# Patent

## Title
CO2 and SO2 capture method

## Abstract

The invention relates to a CO2 y SO2 capture method comprising the following steps consisting in: a) introducing an aqueous stream of a hydroxide of an alkali or alkaline-earth metal and another gas stream of CO2 into a bubble column purifier/reactor, in order to form a carbonate of the alkali or alkaline-earth metal; b) introducing the carbonate of the alkali or alkaline-earth metal into a bubble column purifier/reactor, into which a stream of a gas mixture of CO2 and SO2 is introduced in order to form sulphite of an alkali or alkaline-earth metal and carbon dioxide; c) transforming the sulphite from step (b) into sulphate of said metal by means of oxidation with air; and d) re-circulating the unreacted CO2 produced during step (b) by reacting the slurry with the SO2, in the reactor from step (a).

## Background
This invention refers to a process for using the product of the mineral sequestration of carbon dioxide. The process described here comprises the use of the product of the mineral sequestration of CO2 for fixing SO2. Specifically, the various processes described here are based on both reuse of industrial waste and use and exploitation of the products obtained from CO2 sequestration. The aim of this new process is to reduce emissions of both of the greenhouse gases, CO2 and SO2.
BACKGROUND OF THE INVENTION
One of the most promising technologies in the capture and storage of carbon dioxide (CO2) is related to the fixation of this gas in the form of insoluble inorganic carbonates. This fixation is achieved by a chemical reaction, known as mineral carbonation or mineral sequestration. The use of calcium-rich minerals from industrial waste or urban solid waste, Journal of Hazardous Materials B128, 73-79 (2006), is one strategy proposed for increasing technological and economic viability of mineral sequestration of CO2. For example, techniques for reusing residues rich in calcium hydroxide from the paper industry (Journal of Hazardous Materials 161, 1347-1354 (2009)) or the acetylene production industry (Chemical Engineering Journal 166, 132-137 (2011)) have been proposed. These lines of work have been studied at a theoretical level. Lackner et al., (2nd U.S.-China Symposium on CO2 Emissions Control Science & Technology May 28-30, 2008) for example compared renewable energy technologies (aerogenerators and photovoltaic plates) to a combined technology of energy generation plants based on fossil fuels together with CO2 sinks. The main problem with this mineral sequestration technique for CO2 is the large amount of calcite generated as a result of the currently enormous CO2 emissions.
Other authors in basic research studies have proposed the use of lime from mineral calcite for separating mixtures of industrial gases (U.S. Pat. No. 7,618,606B2). Strategies have been developed for temporary capture of CO2 by mineral fixation and its regeneration by cycles of calcination and carbonation (Energy Fuel 2006; 21:163-70), considering methods for regenerating and reactivating the sorbent, lime (Chemical Engineering Journal 2010; Volume 156, Issue 2, Pages 388-394). These routes have been proposed for separating CO2 from a mixture of gases for its geological sequestration (Progress in Energy and Combustion Science 2010; Volume 36, Issue 2, Pages 260-279).
The technology and current process for reducing SO2 emissions in combustion gas currents is based on contact between the gas and an aqueous suspension of mineral calcite. This aqueous suspension is obtained by crushing the calcite obtained from mines and subsequent addition of water to create a calcite slurry. This process requires mining activities, with the consequent harm to the landscape, CO2 emissions due to huge energy consumption during extraction (5-11 kg CO2 per hour), crushing (174-412 kg CO2 per hour) and transport of the mineral (50-118 kg CO2 per hour); currently there are studies seeking cycles of calcination and carbonation to reactivate the calcite in the process of capturing SO2 (Energy Fuel 2008; Volume 87, Issue 13-14, Pages 2923-2931); there are also patents where the mineral calcite is prepared with certain physical properties, large surface area and high pore density that make it more reactive toward SO2 (U.S. Pat. No. 5,779,464 (A)).
In one of the option currently used, this slurry is led to a damp scrubber (EP1958682A1 and JP61167432A) where it is pumped from the bottom of the scrubber to sprayers at the top. There it atomises and comes into contact with a countercurrent of SO2, which is absorbed in the form of CaSO3. The calcium sulphite falls to the bottom of the scrubber where bubbling air oxidises the CaSO3 to CaSO4 for removal from the process (Fuel 1995; Volume 74, Issue 7, Pages 1018-1023).
Another option that is currently used is a semi-dry scrubber. The difference between this and the wet scrubber is based on the pumping of the slurry, which is performed with just the right amount of water so that it is completely evaporated by spraying. The absorption of SO2 takes place while the slurry evaporates, thus producing the dry product, CaSO4.
These two options have the drawback that, on only capturing the SO2, the used calcite generates CO2 that is emitted to the atmosphere.
The removal of SO2 from the gases by scrubbers has given rise to new studies and/or patents seeking ways of regenerating the sorbent that captures the SO2. This regeneration is mainly based on adding a reagent to the products generated in the capture of the SO2 to obtain the initial sorbent and other secondary products. Thus, JP2000051649A reveals the use of Mg(OH)2 for capturing SO2. Subsequently a calcium salt is added in caustic soda to regenerate Mg(OH)2 and also to form gypsum and a sodium salt. Another process proposed in U.S. Pat. No. 7,247,284B1 is based on the capture of SO2 with caustic soda, followed by subsequent addition of Ca(OH)2 to the Na2SO4 formed, thereby regenerating the caustic soda and precipitating the gypsum.
These processes are applied only to the reduction of SO2 emissions, this being their main negative aspect, as well as the generation of large amount of gypsum and other products such as sodium salts (Fuel 1995; Volume 74, Issue 7, Pages 1018-1023), which affect the aquatic environment as they are in the form of brine. Envirotech Corporation (U.S. Pat. No. 3,873,532 (A)) proposed the prior absorption of SO2 with a caustic soda solution, subsequently adding lime to regenerate the original soda.
For the combined reduction of CO2 and SO2, U.S. Pat. No. 5,958,353A proposed the absorption of CO2 and/or SO2 with a basic solution, subsequently adding a soluble calcium salt and so fixing the CO2 and/or SO2 as CaCO3 and CaSO3 respectively and together, using commercial pure sorbents at all times.
Therefore it is necessary to develop a process for capturing CO2 and SO2 that avoids the problems described above.
DESCRIPTION OF THE INVENTION
This invention refers to a process of capturing CO2 and SO2 that solves the drawbacks described in the state of the art, given that:

    
    
        The solution it proposes is the use of calcite generated by mineral sequestration of CO2 for the capture of SO2.
        It does not use cycles of calcination and carbonation, but instead proposes definitive fixation of the greenhouse gases using fresh sorbent derived from the wastes of other industries and its reaction with one of the gases giving a by-product that helps to remove the other gas.
        The process does not require mining operations, or crushing, or transport of the mineral; this implies a saving of CO2 emissions. There are also no sorbent reactivation cycles required, because sorbent is continuously produced fresh from the capture of the other gas. The physical properties of the generated calcite, small particle size and high pore density, make prior preparation to obtain a large specially reactive surface area unnecessary because of the nature of the waste from which it comes.
        The CO2 produced is also sequestrated, avoiding its emission to the atmosphere.
        The gypsum is not the final product but is used in the process to regenerate a reagent, Ca(OH)2, and another commercially useful by-product (Na2SO4), which is not produced in such large amounts as the gypsum, and the main advantage is that of removing both SO2 and CO2.
        The capture of CO2 and SO2 takes place in distinct phases, so the products produced are not mixed, an advantage for their commercialisation; neither are soluble salts used in the process, either prepared previously or from mining operations, but all the salts or solutions used are waste products.
    
    


Therefore the present invention reveals a process for the use of the product of the mineral sequestration of carbon dioxide. The process described comprises the use of the product of mineral sequestration of CO2, calcite, for the fixation of SO2. Specifically, the distinct processes described are based on the reuse both of industrial wastes and the use and exploitation of the products obtained from the sequestration of CO2. The aim of this process is to reduce emissions of both greenhouse gases, CO2 and SO2. The complete cycle will produce other species that may be used to generate the initial reagent or may be exploited and commercialised.
Therefore this invention comprises a process of capturing CO2 and SO2 that comprises the following stages:

    a) introduction of one aqueous current of an alkali or alkaline earth metal hydroxide and another of gaseous carbon dioxide into a bubble column scrubber-reactor, where the bubbling of CO2 in the aqueous current forms a carbonate of the alkali or alkaline earth metal;
    b) introduction of the alkali or alkaline earth metal carbonate from stage a) into a bubble column scrubber-reactor in which a current of gaseous mixture of carbon dioxide and sulphur dioxide is introduced, to form an alkali or alkaline earth metal sulphite and carbon dioxide;
    c) transformation of the alkali or alkaline metal sulphite of stage b) into a sulphate of this metal by oxidation with air; and
    d) recirculation of the unreacted carbon dioxide, produced in stage b) by the reaction of the slurry with sulphur dioxide, into the reactor of stage a).


In a preferred embodiment, the alkali or alkaline earth metal hydroxide comes from the acetylene production industry, water softening industry and/or the paper industry.
In another preferred embodiment, the hydroxide is from alkaline earth metals, preferably calcium.
In another preferred embodiment, after stage d) an additional stage e) is performed, in which alkali metal sulphate waste obtained from any industry and/or the sulphate from stage c) is made to react with a caustic soda solution from the milk industry, olive industry, aluminium production by treatment of bauxite industry or as a by-product of chlorine from salt water, and thereby obtaining the alkali or alkaline earth metal hydroxide and a solution of sodium sulphate.
In another preferred embodiment, the hydroxide from stage e) is mixed with the hydroxide of stage a) to be introduced into the reactor of stage a).
In general, the process follows the following reaction schema:
Stage a):

M(OH)x+CO2 - - - >M2(CO3)x+H2O

Stage b):

M2(CO3)x+SO2+CO2 - - - >M2(SO3)x+CO2 

Stage c):

M2(SO3)x+O2 - - - >M2(SO4)x 

Stage e):

NaOH+M2(SO4)x - - - >M(OH)x+Na2SO4 

where:

    
    
        M is an alkali or alkaline earth metal,
        x is a whole number selected from 1 or 2, depending on whether M is an alkali or alkaline earth metal.
    
    


For experts in the field, other objects, advantages and characteristics of the invention will emerge partly from the description and partly from the practice of the invention.
The following examples and figures are provided for illustration purposes and are not intended to be limiting of the invention.



BRIEF DESCRIPTION OF THE FIGURES
FIG. 1. Schema of the process-invention involving the reuse of residues rich in portlandite and reduction of CO2 and SO2 emissions.
FIG. 2. Schema of the extension of the process-invention with the involvement of caustic soda.



EXAMPLES
Example 1
The electricity generating plant “UPT Almeria” in Carboneras according to the Ministry of Environment, Rural and Marine Affairs, emitted: 5,000,000 t CO2 and 15,300 t SO2 in 2008. Based on calculations of the amount of residue necessary for total capture of the SO2, 23,906 t/year of CaCO3 would be required.
In an embodiment of the invention and according to FIG. 1, 65,000 t/year of residue were obtained with 30% by weight of portlandite and traces of other minerals using a suspension-residue supply network from various generating industries (acetylene production, water softening, paper making, etc.). This suspension-residue was introduced directly into the scrubber, capturing 11,594 t/year CO2 by induced carbonation, generating 26,351 t/year of CaCO3 and 4,743 t/year of H2O. The mineral sequestration product of CO2 is an aqueous suspension of calcium carbonate, which contains 34.5% by weight of calcite. Of the total amount of slurry, only 23,906 t/year of CaCO3 were sent to the SO2 scrubber, necessary to fix all the SO2, leaving 2,445 t/year of CaCO3 left over and generating 32,512 t/year of gypsum.
These numbers show that 100% of SO2 emissions and 0.02% of the direct CO2 emissions were removed from the plant. Indirectly, owing to in situ production of calcite by carbonation of residues rich in calcium, CO2 emissions and the costs derived from mining operations, transport and preparation of the slurry, estimated at approximately 229-540 kg CO2 per hour of mine work, were zero. The emission of CO2 that would otherwise have been derived from the capture of SO2 with calcite alone (10,518 t/year) was also eliminated. From another point of view, this embodiment of the invention resulted in the use of part of the CO2 emitted to the atmosphere as a reagent for obtaining another of the materials necessary in the electricity generation plant, calcite.
Example 2
The company TIOXIDE in Huelva, according to the Ministry of Environment, Rural and Marine Affairs, generated emissions of: 132,000 t CO2, 404 t SO2 and 38,400 t of residues rich in gypsum in 2008. In an embodiment of the invention, according to FIG. 2, all the calcium sulphate was used in the reaction with caustic soda to generate portlandite. In this case, 22,560 t/year of NaOH were also used. This reaction produced 20,868 t/year of Ca(OH)2 and 40,055 t/year of Na2SO4. With the generated portlandite, 12,408 t/year of CO2 were captured, producing 28,200 t/year of calcite, of which 23,906 t were recycled for fixing all the SO2 emitted, as shown in the previous example.
In summary, the total balance of products of the process were: 857 t/year of gypsum, 4,294 t/year of calcite and 40,044 t/year of sodium sulphate. The emissions per year were: 10% less of CO2 and 100% less of SO2.

## Claims

1. Process for capturing CO2 and SO2 consisting of the following stages:
a) introduction of one aqueous current of calcium hydroxide and another of gaseous carbon dioxide into a bubble column scrubber-reactor to form calcium carbonate;
b) introduction of the calcium carbonate from stage a) into a bubble column scrubber-reactor in which a current of a gaseous mixture of carbon dioxide and sulphur dioxide is introduced to form calcium sulphite and carbon dioxide;
c) transformation of the calcium sulphite of stage b) into the sulphate of this metal by oxidation with air; and
d) recirculation the unreacted carbon dioxide, produced in stage b) by reaction with the slurry with sulphur dioxide, into the reactor of stage a);
wherein an additional stage e) is performed in which alkali metal sulphate obtained as waste from any industry and/or the sulphate from stage c) is made to react with a caustic soda solution to obtain calcium hydroxide and a solution of sodium sulphate.

2. The process of claim 1 wherein the caustic soda comes from the milk industry, olive industry, aluminium produced by treatment of bauxite industry or a by-product of chlorine from salt water.

3. The process of claim 1 wherein the hydroxide of stage e) is mixed with the hydroxide from stage a) to be introduced into the reactor of stage a).

4. The process of claim 3 wherein the alkaline earth metal is calcium.

5. The process of claim 1 wherein after stage d) an additional stage e) is performed in which alkali metal sulphate obtained as waste from any industry and/or the sulphate from stage c) is made to react with a caustic soda solution to obtain the alkali or alkaline earth metal hydroxide and a solution of sodium sulphate.

6. The process of claim 5 wherein the caustic soda comes from the milk industry, olive industry, aluminium production by treatment of bauxite industry or as a by-product of chlorine from salt water.

7. The process of claim 5 wherein the hydroxide from stage e) is mixed with the hydroxide of stage a) to be introduced into the reactor of stage a).