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ENERGIA DE CARBON Y GAS

SIN EMISIONES
GASOLINE DE HIDROGENO CON SOL A GAS

RECICLAJE DE 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
CÁLCULOS PARA EL INVERSIÓN
EN UN 500 MW CENTRAL DE CARBÓN

Ingresos de la inversión
1
Un 500 MW central de carbón emite 2 Mega toneladas de CO2 al año que absorbe 363,636,000
kilogramos de hidrogeno verde, que resulte en 1,763,636,000 litros de gasolina
4
valorada a 1,700,000,000 € .
Los costes de electricidad y carbón para el proceso Boudouard y Fischer-Tropsch son estimados al
4
603,635,000 €
4
Costes para el almacenamiento por la noche con LOHC están estimadas en 90,909,000 €
Que resulta en un ingreso estimado en 1 mil millones euros al año.

Inversión estimada
7 8
El inversión en 6.2 GW los placas solares es aproximadamente 2,25 mil millones de euros. .
9
El inversión en el electrolizador esta estimado en 300 millones de euros
10
El capital para el proceso Boudouard y Fischer-Tropsch seria estimado en 200 millón.
11
El almacenamiento para el hidrogeno seria estimado en 100 millón euros.
El inversión total es 2.8 mil millones.

Retorno de la inversión
El retorno bruto de la inversión esta estimada a aproximadamente 35% al año.

Combustión oxy-fuel

Electrolisis produce hidrogeno y oxigeno. El oxigeno puede ser utilizado para el combustión en un planta
12 13
de carbón. En Teoría este puede aumentar el producción de un planta de carbón por 13% a 20% .
Se aumenta porque combustión con oxigeno solo no lo demanda calentar el nitrógeno, así aumenta el
temperatura de la llama de 1900C a 2500C.
1
https://en.wikipedia.org/wiki/Fossil_fuel_power_station#Carbon_dioxide un 1500 MW central de carbón emite 5.97 Mega toneladas. /3= 2Mton
2 2,000,000,000 kilogramos de CO2 / 5.5 kilogramos de CO2 mezclado con 1 kilogramo de hidrogeno= 363,636,000 kilogramos de hidrogeno al año.
3 Un kilogramo de hidrogeno se mezcla con 5.5 kilogramos de dióxido de carbón y un medio kilogramo de carbón que resulta en 4.85 litros de
isooctane. 363,636,000><4.85= 1,763,636,000 €
4 https://www.racfoundation.org/data/wholesale-fuel-prices-v-pump-prices-data
5 1.66 por kilogramo de hidrogeno >< 363,636,000 kilogramos de hidrogeno= 603,635,000 €
6 Hidrogenación y dehidrogenación de LOHC consume 20 KW-h, por la noche esta estimado al 0.03 cents al kw-h y consumición al día esta
estimado a un consumición de 0.02 Kw-h. 50 Céntimos >< (363,636,000 kilogramos de hidrogeno / medio dia) = 181,818,000/2= 90,909,000 €
7 1 KW-P produce 57 kilogramos de hidrogeno al año (2400Kw-h al año /42= 57) → 363,636,000/57= 6,379,000 KW-p o mas o menos 6.4 GW.
8 6,379,000KW-p><300 E por KW-p + 100 € para el instalación= 2,251,600,000 €. https://www.pv-magazine.com/features/investors/module-price-index/
economía de escala son estimadas a un 35% reducción de coste. 1,463,540,000 €
9 The exact costs still have to be obtained from the assigned constructor.
10 The exact costs still have to be obtained from the assigned constructor.
11 The exact costs still have to be obtained from the assigned constructor.
12 Habían varios proyectos pilotos con oxy-fuel combustión.http://callideoxyfuel.com/wp-content/uploads/2018/03/COP-Public-Report-March-2018.pdf
Normalmente le nitrógeno esta quitado del aire con un ASU- air separation unit.
13 P34 Oxy-fuel Combustion: Fundamentals, Theory and Practice
1
COAL PLANT CO2 RECYCLING

El proceso Boudouard y Fischer-Tropsch convierte dióxido de carbono,


carbon y hidrogeno a gasolina.

OXOSYNTHESIS EL PROCESO FISCHER-TROPSCH

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

Electricidad
RED ELECTRICO de carbon
sin emisiones

CAMIONES TANQUE CENTRAL ELECTROLISIS PLACAS


CON DE DE CARBON SOLARES
GASOLINA GASOLINA
Gasolinera Tanque de Reacción Boudouard H2 y O Electricidad
almacenamiento

1. PLACAS SOLARES 2. ELECTROLISIS 3. CENTRAL DE CARBON

4. GASOLINA 5. GASOLINERA

2
NUMEROS DE HIDROGENO VERDE

1 kilogramo de hidrogeno cuesta 42 kw-h 14 de electricidad


solar y se mescla con 5.5 kilogramos de dióxido de carbono, que vale 10 centimos
en creditos de carbono, este
reacción tambien produce 4.85 litros de isooctane (Trimethylpentane) gasolina,
con un valor industrial de 5 € (SMALL 15). 15

En Chile 1 KW-p produce 2400 KW-h al año que puede generar


aproximadamente 57 kilogramos de hidrogeno al año, que resulta en un valor
marcado de 285 €.
1 KW-p de placas solar cuesta aproximadamente 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
FONDOS PARA CENTRALES DE CARBON

INTERES DE UNA CENTRAL DE CARBON

• Funcionamiento de un planta de carbon seria extendido

• Ingresos de la venta de gasolina

• Ingresos total de 5 € por kilogramo de hidrogeno

• Precio industrial de hidrogeno gris es 1€ al kilogramo

• El oxigeno de electrolisis puede aumentar el producción


de un central de carbon con 13%-20%

CALCULOS DE LOS CREDITOS DEL DIOXIDO DE CARBONO

El U.E. tiene un 20 euros al tonelada sistema de comercio de emisiones de


carbono. 1 kilogramo de hidrogeno lleva 5.5 kilogramos de dióxido de carbon del
aire, que esta valorada a 10 centimos.

CÁLCULOS DEL VENTA DE GASOLINA

3.35 kilogramos de isooctane (Trimethylpentane) viene con 1 k.g. de hidrogeno


cuando esta mezclado con 5.5 kilogramos de CO2. 3.35 kilogramos de isooctane
es 4.45 litros de isooctane.

4
INFRASTRUCTURE SYSTEM

5
MERCADOS DE HIDROGENO

Hidrogeno gris industrial es producido del metano utilizando, con el proceso grandes cantidades

de carbon dioxido esta emitido en el aire.

0.025 MWhe 1 MWhe natural gas


@ £ 95 / MWhe HHV @ £15 / MWh
HIDROGENO ESTA USADO EN

05 MWhe
@ £95 /
• Fabrication MWhe

de metal Steam methane


reformer

Capture £33-£ 23 / MWh,


CO2 to CCS Transport £10-£ 5 / MWh,

• Craqueo
CARBON CAPTURE REWARDS 53 £ / MWh

de petroquímico
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

• Industria Water-gas shift reaction


0.025 MWh electricity = £2.4

CO + H2O › CO2 + H2 (+ small amount of heat)


0.5 MWh electricity / hilt = £47.5
METHANE RESALE PRICE
del amoniaco Combined
CH4 + 2H20 › CO2 + 4H2
Total cost for 1 MWh of H2 = £100
METHANE RESALE PRICE
Very large industrial = £15 / MWh
Domestic = £45 / MWh

• Tranporte en Japon

• Respaldas para el red eléctrico

• Reciclaje de dióxido de carbon

6
GEOGRAFIA DE PRODUCIÓN

Placas solares son lo mas productivo en regiones desérticas, en particular en Chile


lo mas del mundo. Implementaciones de los instalaciones esta propuesto
para los siguientes países en futuro.

Chile
Australia

• Egipto

• Túnez

• Jordania

• Palestina

• Siria

• Namibia

• Mexico

EL GOBIERNO REGIONAL PODRÍA PARTICIPAR EN EL PROYECTO


PARA LOS SIGUIENTES RAZONES

• El inversion va a empleo y productividad

• Turismo de negocio

• Reduced inequality

• Mejor imagen en el mundo por conocimiento y tecnologia

• Nuevas industrias de conocimiento

• Desarrollar una econimía de conocimiento.

7
UBICACIONES PARA UTILIZAR HIDRÓGENO LIMPIO

• Chile

• Australia

• Namibia

https://globalsolaratlas.info
8
EL LOHC TASA DE COVERSION PARA TRANSPORTE
Y PARA USO DE NOCHE

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: UTILIZANDO
OXIGINO EN UN GENERADOR

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 CONTINUADA

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 CONTINUADA

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 CONTINUADA

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
EL PROCESO FISCHER-TROPSCH PARA EL PRODUCCION
DE IS0-HYDROCARBONS (GASOLINA)

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
EL PROCESO FISCHER-TROPSCH CONTINUADA

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
EL PROCESO FISCHER-TROPSCH CONTINUADA

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
EL PROCESO FISCHER-TROPSCH CONTINUADA

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
EL PROCESO FISCHER-TROPSCH CONTINUADA

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
EL PROCESO FISCHER-TROPSCH CONTINUADA

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
EL PROCESO FISCHER-TROPSCH CONTINUADA

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$
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EL PROCESO FISCHER-TROPSCH CONTINUADA

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/
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EL PROCESO FISCHER-TROPSCH CONTINUADA

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

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EL PROCESO FISCHER-TROPSCH CONTINUADA

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.

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EL PROCESO FISCHER-TROPSCH CONTINUADA

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.

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EL PROCESO FISCHER-TROPSCH CONTINUADA

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.

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EL PROCESO FISCHER-TROPSCH CONTINUADA

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

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EL PROCESO FISCHER-TROPSCH CONTINUADA

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),

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EL PROCESO FISCHER-TROPSCH CONTINUADA

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)

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EL PROCESO FISCHER-TROPSCH CONTINUADA

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

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EL PROCESO FISCHER-TROPSCH CONTINUADA

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.

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EL PROCESO FISCHER-TROPSCH CONTINUADA

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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EL PROCESO FISCHER-TROPSCH CONTINUADA

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
PROYECTO SUNSHYDROGEN

Países con aplicación

Australia y Chile tiene ambiciones de establecer sus propios economías hidrogeno.


El proceso usado seria PV2G: convirtiendo energía solar a hidrogeno con un proceso
que se llama electrolisis, que rompe agua en hidrogeno y oxigeno con electricidad. El
oxigeno
seria utilizado para aumentar el production del electricidad del planta de carbon y el
hidrogeno
para generar gasolina.

Hay muchos centrales de carbon que puede utilizar su CO2 para producir comustibles.

CO2 puede ser considerado un materia prima, para crear gasolina y reducir
emisiones de CO2.

Países que implementan el proceso pueden después exportar el LOHC o importar dióxido
de carbono.

Paises para exportarlo a son China, Alemania y E.U., donde hay muchos plantas
de carbon y que no tienen gasolina.

Coches de hidrogeno y coches eléctricos solo tiene un pequeño cuota de mercado y va a


durar mucho tiempo y regulación
para hacer esto se cambio. Ademas el experiencia de conducir un coche
de combustible es mejor.

Hay muchos problemas con implementar grandes cantidades de energía solar, un gran
problema es congestión en el red teléctrico; que significa que hay mas producción de
energía que demandan los consumidores, y el precio del energía va negativo.
Esto limite la cantidad de solar que un país con mucho solar puede implementar.
Cuando produces gasolina con energia solar se puede instalar mucho mas que el red
eléctrico demanda y produces un producto con alta valor que tiene uso
y que reduce los emisiones.

Paises con desiertos que hoy son importadores de gasolina pueden ser exportadores de
gasolina.

33
THE SUNS HYDROGEN

Suns hydrogen es un organisation que se enfoca en desarrollar mercados


de oferta y demanda de hidrogeno verde.

info@sunshydrogen.com

34