WO2018056787A1 - Carbon dioxide conversion process using carbon dioxide mineralization process and metabolic reaction of sulfur-oxidizing microorganisms linked thereto - Google Patents

Abstract

In a carbon dioxide conversion process of the present invention, a carbon dioxide mineralization reaction is linked to a metabolic reaction of sulfur-oxidizing microorganisms, so that carbonates in the carbon dioxide mineralization reaction are converted into a useful material form without the supply of additional energy sources (light, electric energy, etc.) and mineral resources (metal ions) from the outside and metal ions necessary for the carbon dioxide mineralization reaction are reused, thereby realizing a continuous process.

Description

CO2 conversion process that combines carbon dioxide mineralization and metabolism of sulfated microorganisms

The present invention relates to a method for converting carbon dioxide into a useful material, and more particularly, to a method capable of continuously converting carbon dioxide to a useful material by linking the mineralization process of carbon dioxide and the metabolic reaction of sulfated microorganisms.

The burning of fossil fuels such as coal, petroleum and natural gas for energy production is a major cause of increasing atmospheric CO2 concentrations, which contributes to global warming. 0.95 kg of carbon dioxide is generated to produce 1 kWh. To reduce the carbon dioxide emissions, various technologies such as geological carbon capture, storage and conversion have been developed. In particular, the carbon dioxide mineralization process is a representative method of carbon sequestration to reduce carbon dioxide by sequestering carbon dioxide in the atmosphere for a long time. The technology for mineralizing carbon dioxide to metal carbonate compounds such as calcium carbonate has been reported (KR 10-2016-0056420). However, the carbon dioxide mineralization process is only converted to carbonate form for simple storage. Therefore, the application to cement and paper, etc., which are mentioned as application fields, is limited. In addition, there is a problem in that a large amount of feed is required due to the excessive amount of feed compared to the conversion of carbon dioxide.

As a method of fixing and converting carbon dioxide, biological treatment and chemical methods of carbon dioxide using microorganisms have been developed, and hydrogen and reducing power are required to convert carbon dioxide into useful organic materials. In the case of conversion to a chemical method, a reforming reaction of methane or ethane or electrolysis of water is required, and there is a problem of generating carbon dioxide during the reforming reaction of methane or ethane. However, photosynthetic or chemical inorganic nutrient reactions are naturally occurring carbon dioxide immobilization reactions that can reduce carbon dioxide without supplying additional energy sources. In addition, chemical inorganic nutrients are faster than the photosynthetic growth rate and excellent carbon dioxide fixation rate of 5 to 10 times, if the inorganic source is sufficient, it is advantageous to be applied to commercial processes compared to photosynthetic organisms.

Therefore, the present inventors linked the mineralization reaction of carbon dioxide and the metabolic reaction of sulfated microorganisms, converting the carbonate of the mineralization reaction of carbon dioxide into a useful material form without supplying additional energy sources and mineral resources (metal ions). It was confirmed that the mineralization reaction of carbon dioxide proceeds continuously, and the present invention was completed.

The above information described in this Background section is only for improving the understanding of the background of the present invention, and therefore does not include information that forms a prior art known to those of ordinary skill in the art. You may not.

Summary of the Invention

It is an object of the present invention to provide a method for continuously converting carbon dioxide to a useful material without the addition of external additional energy sources (light, electrical energy, etc.) and mineral resources (metal ions).

In order to achieve the above object, the present invention (a) carbon dioxide mineralization step of producing a metal-carbonate product and sulfuric acid by reacting carbon dioxide and metal sulfate; (b) culturing the sulfated microorganism in the presence of the prepared metal-carbonate product and sulfur to prepare a useful substance and metal sulfate produced by the sulfated microorganism; And (c) recovering the useful material and the metal sulfate produced in step (b), and recycling the recovered metal sulfate to the carbon dioxide mineralization step of step (a). Provide a way to.

Figure 1 is switched to a metal sulfate (MeSO ₄₎ a sulfuric acid and a metal carbonate (MeCO ₃₎ by the mineralization reaction of the carbon dioxide, the sulfated microbial growth using the metal carbonate (MeCO ₃₎ and sulfur (sulfur) It illustrates a process of producing an organic material (System100: metal through the mineralization reaction of carbon dioxide sulfate (MeSO ₄₎ a metal carbonate (MeCO ₃₎ the process is switched to and sulfuric acid is produced; system 200: microbial metal carbonate (MeCO ₃ ) And fermentation process for independent nutrient growth using sulfur.

FIG. 2 specifically illustrates the system100 process of FIG. 1 (apparatus 101: an enzyme immobilization apparatus that effectively converts carbon dioxide to bicarbonate using carbonic anhydrase; apparatus 102: alkaline solution) a carbon dioxide capture device for reacting (alkali solution) with bicarbonate to produce a mixture of water soluble carbonates; device 103: electrochemical separation of aqueous sulphates into respective acids and bases sulfuric acid (H ₂ SO ₄ ) and base solution (electrochemical) reaction apparatus; apparatus 104: mineralization apparatus for reacting a water soluble carbonate with a metal sulphate to produce a metal carbonate and a water soluble sulphate; and apparatus 105: separating the produced metal carbonate and supplying a water soluble sulphate (electrolyte) to the apparatus 103 Separation device).

3 is a schematic diagram showing the mineralization reaction of carbon dioxide.

4 is a schematic diagram showing a sulfur denitrification process.

Figure 5 shows the results of culturing microorganisms in conjunction with the mineralization reaction of carbon dioxide and the fermentation process.

Figure 6 is the result of analyzing the S-adenosylmethionine (s-adenosylmethionine) prepared according to the present invention using HPLC chromatography.

Figure 7 is the result of analyzing the spermidine prepared according to the present invention using GC-FID.

{Description of the sign}

100: mineralization process; 101: enzyme immobilization device;

102: carbon dioxide capture device; 103: electrochemical reaction apparatus;

104: mineralization apparatus; 105: separation device;

200: fermentation process

Detailed description of the invention and preferred Embodiment

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is well known and commonly used in the art.

In the present invention, the mineralization reaction of the existing carbon dioxide requires a large amount of metal ions, in order to overcome the disadvantage of storing only carbon dioxide in the form of a simple carbonate, by combining the mineralization reaction of carbon dioxide and metabolism of sulfated microorganisms It was confirmed that carbon dioxide can be converted into useful materials and reused metal ions without the need for additional external energy sources and mineral resources (metal ions) to proceed with the continuous conversion of carbon dioxide.

Accordingly, the present invention in one aspect, (a) carbon dioxide mineralization step of reacting carbon dioxide and metal sulfate to produce a metal-carbonate product and sulfuric acid; (b) culturing the sulfated microorganism in the presence of the prepared metal-carbonate product and sulfur to prepare a useful substance and metal sulfate produced by the sulfated microorganism; And (c) recovering the useful material and the metal sulfate produced in step (b), and recycling the recovered metal sulfate to the carbon dioxide mineralization step of step (a). It is about how to.

In the present invention, the metal is characterized in that the alkali metal, in detail is selected from the group consisting of Ca, Mg, Fe, Si and Al, but is not limited thereto.

In the present invention, step (a) comprises the steps of (i) converting to carbonate / bicarbonate in a reactor containing carbon dioxide, a base solution and a metal sulfate; (ii) reacting the carbonate / bicarbonate with a base solution to produce a water soluble carbonate; (iii) reacting the water-soluble carbonate with the metal sulfate to form a metal-carbonate and a water-soluble sulfate; (iv) electrolyzing the water-soluble sulfate to separate the sulfuric acid and the base solution; And (v) recovering the base solution generated in step (iv) to recycle the step (ii) to produce a water-soluble carbonate.

In the present invention, the step (i) may be characterized by being promoted by carbonic anhydrase.

The step (i) in the present invention include carbon dioxide (CO ₂₎ the hydrogen carbonate (HCO ₃ ^-) due to it is sodium carbonate (Na ₂ CO ₃₎ formed after the transition, by using the enzyme hydration acid free acid (H ₂ CO ₃₎ Solubility in sodium bicarbonate shortens the reaction with sodium hydroxide (NaOH).

In the present invention, oxygen, nitrate (NO ₃ ^-) as an electron acceptor in step (b) ^- can be characterized by additionally adding at least one from the group consisting of and nitrite (NO _2).

In the present invention, the recovery of the metal sulfate in step (c) may be characterized in that the mixture produced in step (b) is passed through a filter to filter out the metal sulfate and then dried.

In the present invention, the sulfated microorganism is Acydianus ambivalans, Acydianus brierleyi, Aquifex pyrophylus, Hydrogenobacter acidophilus ), Hydrogenobacter thermophiles, Thiobacillus denitrificans, Thiomicrospira crunogena, Sulfurmonas genus, Halothiobacillus genus , Ecidithiobacillus (Acidithiobacillus) genus and Termithiobacillus tepidarius (Thermithiobacillus tepidarius) may be selected from the group consisting of, but is not limited thereto.

In the present invention, the Sulfurmonas (Sulfurimonas) genus is Sulfurmonas autotrophica (Sulfurimonas autotrophica), Sulfurmonas denitrificans (Sulfurimonas denitrificans), Sulfurmonas gotlandica (Sulfurimonas gotlandica) and Sulfurmonas It can be characterized in that it is selected from the group consisting of Sulfurimonas paralvinellae, the genus Halothiobacillus (Halothiobacillus) is Halothiobacillus halophilus (Halothiobacillus halophilus), Halothiobacillus hydrothermalis (Halothiobacillus hydrothermalis), Halothiobacillus kellyi and Halothiobacillus neapolitanus (Halothiobacillus neapolitanus) can be characterized in that it is selected from the group consisting of, the Ecidithiobacillus (Acidithiobacillus) genus is Ecidithiobacillus Albertensis ( Acidithiobacillus albertensis) Acidithiobacillus caldus, Acidithiobacillus cuprithermicus, Acidithiobacillus ferridurans, Acidithiobacillus ferrivorans, Ecidithiobacilli (Acidithiobacillus ferrooxidans) and Ecidithiobacillus thiooxidans (Acidithiobacillus thiooxidans) may be characterized in that it is selected from the group consisting of, and preferably characterized in that it is Acidithiobacillus thiooxidans (Acidothiobacillus thiooxidans) It is not limited.

In the present invention, the useful material produced by the sulfated microorganism is PHA (polyhydroxyalkanoate), ethanol (ethanol), acetic acid (acetic acid), lactic acid, glycerol (glycerol), 3-hydroxypropionic acid (3 -hydroxypropionic acid, isobutanol, isobutyric acid, succinic acid, butyric acid, normal butanol, 1,3-propanediol (1,3-PDO) , 2,3-butanediol (2,3-BDO), 1,4-butanediol (1,4-BDO), glutamate, isoprene, adipic acid, muconic acid ), Amino acid, glutathione, polypeptide, polypeptide, phospholipid, polyamine, S-adenosylmethionine and fatty acid This is not restrictive.

In the present invention, the metabolite of Acidothiobacillus thiooxidans may be glutamic acid, aspartic acid, glutathione, licantantase, phosphatidylinositol, or spermidine. This is not restrictive.

The useful substance in the present invention can be detected using high performance liquid chromatography (HPLC), gas chromatography (GC), or the like.

In the present invention, step (a) includes a carbonation process and a mineralization process as a mineralization reaction of carbon dioxide. In the carbonation process, carbon dioxide is converted into a carbonate / bicarbonate form, so that carbon dioxide may be dissolved in water, or a biocatalyst such as carbonic anhydride may be used. In the present invention, the carbonic anhydride enzyme was used to promote the production of carbonate / bicarbonate.

In addition, step (a) reacts the carbonate / bicarbonate with a base solution to produce a water-soluble carbonate. In the present invention, the base solution includes, but is not limited to, sodium hydroxide (NaOH), potassium hydroxide (KOH) and the like. In addition, the water-soluble carbonates include, but are not limited to, sodium carbonate (Na ₂ CO ₃ ), sodium bicarbonate (NaHCO ₃ ), potassium carbonate (K ₂ CO ₃ ), potassium hydrogen carbonate (KHCO ₃ ).

In addition, step (a) includes the reaction of the water-soluble carbonate and the metal sulfate to produce a metal carbonate (solid carbonate) and a water-soluble sulfate. The metal sulfate may be CaSO ₄ , MgSO ₄ , and the water-soluble sulfate may be Na ₂ SO ₄ , K ₂ SO ₄ , but is not limited thereto. The solid carbonate may precipitate and be separated from the aqueous solution.

The water soluble sulfate can be separated into sulfuric acid (H ₂ SO ₄ ) and a base solution (NaOH, KOH) by an electrochemical process (Electrochemical process). The generated base solution may be used again in the step of producing the water-soluble carbonate.

In order to produce the metal carbonate (solid carbonate), a metal element is required, and alkali conditions are required to complete the reaction and to increase the water solubility of the carbon dioxide in the carbonation process. Preferably, the metal element of the present invention uses a divalent metal, such as Ca, Mg, but is not limited thereto. The metal carbonate (solid carbonate) may be CaCO ₃ , MgCO _3, etc., but is not limited thereto.

The production reaction is shown in Table 1 below.

In the present invention, the carbonic anhydrase can be used as a biocatalyst to form a bicarbonate by a nucleophilic reaction with carbon dioxide and then exchange by water to promote the production of bicarbonate. The carbonic anhydrase includes enzyme forms of alpha, beta, gamma, and delta, but is not limited to specific derivatives of enzymes such as plants, animals, archaea, bacteria, and fungi. The reaction scheme is shown in Table 2 below.

In the present invention, the step (b) is to use the metabolic reaction of the aerobic chemical aerobic nutrients, using the energy generated by the oxidation reaction of sulfur using the electron donor sulfur and the electron acceptor oxygen in the growth conditions of the microorganisms Fixing the carbon dioxide.

When oxygen is used as the electron acceptor in the metabolic reaction using the chemical inorganic nutrient of the present invention, the nitrate is used as the electron acceptor in the sulfur-limestone autotrophic denitrification (SLAD), which is a metabolic reaction using the conventional chemical inorganic nutrient. In comparison with the above, productivity and capacity are improved.

In addition, the process includes producing a metal sulfate (solid sulfate) and carbon dioxide by the reaction of the sulfate ion and the metal carbonate obtained by the oxidation reaction. The metal carbonate may protect the microorganism from the sulfate. The growth conditions of the microorganisms are characterized by following the optimum growth conditions of the microorganisms used in aerobic conditions. In addition, the carbon dioxide can be converted into useful substances such as polyhydroxyalkanoates (PHA), glutamic acid, etc. by the microorganism.

In the present invention, the step (c) includes the process of recovering the metal sulfate (solid sulfate) and reusing in the step (a).

In the present invention, the sulfated microorganism is grown under aerobic conditions by using carbon dioxide, which is generated by oxidizing sulfur to sulfate, as a carbon source, PHA (Polyhydroxyalkanoates), ethanol, acetic acid, lactic acid, glycerol, 3-hydroxypropionic acid, isobutanol, Isobutyric acid, succinic acid, butyric acid, normal butanol, 1,3-propanediol (1,3-PDO), 2,3-butanediol (2,3-BDO), 1,4-butanediol (1,4-BDO), glutamate , Isoprene, adipic acid, muconic acid, fatty acids and the like, characterized in that the conversion to organic materials.

Representative chemical inorganic nutrients and their characteristics are shown in Table 3.

In another aspect, the present invention comprises the steps of: (i) converting carbon dioxide, a base solution and a carbonic anhydrase to carbonate / bicarbonate; (ii) a carbon dioxide capture step of reacting the carbonate / bicarbonate with a base solution to produce a water-soluble carbonate; (iii) mineralizing the metal sulphate to form the metal carbonate and the water soluble sulfate by adding the metal sulfate to the produced water-soluble carbonate; (iv) separating the metal carbonate and the water soluble sulfate formed in step (iii); (v) electrolyzing the separated aqueous sulphate to separate the sulfuric acid and the base solution, and recovering the base solution and recycling the carbon dioxide collection step of step (ii); (vi) adding sulfur, an electron acceptor, and a sulfated microorganism to the metal carbonate separated in step (iv), followed by culturing to prepare a mixture of the useful substance and the metal sulfate; And (vii) passing the mixture prepared in step (vi) through a filter to recover the useful materials and the metal sulfate, respectively, and drying the recovered metal sulfate, followed by recycling to the carbon dioxide mineralization step of step (iii). It relates to a method of converting carbon dioxide to a useful material comprising the step.

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are only for illustrating the present invention, and it will be apparent to those skilled in the art that the scope of the present invention is not to be construed as being limited by these examples.

Example 1 Mineralization of Carbon Dioxide

1, the metal sulfate (MeSO ₄₎ by the mineralization reaction of the carbon dioxide being converted into sulfuric acid and the metal carbonate (MeCO _3), the sulfated microbial growth using the metal carbonate (MeCO ₃₎ and sulfur (sulfur) The process for producing organic matter is shown.

As shown in FIG. 2, carbon dioxide anhydrous enzyme was used to convert carbon dioxide to bicarbonate in the enzyme immobilization apparatus 101 of the mineralization process system. The scheme is shown below.

^{_{E, ZnH 2 O↔E, ZnOH -}} + H +

_{^{E, ZnOH - + CO 2 ↔E}} , ZnHCO 3 2 -

_{^{E, ZnHCO 3 2 - + H}} 2 O↔E, ZnH 2 O + HCO 3 2 -

In order to produce a mixture of water-soluble carbonates, a base solution of NaOH and bicarbonate were reacted in a carbon dioxide capture device 102 to secure a water-soluble carbonate of Na ₂ CO ₃ and NaHCO ₃ .

In the mineralization device 104, the water-soluble carbonate and the solid sulfate of CaSO ₄ (MeSO ₄ ) was reacted to produce a solid carbonate of CaCO ₃ (MeCO ₃ ) and a water-soluble sulfate of Na ₂ SO ₄ . The metal carbonate was separated and the solid carbonate was separated in the separating device 105. The scheme is shown below.

CaSO ₄ + CO ₂ + H ₂ O → H ₂ SO ₄ + CaCO ₃

The water-soluble sulfate remaining after separation in the separation unit 105 was separated into a basic solution of sulfuric acid (H ₂ SO ₄ ) and NaOH using an electrochemical process in the electrochemical reaction unit (103). The base solution may react with bicarbonate again in the carbon dioxide capture device 102.

Under the optimum growth conditions of Acidithiobacillus thiooxidans in the fermentation process apparatus 200, sulfur (sulfate, SO ₄ ² ) is dissolved using sulfur (energy source: electron donor) and oxygen (electron acceptor). ^- ). The sulfate ion reacted with the solid carbonate of CaCO ₃ (MeCO ₃ ) to produce solid sulfate and carbon dioxide of CaSO ₄ . In addition, biomass was produced using the carbon dioxide as a carbon source.

The produced solid sulfate of CaSO ₄ was recovered and reused in the mineralization apparatus 104 to conduct a mineralization reaction of carbon dioxide.

In order to recover the produced solid sulfate, CaSO ₄ was filtered through a 20 um filter and dried overnight in an oven at 50 ° C.

In addition, in order to mineralize the carbon dioxide, a carbon dioxide capture process of reacting carbon dioxide with sodium hydroxide (NaOH) to produce sodium carbonate (Na ₂ CO ₃ ) was performed. The scheme is shown below.

2NaOH + CO _2- > Na ₂ CO ₃ + H ₂ O

The sodium carbonate was mineralized with calcium sulfate (CaSO ₄ ) to produce calcium carbonate (CaCO ₃ ) and sodium sulfate. The scheme is shown below.

Na ₂ CO ₃ + CaSO _4- > CaCO ₃ + Na ₂ SO ₄

Through the separation process, the produced calcium carbonate was subjected to a fermentation process in an incubator with a medium containing oxygen, oxygen and microorganisms.

The produced biomass and calcium sulfate are separated in a separator to recover biomass, and calcium sulfate is recovered and reused in the mineralization process.

In addition, the sodium sulfate produced by the mineralization reaction is separated into sulfuric acid and sodium hydroxide through electrolysis, the separated sodium hydroxide is recovered and reused by a carbon dioxide capture process, sulfuric acid is discharged. The reaction scheme of the electrolysis process is shown below.

Na ₂ SO ₄ + 2H ₂ O-> H ₂ SO ₄ + 2NaOH

Example 2: Fermentation Process

The fermentation process uses calcium carbonate obtained by the mineralization reaction to obtain a useful material through microbial fermentation (FIG. 5).

In order to confirm that a useful material is obtained through the fermentation process, 200 ml of medium was added to a 1000 ml flask, and then inoculated with 0.25% of Acidothiobacillus thiooxidans, and preincubated at 30 ° C. and 150 rpm. . Thereafter, 1L medium (Table 4) was placed in a 3.5 L fermenter and then inoculated with 2.5% of the preculture. At this time, the pH was dropped from 4.6 to 2.0, while incubating in air 1 vvm, 350 rpm conditions while maintaining pH 3.0 with 200g / L CaCO ₃ solution. As a result, it was confirmed that cell growth increased with incubation time (Table 5).

The composition of the medium is shown in Table 4.

The number of cells according to the incubation time is shown in Table 5.

Example 3: Useful Substance Analysis

In order to detect S-adenosylmethionine in the useful material produced in Example 2, HPLC-UV method and GC-FID method were used.

HPLC-UV method used water symmetry C18 column 4.6 × 250mm as a column, UV detector was used at 254 nm. The flow rate was 1.0 ml / min, mobile phase A used water and mobile phase B used acetonitrile. Elution 2 minutes at 85% water and 15% acetonitrile, 10 minutes at 100% acetonitrile, 15 minutes at 100% acetonitrile, 16 minutes at 15% acetonitrile and 25 minutes at 15% acetonitrile Was performed.

As a result, it was confirmed that S-adenosylmethionine was detected at a retention time of 6.430 minutes (FIG. 6).

In order to detect spermidine in the useful substance produced in Example 2, 200 μl of the sample obtained in Example 2 and 200 μl of a mixture of chloroform and isooctane in a volume ratio of 1: 4 were mixed, followed by pH12.2 50 μl of K ₂ CO ₃ -KHCO ₃ buffer was added. Then, 1 μl of propyl chloroformate was added and then vortexed. Thereafter, centrifugation was performed for 5 minutes at 13000 rpm. The resulting 100 μl top organic layer was analyzed using GC.

The GC-FID method used HP-5 30m × 320um × 0.25um as the column, the detector used the Flame Ionization Detector (FID), and the detection temperature was 250 ℃. The carrier gas was helium, and the oven temperature was maintained at 50 ° C. for 1 minute, then increased to 20 ° C. per minute to 280 ° C., and maintained for 5 minutes.

As a result, it was confirmed that spermidine was detected at a retention time of 15.075 minutes (FIG. 7).

As described above in detail specific parts of the present invention, it will be apparent to those skilled in the art that these specific descriptions are merely preferred embodiments, and thus the scope of the present invention is not limited thereto. will be. Thus, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

The brain stimulation device according to the present invention has an advantage of enhancing memory or reducing memory degradation due to dementia. In addition, the brain stimulation device according to the present invention has the advantage that it can enhance hippocampus-dependent memory. In addition, the portable device according to the present invention has the advantage of controlling and monitoring the brain stimulation device. In addition, the method of evaluating the performance of the brain stimulation apparatus according to the present invention has an advantage of evaluating the performance of the brain stimulation apparatus.

Claims (13)

1. How to convert carbon dioxide to useful material, which includes the following steps:

   (a) a carbon dioxide mineralization step of reacting carbon dioxide with a metal sulfate to produce a metal-carbonate product and sulfuric acid;

   (b) culturing the sulfated microorganism in the presence of the prepared metal-carbonate product and sulfur to prepare a mixture of the useful substance and metal sulfate produced by the sulfated microorganism; And

   (c) recovering the useful substance and the metal sulfate produced in the step (b), respectively, and recycling the recovered metal sulfate to the carbon dioxide mineralization step of step (a).
2. The method of claim 1,

   The metal is an alkali metal.
3. The method of claim 2,

   The alkali metal is selected from the group consisting of Ca, Mg, Fe, Si and Al.
4. The method of claim 1,

   Step (a) is a method for converting carbon dioxide to a useful material comprising the following steps:

   (i) converting to carbonate / bicarbonate in a reactor containing carbon dioxide, base solution and metal sulfate;

   (ii) reacting the carbonate / bicarbonate with a base solution to produce a water soluble carbonate;

   (iii) reacting the water soluble carbonate and the metal sulfate to form a metal carbonate and a water soluble sulfate;

   (iv) electrolyzing the water-soluble sulfate to separate the sulfuric acid and the base solution; And

   (v) recycling the base solution generated in step (iv) to produce the water-soluble carbonate of step (ii).
5. The method of claim 4, wherein

   The step (i) is characterized in that promoted by carbonic anhydrase (carbonic anhydrase).
6. The method of claim 1,

   Characterized in that further added to any one or more from the group consisting of ^- and nitrite (NO ₂₎ ^- the oxygen (O _2), nitrate (NO ₃₎ as an electron acceptor in step (b).
7. The method of claim 1,

   The recovery of the metal sulfate of step (c) is characterized in that the mixture produced in step (b) is passed through a filter to filter out the metal sulfate, and then dried.
8. The method of claim 1,

   The sulfated microorganism is selected from the following group:

   (A) Acidianus ambivalans or Acidianus brierleyi;

   (B) Aquifex pyrophylus;

   (C) the bacterium Hydrogenobacter acidophilus or Hydrogenobacter thermophiles;

   (D) Thiobacillus denitrificans;

   (E) Thiomicrospira crunogena;

   (F) the genus Sulfurmonas;

   (G) Genus Halothiobacillus;

   (H) genus Acidithiobacillus; And

   (I) Thermithiobacillus tepidarius.
9. The method of claim 8,

   The genus Sulfurmonas (Sulfurimonas) is Sulfurmonas autotrophica (Sulfurimonas autotrophica), Sulfurmonas denitrificans, Sulfurmonas gotlandica (Sulfurimonas gotlandica) and Sulfurmonas paranalus ( paralvinellae).
10. The method of claim 8,

    Halothiobacillus genus is Halothiobacillus halophilus, Halothiobacillus hydrothermalis, Halothiobacillus kellyi and Halothiobacillus napolitanus. Method selected from the group consisting of.
11. The method of claim 8,

    The genus Acidithiobacillus (Acidithiobacillus albertensis), Acidithiobacillus caldus (Acidithiobacillus caldus), Acidithiobacillus cuprithermicus (Acidithiobacillus cuprithermicus), sididithiobacillus Selected from the group consisting of Durans (Acidithiobacillus ferridurans), Acidithiobacillus ferrivorans, Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans. How to.
12. The method of claim 1,

    Useful materials produced by the sulfated microorganism are PHA (polyhydroxyalkanoate), ethanol (ethanol), acetic acid (acetic acid), lactic acid (lactic acid), glycerol (glycerol), 3-hydroxypropionic acid (3-hydroxypropionic acid), Isobutanol, isobutyric acid, succinic acid, butyric acid, normal butanol, 1,3-propanediol (1,3-PDO), 2,3- butanediol (2,3-BDO), 1,4-butanediol (1,4-BDO), glutamate, isoprene, adipic acid, muconic acid, amino acid, glutathione (glutathione), polypeptide (polypeptide), phospholipid (phospholipid), polyamine (polyamine), S-adenosylmethionine (S-adenosylmethionine) and fatty acid (fatty acid).
13. How to convert carbon dioxide to useful material, which includes the following steps:

    (i) reacting carbon dioxide, base solution and carbonic anhydrase to convert to carbonate / bicarbonate;

    (ii) a carbon dioxide capture step of reacting the carbonate / bicarbonate with a base solution to produce a water-soluble carbonate;

    (iii) mineralizing the metal sulphate to form the metal carbonate and the water soluble sulfate by adding the metal sulfate to the produced water-soluble carbonate;

    (iv) separating the metal carbonate and the water soluble sulfate formed in step (iii);

    (v) electrolyzing the separated aqueous sulphate to separate the sulfuric acid and the base solution, and recovering the base solution and recycling the carbon dioxide collection step of step (ii);

    (vi) adding sulfur, an electron acceptor, and a sulfated microorganism to the metal carbonate separated in step (iv), followed by culturing to prepare a mixture of the useful substance and the metal sulfate; And

    (vii) passing the mixture prepared in step (vi) through a filter to recover the useful materials and the metal sulfates, and then drying the recovered metal sulfates and recycling the carbon dioxide mineralization step of step (iii). .

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