attributed
to introduction of the b(v−b) term in the denominator, which improves the representation of
the attractive pressure forces, and in consequence, the ability of the equation to predict
better liquid densities

3. PR does a better job (slightly) for gas and condensate systems than SRK and hence is the
preferred equation of state in the petroleum industry


Disadvantages

1. It hows significant deviation under certain conditions such as relative deviation in calculation
of density of hydrocarbon liquids

2. For polar systems SRK EOS makes better prediction of properties.

3. It is slightly worse than RK for the prediction of the high-temperature second virial
coefficient.

4. For these and other reasons, many modifications to PR equation of state appeared. Some
of them improved the prediction of Psat for heavy hydrocarbons, other improved the vapor-
liquid equilibria for H2O , polar and non-polar compounds , and asymmetric hydrocarbons
containing systems, or the liquid volume , and so on.

Reasons for failure in CCS:

Now as we have seen the basic advantages and disadvantages of Pr EOS we can conclude it is
a little better than the other EOS for predicting properties at critical conditions.But one fact to
keep in mind is that it was derived to compute separation for the natural gas industry where co2
is a minor additive.Thus it's parameters are optimized for critical properties in mixtures.This is
where the PR EOS fails for carbon sequestration as in CCS we are considering properties of
pure co2.Also the supercritical properties of co2 are important for studying transport of co2 but
pr fails beyond critical conditions. A number of modifications are currently being proposed to
extend the PR EOS to supercritical conditions.

Conclusion:
We see that RPnet at the moment is well developed for basic co2 data and accuracy is
increased for subcritical pressure regimes. The RPnet can be further expanded for accounting
ccs pipeline wherein properties of CO2 deviate due to presence of impurities.
(Write more after analysis is done.)