The present invention relates to an assembly to reduce the emission of CO2, the relative plants for the production of energy containing the aforesaid assembly and the processes for the production of clinkers conducted in said plants.
The use of processes and relative plants (an example of which is shown in
The formation and the emission of CO2 in a plant for the production of clinkers is associated with the following processes:
In the state of the art, different methodologies have been used to reduce these emissions, such as the use of low-carbon fuels (such as natural gas) or the use of biomass (with a neutral impact on CO2 emissions), improving the energy efficiency of the plants, reducing the clinker/cement ratio [1]. Nevertheless, the potential reduction of CO2 emissions using these techniques is limited as the above-mentioned methodologies are not able to reduce the CO2 emitted by the raw material calcination, which, as mentioned before, accounts for about 60% of the total emissions of a plant. To achieve significant reductions in CO2 emissions, it is therefore essential to adopt CO2 capture and storage (Carbon Capture and Storage—CCS) systems.
Among the various known technologies proposed for the abatement of greenhouse gases in the cement industry, some of the most promising are based on the Calcium Looping (CaL) system. This process is based on the use of calcium oxide (CaO) as a sorbent for the removal of CO2 from a gas stream, according to the reversible carbonation-calcination reaction:
The CaL process has been integrated in cement plants according to two configurations. The first form of integration of the CaL system is the configuration called “Tail End CaL” (
The second configuration known for the use of the CaL process in a cement plant is “Integrated CaL” (
This configuration is characterized by the following main aspects:
This second configuration was recently studied from a technical and economic point of view by De Lena et al. in [11] and demonstrates better energy performances compared to the “Tail-End CaL” configuration. The documents MI2012A00382, MI2012 A003832012 and WO 2013/024340 A1 illustrate some examples of the second configuration.
The use of the “Integrated CaL” configuration, as mentioned, has advantages from an energy point of view compared to the “Tail End CaL” configuration. The main disadvantages of the “Integrated CaL” configuration are linked to:
The need is therefore felt to have a process for the production of clinkers integrated with the CO2 abatement system that has greater operability without negatively affecting the energy performance of the overall system.
US 2018/0028967 discloses a method and the relative system for capturing and separating carbon dioxide from exhaust gas. The system comprises a first calciner, a carbonator, connected to the first calciner, and a second calciner, connected to the carbonator. The CO2 capture method exploits the calcination reactions of the CO2-rich sorbent (CaCO3) in the CO2-poor sorbent (CaO|) and in CO2, and the inverse carbonation reaction of the CaO and CO2 in CaCO3. The plant comprises a calciner, a carbonator connected to said calciner and to a second calciner to which the rotary kiln is connected. This system provides for a recirculation between the second calciner and the carbonator; therefore, it also features the problems of the Integrated CaL technique associated with the presence of the recirculation between carbonator and calciner, that is the reduction of the activity of the sorbent used for gas absorption, which decreases as the number of carbonation-calcination cycles increases [12]) and the presence of a recirculation of solids between carbonator and calciner, which leads to possible difficulties in controlling the process.
WO2008/151877 A1 discloses a method and the relative plant for the simultaneous production of electricity and cement clinker. The system comprises two separate lines of preheaters, each of which comprises a calciner, a rotary kiln and a clinker cooler, and is characterized in that the combustion air as well as the cement “raw flour”, which are supplied to the calciner, do not contain alkali and chlorides.
The Applicants have now found that it is possible to overcome the problems of the state of the art with an assembly comprising:
This assembly is characterized in that the carbonator is free of recirculation to both said two calciners.
In this way, with the plant comprising the aforesaid assembly, the technical problems of the Integrated CaL system and of the plant disclosed in US 2018/0028967 are overcome.
In fact, the absence of recirculation between the carbonator and the two calciners connected thereto maintains the maximum activity of the sorbent and at the same time there is a greater control over the operating conditions of the process.
Further object of the present invention are the plants comprising said assembly associated with the actual production plant, which differ in the fact that the actual plant is of the conventional type and has been installed before the assembly and is already operational, or it is an ex novo plant in which both the actual plant units and the assembly units have been installed simultaneously with the units belonging to the actual plant for the production of clinkers.
A further object is the clinker production process conducted in the aforesaid plants and which in particular comprises the following steps:
For the purposes of the present invention, the definition “comprising” does not exclude the presence of additional units/steps not expressly listed after this definition; on the contrary, the definition “consisting of” or “constituted by”, excludes the presence of additional steps/units in addition to those expressly listed.
For the purposes of the present invention, assembly means the Dual-calciner calcium looping (Du-CaL) configuration, characterized by the presence of two calciners, between which a carbonator is arranged, and of which one of said calciners is an integral part of a conventional clinker production system.
For the purposes of the present invention, primary calciner means the calciner that receives the preheated raw material and that precedes the carbonator, whereas secondary calciner means the calciner that receives the material exiting from the carbonator and prepares it before being introduced into the rotary kiln. According to a preferred solution in the assembly according to the present invention one of said two calciners is the primary calciner (Primary calciner); while the other calciner, arranged downstream of the carbonator (Carbonator) is the secondary calciner (Secondary calciner). In addition, one of the two calciners is an integral part of the conventional clinker production system and can therefore continue to operate in the clinker production process even if the CO2 capture system which uses the carbonator and the other calciner is disconnected due to malfunctions or maintenance.
The plants containing said assembly or Du-CaL configuration associated with units of plants of conventional type for the production of the clinker and which differ in that the actual units of conventional type dedicated to the production of clinkers existed before or have been installed at the same time as the assembly or Du-CaL configuration are a further object of the invention. It is understood that when the calciner is present in the pre-existing units of the plant for the production of clinkers, this can be adapted in the new configuration to perform the function of both primary calciner and secondary calciner, depending on the specificity of the plant in which the process is integrated.
The assembly object of the invention is arranged, with reference to the stream of solid material, upstream of the units of the conventional plant for the production of the clinker. These two plants are distinguished because in the case of plant 4 of
According to a preferred solution, the calciner indicated in the figures as “Secondary calciner” is also an integral part of the units of the conventional plant intended for the production of clinkers.
In both figures, downstream of the secondary calciner there is arranged the rotary kiln or “Rotary kiln” as shown in the figures followed in turn by the clinker cooler indicated in the figures as “Clinker cooler”.
Preferably, in both types of plants of
The plant can be fed with two separate flour mixtures, the first rich in CaCO3 (>65% by mass) and the second poor in CaCO3 (<65% by mass). The CaCO3-rich flour, after being preheated, is fed to the primary calciner (a) and is used as a sorbent for the removal of CO2 in the carbonator (c). As far as the CaCO3-poor material is concerned, it is preheated and fed to the secondary calciner (d) together with the material exiting from the carbonator (c). The overall mixture exiting from the secondary calciner is fed to the rotary kiln (e) to complete the clinker production steps.
With this type of configuration, it is also easier to operate the plant especially in cases where the carbonator and/or primary calciner are disconnected due to malfunctions or maintenance. In this case the process of the invention would be reduced to steps d), e), f) only.
Preferably in all the three plants according to the present invention represented in
For example, they contain three preheaters arranged in parallel in several steps and, according to a particularly preferred solution such as the one shown in
All three of the aforesaid plants object of the present invention upstream of the preheater are equipped with one or more grinders of the starting raw mineral indicated in
Preferably in the process of the invention, the calcination steps operate with output temperatures between 850° C. and 950° C. and employ as a heat source the combustion reaction of a mixture of fuel and oxygen with low nitrogen content and other gases other than CO2 and H2O, to easily recover the CO2 exiting from said calciners.
In the cooler in step b) of the process according to the present invention the calcined material is preferably cooled to a temperature between 55° and 650° C.
Preferably in the process according to the present invention in step c) of carbonation the combustion gases rich in CO2 and N2, deriving from the processes of combustion in air in the rotary kiln, are employed. The output temperature from this step is preferably between 65° and 750° C.
If reference is made in particular to
In both plants 3 and 4 shown in
The main difference compared to the classic “Integrated CaL” configuration is that the solids exiting from the carbonator do not return to the first calciner, but do not return either to the second calciner as disclosed in US 2018/0028967. Thus, the configuration object of the present invention is also defined as a single passage (“once-through”), without recirculations between the carbonator and the two calciners. Therefore, in the “Du-CaL” configuration, the raw material does not undergo multiple calcination-carbonation cycles and the sorbent used in the carbonator derives from a single calcination process performed in the primary calciner. This allows for better performances in terms of CO2 removal efficiency, because there is no deactivation of the material caused by repeated calcination-carbonation cycles as clearly reported in the graph of
We can therefore conclude that with this type of assembly, or Du-CaL configuration, the following results are obtained:
The presence of the two calciners allows to ensure an adequate calcination degree of the solids entering the rotary kiln and, at the same time, to generate an optimal calcined material for the performance of the carbonator.
Below are the results of the mass and energy balances obtained from process simulations of a possible example of a Du-CaL system (
It has also been imposed, in this particular example, that the solids exiting from the primary calciner (#11) have a temperature of 920° C., a calcination degree equal to 92.5% and a composition completely similar to that presented in [11]. The secondary calciner ensures that the solids entering the rotary kiln have a composition typical of those entering the rotary kiln of a modern cement plant. This means that the operating conditions of the rotary kiln and of the clinker cooler remain similar to those of a modern cement plant with a clinker production of about 2500-3000 t/day.
The table with the thermodynamic properties and the composition of the various streams present in
Table 2 shows the results of the material and energy balance of the particular Du-CaL case shown in
The Du-CaL configuration allows to achieve a reduction of the CO2 emissions of the cement plant by about 95%, a value similar to that obtained in the Integrated CaL case, but with a fuel saving in the system of about 5.2% (5.16 MJLHV/kgelk against 5.44 MJLHV/kgelk). This is mainly due to the lack of solid material recirculation between carbonator and calciner in the Du-CaL configuration and to the increased activity of the sorbent used. In fact, avoiding recirculation between carbonator and calciner also avoids the energy expenditure due to heating from about 700° C. (carbonator output temperature) to about 920° C. (calciner output temperature) of the aggregates accumulated in the system, while the presence of more active material, allows to achieve high CO2 removal efficiencies with a lower recirculation of solids in the carbonator. Since there is less fuel consumption in the Du-CaL system, the advantage of smaller dimensions being required for very expensive components common to the two plants, such as the air separation unit (ASU) and the CO2 compression and purification unit (CPU), compared to the Integrated CaL case, is also achieved. The lower fuel consumption in the Du-CaL case is also associated with a smaller steam cycle which therefore produces a lower electrical power compared to the Integrated CaL case.
Number | Date | Country | Kind |
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102021000019547 | Jul 2021 | IT | national |
Number | Date | Country | |
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Parent | PCT/IB22/56756 | Jul 2022 | WO |
Child | 18418837 | US |