NZ625687B2 - Process and system for conversion of carbon dioxide to carbon monoxide - Google Patents
Process and system for conversion of carbon dioxide to carbon monoxide Download PDFInfo
- Publication number
- NZ625687B2 NZ625687B2 NZ625687A NZ62568712A NZ625687B2 NZ 625687 B2 NZ625687 B2 NZ 625687B2 NZ 625687 A NZ625687 A NZ 625687A NZ 62568712 A NZ62568712 A NZ 62568712A NZ 625687 B2 NZ625687 B2 NZ 625687B2
- Authority
- NZ
- New Zealand
- Prior art keywords
- carbon
- converter
- hydrocarbon
- synthesis gas
- hydrogen
- Prior art date
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- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 133
- UGFAIRIUMAVXCW-UHFFFAOYSA-N carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 117
- 238000000034 method Methods 0.000 title claims abstract description 89
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 title claims description 40
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 193
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 86
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 85
- 230000002194 synthesizing Effects 0.000 claims abstract description 85
- 238000004519 manufacturing process Methods 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 167
- 229910052799 carbon Inorganic materials 0.000 claims description 148
- 239000004215 Carbon black (E152) Substances 0.000 claims description 144
- 239000007789 gas Substances 0.000 claims description 131
- 239000001257 hydrogen Substances 0.000 claims description 89
- 229910052739 hydrogen Inorganic materials 0.000 claims description 89
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 76
- 238000002156 mixing Methods 0.000 claims description 43
- 239000012530 fluid Substances 0.000 claims description 30
- 230000005611 electricity Effects 0.000 claims description 22
- 210000002381 Plasma Anatomy 0.000 claims description 19
- 238000000926 separation method Methods 0.000 claims description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 13
- 150000002431 hydrogen Chemical class 0.000 claims description 13
- 239000003345 natural gas Substances 0.000 claims description 11
- 230000001105 regulatory Effects 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 7
- 229940035295 Ting Drugs 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 230000001276 controlling effect Effects 0.000 claims description 5
- 239000000969 carrier Substances 0.000 claims description 2
- 239000000295 fuel oil Substances 0.000 claims description 2
- 230000002829 reduced Effects 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 26
- 239000000047 product Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 8
- 239000006229 carbon black Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000012188 paraffin wax Substances 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000003245 coal Substances 0.000 description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 5
- 238000007599 discharging Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000004071 soot Substances 0.000 description 4
- 230000001131 transforming Effects 0.000 description 4
- 239000000443 aerosol Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000005039 chemical industry Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006011 modification reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- ABDKAPXRBAPSQN-UHFFFAOYSA-N 1,2-Dimethoxybenzene Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 235000010599 Verbascum thapsus Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000004429 atoms Chemical group 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000001010 compromised Effects 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 230000001627 detrimental Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- -1 fertilisers Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000670 limiting Effects 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 230000001264 neutralization Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000036961 partial Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
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- 238000000197 pyrolysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000004642 transportation engineering Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000003245 working Effects 0.000 description 1
Classifications
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
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- C01B2203/0255—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a non-catalytic partial oxidation step
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- C01B32/40—Carbon monoxide
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C10J2300/00—Details of gasification processes
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
- C10J2300/1656—Conversion of synthesis gas to chemicals
- C10J2300/1659—Conversion of synthesis gas to chemicals to liquid hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
- C10K3/06—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by mixing with gases
Abstract
process and an apparatus for converting carbon dioxide CO2 into carbon monoxide CO using hydrocarbons are described. In further embodiments, processes and apparatuses for generating synthesis gas and processes and apparatuses for converting synthesis gas into synthetic functionalised and/or non-functionalised hydrocarbons using CO2 and hydrocarbons are described. The processes and apparatuses are adapted to convert CO2 emitted by industrial processes, and thus the amount of carbon dioxide emitted into the atmosphere may be reduced. nctionalised hydrocarbons using CO2 and hydrocarbons are described. The processes and apparatuses are adapted to convert CO2 emitted by industrial processes, and thus the amount of carbon dioxide emitted into the atmosphere may be reduced.
Description
Process and System for Conversion Carbon Dioxide into Carbon Monoxide
The present invention relates to a process and a system for generating carbon de from
hydrocarbons and C02.
Large amounts of carbon dioxide (C02), which is regarded as climate ng gas, are
generated in power generation and other industrial processes. Great efforts are made to avoid
generation of carbon dioxide. rmore, ts are made to separate the generated
carbon dioxide from flue gases and to store the carbon dioxide. One example is the C02
storage or Carbon-Capture-to-Storage concept, abbreviated CCS concept, where the C02 is
separated from the flue gases, thereafter compresses and stored in appropriate geological
ions. The CCS s is expensive, energy intensive, limited in the e capacities
and is - for various reasons - strongly opposed by the respective population. At least in
Germany, the technical and political ility seems to have failed.
Another possibility is the use of carbon dioxide as starting material for other industrial
processes, i.e. as starting material in the plastics industry for producing polyurethane, as it is
done by the Bayer AG in the project COZRRECT. Regarding the amounts of involved C02, the
use of 002 as starting material is only a niche application, since the total global production of
the end products of such an application is too low to convert a significant amount of the emitted
carbon dioxide.
None of these ts ed in applications that are able to bind large amounts of carbon
dioxide or that are socially acceptable in their entation.
Synthesis gas, or abbreviated syngas, is a gas mixture ning carbon monoxide and
hydrogen that may also contain carbon dioxide. For example, the syngas is generated by
gasification of carbon containing fuel to a gaseous product having a n calorific value. The
sis gas has approximately 50% of the energy density of natural gas. The synthesis gas
may be burned and thus used as a fuel source. The synthesis gas may alSo be used as an
intermediate product in the generation of other chemical products. For example, the synthesis
gas may be generated by gasification of coal or waste. ln the generation of synthesis gas,
carbon may be reacted with water, or a hydrocarbon may be reacted with oxygen. There are
commercially available technologies for processing sis gas in order to generate industrial
gases, fertilisers, chemicals and other chemical products. However, most known technologies
(e.g. water—shift—reaction) for the generation and conversion of synthesis gas have the problem
that synthesising the required amount of hydrogen causes the generation of a larger amount of
s C02 which is finally emitted into the atmosphere as a climate damaging gas. Another
known technology for the production of synthesis gas, the partial oxidation of methane
according to the equation 2 CH4 + Oz —> 2 C0 + 4 H2 is able
, to reach a maximum ratio of
H2:CO of 2.0. However, the disadvantage thereof is the use of pure oxygen that is energy
intensively produced.
DD 276 098 A1 describes a more complete material utilisation of natural gas in steam reforming
plants. In particular, a process for generating soot from natural gas by means of arc plasma
pyrolysis is described among others. Further, US 4 040 976 A describes treatment of a
aceous al, especially coal, with carbon dioxide for generating a carbon monoxide
gas. In said treatment, the carbon dioxide is first mixed with the carbonaceous material and
thereafter is rapidly heated in a reactor together with carbon dioxide at a rate of > 500°C/s, and
afterwards is rapidly cooled, wherein the heating phase lasts from 0.1 to 50 ms and the entire
contact time of the reactants is limited to a time range of 10 ms to 5 s. Furthermore, ting
carbon de in a plasma is known from US 4 190 636 A, where a plasma is generated from
carbon dioxide, into which solid carbon is introduced. The resulting products are thermally
quenched and ed so as to obtain carbon monoxide.
EP 0 219 163 A2 discloses a method for generating synthesis gas, n hydrocarbonaceous
material is decomposed into carbon and hydrogen in a first reactor chamber, and wherein the
carbon is transferred to a second reactor chamber and reacts with H20 steam in the second
reactor chamber.
GB 873 213 A2 discloses a method for generating synthesis gas, wherein first hydrocarbon is
decomposed to carbon by means of a catalyst, and thereafter the st in contact with the
carbon is exposed to 002.
ore, a problem to be solved is to e a method for converting C02, the method being
able to efficiently reduce the amount of carbon dioxide emitted by industrial processes and to
enable tion of chemical products in demand.
The invention provides a method according to the present invention and an apparatus according
to the present invention.
Unless the context clearly requires vise, throughout the ption and the claims, the
words ‘comprise’, ‘comprising’ and the like are to be construed in an inclusive sense as opposed
to an exclusive or exhaustive sense; that is to say in the sense of “including but not limited to”.
[FOLLOWED BY PAGE 2a]
In particular, a method for converting carbon e 002 into carbon monoxide CO comprises
decomposing a hydrocarbon ning fluid into carbon and hydrogen by means of introduction
of energy that is at least partially provided by heat, whereby the carbon and the hydrogen have
a temperature of at least 200°C after the decomposing step. Subsequently, at least a portion of
the carbon generated by the decomposing step is mixed with 002 gas, wherein the carbon
generated by the decomposing step cools down by not more than 50% in °C with respect to its
temperature after the decomposing step upon mixing with 002 gas, and wherein at least a
portion of the 002 gas and a portion of the carbon generated by the decomposing step is
converted to CO at a temperature of 800 to 1700°C. This method enables, in a simple and
efficient way, converting C02 to CO, wherein at least a portion of the energy required for
providing carbon (by decomposing arbon) is employed in the converting step in form of
heat
[FOLLOWED BY PAGE 3]
This is particularly true, if the decomposing step takes place at a ature over 1000°C) and
the carbon is mixed with the 002 gas at a temperature of at least 800°C, since in this case no
additional heat or only a small amount of additional heat needs to be provided for converting
002 to CO. Preferably, the heat required to reach the temperature of 800 to 1700°C (specifically
about 1000°C) for the 002 conversion is essentially completely provided by the heat that is
used for decomposing the hydrocarbon containing fluid. Here, essentially completely means that
at least 80%, specifically at least 90% of the required heat originates from the decomposing
step.
In one ment, the carbon obtained by the decomposing step and the hydrogen ed
by the decomposing step are both jointly mixed with the 002 gas. Hydrogen does not
compromise the conversion and may serve as an additional heat transfer substance. This is
ularly advantageous, if the carbon and the hydrogen have a temperature of 1000°C (a
preferred sion or transformation temperature) or above. ln this case, the gas after
conversion is not pure CO but a synthesis gas.
Alternatively, the carbon obtained by the decomposing step may be separated from the
hydrogen obtained by the decomposing step prior to mixing with C02 gas.
In order to increase the energy ency of the method, at least a portion of the heat of at least
a portion of the carbon and/or the a portion of hydrogen obtained by the decomposing step may
be used to heat the (302 gas prior to the step of mixing the 002 gas with the carbon and/or to
may be used to heat the process r, in which the 002 gas is mixed with the carbon. In
this sense it should be noted that the CO has a ature of 800 to 1700°C after conversion
and that at least a portion of its heat may be used to t the C02 gas prior to the step of
mixing the C02 gas with carbon. lt is also possible that at least part of the heat of at least a
portion of the carbon and/or a portion of the hydrogen obtained by the decomposing step and/or
a portion of the CO after conversion may be used to generate electricity which may be used as
energy carrier for introducing energy for decomposing the hydrocarbon ning fluid.
Preferably, the energy for decomposing the hydrocarbon is primarily introduced via a plasma.
This is a particularly direct and thus efficient method to introduce energy. Preferably, the
decomposing step is performed in a Kvaemer reactor that enables continuously decomposing a
stream of hydrocarbons.
In the method for generating a synthesis gas, at first 002 is converted or transformed into CO
as described above and, subsequently, the CO is mixed with en. ably, the
hydrogen originates from decomposing a hydrocarbon containing fluid into carbon and hydrogen
by introducing energy that is at least partially performed by heat. Therefore, the decomposing
step may provide the carbon and also the hydrogen necessary for the 002 conversion in one
step. in one embodiment, at least a portion of the hydrogen is generated by decomposing a
hydrocarbon containing fluid at a temperature below , specifically below 600°C, by
means of a microwave plasma. Where onal hydrogen (more than the amount that is
ed by the production of the carbon necessary for the 002 conversion) is required to reach
the mixing ratio of a synthesis gas, it is preferred to produce said en in an energy efficient
manner at low temperatures from a hydrocarbon containing fluid. Preferably, the ratio of CO to
hydrogen in the synthesis gas is adjusted to a value between 1:1 and 1:3, specifically to a value
of 12.1.
In the method for generating synthetic functionalised and/or non-functionalised hydrocarbons, at
first a synthesis gas is generated as described above, and the synthesis gas is brought into
contact with a suitable catalyst in order to cause a conversion of the synthesis gas into tic
functionalised and/or non-functionalised hydrocarbons, wherein the temperature of the catalyst
and/or the synthesis gas is (open loop) controlled or (close loop) regulated to a ined
temperature range. in this way, the synthesis gas may be generated by mixing CO with
hydrogen, either before or upon bringing it into t with the catalyst.
In one embodiment, the conversion of the sis gas is performed by a r—Tropsch
process, specifically a SMDS process. Alternatively, the conversion of the synthesis gas may be
performed by a Bergius-Pier process, a Pier process or a combination of a Pier s with a
MtL process (MtL = methanol to liquid). it is the choice of the process, which largely determines
the nature of the synthetic functionalised and/or non-functionalised hydrocarbons.
ably, the hydrocarbon containing fluid to be decomposed is natural gas, methane, wet
gas, heavy oil, or a mixture thereof.
The apparatus for converting carbon dioxide COZ into carbon monoxide CO comprises a
hydrocarbon converter for decomposing a arbon containing fluid into carbon and
hydrogen, wherein the hydrocarbon ter comprises at least one process chamber having
at least one inlet for a hydrocarbon containing fluid and at least one outlet for carbon and/or
hydrogen and at least one unit for introducing energy into the process chamber, the energy
consisting at least partially of heat. Further the apparatus comprises a 002 converter for
converting C02 into CO, the 002 converter comprising at least one additional process chamber
having at least one inlet for C02, at least one inlet for at least carbon and at least one ,
wherein the inlet for at least carbon is directly connected to the at least one outlet of the
hydrocarbon converter. Here, the term "directly connected" describes that carbon coming out of
the arbon converter does not cool down by more than 50% of its temperature in °C,
preferably not more than 20%, on its way to the C02 converter without the utilisation of
additional energy to heat up the carbon. A separating unit, which separates the carbon from the
hydrogen, may be provided n the location of the decomposing step and the at least one
exit of the hydrocarbon converter. This separating unit may form a part of hydrocarbon converter
or may be located outside the hydrocarbon converter as a separate unit. A separating unit
n the exit of the hydrocarbon converter and the entrance of a C converter does not
compromise a direct connection as long as the above condition is met.
Preferably, the at least one unit for introducing energy into the process chamber is constructed
in such a way that it is able to at least locally generate temperatures above 1000°C, specifically
above 1500°C. In one embodiment, the at least one unit for introducing energy into the process
chamber is a plasma unit. Particularly, if the decomposing temperature shall be kept below
1000°C, the at least one unit for introducing energy into the process chamber preferably
comprises a microwave plasma unit.
For a ularly simple embodiment of the apparatus, the s chamber of the 002
converter is formed by an outlet pipe of the arbon converter which is connected to a
supply pipe for 002 gas.
In one embodiment of the ion, a separation unit for separating the carbon and the
hydrogen generated by decomposing is provided in the vicinity of the hydrocarbon converter,
and separate outlets from the separation unit are provided for the separated materials, n
the outlet for carbon is connected to the 00;; converter.
Preferably, the hydrocarbon converter is a Kvaerner reactor that can provide the necessary
temperatures for a continuous decomposing of a hydrocarbon containing fluid for long operating
periods.
The apparatus for generating synthesis gas comprises an apparatus of the previously described
type as well as at least one separate supply pipe for supplying hydrogen into the 002 converter
or a downstream mixing chamber. Such an apparatus enables a simple and efficient generation
of a synthesis gas from C02 and arbon containing fluid.
In one ment, the tus for generating synthesis gas ses at least one
additional hydrocarbon converter for decomposing a arbon containing fluid into carbon
and en. The at least one additional hydrocarbon converter again comprises at least one
process chamber having at least one inlet for the hydrocarbon containing fluid, at least one unit
for introducing energy into the process chamber, wherein the energy at least partly consists of
heat, and a separation unit for separating the carbon and the hydrogen, which were ed by
decomposing, with the separation unit having separate outlets for carbon and hydrogen,
n the outlet for hydrogen is connected to the separate supply pipe for hydrogen. For
reasons of energy efficiency, the at least one onal hydrocarbon converter is preferably of
the type that carries out osing at temperatures below 1000°C, specifically below 600°C,
by means of a microwave plasma.
The apparatus for converting a synthesis gas into synthetic functionalised and/or non—
functionalised hydrocarbons comprises an apparatus for generating synthesis gas of the above
specified type and a CO converter. The CO converter comprises a process chamber equipped
with a catalyst, means for bringing the synthesis gas into contact with the catalyst and a control
unit for(open loop) controlling or (close loop) regulating the temperature of the catalyst and/or
the synthesis gas to a predetermined temperature. In this way, parts of the apparatus for
generating synthesis gas may be integrated into the CO converter, eg. a mixing chamber for
CO and additional hydrogen. In one embodiment, the CO converter comprises a r—
Tropsch converter, ularly a SMDS converter. Alternatively, the CO converter may comprise
a Bergius-Pier converter, a Pier converter or a combination of a Pier converter and a MtL
converter. it is also possible that several CO converters of the same type or of ent types
are provided in the apparatus.
ably, the apparatus comprises a control unit for controlling or regulating the pressure of
the synthesis gas inside the CO converter.
Below, the ion is explained in more detail with reference to certain ments and
drawings, wherein
Fig. 1 is a schematic representation of a plant for ting carbon de;
Fig. 2 is a schematic representation of a plant for generating synthesis gas;
Fig. 3 is a schematic representation of a plant for generating functionalised and/or nonfunctionalised
hydrocarbon;
Fig. 4 is a schematic entation of another plant for generating functionalised and/or
non-functionalised hydrocarbons according to another embodiment;
Fig. 5 is a schematic representation of a plant for generating functionalised and/or non-
functionalised hydrocarbons according to another ment;
Fig. 6 is a schematic representation of a plant for ting functionalised and/or non-
functionalised hydrocarbons according to another embodiment;
Fig. 7 is a schematic representation of a plant for generating synthesis gas according to
another embodiment; and
Fig. 8 is a schematic representation of a plant for generating functionalised and/or non-
functionalised hydrocarbons according to r embodiment.
It shall be noted the terms top, bottom, right and left as well as similar terms in the following
ption relate to the orientations and arrangements, respectively, shown in the figures and
are only meant for the description of the embodiments. These terms are not limiting. Further, in
the different figures, the same reference numerals are used for describing the same or similar
parts.
in the following description, processes and apparatuses are described that handle “hot”
materials or carry out “hot” processes. In the context of this description, the expression “hot”
shall describe a temperature above 200°C and preferably above 300°C.
Fig. 1 schematically shows a plant 1 for converting carbon dioxide to carbon monoxide. Fig. 1
also clarifies the basic s steps for converting carbon dioxide to carbon monoxide
according to this description.
Plant 1 comprises a hydrocarbon converter 3 that comprises a hydrocarbon inlet 4 and a first
carbon outlet 5, an al hydrogen outlet 6 as well as an optional second carbon outlet 7.
Plant 1 for generating carbon monoxide further comprises a COZ ter 9 having a CO; inlet
, a carbon outlet 11 (also referred to as C inlet) and an outlet 12. The hydrocarbon converter
3 and the COZ converter 9 are arranged such that the carbon outlet 5 of the hydrocarbon
converter 3 is connected to the carbon inlet 11 of the (302 converter 9 via a direct connection 8,
wherein the outlet 5 may directly define the carbon inlet 11 of the C02 converter 9. In this way,
carbon may be directly transported from the arbon converter 3 into the COg converter 9.
The hydrocarbon converter 3 is any hydrocarbon converter that can t or decompose
introduced hydrocarbons into carbon and hydrogen. The hydrocarbon converter 3 comprises a
process r having an inlet for a hydrocarbon containing fluid, at least one unit for
introducing osing energy into the fluid and at least one outlet. The decomposing energy
is provided at least partially by heat, which is for instance ed by a . Nevertheless,
the decomposing energy may also be provided by other means and, if decomposing is primarily
effected by heat, the fluid should be heated to above 1000°C and particularly to a ature
above 1500°C.
in the described embodiment, a Kvaerner reactor is used, which provides the required heat by
means of a plasma arc and a plasma torch. However, other reactors are known, which operate
at lower temperatures, particularly below 1000°C, and uce additional energy besides heat
into the hydrocarbon, eg. by means of a ave plasma. As is further ned below, the
ion considers both types of reactors (and also those which operate without ), in
particular also both types of rs in combination with each other. Hydrocarbon converters
operating at a temperature above 1000°C are referred to as high temperature reactors, whereas
those converters operating at temperatures below , particularly at temperatures between
200°C and 1000°C, are referred to as low temperature reactors.
Within the hydrocarbon converter, hydrocarbons (CnHm) are decomposed into hydrogen and
carbon by means of heat and/or a plasma. These hydrocarbons are preferably introduced into
the reactor as gases. Hydrocarbons that are liquids under rd conditions may be
vaporised prior to introduction into the reactor or they may be introduced as micro-droplets. Both
forms are referred to as fluids in the following.
Decomposing of the hydrocarbons should be done, if possible, in the absence of oxygen in
order to suppress the formation of carbon oxides or water. Nevertheless, small amounts of
oxygen, which might be introduced together with the arbons, are not detrimental for the
process.
The Kvaerner reactor described above decomposes hydrocarbon containing fluids in a plasma
burner at high temperatures into pure carbon (for instance as activated coal, carbon black,
graphite or industrial soot) and hydrogen and, possibly, impurities. The hydrocarbon containing
fluids used as starting material for the hydrocarbon converter 3 are for instance methane,
natural gas, biogases, wet gases or heaw oil. However, synthetic functionalised and/or non-
functionalised hydrocarbons may also be used as starting material for the hydrocarbon
converter 3. After the initial decomposing step, the elements are usually present as a e,
particularly in form of an aerosol. This mixture may, as described below, be introduced into
another process in this form, or the mixture may be separated into its individual elements in a
separation unit, which is not shown. In the context of this application, such a separation unit is
considered as part of the hydrocarbon converter 3, although the separation unit may be
ucted as a separate unit. If no tion unit is provided, the carbon outlet 5 is the only
outlet of the hydrocarbon converter 3 and directs a mixture (an aerosol) of carbon and hydrogen
directly into the C02 converter 9. If the separation unit is provided, carbon, which is at least
partially separated from hydrogen, may be directed into the COZ converter 9 using the carbon
outlet 5. Separated hydrogen and, ly, additional carbon may be discharged by means of
the al outlets 6 and 7.
The C02 ter 9 may be any suitable 002 converter that can generate carbon monoxide
(CO) from carbon (C) and carbon dioxide (C02). in the embodiment of Fig. 1, the C02 converter
9 operates according to a part of a known reaction in a blast furnace, wherein said part reaction
takes place at temperatures between about 750°C and 1200°C without the necessity of a
catalyst. Preferably, the C02 converter operates at a temperature between 800°C and 1000°C,
wherein the heat required to reach that temperature primarily is provided by the exit material of
the arbon converter 3, as will be described below in more detail. In the C02 converter 9,
C302 is directed over hot carbon or is mixed with hot carbon (and possibly hydrogen) so as to be
converted according to the chemical reaction C02 + C ——> 2 CO. The C02 converter 9
es best at the ard equilibrium and at a temperature of 1000°C. At temperatures of
around 800°C, about 94% carbon monoxide will be provided, and at temperatures of around
, around 99% carbon de will be provided. Afurther increase in temperature does
not result in significant changes.
The operation of plant 1 for converting carbon dioxide into carbon monoxide is described in
more detail below, with reference to Fig. 1. In the following, it is assumed that the hydrocarbon
converter 3 is a high temperature (HT) reactor of the Kvaerner type. Hydrocarbon containing
fluids fically in gaseous form) are introduced into the hydrocarbon converter 3 via the
hydrocarbon inlet 4. If the hydrocarbon is for instance methane (CH4), then 1 mol carbon and 2
mol hydrogen will be ed from 1 mol e. The hydrocarbons are decomposed at
about 1600°C in the hydrocarbon converter 3 according to the following reaction equation,
wherein the uced energy is heat that is generated in the plasma by means of electric
CnHm + Energy —> n C + m/2 H2
With appropriate process control, the Kvaerner reactor is capable to convert almost 100% of the
hydrocarbons into their components in a continuous ion.
In the following, it is assumed that the carbon and the hydrogen are separated in the
hydrocarbon converter 3 and that carbon and hydrogen will be discharged largely ted.
However, it is also possible that separation does not occur but carbon and hydrogen will be
discharged and introduced into the 002 converter 9 as a mixture. The hydrogen does not
compromise the conversion process in the 002 converter 9, but may serve as an onal heat
transfer substance. The carbon is at least partially directed directly via the carbon outlet 5 into
the carbon inlet 11 of the C02 converter 9. The term “directly" directing from outlet 5 of the
hydrocarbon converter 3 to the carbon inlet 11 of the COZ converter 9 shall include all
embodiments wherein the directed als do not experience a cooling down of more than
50% of the temperature (preferably not more than 20%, Le. 80% residual energy/temperature).
Since the carbon that exits from the hydrocarbon converter 3 has a high temperature, preferably
over 1000°C, the heat energy contained therein may be used to maintain the temperature
ary for the conversion process in the COZ ter 9, which preferably operates at a
temperature of about 1000°C.
The connection 8 between the hydrocarbon converter 3 and the 002 converter 9 is designed
such that the carbon does not cool down much (less than 50%, preferably less than 20% with
respect to the temperature) on its way from the hydrocarbon converter 3 to the CO; converter 9.
For instance, the connection 8 may be specially insulated and/or actively heated, wherein the
system is preferably not provided with additional heat -— i.e. not in on to the heat introduced
in the hydrocarbon converter 3. The hydrogen generated in the hydrocarbon converter 3 also
contains heat energy because of the operating temperature in the hydrocarbon converter 3.
Therefore, one possibility for heating the connection 8 is to use the heat energy of the hydrogen
that exits h the hydrogen outlet 6 to heat the connection 8 between the hydrocarbon
converter 3 and the 002 converter 9 either directly or indirectly via a heat exchanger unit.
In the 002 converter, C02, which is introduced through the C02 inlet 10 of the 002 converter 9,
is directed over hot carbon and/or is mixed with hot carbon. The 002 ter operates best at
the Boudouard equilibrium, which occurs during the on of carbon dioxide with hot .
The reaction, which is known to the person skilled in the art, depends on pressure and
temperature and will not be described in detail. Either the amount of the COZ or the amount of
carbon introduced into the 002 converter 9 may be (open loop) controlled and/or (close loop)
regulated by appropriate means.
C02 + C —> 2 CO A H = + 172.45 kJ/mol
The C02 may originate eg. from a power plant (coal, gas and/or oil operated) or from another
industrial process (eg. steel or cement production) ting riate amounts of 002.
Depending on the temperature of the 002 from the C02 source, it is advantageous to preheat
the C02 introduced into the 00;; inlet 10 of the 002 converter 9, as the 00;, converter 9
operates at a temperature between 800 and 1200°C. ting of the 002 may be achieved
eg. by using the heat energy ned in the hot hydrogen either directly or indirectly via a
heat exchange unit to preheat the 00;. Preferably, the heat contained in the carbon is sufficient
to heat the 002 to the desired temperature. Only in the case where the heat generated in the
hydrocarbon converter 3 is not ient to reach the desired conversion temperature of about
1000°C, an optional additional heating unit for heating the 002 converter 9 or elements
contained therein may be provided. Such a unit may also be provided as a preheating unit in the
vicinity of a supply line for C02 or carbon. Such a unit may also be provided only for the start—
up phase of the plant in order to bring the C02 converter 9 or media containing parts of the plant
to a starting temperature so that the system can faster reach a desired temperature state.
Heating of all media containing parts exclusively via the heat generated in the hydrocarbon
converter 3 might take too long in the beginning.
Hot carbon monoxide (CO) having a temperature of about 800 to 1000°C (depending on the
operating temperature of the CO; converter 9) exits from the COZ converter 9. The carbon
monoxide that exits from the C02 converter 9 also contains heat energy, which may be used
e.g. to preheat the COZ uced into the C02 inlet 10, either ly or indirectly via a heat
exchange unit (not shown in Fig 1).
As mentioned above, the hydrocarbon converter 3 may comprise a second carbon outlet 7 to
discharge . The carbon generated in the hydrocarbon converter 3 may be discharged —
after a respective separation step (or as a C'Hg mixture) - in different proportions through the
first carbon outlet 5 and the second carbon outlet 7. The second carbon outlet 7 is used to
rge a portion of the generated carbon that is not used in the CO2 converter 9 to generate
carbon monoxide. The carbon discharged h the second carbon outlet 7 may be
discharged as ted carbon, graphite, carbon black or r modification such as carbon
cones or carbon discs. Depending on the form and the quality of the discharged carbon, the
discharged carbon may be used as raw material for the chemical industry or the electronics
industry. Possible applications are for instance the manufacture of nductors, the
production of tires, inks, toner or similar products. The carbon generated by the arbon
converter 3 is a highly pure raw material that can be processed very well.
By means of the method described above for converting carbon dioxide into CO, it is possible to
convert the hot carbon from the hydrocarbon converter 3 in the C02 converter 9 with warm or
hot carbon dioxide from the exhaust gas from industrial processes to CO without or at least
without significant external energy supply. Preferably, at least 80%, specifically at least 90%, of
the heat ary to reach the conversion temperature should originate from the hydrocarbon
converter 3.
Fig. 2 shows a plant 20 for generating synthesis gas that comprises the above described
elements of plant 1 for generating carbon monoxide as well as a mixing chamber 21, the mixing
chamber 21 comprising a CO inlet 22 for introducing carbon monoxide and a H2 inlet 23 for
introducing hydrogen as well as a synthesis gas outlet 24 for discharging synthesis gas. The CO
inlet 22 is connected to the CO outlet 12 of the C02 converter 9. The H2 inlet 23 of the mixing
r 21 is connected to the H2 outlet 6 of the hydrocarbon converter 3. As is obvious to the
skilled person, the embodiment, which introduces a C—Hg mixture into the C02 converter 9
through the carbon outlet 5 tically generates a synthesis gas having a mixing ratio of
CO—H2 of about 1:1. In such a case, the mixing chamber 21 may not be t, or the mixing
chamber 21 may be used to produce a different mixing ratio.
The mixing chamber 21 may be any le apparatus for mixing gases and, in a simple case,
the mixing chamber 21 may be in the form of a pipe having suitable inlets and an outlet. By
means of the mixing chamber 21 and specifically by means of controlling/regulating
closed loop) the amount of (additional) hydrogen introduced through the H2 inlet 23 of the
mixing unit 21, the mixture of the synthesis gas at the synthesis gas outlet 24 may be influenced
such that a composition can be achieved, which is suitable for subsequent processes.
For many processes, for instance the Fischer-Tropsch synthesis, the ratio of hydrogen to CO
should be high. By means of the mixing chamber 21, any d ratio of hydrogen to CO may
be achieved at the synthesis gas outlet 24. It is considered that only a portion of the CO and/or
part of the en is introduced into the mixing chamber 21, whereas those portions of CO
and hydrogen that are not introduced into the mixing chamber are each discharged from the
process as pure gases. Therefore, it is for instance possible, a) to discharge only CO, b) to
discharge only hydrogen, c) to discharge a synthesis gas mixture of CO and hydrogen or d) to
discharge a stream of CO, a stream of hydrogen and a stream of a synthesis gas mixture (CO +
hydrogen).
Furthermore, the plant 20 for generating synthesis gas shown in Fig. 2 ses a first heat
exchange unit 25, a second heat exchange unit 26 and a third heat exchange unit 27. The first
heat exchanger unit 25 is in thermally conductive contact with the connection 8 n the
hydrocarbon converter 3 and the C02 converter 9 and is adapted to, if ary, extract
surplus heat not required to reach the conversion temperature in the C02 converter 9 from the
connection or to introduce heat from other areas of the plant, if necessary.
The second heat exchanger unit 26 is in thermally conductive contact with the connection
between the C02 converter 9 and the mixing chamber 21 and is adapted to t surplus heat
from the connection and thus to t surplus heat contained in the hot CO. This surplus heat
may be used e.g. to preheat the C02 that is introduced into the C02 converter 9. For this heat
transfer a so-called counter flow heat exchanger unit as known in the art would be particularly
suitable.
The third heat exchanger unit 27 is in thermally conductive contact with the connection between
the hydrocarbon converter 3 and the mixing chamber 21 and is adapted to extract surplus heat
from the connection and thus from the hot en contained therein. The heat extracted at
one of the first, second or third heat exchanger units may be used to heat other areas of the
plant, specifically to keep the 002 converter warm or to t the C02 that is introduced into
the C02 converter. A portion of the heat may be converted into electricity, for instance by a
steam generator and a steam turbine or by another suitable apparatus.
The operation of plant 20 for generating sis gas is, with respect to the operation of the
arbon converter 3 and the C02 converter 9, similar to the above described operation of
plant 1 according to Fig 1. ln plant 20 for generating synthesis gas, a desired mixing ratio of
en to CO is set in the mixing chamber and is discharged through the synthesis gas outlet
24 of the mixing chamber, depending on the desired composition of the synthesis gas.
Preferably, but not necessarily, the hydrogen is provided by the arbon converter 3, as
was described. Other hydrogen sources may be considered, particularly a second hydrocarbon
converter 3, particularly a low ature hydrocarbon converter. If not the entire available
amount of CO and/or the entire available amount of H2 are used, those parts of the gases CO
and H2 that are not mixed in the mixing r may be processed separately.
Fig. 3 shows a plant 30 for generating tic functionalised and/or non-functionalised
hydrocarbons that comprises a plant 1 for converting carbon e into carbon monoxide (as
shown in Fig. 1) and a CO converter 31. Those parts of the plant corresponding to plant 1 are
not explained in detail in order to avoid repetitions. The CO converter 31 is located downstream
from the 002 converter 9 and comprises a CO inlet 32 for introducing CO, a H2 inlet 33 for
introducing hydrogen and a hydrocarbon outlet 34 for discharging synthetic functionalised
and/or non-functionalised hydrocarbons. The CO inlet 32 of the CO converter 31 is connected to
the CO outlet 12 of the CO2 converter 9 by means of the CO connection 35. The H2 inlet 33 of
the CO converter 31 is connected to the H2 outlet 6 of the hydrocarbon converter 3 by means of
the H2 connection 36.
The plant 30 for generating hydrocarbons optionally also comprises the heat exchanger units
, 26, 27 bed in conjunction with plant 20 (Fig. 2), wherein all of these operate in the
above bed way (see description to Fig. 2).
The CO converter 31 may be any CO converter for generating synthetic onalised and/or
non-functionalised hydrocarbons. In the embodiment shown in Fig. 3, the CO converter is
preferably a Fischer—Tropsch converter, a Bergius-Pier converter or 3 Pier converter with a
suitable catalyst and a control unit for temperature and/or pressure.
In one embodiment, the CO converter 31 comprises a Fischer-Tropsch ter. A Fischer—
Tropsch converter catalytically converts a synthesis gas into hydrocarbons and water. Several
embodiments of Fischer-Tropsch reactors and Fischer-Tropsch processes are known to the
person skilled in the art and are not explained in detail. The main reaction equations are as
follows:
n CO + (2n +1)H2 —> CnH2n+2 + n H20 for alkanes
n CO + 2n H2 —> CnHzn + n H20 foralkenes
n CO + 2n H2 —> CnH2n+1OH + (n—1)HZO for alcohols
The Fischer—Tropsch processes may be carried out as high temperature processes or as low
ature processes, wherein the process temperatures are usually in the range of 200 to
400°C. Known variants of the Fischer-Tropsch process are, among others, the Hochlast
synthesis, the Synthol synthesis and the SMDS process of Shell (SMDS = Shell Middle Distillate
Synthesis). A Fischer-Tropsch ter typically produces a hydrocarbon compound of wet
gases ne, butane), petrol, kerosene, soft paraffin, hard paraffin, methanol, e,
Diesel fuel or a mixture of several of these. It is known to the person skilled in the art that the
Fischer-Tropsch synthesis is exothermic. The heat of reaction from the Fischer-Tropsch process
may be used e.g. by means of a heat exchanger unit (not shown in the s) to preheat the
002. As an example, a two—step preheating process for the 002 to be introduced into the 002
converter 9 is ered, wherein a first preheating step is ed with the surplus heat of the
CO converter 31 (in the embodiment of a Fischer—Tropsch converter) and subsequently a step
of further g of the 002 by means of the heat from one or more of the heat exchanger units
, 26, 27.
in an alternative ment, the CO converter 31 comprises a Bergius—Pier ter or a
combination of a Pier converter with a MtL converter (MtL = Methanol—to-Liquid).
In a Bergius-Pier reactor, the Bergius-Pier process, which is well known to a person skilled in
the art, is carried out, wherein hydrocarbons are generated by hydrogenation of carbon with
hydrogen in an exothermic chemical reaction. The range of products from the Bergius-Pier
process depends on the reaction conditions and control of the reaction process. Mainly liquid
products are obtained, which may be used as transportation fuels, for instance heavy and
medium oils. Known variants of the Bergius—Pier s are for instance the Konsol process
and the H-Coal process.
In the above mentioned ation of a Pier ter with a MtL converter, at first sis
gas is converted into methanol according to the Pier process. The MtL converter is a converter
that converts methanol into petrol. A widespread process is the MtL process of ExxonMobil
tively Esso. Starting material of the MtL converter is typically methanol, for instance from
the Pier converter. The exit product generated by the MtL converter typically is , which is
suitable for the operation of an Otto engine.
it may be summarized that the CO converter 31, less of the operating principles
ned above, generates synthetic functionalised and/or non—functionalised hydrocarbons
from CO and H2 as its output or end products. By means of a heat exchanger unit, the process
heat produced during the exothermic conversion in the CO converter 31, may be used to heat
different sections of the plant or to generate electricity in order to se the efficiency of the
described plant.
As far as a mixture of hydrocarbons, which cannot be further processed ly or sold
profitably as a final product after separation and specification, is obtained as exit products of the
CO converter 31, these hydrocarbons, for instance methane or short—chain paraffins, may be
recycled into the process described above. For this purpose, the plant 30 ses a recycle
connection 39, which can direct a portion of the synthetically generated hydrocarbons back to
the hydrocarbon inlet 4 of the hydrocarbon converter 3. Depending on the composition of the
recycled, synthetically generated hydrocarbons, a treatment or separation step of unsuitable
hydrocarbons is carried out prior to introducing the unsuitable hydrocarbons into the
hydrocarbon inlet 4.
Fig. 4 shows a further ment of a plant 40 for generating synthetic functionalised and/or
non-functionalised arbons. The plant 40 ses the above described plant 20 for
generating a synthesis gas as well as a CO converter 31 as described above with nce to
the ment in Fig 3. The synthesis gas outlet 24 of the mixing chamber 21 is connected to
the CO converter 31. The mixing chamber 21 is set in such a way that it provides a synthesis
gas specifically adapted to the needs of the CO converter 31 in use at the synthesis gas outlet
24. The other elements of plant 40 are the same as described above and the operation of the
individual elements essentially takes place in the way bed above.
It is considered that, depending on the size of the plant, a plurality of hydrocarbon converters
are operated in parallel in order to provide the desired conversion capacity. As mentioned
above, the hydrocarbon converters may be constructed as high temperature hydrocarbon
converters and/or as low temperature hydrocarbon converters. A high temperature hydrocarbon
ter operates at temperatures above 1000°C and a low temperature hydrocarbon
converter operates at temperatures between 200 and 1000°C, wherein an additional source of
, for instance a microwave unit, may be provided in order to achieve decomposition of the
arbon into carbon and hydrogen.
As an example for a plant with a plurality of parallel operated arbon converters, Fig. 5
shows a further embodiment of plant 30 for generating synthetic functionalised and/or non-
functionalised hydrocarbons. Fig. 5 uses the same reference numerals as in earlier
embodiments, as far as the same or similar elements are described. in the embodiment shown
in Fig. 5, a combination of a high temperature hydrocarbon converter 33 and a low temperature
hydrocarbon converter 3b is shown instead of a single hydrocarbon converter 3.
The high ature hydrocarbon converter 3a comprises a hydrocarbon inlet 4a, a first outlet
5a to discharge carbon and a second outlet 6a to discharge hydrogen. Again, a single outlet 5a
may be provided for a e (particularly an aerosol) of carbon and en. The outlet 5a is
ted to the inlet 11 of the COZ converter 9 by a connection 8. The optional outlet 6a of the
high ature arbon converter 3a is connected to the H2 inlet 33 of the CO converter
31. The high temperature hydrocarbon converter 3a may optionally comprise a further outlet for
carbon (not shown in Fig 5).
The low temperature hydrocarbon converter 3b comprises a process r having a
hydrocarbon inlet 4b, a first outlet 5b to divert carbon, a second outlet 6b for discharging
hydrogen and an optional third outlet 7b for discharging carbon. Preferably, the low temperature
arbon converter 3b comprises a separation unit for separating hydrogen and carbon after
decomposition and for directing the en and carbon to their respective outlets. The first
outlet 5b is optionally connected to inlet 11 of the C02 converter 9 via connection 8, but may
also be connected to a carbon collection unit. The outlet 6b of the low temperature arbon
converter 3b is connected to the H2 inlet 33 of the CO converter 31. The optional third outlet 7b
is ted to a carbon collection unit from which collected carbon may be withdrawn, for
instance as carbon black, activated coal or in another form.
The hydrocarbon introduced into the hydrocarbon inlet 4a and the hydrocarbon introduced into
the hydrocarbon inlet 4b may be the same hydrocarbon or may be different hydrocarbons. A
hydrocarbon from a first hydrocarbon source may be introduced into the hydrocarbon inlet 4a,
for instance natural gas from a l gas source. However, e.g. functionalised and/or non-
functionalised, synthetically generated hydrocarbon may be introduced into the hydrocarbon
inlet 4b of the low temperature hydrocarbon converter 3b, for instance via the earlier mentioned
optional recycle connection 39. Because of the utilisation of several parallel operated
hydrocarbon converters 3a, 3b, the plant 30 may be scaled easier, may be controlled ,
and different kinds of carbon may be produced.
Furthermore, the high ature hydrocarbon converter 3a may for instance be used
advantageously to generate “hot” carbon, preferably at a temperature over 1000°C, for the 002
conversion process in the C02 converter 9. In particular, the high temperature hydrocarbon
ter 3a may operate in this case without a separation unit, since the C-Hz mixture,
obtained by decomposing, may be introduced directly into the COZ converter. In this case, the
002 converter 9 produces a synthesis gas having a C-Hz mixing ratio of e.g. about 1:1 at the
outlet.
The low temperature hydrocarbon converter 3b, however, is primarily used in order to provide
additional hydrogen for the generation of a synthesis gas or a C'Hz mixture having a C-Hz
mixing ratio of greater than 1:1, in ular greater than 1:2 in the CO converter 31. As no heat
transfer from the low ature arbon converter 3b to a subsequent process is
necessary, the low temperature hydrocarbon converter 3b may advantageously be operated at
temperatures below 1000°C and preferably at the lowest possible temperature.
Thus, a portion of the carbon produced in the hydrocarbon converters 3a, 3b rably the
portion from the high temperature hydrocarbon converter 3a) may be introduced into the 002
converter 9 during the ion of plant 30, whereas another portion (preferably the portion
from the low temperature hydrocarbon ter 3b) may be discharged from the process as
raw material for producing further products. Such products are for instance carbon black or
rial soot, activated coal, special kinds of carbon such as carbon discs and carbon cones
etc., which is obtained as black powdery solid matter. This carbon is an important technical
product, which may be used e.g. as filler in the rubber industry, as pigment soot for printing
colours, inks, paints or as starting al for the generation of electrical components, for
ce zinc-carbon-batteries and for the production of cathodes or anodes. Any surplus
hydrogen may be discharged for the chemical industry or may be used for generating electricity
(by burning), whereby the low temperature hydrocarbon ter 3b is preferably operated in
such a way that it only provides the necessary additional hydrogen.
Fig. 6 shows an alternative embodiment of the above described plant 40 for generating
synthetic functionalised and/or non—functionalised hydrocarbons, for which a plurality of parallel
operated high temperature and/or low temperature hydrocarbon converters are provided as
well.
The plant 40 for generating hydrocarbons shown in Fig. 6 differs from the plant 30 shown in Fig.
in such a way that a mixing chamber 21 is located am of the CO converter 31. The
mixing chamber 21 mixes a synthesis gas specifically adapted to the CO converter 31 and
es the synthesis gas to the CO converter 31. The ts depicted in Fig. 6 have
already been described above and work ing to the principles described above. Therefore,
no ed description is given in order to avoid repetitions.
Fig. 7 and 8 show embodiments of the plants 20 and 30 comprising a first heat exchanger unit
, a second heat exchanger unit 26 and a third heat exchanger unit 27, wherein each is
connected to an engine/generator device 45. The engine/generator device 45 is d to at
least partially generate electricity from surplus heat from ent sections of the plant, wherein
said electricity may either be fed into the main grid or may be used to operate the plant 20,
especially the hydrocarbon converter(s). Further, the engine/generator device 45 may be
connected to a heat exchanger unit (not shown in Fig. 8), which dissipates the heat generated
by the exothermic conversion process taking place inside the CO converter 31. Thus, on the
one hand the CO converter may be cooled in a controlled and regulated way, which is
advantageous for the operation of the process, and on the other hand electricity may be
generated. The engine/generator device 45 may be any device that is adapted to transform heat
energy into electricity, for instance a combination of a steam turbine and a generator or a piston
engine and a generator.
During operation, the /generator device 45 transforms the surplus heat of the plant into
electricity, i.e. the heat that is not necessary for 002 conversion.
The engine/generator device 45 and the heat exchanger units 25, 26 and 27 are optional
ts that may be used at all plants described above. Due to the operation temperature in
the respective arbon converter 3, 3a, 3b, the carbon discharged from the respective
second outlets 7, 7a, 7b also contains significant amounts of heat energy. Depending on the
desired temperature of the discharged carbon, a large amount of this heat energy may be
dissipated by means of heat exchanger units (not shown in the figures) and the heat may be
reused in the processes bed herein and/or may be transformed into electricity using the
engine/generator device 45.
In the plants 30 and 40 for generating synthetic functionalised and/or non-functionalised
hydrocarbons, cooling of the hydrogen from the hydrocarbon converters 3, 3a, 3b and/or cooling
of the CO from the C02 converter 9 is performed only as far as the temperature of the
hydrocarbons and of the hydrogen does not fall below the operating temperature of the CO
converter 31. The operating ature of the CO converter 31 is usually between 200 and
400°C, ing on the chosen process.
in all plants bed above, the hydrocarbon converter 3 may be a high ature reactor
operating at a temperature of more than 1000°C (e.g. a high temperature Kvaerner reactor) or a
low temperature reactor operating at a temperature between 200°C and 1000°C (e.g. a low
temperature Kvaerner r). A presently tested low temperature reactor operates at
temperatures between 300 and 800°C. In the case of a low temperature reactor operating at
temperatures n 200 and 800°C, it is considered that the introduced carbon is preheated
in the connection 8 between the hydrocarbon converter 3 and the C02 converter 9, as the C02
converter 9 operates at temperatures between 800 and 1000°C. Further, it becomes clear from
Fig. 7 and 8 that a combination between high temperature and/or low temperature converters
may be used in all plants 1, 20, 30 and 40 described above.
In all plants 1, 20, 30 and 40 bed above, a portion of the carbon generated in the
hydrocarbon ters 3, 3a, 3b may be discharged as carbon black, as ted coal or as
another raw al as long as said carbon is not converted in the C02 converter 9 of plant 1,
, 30, 40. It shall further be noted that also a n of the hydrogen ed in the
hydrocarbon converter 3 may be directly discharged out of the process and may be sold as
commodity. Further, undesired synthetic functionaiised and/or nctionalised hydrocarbons
generated in the CO converter 31 may be returned and fed into the hydrocarbon inlets 4, 4a, 4b
of the hydrocarbon converter 3 in all plants 30 and 40 described above.
it is considered that the C02 introduced into the 002 converter 9 is a exhaust gas from a
combustion power plant or that the 002 is generated in another rial process. Recently,
emphasis is put on releasing smaller amounts of 002 into the environment, as C02 is seen as a
climate poiiutant. In the above mentioned exhaust gases, the 002 is mixed with other gases
including, amongst others, a large amount of nitrogen from the air. With none of the above
bed plants 1, 20, 30, 40 is it necessary to te the nitrogen prior to introducing the
mixture of 002 and other gases into the C02 converter 9. As far as these other gases are only
present in small amounts or are chemically inert (e.g. nitrogen), the operation of the C02
converter 9 is not compromised by the additional gases. A residual component of oxygen is
burned in the C02 converter at the high operating temperature in presence of carbon.
Some examples follow for further clarification:
Example 1: CO_2 neutral gas power plant
By means of a Kvaerner reactor as the hydrocarbon converter 3, methane is decomposed into
carbon and hydrogen. For each atom of carbon, two molecules of en will be obtained
(CH4 —> C + 2 H2). Starting from a conventional natural gas power station, for ce of the
type lrsching lV, manufactured by Siemens AG, having a nominal capacity of 561 MW, the CO;
contained in the t gas is introduced into the 002 converter 9 — about 1.5 million tons a
year. The 002 from the exhaust gas of the natural gas power plant is reduced with half of the
carbon discharged from the hydrocarbon converter 3. The hydrogen from the hydrocarbon
converter 3 is cooled down and the dissipated heat is transformed into electricity by means of
the engine/generator device 45. The C02 from the l gas power plant is directed over hot
carbon inside the C02 converter 9 and is converted into twice the amount of carbon monoxide
according to the Boudouard brium (C02 + C —> 2 CO). The hot carbon monoxide exiting
from the C02 ter 9 is cooled down, and the dissipated heat is transformed into electricity.
The carbon monoxide from the C02 ter 9 (Boudouard equilibrium) and the hydrogen from
the hydrocarbon converter 3 (Kvaerner process) are converted in a CO converter 31 (Fischer—
Tropsch plant) to form arbons. A Heavy Paraffin Synthesis module connected to a
subsequent Heavy Paraffin Conversion module from the SMDS-process (= Shell Middle
Distillate Synthesis process) manufactured by Shell is preferred. The heat from the process is
transformed into electricity. The nature of the resulting hydrocarbons depends on the chosen
Fischer-Tropsch process and may be varied in the Shell SMDS process.
In the specific natural gas power plant (561 MW) having an efficiency of 60.4%, assuming an
efficiency of 60% when transforming the process heat into electricity and assuming an efficiency
of 50% when transforming dissipated heat into electricity, the process has the following
parameters:
Consumption of methane 2515 million 8 m3 CH4 per year
Generation of electricity 313 MW
Carbon black tion 447 000 tons per year
Paraffin production 1.0 million tons per year
C02 on almost 0
ency natural gas power plant 33.7%
Total 66.8%
Example 2: Gas-to-Liguid Plant
If the plant from example 1 is operated without transforming the process heat and the dissipated
heat into electricity, then no significant amount of electricity is generated. in this case, the
e is a process for converting gaseous materials (carbon dioxide and methane) into liquid
fuels (Otto and Diesel fuels, kerosine), Le. a Gas—to-Liquid or GtL plant. in the present example,
an additional amount of carbon is produced.
The ters are as follows:
Consumption of methane 2515 million S m3 CH4 per year
Generation of electricity 0 MW
Carbon black tion 447 000 tons per year
Paraffin production 1.0 million tons per year
002 emission almost 0
The ion has been explained in some detail with respect to specific embodiments and
examples without being limited to these examples. In particular, the elements of the individual
embodiments may be combined and/or exchanged with each other, if compatible. The skilled
person will become aware of manifold modifications and ions within the scope of the
following claims. In a particularly simple embodiment of the plant for generating synthetic
functionalised and/or non—functionalised hydrocarbons, the 002 converter may be designed e.g.
as a simple pipe (for instance as an outlet pipe of a high temperature hydrocarbon ter not
having a separation unit), wherein a COZ pipe leads to said pipe. The 002 pipe should join said
pipe such that the two gas streams get well mixed. The pipe should be insulated and could be
connected to a heating unit e.g. at an inlet n in order to heat up the pipe (especially at the
beginning of the operation) to an operating temperature. Further downstream, the pipe could be
connected to a heat exchanger unit adapted to extract surplus heat and to use this heat for
heating other sectors of the plant and/or for generating electricity. Additionally, the pipe may
comprise an inlet pipe for hydrogen (for instance downstream of the heat exchanger unit) so
that the same pipe not only functions as a 002 converter, but also functions as a mixing
chamber for generating a synthesis gas. The inlet pipe for en may ate e.g. from an
outlet for hydrogen of a low ature hydrocarbon converter (having a separation unit). In
this case, an output end of the pipe, where a synthesis gas having a predetermined mixing ratio
may be discharged, could end in a CO converter.
Claims (37)
1. A method for converting carbon dioxide 002 into carbon monoxide CO comprising the following steps: decomposing a hydrocarbon containing fluid into carbon and hydrogen by means of introduction of energy in a hydrocarbon converter, the energy at least partially being provided by heat, wherein the carbon and the hydrogen have a temperature of at least 200°C after the decomposing step; directing at least a portion of the carbon generated by the decomposing step from the arbon converter into a C02 converter; introducing 002 gas from a power plant or from another industrial process into the C02 ter; mixing the CO; gas with at least a portion of the carbon generated by the decomposing step, wherein upon mixing the carbon with the C02 gas, the carbon obtained by the decomposing step has cooled down by no more than 50% in °C with respect to its temperature after the decomposing step; converting at least a portion of the C02 gas and the carbon obtained by the osing step into CO at a temperature between 800 and 1700°C.
2. The method for converting 002 into CO according to claim ‘I, wherein the decomposing step takes place at a temperature above 1000°C, and wherein the carbon is mixed with the C02 gas at a temperature of at least 800°C.
3. The method for converting C02 into CO ing to claim 1 or 2, wherein the heat required to reach the temperature of between 800 and 1700°C for the 002 conversion originates essentially tely from the heat that is provided for decomposing the hydrocarbon containing fluid.
4. The method for ting C02 into CO according to any one of the preceding claims, n the carbon obtained by the decomposing step and the en obtained by the decomposing step are jointly mixed with the C02 gas.
5. The method for converting C02 into CO according to any one of claims 1 to 3, wherein the carbon obtained by the decomposing step is separated from the hydrogen obtained by the osing step prior to the step of mixing the carbon with the 002 gas.
6. The method for converting CO; into CO according to any one of the preceding claims, wherein at least a portion of the heat of at least a portion of the carbon obtained by the decomposing step and/or of a portion of the hydrogen obtained by the decomposing step is used to heat the 002 gas prior to mixing the C02 gas with carbon and/or is used to heat the process chamber, in which the C02 gas is mixed with the carbon.
The method for converting COz into CO ing to any one of the preceding , wherein the CO has a temperature of 800 to 1700°C after conversion, and wherein at least a portion of its heat is used to preheat the C02 gas prior to mixing with the carbon.
The method for converting C02 to CO according to any one of the preceding claims, wherein at least a portion of the heat of at least a portion of the carbon obtained by the decomposing step and/or a portion of the hydrogen obtained by the decomposing step and/or a portion of the CO, after conversion to CO, is used for generating electricity, wherein the electricity may be provided as energy carrier for introducing energy for decomposing the hydrocarbon containing fluid.
The method for converting C02 into CO according to any one of the preceding claims, wherein the energy is primarily introduced by means of a plasma.
10. The method for converting CD; into CO according to any one of the preceding claims, wherein the decomposing step is performed in a Kvaerner reactor.
11. A method for generating a synthesis gas, n C02 is converted into CO according to the method of any one of the preceding claims; and wherein hydrogen is mixed with the CO.
12. The method for generating a synthesis gas ing to claim 11, wherein onal hydrogen is added to the synthesis gas, and wherein the additional en is generated by decomposing a hydrocarbon containing fluid into carbon and en by introduction of energy that is at least partially provided by heat.
13. The method for generating a synthesis gas according to claim 12, n at least a portion of the additional en is generated by decomposing a hydrocarbon containing fluid at a temperature below 1000°C by means of a microwave plasma.
14. The method for generating a synthesis gas ing to claim 13, wherein the temperature is below 600°C.
15. The method for generating a synthesis gas according to any one of claims 11 to 14, wherein the ratio of CO to hydrogen of the synthesis gas has a value of 1:1 to 1:3.
16. The method for generating a synthesis gas according to claim 15, wherein the ratio of CO to hydrogen of the synthesis gas has a value of about 122.1.
17. A method for generating synthetic functionalised and/or non-functionalised arbons, wherein at first a sis gas is generated according to the method of any one of claims 11 to 16, and wherein the synthesis gas is brought into contact with a suitable catalyst in order to cause conversion of the synthesis gas into synthetic functionalised and/or non- functionalised hydrocarbons, wherein the temperature of the catalyst and/or the synthesis gas is open-loop lled or close-loop regulated to a ermined range of temperature.
18. The method for generating synthetic functionalised and/or non-functionalised hydrocarbons according to claim 17, wherein the conversion of the synthesis gas is carried out by means of a Fischer-Tropsch process.
19. The method according to claim 18, wherein the Fischer-Tropsch process is a Shell Middle Distillate Synthesis (SMDS) process.
20. The method for generating synthetic functionalised and/or non-functionalised hydrocarbons according to claim 17, wherein the sion of the synthesis gas is carried out by means of a Bergius-Pier process, a Pier process or a combination of a Pier process and a Methanol-to-Liquid (MtL) s.
21. The method according to any one of the preceding claims, n the hydrocarbon containing fluid to be decomposed is natural gas, methane, wet gases, heavy oil or a e thereof.
22. An apparatus for converting carbon dioxide C02 into carbon monoxide CO comprising: a hydrocarbon ter for decomposing a hydrocarbon containing fluid into carbon and hydrogen, wherein the hydrocarbon converter comprises at least one process chamber having at least one inlet for a hydrocarbon containing fluid and at least one outlet for carbon and/or hydrogen and wherein the hydrocarbon converter comprises at least one unit for introducing energy into the process chamber, the energy consisting at least partially of heat; a C02 converter for converting C02 into CO, the C02 converter comprising at least one further process r having at least one inlet for C02 d to introduce 002 from a power plant or from another industrial process into the C02 converter, at least one inlet for at least carbon, and at least one outlet, wherein the inlet for at least carbon is directly connected to the at least one outlet of the hydrocarbon converter.
23. The apparatus for converting carbon dioxide C02 into CO according to claim 22, wherein the at least one unit for introducing energy into the process chamber is designed in such a way that it can generate, at least y, temperatures above 1000° C. 24. The tus for converting carbon dioxide C02 into carbon monoxide CO according to claim 22 or 23, wherein the at least one unit for introducing energy into the process r comprises a plasma unit.
24. The apparatus for converting carbon dioxide C02 into carbon monoxide CO according to claim 24, wherein the plasma unit is a microwave plasma unit.
25. The apparatus for converting carbon dioxide C02 into carbon monoxide CO according to any one of claims 22 to 24, wherein the process chamber of the 002 converter is formed by an outlet pipe of the hydrocarbon converter, wherein the outlet pipe is connected to an inlet for 00;; gas.
26. The apparatus for converting carbon dioxide C02 into carbon monoxide CO according to any one of claims 22 to 25, further comprising a tion unit for separating the carbon obtained by osing and the hydrogen obtained by decomposing and having separate outlets for the separated materials coming from the tion unit, wherein the outlet for carbon is connected to the C02 converter.
27. The tus for converting carbon dioxide CO; into carbon monoxide CO according to any one of claims 22 to 26, wherein the hydrocarbon converter comprises a Kvaerner reactor.
28. An apparatus for generating a synthesis gas comprising an apparatus according to any one of claims 22 to 27 and at least one separate inlet pipe for hydrogen leading into the CO converter or into a mixing chamber located ream the C02 converter.
29. The apparatus for generating a sis gas according to claim 28 having at least one additional hydrocarbon converter for decomposing a hydrocarbon containing fluid into carbon and hydrogen, the additional hydrocarbon converter comprising: at least one process chamber having at least one inlet for the hydrocarbon containing fluid; at least one unit for introducing energy into the process chamber of the additional hydrocarbon, the energy at least partially consisting of heat; a separation unit for separating the carbon obtained by decomposing and the hydrogen obtained by decomposing, the separation unit having separate outlets for carbon and hydrogen, wherein the outlet for en is connected to the separate inlet pipe for
30. The apparatus for generating a synthesis gas according to claim 29, wherein the at least one additional hydrocarbon converter is of a type ng out decomposing at temperatures below 1000°C by means of a microwave plasma.
31. The apparatus for generating a synthesis gas ing to claim 30, wherein the temperature is below 600°C.
32. An apparatus for converting a synthesis gas into synthetic functionalised and/or non- functionalised arbons comprising: an apparatus according to any one of claims 28 to 31; and a CO ter having a process chamber, in which a catalyst is located, and means for bringing the synthesis gas into contact with the st, and a control unit open-loop controlling or close-loop regulating the temperature of the catalyst and/or the synthesis gas to a predetermined temperature.
33. The apparatus ing to claim 32, wherein the CO converter comprises a Fischer- h converter.
34. The apparatus according to claim 33, wherein the Fischer-Tropsch converter is a SMDS converter.
35. The apparatus according to claim 32, wherein the CO converter comprises a Bergius pier converter, a Pier converter or a combination of a Pier ter with a MtL converter.
36. The apparatus ing to any one of claims 32 to 35 further comprising a l unit for open—loop controlling or close-loop regulating the pressure of the synthesis gas in the CO converter.
37. The method according to any one of claims 1 to 21, substantially as herein described with reference to any one of the Examples and/or
Applications Claiming Priority (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102011122562 | 2011-12-20 | ||
DE102011122562.9 | 2011-12-20 | ||
DE102012008933 | 2012-05-04 | ||
DE102012008933.3 | 2012-05-04 | ||
DE102012015314.7 | 2012-08-02 | ||
DE102012015314A DE102012015314B4 (en) | 2011-12-20 | 2012-08-02 | Process and plant for the production of carbon monoxide |
PCT/EP2012/005309 WO2013091878A1 (en) | 2011-12-20 | 2012-12-20 | Process and system for conversion of carbon dioxide to carbon monoxide |
Publications (2)
Publication Number | Publication Date |
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NZ625687A NZ625687A (en) | 2016-06-24 |
NZ625687B2 true NZ625687B2 (en) | 2016-09-27 |
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