The invention relates to a method for separating carbon dioxide (CO2) from flue gases by using an adsorption method, wherein the CO2 is accumulated on an adsorber. In addition, the invention relates to an associated device for executing the method.
The reduction in the emission of the greenhouse gas carbon dioxide (CO2) from power plants and industrial plants can be achieved through the use of low-carbon fuels.
The latter is however not a solution for existing plants which are designed to use high-carbon fuels, such as lignite-fired power plants in particular. Separation processes are required here which remove the CO2 for example from the flue gas, or the waste gas.
All the gases arising during the combustion process are referred to as flue gases, whereby the expression waste gas is used throughout in the following.
The removal of CO2 from waste gas can take place by means of physical or/or chemical binding in the bulk (“absorption”) or by means of accumulation on active surfaces (“adsorption”).
With regard to the physical or chemical absorption, in both cases these are multi-step processes in which the waste gas containing CO2 is brought into contact with a physical or chemical absorber until the latter is completely charged with CO2. Thereafter the absorber must be discharged, whereby the CO2 is released in the presence of a scrubbing gas and is finally separated from the absorber.
Potential problems in this situation are the slippage of the substance required for the binding, in other words the absorber, the separation of the CO2 from the scrubbing gas in a form which permits the further use of the CO2, and where applicable the high energy requirement for the regeneration, particularly in the case of chemical binding.
The binding of CO2 by means of ammonia has recently been proposed, a method that has long been known from the synthesis of ammonia (see Parrish, Roger Warren: “Process for manufacture of ammonia”, EP 0247 220 B1 and the publication cited therein Uhde, Georg Friedrich: “Method of separating ammonia from gases and mixtures of gases containing ammonia”, U.S. Pat. No. 1,745,730 A), whereby ammonia slip can occur in the case of the separation of CO2 from waste gas, and moreover the separation of CO2 and NH3, which is present in bound form as ammonium carbonate or ammonium hydrogen carbonate, presents problems.
Alternatively, it is possible to work with adsorbers, on which the CO2 is accumulated in a first process step for example at low temperature or high pressure and is desorbed in a second process step at high temperature or low pressure (so-called “pressure swing adsorption” or “temperature swing adsorption”). A problem regarding the level of efficiency exists here because the adsorption capacity is considerably less than the capacity of absorbers, whereby a high energy requirement results in order to be able to handle temperature and pressure cycles.
A method is described in DE 1 911 670 A for cleaning gases which contain acidic components such as CO2, whereby here as well as in the following three publications the further use of the cleaned gas is the primary objective and not the further use of the gas bound on an adsorber. The separation of CO2 from process gases for the semiconductor industry by means of adsorption on zeolites charged with ammonia is known from JP 04-022415, whereby the CO2 remains chemically bound at ambient temperature through reaction with the ammonia. The separation of CO2 from waste gases, for example from thermal power plants, through carbonation at temperatures between 600° C. and 800° C., is described in JP 10-272336 A. Finally, it is demonstrated in a paper published from “Applied Surface Science”, Vol. 225, No. 1-4, pp. 235-242 (2004) that a preparation of activated carbon using ammonia leads to improved binding of CO2. In none of the cases is a method disclosed which enables the CO2 removed from the gas undergoing cleaning to be prepared for further use or disposal with a justifiable expenditure of energy.
In addition, membrane methods for separating CO2 are possible which hitherto however have been unsuitable for applications in large plants for reasons of cost and efficiency level, in other words the low selectivity of the separation process between CO2 and for example N2.
Starting from this basis, the object of the invention is to propose an improved method for the large-scale reduction in emissions of carbon dioxide (CO2) and to create an associated device. In this situation, the CO2 should be separated from the waste gases such that the subsequent use for disposal of the CO2 is made possible.
This object is achieved in respect of the method by the measures described in the claims, whereby the invention emerges as a sequence of individual process steps. An associated device is the subject matter of the claims. Developments of the method and the associated device are set down in the respective dependent claims.
According to the invention it is proposed that the binding of CO2 from waste gas be performed in an adsorption reactor by means of a heterogeneous catalytic reaction with ammonia as the chemical absorber which is bound to the catalytic surface. In this situation, the process is conducted at a low temperature T with the result that the reaction products containing carbon, such as isocyanic acid (HNCO) and urea ((NH2)2CO) for example, are also bound to the catalytic surface in accordance with the following reaction equations, whereby the molecules bound to the catalytic surface are identified by an “s”:
NH3(s)+CO2⇄HNCO(s)+H2O (1)
HNCO(s)+NH3(s)⇄(NH2)2CO(s) (2)
A suitable temperature window is dependent on the catalyst used, in particular at temperatures below T=200° C., and in the case of the invention is advantageously:
70° C.<T<140° C. (1a)
At low temperatures and high surface concentrations of NH3 the equilibrium of the reaction (2) lies on the right-hand side of the reaction equation, at high temperatures or low surface concentrations of NH3 however on the left-hand side.
The catalyst is subsequently regenerated, whilst excluding the waste gas, at a higher temperature in a gas mixture consisting of water vapor and CO2, whereby CO2 is selectively released and is thereby definitively separated, while the absorption agent is returned to its original state and remains bound to the surface in this situation:
HNCO(s)+H2O→NH3(s)+CO2 (3)
Reaction (3) represents the converse of the reaction (1), which is forced to take place as a result of the fact that water vapor is made available in excess and the temperature is raised such that it lies above the window specified in (1a). As a result the equilibrium of the reaction (2) is shifted to the left-hand side because isocyanic acid (HNCO) is constantly eliminated through the hydrolysis reaction (3).
The subsequent separation of water vapor and CO2 can be achieved through condensation by means of suitable pressure and temperature control.
Alternative reaction mechanisms, which for example lead to the formation of ammonium carbamate NH2CO2−NH4+, can likewise be represented when suitable reaction parameters (low temperature) and catalysts are chosen:
2NH3(s)+CO2→NH2CO2−NH4+(s) (4)
Ammonium carbamate (NH2CO2NH4+) can be converted to ammonium carbonate by hydrolysis in an aqueous solution or on a suitable catalytic surface even at low temperatures:
NH2CO2−NH4+(s)+H2O→(NH4)2CO3 (5)
The ammonium carbonate decomposes thermally on an increase in temperature into NH3 and CO2 and water is split off:
(NH4)2CO3→2NH3(s)+CO2+H2O (6)
By using suitable catalysts it is possible to ensure that NH3 remains bound on the surface. The subsequent separation of water vapor and CO2 can again be achieved through condensation by means of suitable pressure and temperature control.
With regard to the device according to the invention, at least two reactors are present. In this situation, for the purposes of execution of the inventive method described above in terms of flow implementation it is possible to implement the following as different arrangements:
One option for the latter is to design the catalyst for example as a rotatable stack of disks which is arranged such that the catalytic surfaces alternately pass through the adsorption reactor and the regeneration reactor. As an alternative to this, the passage of catalyst particles in counterflow is possible.
The advantages of the invention described above compared with the previous methods, which function with liquids such as ammonia in aqueous solution, lie essentially in the fact that by choosing suitable catalysts with binding sites for NH3 the ammonia slip can be greatly reduced. In addition, the reaction kinetics can as a result be configured considerably more selectively, such that the formation of undesired byproducts is suppressed, which consume the absorber or result in a binding of the CO2 which is energetically strong and can be released only with a high expenditure of energy.
It is furthermore advantageous that a considerable portion of the CO2 from waste gases is separated in such a form which enables the subsequent use of the CO2 with a low expenditure of energy in order to arrive at a sustainable reduction in CO2 emissions.
By preference, oxides and mixtures of oxides such as TiO2 and V2O5 for example come into consideration as catalytic materials, whereby titanium dioxide for example is a suitable hydrolysis catalyst, while V2O5 is favorable for binding ammonia on the surface. Alternatively, ion exchanged zeolites can be employed as catalysts, which are likewise capable of binding ammonia very selectively.
Use of the method according to the invention is of particular interest with regard to CO2 separation by way of ammonia solutions at process temperatures >10° C. since in this case a proportion of NH3, dependent on temperature, in the region of several percent by volume, is still present in the separated CO2, which cannot be eliminated economically by conventional methods.
Further details and advantages of the invention will emerge from the following description of figures for exemplary embodiments with reference to the drawing in conjunction with the claims.
In schematic representation in the drawings:
In the following, the two figures are described individually in each case. In this situation the essential elements, such as the reactors and valves including the lines which comprise the same function have the same reference characters.
With regard to the
The two reactors 10 and 10′ in
At any one time one of the reactors 10, 10′ is therefore in adsorption operation while the other reactor is in regeneration operation. To this end, a reaction gas mixture, which is also referred to as regenerate, is fed from the other side of the reactors by way of the line 6 with the parallel line 6a and the respective branch lines 7 and 7a to the two reactors in alternating operation. For this purpose, valves V3, V4, V5 and V6, whose function emerges from the description of the alternating operation, are connected in the lines 6, 6a. CO2-reduced waste gas is taken away by way of the line 8 and regenerate containing CO2 is delivered to the unit 5 by way of the line 3. The separation of CO2 from the regenerate takes place in the unit 5, with the result that pure recovered CO2 is taken away here. The container for the absorption agent is designated by 4 and is operatively connected by way of a valve V9 to the fluid circuit.
The two reactors 10, 10′ in
Other embodiments according to the invention include plate reactors coated with catalysts, in particular those having movable plates or other structures having a large specific surface, in which the plates are transported in a rotary fashion from the charging area (flue gas, CO2 gas stream) by way of a lock system into the discharging area for CO2 separation purposes and back into the charging area.
In deviation to the
In the simplified illustration according to
To this end, two reactors 30 and 30′ are shown in
Otherwise, the device according to
The sensor system on the one hand and also the signal processing are not contained in the examples illustrated in
In
In
In the desorption reactor 50, a sensor 52 is provided at the input for the temperature T and a sensor 53 is provided at the output for the concentration c(Abs) of the absorption agent. The signals for the concentrations on the one hand and the temperatures on the other hand are processed in a control device which is not described individually, a known microprocessor control unit for example. An important criterion concerning the control in this situation is the fact that the adsorption capacity of the catalytic material for CO2, which is determined from current CO2 measurement values at the adsorption reactor, is maintained in an adequate manner through the storage of absorption agent on the catalytic surface. For this purpose, a valve V12 is closed in order to stop the delivery of desorption gas mixture. Valve V14 is then opened in order to deliver absorption agent (ammonia for example). Shortly thereafter valve V13 is closed in order to avoid any slip of the absorption agent. As soon as the sensor 53 in the output area of the desorption reactor 50 identifies absorption agent concentrations above a first limit value, valve V14 is closed.
During operation of the device as intended, temperature T and absorption agent concentration c(Abs) are monitored by sensors: As the temperature T drops, with an intact catalyst the storage capacity for the absorption agent rises such that the concentration c(Abs) of the absorption agent still contained in the gas phase falls below a second limit value classed as uncritical after a short waiting time and the reactor, or the catalyst charged with absorption agent, can be taken into operation again. Deviations from this behavior give indications of damage to the catalyst as a result of either mechanical, thermal or also chemical influences, whereby maintenance of the system can be undertaken where necessary.
The devices having two reactors described with reference to the figures can advantageously be used for separating CO2 from waste gases containing CO2. In this situation, the following process steps in particular take place:
As a result of this temperature control the pure dry CO2 above the water surface can then be pumped away and delivered for a further use.
Overall, it can be noted that by using the method described above and also the devices created to implement the method the separation of CO2 in particular from flue gases and in principle from CO2-containing waste gases of all types takes place in a single manner. A reduction in the CO2 emissions of climate damaging greenhouse gases is thereby made possible. It is important in this situation that the CO2 is present at the end of the stated process in an almost pure form in order that it can be compressed for example for storage in natural gas fields or oil fields whilst simultaneously increasing the production volume (so-called “enhanced oil recovery”, “enhanced gas recovery”). Of secondary significance however is the completeness of the separation of the CO2 from the flue gas: A residual quantity of 10% of the original CO2 content can remain in the flue gas without further ado if as a result for example the energy requirement for the separation can be minimized compared with the energy turnover of the plant which is emitting the flue gas.
An oxidic catalyst is advantageously used as the adsorber for the plant. In this situation the catalyst consists for example of titanium oxide (TiO2) or a mixture of titanium oxide (TiO2) and a further metal oxide, in particular dosed with vanadium oxide (V2O5). It can also consist of an ion exchanged zeolite.
The desired objective of being able to produce carbon dioxide (CO2) in pure form at the end of the process according to the invention for the purpose of further use or disposal can henceforth be achieved in an efficient manner.
Number | Date | Country | Kind |
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10 2007 030 069.9 | Jun 2007 | DE | national |
This application is the US National Stage of International Application No. PCT/EP2008/058240, filed Jun. 27, 2008 and claims the benefit thereof. The International Application claims the benefits of German application No. 10 2007 030 069.9 DE filed Jun. 29, 2007, both of the applications are incorporated by reference herein in their entirety.
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/EP2008/058240 | 6/27/2008 | WO | 00 | 12/17/2009 |