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COAL AND GAS POWER

WITHOUT EMISSIONS
PETROL FROM HYDROGEN WITH SUN TO GAS

RECYCLING CO2 SUNSHYDROGEN.COM


Table of contents

Investment calculations for a 1500 megawatt coal power plant………………… P1

Coal power plant CO2 recycling………………………………………………………………………… P2

Clean hydrogen numbers…………………………………………………………………………………… P3

Funds for coal plants…………………………………………………………………………………………… P4

Infrastructure system………………………………………………………………………………………… P5

Hydrogen markets……………………………………………………………………………………………… P6

Geographic’s…………………………………………………………………………….………….………….… P7

Locations to utilize clean hydrogen………………………………………………….………….… P8

The LOHC conversation rate for night time storage or transport………………… P9

Oxy-fuel combustion: using oxygen in generators…………………………………….… P10

The Fischer-Tropsch calculations for petrol production……………………………… P14

Project Sunshydrogen……………………………………………………………………………………… P33

Contact……………………………………………………………………………………………………………… P34
INVESTMENT CALCULATIONS
FOR A 1500 MEGAWATT COAL POWER PLANT

Investment returns
1
A 1500 MW power plant emits 6 Mton of CO2 a year which absorbs with 1,090,909,000 kilograms of clean
1 3 4
hydrogen that results in 5,236,363,000 litres of petrol worth about 5,200,000,000 € .
The energy and coal costs for the Boudouard and Fischer-Tropsch process are estimated to be around
5 6
1,800,000,000 € a year. Night time storage with LOHC is estimated to add another 250,000,000€.
Resulting in an estimated gross profit of 3,150,000,000 € a year.

Estimated investment
7 8
PV power investment is around 26GW costing around 3.5 billion .
9
Electrolyser investment is estimated around 500 million
Boudouard and Fischer-Tropsch processes investment is estimated around
10
500 million.
11
Hydrogen night time storage is estimated to be around 100 million.
Totalling the investment to 3.7 billion.

Return of investment
The gross return of investment is estimated around 85% a year.

Oxy-fuel combustion

With electrolysis comes hydrogen and oxygen. The oxygen can be used for the combustion in the power
12
plant. This in theory can increase the output of a coal power plant by 13% (see oxygen calculations)
13
to 20% . This is due to the foregoing of heating the nitrogen gas in air, thereby increasing the flame
temperature from 1900C to 2500C.

1
https://en.wikipedia.org/wiki/Fossil_fuel_power_station#Carbon_dioxide
2 6,000,000 kilograms of CO2 / 5.5 kilogram of CO2 mixed with 1 kilogram. of hydrogen= 1,090,909 k.g. of hydrogen a year.
3 One kilogram of hydrogen mixes with 5.5 kilograms of carbon dioxide plus half a kilogram of coal, this results in 4.85 litres of isooctane.
4 https://www.racfoundation.org/data/wholesale-fuel-prices-v-pump-prices-data
5 1.66 per k.g. of hydrogen >< 1,090,909 k.g. of hydrogen= 1,810,908.94
6 Hydrogenation and dehydrogenation of LOHC consumes 20 KW-h, for night time consumption is estimated at 0.03 cents a kw-h and daytime
consumption 0.02 Kw-h. 50 Cents >< (1,090,909 k.g. of hydrogen / half a day) = 250,000
7 1 KW-P produces 42 k.g. of hydrogen a year à 1090909/42= 25,974 KW-P or about 26 MW.
8 25,974KW-p><300 E per KW-p= 7,792,207.
https://www.pv-magazine.com/features/investors/module-price-index/
Economies of scale estimated at 50% for 26 gigawatt solar field.
9 Costs to be obtained
10 Costs to be obtained
11 Costs to be obtained
12 Several pilots have been done in oxy-fuel combustion generation.http://callideoxyfuel.com/wp-content/uploads/2018/03/COP-Public-Report-March-2018.pdf
Normally the nitrogen is cleaned from the air by an ASU air separation unit, twhich consumes about 15% of plants energy.
13 P34 Oxy-fuel Combustion: Fundamentals, Theory and Practice 1
COAL PLANT CO2 RECYCLING

The Boudouard and Fischer-Tropsch processes convert carbon


dioxide and hydrogen into petrol

OXOSYNTHESIS THE FISCHER–TROPSCH PROCESS

nCO+(2n+1)H2 > Cn H2n+2+ nH2O

Emissions
ELECTRICAL GRID free coal
power

PETROL PETROL COAL ELECTROLYSIS SOLAR


TRANSPORT STORAGE POWER PLANT FIELDS
TRUCKS TANKER
Petrol station Storage tank Boudouard reaction H2 and O Direct current
Fischer-Tropsch

1. Solar power 2. Electrolysis 3. Coal power plant

4. Petrol 5. Petrol station

2
CLEAN HYDROGEN NUMBERS

1 kilogram of hydrogen costs 42 KW-h 14 of solar power and mixes with 5.5
kilograms of carbon dioxide worth around 10 cents in carbon credits,
this reaction produces 4.85 litres of isooctane
(Trimethylpentane) petrol with an wholesale worth of about 5 €. 15

In Australia 1 KW-p of solar produces 1800 KW-h per year which is around 42
kilograms of hydrogen, which results in 210 € of value generated.
1KW-P of solar costs around 300 €. 16

14 https://www.quora.com/How-much-electricity-is-needed-to-produce-hydrogen-from-water
15 https://www.racfoundation.org/data/wholesale-fuel-prices-v-pump-prices-data
16 https://www.pv-magazine.com/features/investors/module-price-index/

3
FUNDS FOR COAL PLANTS

COAL POWER PLANT INVESTMENT INTEREST

• Coal power plant operations extended

• Revenues from petrol resale

• Total revenue about 5 € per kilogram of hydrogen

• Market price of grey hydrogen is 1 € per kilogram

• The oxygen of the electrolysis process increases output of the coal


power plant by 13% to 20%.

CARBON DIOXIDE CREDITS CALCULATIONS

The EU has an 20 euros an ton, carbon emissions trading system. 1 kilogram of


hydrogen takes out of the air 5.5 kilos of carbon dioxide, this is valued at an 10
cents and increases the hydrogen value therewith.

PETROL RESALE CALCULATIONS

3.35 kg of isooctane (Trimethylpentane) comes from 1 kg of Hydrogen when it is


mixed with 5.5 kg of CO2. 3.35 kg of isooctane is 4.45 litres of isooctane.

4
INFRASTRUCTURE SYSTEM

5
HYDROGEN MARKETS
Industrial ‘grey hydrogen’ is produced from methane (CH4), using steam reforming

In the process large amounts of carbon dioxide are emitted into the air.

0.025 MWhe 1 MWhe natural gas

HYDROGEN IS USED IN THE


@ £ 95 / MWhe HHV @ £15 / MWh

05 MWhe
@ £95 /
• steal making MWhe

industry Steam methane


reformer

Capture £33-£ 23 / MWh,


CO2 to CCS Transport £10-£ 5 / MWh,
CARBON CAPTURE REWARDS 53 £ / MWh

• petrochemical

industry 1.21 MHh Efficiency =1.21 / 1+0.025+0.5 = 79% 1.21


Hydrogen HHV MWh Hydrogen
gas to grid

Steam-methane reforming reaction Cost


CH4 + H20 (+ heat) › CO2 + 3H2 1 MWh methane = £15
0.025 MWh electricity = £2.4
Water-gas shift reaction
CO + H2O › CO2 + H2 (+ small amount of heat)
0.5 MWh electricity / hilt = £47.5

• ammonia Combined
METHANE RESALE PRICE

Total cost for 1 MWh of H2 = £100


CH4 + 2H20 › CO2 + 4H2
industry METHANE RESALE PRICE
Very large industrial = £15 / MWh
Domestic = £45 / MWh

CH4 + 2H20 CO2 + 4H2

• transport
industry in Japan

• electrical grid back up services

• carbon dioxide recycling

6
GEOGRAPHIC'S

PV plants produce most hydrogen in desert regions future implementation is proposed


to be expanded to the in the following countries:

Chile
Australia

• Egypt

• Tunisia

• Jordan

• Palestine

• Syria

• India

• Namibia

• Mexico

WHY THE LOCAL GOVERMENT SHOULD ENGAGE IN THE PROJECT

• Increase in high technology economy, from local work and expertise

• Induced employment and businesses, the funds will go to

productivity and employment


• Business tourism

• Reduced inequality

• A better image in the world in know how and technology

• New know how industries

• Develop an knowledge economy

7
LOCATIONS TO UTILISE CLEAN HYDROGEN

• Chile

• Australia

• Namibia

https://globalsolaratlas.info
8
THE LOHC CONVERSATION RATE FOR TRANSPORT

The energy it costs to convert 1 k.g. of hydrogen to LOHC and the energy it costs to convert
LOHC to 1 k.g. of hydrogen

LOHC’s are liquids or low-melting solids which can be used as a flexible media for storage
and transportation of H2. It means that we can use LOHC as a “solvent” for H2 gas. Thereby
in this case no chemical reactions take place. H2 gas dissolves into LOHC due to physical
absorption, and of course it is necessary to decrease temperature and apply high pressure
to store hydrogen efficiently by physical absorption.

One should also use heterogeneous metal catalysts which assist hydrogenation and
dehydrogenation in the LOHC systems.
Different organic compound as a LOHC can be suitable. For basic calculation we can select
benzene (C6H6). Typically, hydrogen storage capacities in cyclic hydrocarbons like benzene
are in a range 6-8 weight %. Heat of hydrogenation and dehydrogenation is in the range of
62–71 kJ mol-1 (H2)

Calculation:
For the calculation we can choose 6 weight % and 70 kJ/mol for heat of hydrogenation
and dehydrogenation.
1. In order to fully dissolve 1 kg of H2 in benzene we need:
m(solution) = 1 kg (H2) / 0.06 = 16.66 kg (it is mass of the solution: H2+benzene),
m (benzene) = m(solution) – m (H2) = 16.66 kg – 1 kg = 15.66 kg

2. For dehydrogenation of 2 g or 1 mole of H2 absorbed in benzene we need to spend 70 kJ.


In our case we have 1 kg or 500 mole of H2, thereby for this quantity total energy for
dehydrogenation is equal to:
1 mole – 70 kJ
500 mole – x kJ
x = 35000 kJ
35000 kJ = 0.97 Kw-h

10 KW-h for 1 k.g. of hydrogen per hydrogenation and per dehydrogenation

Therefore, it costs 25 cents for the hydrogenation and 40 cents for dehydrogenation, about
0.75 euro total for the hydrogenation and for the dehydrogenation. Thereby adding 0.75
euro in variable cost to transport the clean hydrogen to the processing location.
t
9
OXY-FUEL COMBUSTION: USING OXYGEN IN GENERATORS

Reaction of solid coal burning:


C (s) + O2 (g) = CO2 (g),
Enthalpy of combustion, ΔН (at 25 C) = -394 kJ/mole
If we take 1 kg of coal (1000/12 = 83.3 mole), burning of such amount of coal will give:

12 g – 394 kJ
1000 g – x
x= 32833 kJ = 32.83 MJ/kg

This energy is a calorific value of pure coal (without impurities).


In practical case different types of coal can ensure different amount of heat, depending of
impurities content.
Firstly, we should calculate a theoretical flame temperature of coal burning in air:
Heat balance equation can be written as follows:

Q = Vcp(Tt-Tb),

Q – calorific value of coal, kJ/kg;


V - the volume of combustion products formed during combustion of 1 kg of coal, m3/kg;
cp – specific heat capacity of combustion products, kJ/(m3*C);
Tt – theoretical burning temperature, C
Ts - initial temperature, C
At burning in normal condition (Ts = 0 C), we have

Q = VcpTt;
and
Tt = Q/Vcp

Since the products of combustion of real coal, usually, consist of different gases, the heat
capacity and density of which are different we should write:

Q = V1c1Tt + V2c2Tt + ..TtΣVici;

Tt = Q/ TtΣVici;

For estimated calculations, we can take the average values of heat capacity:
Average heat capacity (cp) of gases in the temperature range (1000 - 3000)°С
10
OXY-FUEL COMBUSTION CONTINUED

Gas CO2 SO2 H2O H2 N2 CO O2

kJ/(m3*С) 2.13 2.13 2.09 1.42 1.42 1.42 1.42

For the calculation we can take some real composition of coal:

Element C H S N O water content ash content

%, mass 76 4.5 4.7 1.8 3.5 3.0 6.5

mass fraction 0.76 0.045 0.047 0.018 0.035 003 0.065

For solid fuels, in particular coal, Mendeleev’s formula can be used to calculate the
calorific value of real coal with such impurities:

Qcoal=0.339[C]+1.025[H]+0.1085[S] – 0.1085[O] – 0.025[W] = 29.92 MJ/kg


Now, using the formula Tt = Q/Vcp we are able to calculate flame temperature.

1) in case of air using without air excess (i.e. excess air ratio α = 1) we get Tt = 21600С
2) in case of air using air excess α = 1.2, typically in practice: we get Tt= 19000С
3) in case of air using air excess α = 1.5, just for example we get Tt = 16000С

As one can see, flame temperature is considerably depends on excess air using for coal
burning due to additional nitrogen gas heating.

In case of air excess α = 1.2 we need to heat 8 kg of N2


For nitrogen gas - N2 specific heat capacity - cp - is 1.05 (kJ/(kg*K))
For 8 kg of N2 heat capacity is 8.4 kJ/K.
In case of using air excess α = 1.2 flame temperature 19000C is achieved, hence:
In order to heat 8 kg of N2 from 20 C to 1900 C (1880 C) we need to spend:
8.4 kJ – 1 C
z kJ – 1880 C
z = 15800 kJ (N2)

11
OXY-FUEL COMBUSTION CONTINUED

In ideal case we could economize the energy z = 15800 kJ (N2), required for N2 (from
air) heating, but in real situation we face with another problem. The same calculation
approach (above) using only pure O2 for burning gives Tt = 47000C, but such very high
temperature has not been fixed in practical case. Usually, flame temperature of coal
burning in pure oxygen is established near 2500-27000С depending on experimental
setup. At high temperature, especially at temperature > 22000C dissociation of CO2
molecules is occurred. Therefore energy z = 15800kJ will be consumed partly by CO2
dissociation process:

CO2 = C + 2O, E(C-O) = 803 kJ/mole

At 25000C it was established ~30-40% of CO2 dissociation. Totally, ehe energy z = 15800 kJ
is consumed for some heat losses, for heating of CO2 up to 2500 C, for CO2 dissociation
and some part of surrounding heating.

For formatted CO2 – heat capacity is 0.85 (kJ/(kg*K)).


0.85 kJ – 1 kg
n kJ - 3.66 kg
n = 3.11 kJ

3.11 kJ – 1 C
p kJ – 600 C (from 1900 C to 2500 C)
p=1866 kJ (CO2)

e=z-p=15800-1866 = 14234 kJ

To estimate heat consumed for CO2 dissociation twe can use the following equation:

Qdis (CO2) = 12640*α*m(CO2) = 12640*0.3*3.66 = 13879 kJ – per 1 kg of coal burning in

pure O2.

The other residual energy could be spend for surrounding heating

12
OXY-FUEL COMBUSTION CONTINUED

Transient conclusions:
Above calculations have resulted in two different situations:
1. Coal burning in air (air excess α = 1.2)
Flame temperature – 1900 C
2. Coal burning in pure oxygen
Flame temperature ~2500 C

Thereby, calorific value of coal is the same in the two cases above, but a rate of water
heating (in power plant) in case of oxygen using will be higher. With temperature raising
the average gas movement increases according to the kinetic theory:

v = √(3RT)/Mr,
v – average gas molecules movement;
R – gas constant, 8.3 J/(K*mol)
T – temperature, K
Mr – molecular weight

v (2173 K) = 35
v (2773 K) = 39.6

gas velocity increment = 39.6/35 = 1.13


at T>700 C we also need to take into account a heat transfer due to thermal radiation
increasing of CO2, but it requires some more time to count and check some physical
details regarding this one and it could be done in future.

Conclusions

1. If we consider only heat transfer only due to heat conduction of CO2 we need to spend
in 1.13 less time, when CO2 is burning in pure O2 comparatively CO2 burning in air (air
excess α = 1.2).
2. In other words, when coal burns in air (air excess α = 1.2) and in pure O2 we can
generate in the second case in 1.13 times more energy for the same time.
3. Due to thermal radiation increasing with temperature rising we can expect even faster
generation of the same energy, then in 1.13 times.
13
FISCHER-TROPSCH PROCESS
FOR THE ISO-HYDROCARBONS (PETROL) PRODUCTION

Autoclave
co

CO2 + C ↔ 2CO
coal line 1

compressor coal

coal line 2

CO2, coal
O2,
N2 C + O2 ↔ CO2

pump

O2 / Air

unreacted

atm

Fresh

petrol

We can obtain linear hydrocarbons using the following approach:


A mixture CO and H2 («synthesis gas») can be mixed in various proportion and is suitable
for synthetic fuel fabrication.
A general chemical reaction which takes place can be written as:
nCO+(2n+1)H2 > CnH2n+2 + nH2O
The conditions for this reaction are 3000C and catalysts applying (usually Fe or Co as
the most common, the reason is to decrease the temperature of the reaction when the
catalysts are used) and pressures from one to several tens of atmospheres.
Usually, this reaction between CO and H2 produces a mix of different linear hydrocarbons
and for precise calculation

For the first draft we can assume only isooctane formation (as a main component of
petrol) with general formula C8H18:

8CO+17H2 > C8H18 + 8H2O

In our case:

1) m(H2) = 1 kg or > mole(H2) = 1000 g/ 2 g/mole = 500 mole (H2)

14
THE FISCHER-TROPSCH PROCESS CONTINUED

2) from the reaction above one can see that 8 volume parts of CO react with 17 volume
parts of H2, i.e. 500 mole of H2 will react with 235,3 mole of CO ( (500*8)/17 ).
3) m(CO) can be derived from mole of CO:
m(CO) = 235,3 mole * 28 g/mole = 6588,4 g = 6,588 kg
4) from the reaction we see, that 8 mole of CO and 17 mole of H2 produces 1 mole of
C8H18 or m(C8H18) = ((8*12)+(1*18)) = 114 g.
We have 500 mole of H2 and this quantity can produce 29.4 mole of C8H18 ((500*1)/17)
5) Converting 29.4 mole of C8H18 into mass we obtain:
1 mole C8H18 – 114 g C8H18
29.4 mole C8H18 – x g C8H18

x = 3351.6 g = 3.352 kg (C8H18)

Summarizing, 1 kg of H2 can be mixed with 6.59 kg of CO and it produces 3.35 kg


of isooctane this is 4.85 liters of isooctane.

Conventional petrol represents a mixture between isooctane C8H18 and linear heptane
C7H16 If we want to make petrol with octane number (ON) 95 it means, that 100 volume
parts of such petrol contain 95 volume part of isooctane and 5 volume part of heptane.
In other words, if you mix 95 liter of isooctane with 5 liter of heptane to get
100 liter petrol with ON=95.

Design and energetic calculation of the apparatus for the Fischer-Tropsch


process for the iso-hydrocarbons production

15
THE FISCHER-TROPSCH PROCESS CONTINUED

Outline
1. Feedstocks
a) Boudouard reaction CO2 - CO conversion
2. Syngas purification
3. Synthesis of hydrocarbons and process conditions
a) The iso-FT-synthesis
b) Catalysts
4. Reactor for the Fischer–Tropsch synthesis
a) Cooling system
b) Reactor
c) General scheme for the FT process, including CO2
into CO conversion
d) Conclusions

1. Feedstocks

In our case we have initial materials – H2 and CO2

1 kg of H2 we mix with 5.5 kg of CO2 to achieve a suitable ratio of syngas H2:CO=2:1.

For CO2-CO conversion :

m(H2) = 1 kg
m (CO2) = 5.5 kg

m(H2) = 1 kg
m(CO2) = 10.5 kg

v(H2) = 1000 g/2 g/mole = 500 mole


v(CO2) = 10500 g/44 g/mole = 238 mole

For the Fischer-Tropsch process:

The first heating requires:


z=0.20 kg of coal
For 0.2 kg of coal ~ 0.06$

16
THE FISCHER-TROPSCH PROCESS CONTINUED

Boudouard reaction Autoclave


co CO coal
storage

CO2 + C ↔ 2CO

compressor coal

CO2, coal
O2,
N2 C + O2 ↔ CO2

pump

Aa) CO2 - CO conversion O2 / Air

To carry out the Fischer-Tropsch synthesis (FTS) we need to have CO gas.


To get CO it is possible to use at least three different approaches:

1) get CO from CO2 applying the reduction by coal:


CO2 + C ↔ 2CO, (ΔH = 172 kJ/mole, ΔS = 176 J/K) (1), Boudouard reaction

2) CO2+H2 ↔ CO+H2O, ΔH = -41 kJ/mole (2)

3) thermal decomposition of CO2:


2CO2 ↔ 2CO + O2 (3)

For the calculation we consider reaction (1) which ensures full conversation CO2 into CO.
According to this reaction (1) from 238 mole of CO2 we can get maximum: 2*238=476
mole of CO. In practice we face with a dynamic equilibrium and to shift the reaction
towards CO a temperature increasing up to 1000oC to get almost ~100% conversation
into CO is required.

Fig.1. Dependence of CO mole fraction on temperature (reaction (1) )


17
THE FISCHER-TROPSCH PROCESS CONTINUED

So, it is available 500 mole of H2 and 476 mole of CO, ration H2:CO is 1.05. Ideal ration
H2:CO for alkanes is around 2. It is crucial to know initial the ratio of the gases, because it
will be define a type of the reactor and catalyst and some other technological processes
and can lead to considerable change of energy, accordingly.

At first, we could achieve the ration H2:CO, for example, by decreasing of CO amount from
476 mole to 250 mole. 250 mole of CO is equal to 7.0 kg.
In order to obtain this mass of CO using the reaction (1) we need
44 g of CO2 – (2*28) = 56 g of CO
x g of CO2 – 7000 g of CO
x = 5500 g of CO2.

Also for the reaction (1) we need coal:


For 250 mole of CO we need 125 mole of coal (C) or 1.5 kg
To estimate we can use 300$ per 1 tone for coal%
300$ – 1000 kg
x$ – 1.5 kg
x=0.45$

To perform heating till 1000oC it is possible to use a furnace which converts electrical
energy into thermal one. Furnace’s power depends on its dimension, for the calculation
we can use some real value for such type of a furnace with free volume 1m3 – ~10 Kw-h.
We need some time to achieve «working» temperature that is suitable for the reaction
(1), it also requires energy. So-called «starting currents» – +30-40% of extra current starts
flow in the moment, when an equiptment is just switched on – are also disregarded in
our case, they could be counted exactly in real practical case.
The rate of the reaction CO2 + C ↔ 2CO is defined by CO2 concentration (or partial
pressure): v = k[CO2] = kPCO2, k – rate constant of the reaction (1)
As k is a function of T, pressure, gas contact time with coal, gas flow velocity and reaction
vessel for the beginning we can assume that at 10000C CO2 can be fully converted into
CO for 1 hour.

18
THE FISCHER-TROPSCH PROCESS CONTINUED

So, we need to spend ~4 h (for example) to heat a furnace till 10000С and 1 hour to
complete the reaction (1).
Totally, we use 5*10kW-h = 50kW for the conversion of 5.5 kg of CO2 into 7.0 kg of CO

A) coal for CO2-CO conversion:

m (coal) = 1.5 kg
For 1.5 kg of coal ~ 0.47$

B) heating by an electric furnace:

50kW (10kW-h = 4 h heating from 20 C to 1000oC, and a dwell at 1000oC for 1 hour)

С) heating by coal burning:

the calculation for coal burning:


1. In our we need heat for CO2 - CO conversion
m (CO2) =5.5 kg
CO2 + C ↔ 2CO, {ΔH = 172 kJ/mole, ΔS = 176 J/K) (1), Boudouard reaction
m (CO) = 7.0 kg (max. = theoretically obtained)

To transform 5.5 kg of CO2 in 7 kg CO we need 1.5 kg of coal.

To perform heating till 10000C instead a furnace which converts electrical energy into
thermal one it is possible to use the heat of coal burning according to the reaction:

C (s) + O2 (g) = CO2 (g),

Theoretical enthalpy of combustion, ΔН (at 25 C) = -394 kJ/mole

For the calculation we need to know a specific heat capacity - cp of coal. It can be slightly
different depending on coal type. For the calculation we can use some average value for
specific heat capacity – 1.3 kJ/(kg*C).
We need to heat coal from 25C to 1000oC = Δ975 C (difference):

1.3 kJ – 1 C , x kJ – 985 C, x= 1281 kJ for 1 kg of coal

As we need to heat 1.5 kg of coal it requires 1281*1.5 = 1921 kJ


As well as we need to heat 5.5 kg of CO2 from 25 to 1000 C = Δ975 C (difference)
19
THE FISCHER-TROPSCH PROCESS CONTINUED

Specific heat capacity of CO2 is 0.85 kJ/(kg*C)).

0.85 kJ - 1 C
y kJ – 975 C
y = 829 kJ for 1 kg of CO2 heating
for 5.5 kg of CO2 the required energy is 829*5.5 = 4559 kJ

Totally, we need to spend 1921 kJ + 4559 kJ = 6480 kJ

6480 kJ – it is the total energy, required for heating 1.5 kg of coal and 5.5 kg of CO2 from
250C to 10000C, that is necessary for the reaction C (s) + O2 (g) = CO2 (g) performance.

According to the reaction:

C (s) + O2 (g) = CO2 (g), ΔН (at 25 C) = -394 kJ/mole - theoretical enthalpy of combustion,

ΔН (at 25 C) = -394 kJ/mole – it is theoretical value, in practice we always face with lower
energy, for calculation we should you some more real value, for example, for anthracite:
C (s, coal-anthracite) + O2 (g) (from air) = CO2 (g),
combustion heat of 1 kg of anthracite is around 30 MJ/kg
30 MJ – 1 kg of anthracite
6480 kJ = 6.480 MJ = z kg of anthracite
z = 0.22 kg

Conclusion

To heat 1.5 kg of coal and 5.5 kg of CO2 from 25 to 1000oC,


that is necessary for the reaction C (s) + O2 (g) = CO2 (g) performance we need to burn
0.22 kg of anthracite in air.
The losses of heat through the walls of an autoclave were neglected. In practice, certainly,
we will have to burn relatively more mass of anthracite to reach this purpose.
For the estimation:
300$ per 1 tone for coal, For 0.22 kg of coal ~ 0.07$
m (coal) = 0.22 kg, For 0.22 kg of coal ~ 0.07$
20
THE FISCHER-TROPSCH PROCESS CONTINUED

For this step we need to use one additional pump for air or oxygen transfer for coal
burning. A power of one around 2kW-h is sufficient.

+1pump = +2kW-h

D) heating by natural gas burning:

6480 kJ – it is the total energy, required for heating 1.5 kg of coal and 5.5 kg of CO2 from
250C to 1000oC, that is necessary for the reaction C (s) + O2 (g) = CO2 (g) performance.
Composition of natural gas is different, but for the calculations we can take some average
value for natural gas heat combustion – 33 MJ/m3.
33 MJ – 1 m3
6.480 MJ – x m3
x = 196 liter of natural gas.

To heat 1.5 kg of coal and 5.5 kg of CO2 from 25 to 1000oC, that is necessary for the
reaction C (s) + O2 (g) = CO2 (g) performance we need to burn 196 liter of natural gas.

196 liter of natural gas.

For this step we need to use two additional pumps for air or oxygen transfer and for
natural gas transfer into the combustion zone. A power of one around
2kW-h is sufficient.

+2pump = +4kW-h

Feedstocks: summary
To have suitable ratio of syngas H2:CO=2:1 for subsequent chemical hydrocarbons
synthesis we need to have:
m(H2) = 1 kg
m (CO2) =5.5 kg
including 100% conversion degree CO2 into CO according the reaction (1).
EUR ~ 0.5 for 1kg of coal
Energy/$ = 50 kW/15 EUR for the conversion of CO2 into CO.

For Germany (2018) for 1kW-h a price is 0.3 EUR:


https://1-stromvergleich.com/electricity-prices-europe/
21
THE FISCHER-TROPSCH PROCESS CONTINUED

2. Syngas purification

Reactant gases (CO and H2) entering into a Fischer–Tropsch reactor must be purified,
especially – desulfurized, in order to guarantee the performance. Otherwise,
sulfur-containing impurities deactivate the catalysts required for
the Fischer–Tropsch process.

The first step in the cleanup process is to remove carbon particles. For this goal we
should put a filter (which can operate at high-temperature) at the exit of the apparatus
for CO2-CO conversion. That filter will capture carbon particles flowing together with
CO after the reaction (1) in further parts of all apparatus.

For additional purification of syngas from solid particles, various pollutants and dust
particles a scrubber (washer) is used in an industry. In wet scrubber usually water (for
dust) or solutions of reagents that specifically target certain compounds are used to
spray gas which is subjected to purification. In our case to should also use solution of
calcium hydroxide (Ca(OH2)) to remove a small excess part of unreacted CO2 gas.

If we supposed 3% of unreacted CO2 – it will be 5500g*0.05 = 165 g of CO2


According to neutralization reaction:

CO2 + Ca(OH)2 = CaCO3 + H2O (4)


44 g of CO2 reacts with 74 g of Ca(OH)2
165 g of CO2 react with x g of Ca(OH)2
x = 278 g
Solubility of Ca(OH)2 into water is 0.185 g/100 ml
462 g of Ca(OH)2 should be dissolved into:
0.185 g – 0.1 L
278 g – 150 L of water
1 tonne of Ca(OH)2 is around 500 EUR
0.278 kg – 0.14 EUR
https://www.alibaba.com/showroom/calcium-hydroxide.html

22
THE FISCHER-TROPSCH PROCESS CONTINUED

Also for a scrubber performance we need a pump which can provide water supplying into
a «working» area of a scrubber. Power of a pump around 2 kW-h is sufficient for this. It is
supposed, that 1 h will be suitable for this step of purification (2 kW-h = 0.6 EUR)

As in our case we use sufficiently pure H2 and CO from CO2 (not from biomass, where
are a lot of impurities), but nevertheless we should purify syngas mainly from H2S to
be sure. For this aim a dry scrubbing system is used, inside is imposed some amount
of sulfur absorbent like activated alumina compound. In an other approach, which is
known in technology is «alkaline method», especcially is effective when an amount of
sulfur-containing compounds is high:

H2S + 2NaOH = Na2S + 2H2O (5)


RSH + NaOH = RSNa + H2O (6)

Also apparatus for complex CO purification is available, for example:


http://www.saespuregas.com/Products/Gas-Purifier/Carbon-Monoxide-Gas-Purification.html

Sungas purification: summary

To perform purification of 7 kg of CO from undesirable impurities we need:


wet scrubber
150 L of water
0.15$ for 0.278 kg of Ca(OH)2
2 kW-h =

3. Synthesis of hydrocarbons and process conditions

The Fischer–Tropsch process involves a series of chemical reactions that produce a variety
of hydrocarbons, ideally having the formula (CnH2n+2). I.e. eventually we always get a mix
of hydrocarbons.
The more useful reactions produce alkanes, in particular, methane (CH4), heptane (C7H16)
, octane (C8H18) and iso-alkanes like isooctane with ramified chain.

23
THE FISCHER-TROPSCH PROCESS CONTINUED

Main reactions are:


1) paraffins: nCO + (2n + 1)H2 → CnH2n+2 + nH2O
2) olefins: nCO+2nH2 → CnH2n + nH2O
3) methane: CO+3H2 → CH4 + H2O
4) water gas shift (WGS) reaction: CO+H2O → CO2 + H2
Side reactions:
5) alcohols: 2nH2 + nCO → CnH2n+1O + nH2O
6) Boudourad reaction: 2CO → C + CO2, ΔH = -172 kJ/mole
Catalyst modifications:
7) catalyst oxidation/reduction: MxOy + yH2 → yH2O + xM
MxOy + yCO → yCO2 + xM
8) bulk carbide formation:

yC+xM  MxCy

Exact product distribution depends on CO/H2 ratio, temperature, pressure and catalyst
and will be determined by the balance among all reactions occurring during the synthesis.
For illustration, the first apparatus for the FT process yielded around 70 (!) different
compounds. Nowadays, the quantity by-products has decreased, such modern
companies like Sasol and Shell adjusted a technological process to obtain eventually
about 30 or in the best manifestation – only 14 compounds.

Reaction produces alkanes as follows:

nCO + (2n + 1)H2  → CnH2n+2 + nH2O (7)

where n is typically 10–20. In principle, any hydrocarbons conventionally obtained from


petroleum can be produced by the FT synthesis, from CH4 to high molecular weight
waxes.
The formation of methane (n = 1) is unwanted. Most of the alkanes produced tend to
be straight-chain, suitable as diesel fuel. For petrol, hydrocarbons with branched-chain
are appropriate. In addition to alkane formation, competing (side) reactions give small
amounts of alkens, as well as alcohols and other oxygenated hydrocarbons.

24
THE FISCHER-TROPSCH PROCESS CONTINUED

For one –CH2– group produced we have to possess 1 mole part of CO and 2 mole parts
of H2:

CO + 2H2 → -(CH2)- + H2O


8

In case of octane (isooctane) C8H18:

8CO + 17H2  → C8H18 + 8H2O


9

From the chapter 1. we have available 500 mole of H2 and 250 mole of CO:
According to the reaction (9):
8 mole or 96g of CO react with 17 mole or 35g of H2 and produce 1 mole or 114g of
octane
x mole or y kg of CO react with 500 mole or 1 kg of H2 and produce z mole of h g of
octane
x=235 mole of CO or y = 6.58 kg of CO
z = 29.4 mole of octane or h = 3.35 kg of isooctane (4.85 liter).
As we can see 250-235=15 mole of CO is in an excess if we consider only a type of the
reaction like (9). The side reactions mentioned above will also take place in one way or
another.
The excess of unreacted CO can participate in the reaction with H2O:

CO + H2O → H2 + CO2 (10) ΔH = -41.6 kJ/mole

It is one of the most important reaction to adjust the H2:CO ratio, (called “water-gas
shift reaction») which provides a source of H2 at the expense of CO. This reaction can be
driven in either direction by applying Le Chatelier’s Principle. As we can see, the forward
reaction is exothermic (heat is released), the is suppressed at higher temperature, i.e.
an equilibrium is shifted towards CO and H2O; pressure doesn’t not influence on this
reaction equilibrium.
If we want to use H2 obtained from the reaction (10), it must be separated from the CO.
This is primarily done by pressure swing absorption (PSA), amine scrubbing and
membrane reactors.

25
THE FISCHER-TROPSCH PROCESS CONTINUED

a) The iso-FT-synthesis

For isooctane and other isocompounds production (the iso-FT synthesis) it is obligatory to
ensure a specific operation condition during the Fischer-Tropsch process.
The distribution of the formed substances during the FT process is qualitatively governed
by the Anderson-Schulz-Flory (ASF) kinetics:

Wn/n = α(n-1) (1-α)2, α = rp/(rp+rt)

Wn is the weight of product containing n carbon atoms and α is the chain growth
propagation probability. The value α increases with decreasing H2/CO2 ratio, decreasing
reaction temperature and increasing pressure.
In our case typical operating conditions could be in the range:

t =300–350°C, P =100-200 atm

These conditions are designed to produce predominantly branched-chain hydrocarbons,


suitable for petrol. As temperature is increased the faster reaction (7) but it also favors
methane production, since this reaction is endothermic:

CO+3H2 ↔ CH4 + H2O, (11) ΔH = 206.6 kJ/mole


For this reason, the temperature is usually is precisely fitted experimentally and rather
maintained in a lower part of the range.
As for pressure, even higher pressures than 200 atm would be favorable, but the benefits
may not justify the additional costs of high-pressure equipment, and higher pressures can
lead to catalyst deactivation via coke formation.

b) Catalysts

For iso-FT-synthesis ThO2/Al2O3 catalysts are the most appropriate. Yields predominantly
isoparaffins; as temperature is increased, also forms aromatics (both are good for
high-octane petrol).
Prices for ThO2 and Al2O3
https://russian.alibaba.com/g/thorium-oxide.html
350$ for 1 kg of ThO2
1$ for 1 kg of Al2O3

26
THE FISCHER-TROPSCH PROCESS CONTINUED

As we can see, ThO2 is too expensive. Therefore, in practice, iron (Fe) or cobalt (Co)
metals are usually used as catalysts. Iron catalyst can tolerate lower rations H2/CO<1,
due to water gas shift (WGS) reaction. In our case Co metal is more appropriate, as the
initial ratio H2/CO=2:1 had been ensured.

https://www.dailymetalprice.com/metalpricecharts.php?c=co&u=lb&d=0

Comparing prices for Fe and Co metals from that web-site one can see:
Cobalt price: ~14$/pound = 31$/kg
Iron price: ~0.04$/pound = 0.09$/kg
Cobalt is appreciably expensive, but reactions on its surface will proceed faster. This
means that it is possible to produce more petrol per hour. Cobalt catalysts are more
sensitive (than Fe ones) to poisoning by sulfur-containing compounds, hence preliminary
careful syngas purification is obligatory.

How often must we change the Co catalyst - it will show a specific experiment.

Process conditions: summary

Operating conditions for the calculation: t=350 C, P = 100atm, Co catalyst.


According to the classical chemistry, chemical catalysts – is a substance, which accelerates
the reaction, but is not consumed during the reaction. Therefore, buying of the catalysts is
one-time, the same like other apparatus, hence it should not consider a price for catalyst
for such small amount of initial gases in our case.

4. Reactor for the Fischer–Tropsch synthesis

d) Cooling system

The removal of the large amount of excess heat generated by the exothermic synthesis
reaction – is one of the most important challenges in the FT synthesis. As the reaction of
alkanes formation CO + 2H2 → -(CH2)- + H2O is strongly exothermic first of all we need
to solve a problem with temperature stabilization in order to maintain T around defined
value (300 C),

27
THE FISCHER-TROPSCH PROCESS CONTINUED

otherwise it fully destabilize the FT process and we get high carbon deposition, catalyst
deactivation, methane formation at the expense of desired

8CO (g) + 17H2 (g) → C8H18 (l) + 8H2O (g) (12)

gives: ΔH =(ΔH(C8H18(l)) + 8ΔH(H2O (g)) – (17ΔH(H2(g) + 8ΔH(CO(g)) = (-224+(8(-241.8)) – 0


+ 8*(-110.5) = -2158 + 884 = -1274 kJ/mole.

We only need to heat slowly the first portion of syngas to some elevated temperature and
then just maintain the required one (300 C) it at the expense of the alkanes formation
heat (reaction 12).

In order to heat 1 kg of H2 and 5.5 kg of CO2 from 25 C to 300 C (300-25=275 K) we need:


CO2– heat capacity is 0.85 (kJ/(kg*K)).
H2 – heat capacity is 14.3 (kJ/(kg*K)).

H2:
14.3 kJ - 1 K
p kJ – 275 kg
p = 3932 kJ

CO2:
0.85 kJ - 1 kg
x kJ – 5.5 kg
x = 4.68 kJ
4.68 kJ – 1 K
y kJ – 275 K
y = 1287 kJ

114 of C8H18 formation releases 1274 kJ


3350 g ------ n kJ, n = 37437 kJ

The difference is r = n-p-y = 37437-3932-1287 = 32218 kJ

Heat capacity of water Cp = 4.2 kJ/(kg*K)

28
THE FISCHER-TROPSCH PROCESS CONTINUED

If we use water with t=250 C in vessel for cooling system, to heat 1 kg of water from 25 till
80 C we need use
4.2 kJ – 1 K
x kJ – (80-25) = 55 K
x = 231 kJ

I.e. to take away the excess of heat energy from the isooctane formation we need
231 kJ – 1 kg of water
32218 kJ – y kg of water

y = 140 kg of water

If we will consider industry scale, for cooling of the reactor I would propose to use dual
circuit water cooling system as more effective:
1) the first one – is smaller with vessel volume ~3-5 m3.
2) the second one – is bigger with vessel volume ~7-10 m3.

Some part of released heat during the reaction can use for temperature maintenance
inside the reactor, therefore we can economize the energy for syngas heating for the FT
process and don’t take into account energy needed for syngas heating.
If we will consider industry scale, for cooling of the reactor I would propose to use dual
circuit water cooling system as more effective:
+ 8*(-110.5) = -2158 + 884 = -1274 kJ/mole.

Dual circuit water cooling system scheme for cooling the FT reactor includes:
1 – smaller vessel with deionized water
2 – pumps
3 – heat exchanger
4 – rector for the FT synthesis
5 – additional systems of air colling
6 – bigger vessel with water
7 – electrical refrigerator, which maintain well-defined temperature inside the bigger
vessel

29
THE FISCHER-TROPSCH PROCESS CONTINUED

In a smaller water cooling system we have to use deionized water, in order to avoid salts
(CaCO3, MgCO3 and others) deposition on the inner tubes walls. In practice rainwater is
one of the best choice for this aim.
In a bigger water cooling system conventional water with ions Ca2+ and Mg2+ could be
used, because it will not be heat up to higher temperature and insoluble salts will not be
precipitated.

Pumps 2 will be working permanently during the the FT synthesis. A power of such pump
can be really around 2.5 kW-h. For the calculation we take 2 h of the pumps work:
2*(2*2.5 kW-h) = 10 kW = 3 EUR

b) Reactor

The rate of iso-alkanes formation is a function of many variable quantities:


v = dC(iso-alkanes)/dτ = k*f(Cg, τ, T, P),
where k – a constant of the rate reaction iso-alkanes synthesis;
Cg – concentration of components in the initial gas mixture;
τ – contact time the gases (CO and H2) with the catalyst;
T – temperature
P - pressure

As gas velocity increasing a yield of formed iso- and other alkanes is diminished, since
contact time the gases with the catalyst becomes smaller. Therefore, generally, linear
velocity of the gas mixture can be varied from 0.05 m/s till 10 m/s depending on inner
diameter of used tubes and type of the catalyst placement inside the reactor.

At low linear gas velocities that is typical for the FT synthesis reactors, the required
temperature is provided in tubes with a diameter of 20 mm with a catalyst productivity
of no more than, for instance 130–160 m3 CO/(m3cat·s).

A twofold increase in tube diameter limits a possible performance applied catalyst up to


50 m3 CO/(m3cat·s). With linear gas velocity raising an acceptable catalyst performance
is also increased.

30
THE FISCHER-TROPSCH PROCESS CONTINUED

However, even at speed flow of 10 m/s under normal conditions, the use of
high-performance catalysts is possible only in reactors with very small tube diameter.
As a reactor we can consider “Slurry reactor” which is known in the FT technology and
which can operate under our technological conditions. The synthesis gas (CO and H2) is
bubbled through the finely-divided catalyst which is suspended in the liquid medium. This
also provides agitation of the contents of the reactor. The catalyst particle size reduces
diffusional heat and mass transfer limitations. A lower temperature in the reactor leads
to a more viscous product and a higher temperature (>300°C) could give an undesirable
product spectrum.

As a conversion degree from CO+H2 to hydrocarbons could be low, usually this drawback
is solved by using a circulation process. Equipments for that were included to the general
scheme and to the calculation.

Fischer-Tropsch

We need to heat only one time CO and H2 up to 3000C and in the sequel this temperature
could be maintained due to the heat of the reaction of hydrocarbons formation.

H2 – heat capacity is 14.3 (kJ/(kg*K)).


CO – heat capacity is 1.04 (kJ/(kg*K)).
m(H2) = 1 kg
m(CO) = 7 kg

H2 > 1 kg we need to heat from 25 C to 300 C (275 C difference)


14.3 kJ – 1 C
x kJ – 275 C
x=3932 kJ

CO > 7 kg we need to heat from 25 C to 3000C (275 C difference)


1.04 kJ – 1 C
x kJ – 275 C
x=286 kJ – for 1 kgz

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THE FISCHER-TROPSCH PROCESS CONTINUED

we have 7 kg of CO > 286*7= 2002 kJ

Totally we need for heating: 3932 kJ+2002 kJ=5934 kJ

30 MJ – 1 kg of anthracite
5934 kJ = 5.934 MJ = z kg of anthracite

z=0.20 kg
For 0.2 kg of coal ~ 0.06$

Conclusions

For the CO2 in CO conversion (CO2+C=2CO) we need 1.5 kg of coal – 0.45$


To achieve 1000 degress for this CO2+C=2CO reaction we need to burn 0.22 kg of coal -
0.07$

Electricity consumption per hour based on the following general scheme can be
estimated to be ~44 kW-h. Price for this amount of electricity is 0.88 EUR + 0.63 EUR for
coal and 0.15 EUR for Ca(OH)2 => ~ 1.66 EUR.
In order to convert 1 kg of H2 and 5.5 of CO2 into 4.85 liter of petrol, enriched by
iso-compounds, primarily iso-octane we need sufficiently roughly 1.53. This price includes
energy, requires for CO2 – CO conversion, price for coal and Ca(OH)2, price for energy,
requires for all devices operating (pumps, compressors, mixers, conderser) marked in the
scheme above.
In conclusion it worth to note, that the obtained by such synthesis petrol need to be
subjected to inspection in order to establish octane number (ON), and based on this
checking one should tune the technological parameters precisely to achieve ON of the
petrol as high as possible.

32
PROJECT SUNSHYDROGEN

Production countries

Australia and Chile have ambitious targets to establish their own hydrogen economies
and become hydrogen fuel leades.
The process used will be PV2G: converting solar photovoltaic energy into hydrogen by a
process called electrolysis, splitting H2O water into hydrogen and oxygen with electrical
current. The oxygen is to be used to increase the performance of the generator and the
hydrogen to generate petrol.

There are many coal plants whose CO2 can be used to produce fuels with H2 and CO2.

CO2 can be considered a feedstock, to make petrol and reduce CO2 emissions.

Countries that implement the herein described process first can thereafter either import
carbon dioxide from other countries or export the hydrogen in an LOHC form to
other countries to generate petrol onsite.

Potential countries to export to are China, Germany and the US, they have many coal
power plants and no petrol or depleting oil resources.

Electric cars and hydrogen cars only have a small market share and it will probably take
decades for them to catch up and will require strong undesirable government regulation.
In addition the driving experience of a petrol car is in many ways superior to that of a
electric or hydrogen electric or hydrogen combustion car.

There are big problems with implementing large amounts of solar energy, one mayor
problem is grid congestion. In desert regions, implementing too much solar will drop the
prices of electricity since there is no marginal cost and it wouldn’t be possible to add more
solar, even though the country still has much more solar output potential. In addition at
night time there will have to be a big backup system to generate the needed electricity.
By producing petrol from solar, this reduces the problems associated with the grid and
creates a highly valuable product that is useful today and reduces emissions.

While today they may be oil importers, countries with deserts can therefore
become oil exporters.

33
THE SUNS HYDROGEN

Suns Hydrogen is an organization focused on developing hydrogen markets,


both the supply and demand side.
To collaborate or for more information please email us on

info@sunshydrogen.com

34