WO2024029544A1 - Method for producing carbon dioxide immobilization material - Google Patents
Method for producing carbon dioxide immobilization material Download PDFInfo
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- WO2024029544A1 WO2024029544A1 PCT/JP2023/028185 JP2023028185W WO2024029544A1 WO 2024029544 A1 WO2024029544 A1 WO 2024029544A1 JP 2023028185 W JP2023028185 W JP 2023028185W WO 2024029544 A1 WO2024029544 A1 WO 2024029544A1
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- carbon dioxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
Definitions
- the present invention relates to a method for producing a carbon dioxide fixing material.
- ⁇ -type dicalcium silicate which is produced using slaked lime as a by-product when producing acetylene from calcium carbide
- Patent Document 1 to Patent Document 3 ⁇ -type dicalcium silicates
- These ⁇ -type dicalcium silicates can significantly reduce CO 2 emissions derived from raw materials, and the CO 2 emissions intensity during production of ⁇ -type dicalcium silicate can be reduced to 200 kgC/t or less. there were.
- ⁇ -type dicalcium silicate cannot be produced unless the CaO raw material and SiO2 raw material used as raw materials are of high purity, which limits the quantity that can be produced industrially. there were.
- these ⁇ -type dicalcium silicates are heat-treated using a rotary kiln by cooking fuel with a burner, so even if CO 2 emissions derived from raw materials can be reduced, CO 2 emissions caused by fuel combustion are It could have happened.
- the present invention has been made to solve the problems of the prior art described above, and is a method for producing a carbon negative carbon dioxide fixing material that is more effective in reducing CO 2 emissions than conventional methods.
- the purpose is to provide
- the present inventors conducted intensive research to achieve the above object and found that the above problem could be solved by heat-treating a predetermined raw material while creating a reducing atmosphere in an electric furnace.
- the present invention is based on the above knowledge and has the following gist.
- a method for producing a carbon dioxide fixing material in which a raw material containing a CaO source and a SiO 2 source is heat-treated in an electric furnace with a reducing atmosphere inside.
- the impurity is at least one of Fe 2 O 3 , Al 2 O 3 , MgO, TiO 2 , Na 2 O, K 2 O, MnO, and SO 3 as a chemical component labeled as an oxide.
- the carbon dioxide fixing material manufactured in this embodiment is a general term for materials that can chemically fix carbon dioxide (CO 2 ) in a normal temperature environment.
- a chemical component that can be chemically immobilized includes a CaO component, and a compound containing this can be used. This is based on a mechanism in which the CaO component in the compound undergoes a carbonation reaction with CO 2 to generate CaCO 3 and chemically fix it.
- the carbon dioxide fixing material containing a CaO component preferably contains ⁇ -type dicalcium silicate (hereinafter sometimes referred to as " ⁇ -C 2 S").
- ⁇ -C 2 S is known as a low-temperature phase among the compounds represented by 2CaO ⁇ SiO 2 , and is similar to the high-temperature phases ⁇ -2CaO ⁇ SiO 2 , ⁇ ′-2CaO ⁇ SiO 2 , and ⁇ - It is completely different from 2CaO.SiO 2 ( ⁇ -C 2 S). All of these are represented by 2CaO.SiO 2 but have different crystal structures and densities.
- tricalcium silicate 3CaO.SiO 2
- monocalcium silicate ⁇ -wollastonite
- rankinite melilite (gehlenite-akermanite solid solution)
- melvinite melvinite
- Calcium magnesium silicate and the like may also coexist, and when they coexist with ⁇ -C 2 S, they act effectively as a carbon dioxide fixing material. On the other hand, when it coexists with ⁇ -C 2 S, it cannot exhibit its performance as a carbon dioxide gas fixing material.
- ⁇ -C 2 S Since ⁇ -C 2 S is accompanied by a powdering phenomenon called dusting during production, it requires less energy to grind compared to other compounds, and has a large carbon dioxide fixation effect over a long period of time, so it is a carbon negative carbon dioxide gas. Suitable as a fixing material.
- the content of ⁇ -C 2 S in the carbon dioxide fixing material is preferably 25% by mass or more, more preferably 40% by mass or more.
- Powder X-ray diffraction (XRD) can be used to identify ⁇ -C 2 S, ⁇ -C 2 S, etc. in the carbon dioxide fixing material. Based on the identification results, ⁇ -C 2 S, ⁇ -C 2 S, etc. can be quantified by the Rietveld method.
- the carbon dioxide fixing material as described above is obtained by a manufacturing method in which a raw material containing a CaO source and a SiO 2 source is subjected to heat treatment in an electric furnace with a reducing atmosphere inside.
- a reducing atmosphere means a gas composition lower than the oxygen concentration of the atmospheric gas composition, and the oxygen concentration is preferably 10% by volume or less, more preferably 5% by volume or less.
- the oxygen concentration is preferably 10% by volume or less, more preferably 5% by volume or less.
- it is effective to include a reducing gas such as CO gas in the electric furnace, and it is preferable to set the CO gas concentration to about 1 to 10% by volume in a nitrogen atmosphere.
- the electric furnace is not particularly limited as long as it can create a reducing atmosphere, and any known electric furnace can be used. From the viewpoint of the effect of reducing CO 2 emissions, it is preferable to use a carbon electrode as the electrode to be used. Also, from the same viewpoint, it is preferable to use carbon for the furnace body.
- a raw material containing a CaO source and a SiO 2 source includes a mixture of a CaO raw material containing CaO and a SiO 2 raw material containing SiO 2 as a chemical composition, a raw material containing both CaO and SiO 2 as a chemical composition, Mixed raw materials of these may be mentioned.
- the blending ratio of the raw materials is preferably adjusted to such a ratio that ⁇ -C 2 S is produced.
- CaO raw material examples include calcium carbonate such as limestone, and calcium hydroxide such as slaked lime.
- SiO 2 raw material examples include silica stone and clay.
- industrial raw materials may be used as the raw materials described above, but industrial by-products may also be used.
- Industrial by-products include by-product calcium hydroxide, fine powder generated from waste concrete lumps, steel slag, various siliceous dusts generated as industrial by-products such as silica fume and fly ash, etc. It can be used to replace part or all of industrial raw materials. Examples of industrial by-products are given below.
- By-product calcium hydroxide (also referred to as by-product slaked lime) according to the present embodiment is a general term for calcium hydroxide generated as an industrial by-product.
- calcium hydroxide is a by-product in the process of producing acetylene from calcium carbide.
- the by-product calcium hydroxide has a purity of about 95% and contains impurities in a range of 5% or less.
- fly ash is a byproduct generated from a thermal power plant, and is a general term for coal ash and fly ash.
- coal ash which has a large amount of unburned carbon and is difficult to utilize effectively, can also be used.
- the steel slag according to this embodiment is a general term for blast furnace slag (granulated slag, slowly cooled slag), converter slag, electric furnace slag, and stainless steel slag.
- Blast furnace slag is a byproduct generated when producing pig iron in a blast furnace, and includes granulated blast furnace slag, which is quenched with water and vitrified, and slow-cooled blast furnace slag, which is slowly cooled and crystallized.
- Converter slag is a byproduct generated in the converter process, which refines pig iron obtained in a blast furnace.
- Electric furnace slag is a general term for slag generated when scrap is collected and reduced in an electric furnace to obtain iron, and includes electric furnace oxidation stage slag and electric furnace reduction stage slag.
- Stainless steel slag is a general term for slag generated during the production of stainless steel. In this embodiment, both can be used.
- the raw material containing the CaO source and the SiO 2 source is an industrial by-product, and it is possible to obtain ⁇ -type dicalcium silicate even if the amount of impurities on a dry matter basis corrected by loss on ignition is 5% or more.
- the number of coexisting compounds increases with an increase in impurities (although the purity of ⁇ -type dicalcium silicate decreases)
- ⁇ -type dicalcium silicate can be produced even with impurities of about 20%.
- the formation of this compound can induce dusting and cause powdering. Powdering increases the specific surface area, making it useful as a CO 2 absorption material.
- impurities include at least one of Fe 2 O 3 , Al 2 O 3 , MgO, TiO 2 , Na 2 O, K 2 O, MnO, and SO 3 as chemical components labeled as oxides.
- the total amount of the above impurities on a dry matter basis is preferably 5 to 30%.
- the dry matter basis can be corrected for loss on ignition (LOI). Specifically, it is expressed as a relative value when the mass after subtracting the loss on ignition is taken as 100. Further, the CaO content on a dry matter basis corrected by loss on ignition is preferably 30 to 70%, more preferably 40 to 60%, from the viewpoint of productivity and carbon negative.
- the CO 2 absorbing material can be manufactured by charging raw materials into an electric furnace, melting them by heat treatment, and discharging and cooling them. There is no need to prepare the raw materials by mixing and pulverizing them, just measure them and put them into the electric furnace. Because it is melted and subjected to a liquid phase reaction, there is no need to finely grind the raw materials.
- powdered raw materials are available, they can be granulated or briquettered and then fed into an electric furnace in order to prevent dust generation and blow-up during heating.
- the heat treatment temperature is preferably in the range of 1400 to 1800°C, more preferably 1500 to 1700°C.
- the reactor is allowed to react for a certain period of time, and the molten material is poured out of the furnace and cooled. Cooling may be performed by any method other than ultra-rapid cooling, and is not particularly limited, but slow cooling is preferred.
- the electric furnace can be operated using renewable energy. This makes it possible to further reduce the CO 2 emissions per unit of production when producing the CO 2 absorbing material.
- Renewable energies include hydroelectric power, solar power, wind power, biomass power, and geothermal power. In particular, it is preferable to select hydroelectric power generation, solar power generation, and wind power generation. By using renewable energy, energy-derived CO 2 emissions can be reduced.
- Example 1 Using the raw materials shown in Table 1, the blended raw materials shown in Table 2 were prepared. The blended raw materials in Table 2 were heat treated in a rotary kiln and in an electric furnace, and the resulting compounds were visually confirmed by XRD for the presence or absence of dusting, and the amount of CO 2 absorbed was evaluated. The results are listed in Table 3.
- Heat treatment using a rotary kiln A kiln manufactured by Denka Co., Ltd. was used.
- the raw materials were mixed and ground to an average particle size of about 15 ⁇ m using a ball mill.
- the firing temperature was controlled by the burning point temperature of the burner, and was 1450 to 1500°C.
- Heat treatment using an electric furnace An electric furnace at Denka Co., Ltd.'s Omi factory was used. Mixing and pulverizing treatment for raw material preparation was not performed. The melting temperature was 1650°C. A carbon electrode and a carbon furnace body were used for the operation. The exhaust gas composition was measured after steady operation. The gas composition was 80% by volume of nitrogen, 10% by volume of oxygen, 7% by volume of H 2 O, and 2% by volume of CO.
- CH is byproduct slaked lime
- FA fly ash
- BFS granulated blast furnace slag
- LOI weight loss when ignited at 1000°C (mass%)
- the total amount of impurities is as a chemical component labeled as oxide.
- Fe 2 O 3 , Al 2 O 3 , MgO, TiO 2 , Na 2 O, K 2 O, MnO, and SO 3 was determined according to JIS R 5202.
- - Presence or absence of dusting and physical condition Dusting was considered to be present when the 90 ⁇ m passing rate was 50% or more, and dusting was considered to be present when it was less than 50%.
- the physical condition of the product was evaluated by visual observation of the form of the product after production.
- CO 2 absorption amount The carbon dioxide absorption amount was determined when the products obtained in each case were carbonated in air at a carbon dioxide concentration of 5%, a temperature of 30° C., and a relative humidity of 60% for 7 days. At this time, taking into consideration that the sample before carbonation treatment may contain carbon dioxide, the amount of CO 2 absorbed was calculated using the following formula.
- CO2 absorption amount (amount of carbon dioxide in the sample after carbonation treatment) - (amount of carbon dioxide in the sample before carbonation treatment)
- amount of carbon dioxide in the above formula was determined by inorganic total carbon analysis (Coulomatic-C).
- ⁇ -C 2 S is generated even under conditions where the impurity content is very high, around 20%, and a highly active powdered CO 2 absorbing material can be obtained.
- ⁇ -C 2 S was not produced, resulting in pebble-like clinker with low CO 2 absorption capacity.
- melilite is a solid solution of gehlenite and akermanite.
- Example 2 The CO 2 emissions per unit of production of the CO 2 absorbing material was calculated. Using the raw material 1 shown in Table 2, a comparative study was conducted between heat treatment using a rotary kiln and heat treatment using an electric furnace. The results are listed in Table 3.
- Heat treatment using a rotary kiln A Denka Co., Ltd. kiln is used and is operated using purchased electricity. It was manufactured using the following steps: (i) raw material preparation, (ii) granulation, (iii) calcination, and (iv) cooling.
- raw material preparation the raw materials were mixed and ground using a ball mill to an average particle size of about 15 ⁇ m. This is because the raw materials need to be finely pulverized in order to advance the solid phase reaction.
- electricity was consumed.
- the granulation process also consumed electricity.
- the firing process consumed electricity and fuel. Firing was controlled by the burning point temperature of the burner, and was carried out at 1450°C to 1500°C.
- the cooling process consumed electricity.
- the CO 2 emission unit when producing the CO 2 absorbing material can be significantly reduced to 22 kg CO 2 /t.
- the conventional kiln method also has a smaller value compared to the case of producing cement, the value is one order of magnitude larger than that of this example.
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Abstract
Description
本発明は、炭酸ガス固定化材の製造方法に関するものである。 The present invention relates to a method for producing a carbon dioxide fixing material.
各産業界で低炭素化が求められている。２０２０年１０月２６日、第２０３回臨時国会において、「２０５０年カーボンニュートラル、脱炭素社会の実現を目指す」ことが宣言された。また、２０２１年４月２２日、地球温暖化対策推進本部及び米国主催気候サミットにおいて、２０３０年度に温室効果ガスを２０１３年度から４６％削減することを目指すこと、さらに５０％の高みに向け挑戦を続けること等も発言された。このような背景を受け、今まで以上にＣＯ２削減技術への注目が高まっている。とりわけ、カーボンネガティブな材料の開発が強く待たれている。ここで、カーボンネガティブとは、ＣＯ２の排出量よりも吸収するＣＯ２の量が多い状態のことである。 Low carbonization is required in all industries. On October 26, 2020, at the 203rd extraordinary session of the Diet, it was declared that the government ``aims to realize a carbon-neutral and decarbonized society in 2050.'' Furthermore, on April 22, 2021, at the Climate Summit hosted by the Headquarters for the Promotion of Global Warming Countermeasures and the United States, it was announced that we would aim to reduce greenhouse gas emissions by 46% in 2030 compared to 2013, and that we would take on the challenge of achieving a further 50%. There were also statements about continuing. Against this background, CO2 reduction technology is attracting more attention than ever before. In particular, the development of carbon-negative materials is eagerly awaited. Here, carbon negative refers to a state in which the amount of CO 2 absorbed is greater than the amount of CO 2 emitted.
従来、カーボンネガティブな炭酸ガス固定化材としては、例えば、カルシウムカーバイドからアセチレンを生成させる際に副生する消石灰を原料として製造されるγ型のダイカルシウムシリケートが知られている（例えば、特許文献１～特許文献３参照）。これらのγ型のダイカルシウムシリケートは、原料由来のＣＯ２排出量を大幅に減じることができ、γ型のダイカルシウムシリケート製造時のＣＯ２排出量原単位として、２００ｋｇＣ／ｔ以下にできるものであった。 Conventionally, as a carbon-negative carbon dioxide gas fixing material, for example, γ-type dicalcium silicate, which is produced using slaked lime as a by-product when producing acetylene from calcium carbide, is known (for example, Patent Document 1 to Patent Document 3). These γ-type dicalcium silicates can significantly reduce CO 2 emissions derived from raw materials, and the CO 2 emissions intensity during production of γ-type dicalcium silicate can be reduced to 200 kgC/t or less. there were.
しかしながら、この方法では、原料として用いるＣａＯ原料やＳｉＯ２原料の純度が高いものを用いなければγ型のダイカルシウムシリケートを生成させることができず、工業的に生産できる数量が限定される課題があった。また、これらのγ型のダイカルシウムシリケートは、ロータリーキルンを用いて、燃料をバーナーで炊いて熱処理を行うため、原料由来のＣＯ２排出量を減らせても、燃料の燃焼に起因するＣＯ２排出が起こる可能性があった。 However, with this method, γ-type dicalcium silicate cannot be produced unless the CaO raw material and SiO2 raw material used as raw materials are of high purity, which limits the quantity that can be produced industrially. there were. In addition, these γ-type dicalcium silicates are heat-treated using a rotary kiln by cooking fuel with a burner, so even if CO 2 emissions derived from raw materials can be reduced, CO 2 emissions caused by fuel combustion are It could have happened.
不純物が多く含まれるＣａＯ原料やＳｉＯ２原料を用いて、γ型のダイカルシウムシリケートを製造できる方法が確立できれば、副生消石灰に加えて、生コンスラッジ、石炭灰やフライアッシュ、各種のスラグ（高炉スラグ、転炉スラグ、電気炉スラグ、ステンレススラグ）等、産業副産物を原料として利用することも可能となる。また、今日では、カーボンネガティブ材料に求められるＣＯ２削減能力向上の要求が、益々高まってきている。このようなカーボンネガティブ材料の開発が実現しない限り、２０５０年カーボンユートラル宣言の実現は難しいと考えられる。 If a method can be established to produce γ-type dicalcium silicate using CaO raw materials and SiO2 raw materials that contain many impurities, in addition to by-product slaked lime, raw concrete sludge, coal ash, fly ash, various slags (blast furnace It is also possible to use industrial by-products such as slag, converter slag, electric furnace slag, and stainless steel slag) as raw materials. Furthermore, today, there is an increasing demand for carbon negative materials to improve their ability to reduce CO2 . Unless such carbon-negative materials are developed, it will be difficult to realize the 2050 Carbon Utral Declaration.
以上から本発明は、上述の従来技術の問題点を解決するためになされたもので、製造する際に従来よりもＣＯ２排出量の削減効果が高いカーボンネガティブな炭酸ガス固定化材の製造方法を提供することを目的とする。 In view of the above, the present invention has been made to solve the problems of the prior art described above, and is a method for producing a carbon negative carbon dioxide fixing material that is more effective in reducing CO 2 emissions than conventional methods. The purpose is to provide
本発明者らは、上記の目的を達成すべく鋭意研究を進めたところ、電気炉内を還元雰囲気としながら所定の原料を熱処理することにより上記課題を解決できることを見出した。 The present inventors conducted intensive research to achieve the above object and found that the above problem could be solved by heat-treating a predetermined raw material while creating a reducing atmosphere in an electric furnace.
本発明は、上記の知見に基づくものであり、以下を要旨とする。
［１］ 内部を還元雰囲気とした電気炉内で、ＣａＯ源とＳｉＯ２源とを含む原料を熱処理する炭酸ガス固定化材の製造方法。
［２］ 前記原料が産業副産物を含み、該産業副産物の強熱減量で補正した乾物ベースでの不純物の量が５質量％以上である［１］に記載の炭酸ガス固定化材の製造方法。
［３］ 前記不純物が、酸化物標記した化学成分として、Ｆｅ２Ｏ３、Ａｌ２Ｏ３、ＭｇＯ、ＴｉＯ２、Ｎａ２Ｏ、Ｋ２Ｏ、ＭｎＯ、及びＳＯ３の少なくともいずれかである［２］に記載の炭酸ガス固定化材の製造方法。
［４］ 前記産業副産物が、副生水酸化カルシウム及び／又はフライアッシュを含む［２］又は［３］に記載の炭酸ガス固定化材の製造方法。
［５］ 前記原料が鉄鋼スラグを含む［１］～［４］のいずれか１つに記載の炭酸ガス固定化材の製造方法。
［６］ 再生可能エネルギーを用いて前記電気炉を操業する［１］～［５］のいずれか１つに記載の炭酸ガス固定化材の製造方法。
［７］ 前記炭酸ガス固定化材が、γ型のダイカルシウムシリケートを２５質量％以上含む［１］～［６］のいずれか１つに記載の炭酸ガス固定化材の製造方法。
The present invention is based on the above knowledge and has the following gist.
[1] A method for producing a carbon dioxide fixing material, in which a raw material containing a CaO source and a SiO 2 source is heat-treated in an electric furnace with a reducing atmosphere inside.
[2] The method for producing a carbon dioxide fixing material according to [1], wherein the raw material contains an industrial by-product, and the amount of impurities on a dry matter basis corrected by the loss on ignition of the industrial by-product is 5% by mass or more.
[3] The impurity is at least one of Fe 2 O 3 , Al 2 O 3 , MgO, TiO 2 , Na 2 O, K 2 O, MnO, and SO 3 as a chemical component labeled as an oxide. 2], the method for producing a carbon dioxide fixing material.
[4] The method for producing a carbon dioxide fixing material according to [2] or [3], wherein the industrial by-product contains by-product calcium hydroxide and/or fly ash.
[5] The method for producing a carbon dioxide fixing material according to any one of [1] to [4], wherein the raw material contains steel slag.
[6] The method for producing a carbon dioxide fixing material according to any one of [1] to [5], wherein the electric furnace is operated using renewable energy.
[7] The method for producing a carbon dioxide fixing material according to any one of [1] to [6], wherein the carbon dioxide fixing material contains 25% by mass or more of γ-type dicalcium silicate.
本発明によれば、製造する際に従来よりもＣＯ２排出量の削減効果が高いカーボンネガティブな炭酸ガス固定化材の製造方法を提供することができる。 According to the present invention, it is possible to provide a method for producing a carbon negative carbon dioxide fixing material that is more effective in reducing CO 2 emissions than conventional methods.
以下、本発明の一実施形態（本実施形態）に係る炭酸ガス固定化材の製造方法について説明する。なお、本明細書で使用する、「部」や「％」は、特に規定のない限り質量基準である。 Hereinafter, a method for manufacturing a carbon dioxide fixing material according to one embodiment (this embodiment) of the present invention will be described. Note that "parts" and "%" used in this specification are based on mass unless otherwise specified.
まず、本実施形態で製造される炭酸ガス固定化材とは、常温環境下で炭酸ガス（ＣＯ２）を化学的に固定化できる材料を総称するものである。化学的に固定化できる化学成分としては、ＣａＯ成分が挙げられ、これを含む化合物を用いることができる。前記化合物中のＣａＯ成分がＣＯ２と炭酸化反応し、ＣａＣＯ３を生成して化学的に固定化するメカニズムによる。例えば、ＣａＯ成分を含む炭酸ガス固定化材としては、γ型のダイカルシウムシリケート（以下、「γ－Ｃ２Ｓ」ということがある）を含むことが好ましい。γ－Ｃ２Ｓは、２ＣａＯ・ＳｉＯ２で表される化合物のうちで、低温相として知られるものであり、高温相であるα－２ＣａＯ・ＳｉＯ２やα’－２ＣａＯ・ＳｉＯ２、β－２ＣａＯ・ＳｉＯ２（β－Ｃ２Ｓ）とは全く異なるものである。これらはいずれも、２ＣａＯ・ＳｉＯ２で表されるが、結晶構造や密度は異なっている。 First, the carbon dioxide fixing material manufactured in this embodiment is a general term for materials that can chemically fix carbon dioxide (CO 2 ) in a normal temperature environment. A chemical component that can be chemically immobilized includes a CaO component, and a compound containing this can be used. This is based on a mechanism in which the CaO component in the compound undergoes a carbonation reaction with CO 2 to generate CaCO 3 and chemically fix it. For example, the carbon dioxide fixing material containing a CaO component preferably contains γ-type dicalcium silicate (hereinafter sometimes referred to as "γ-C 2 S"). γ-C 2 S is known as a low-temperature phase among the compounds represented by 2CaO・SiO 2 , and is similar to the high-temperature phases α-2CaO・SiO 2 , α′-2CaO・SiO 2 , and β- It is completely different from 2CaO.SiO 2 (β-C 2 S). All of these are represented by 2CaO.SiO 2 but have different crystal structures and densities.
本発明では、上記のγ－Ｃ２Ｓに加えて、トライカルシウムシリケート（３ＣａＯ・ＳｉＯ２）、モノカルシウムシリケート（α-ワラストナイト）、ランキナイト、メリライト（ゲーレナイト-アケルマナイト固溶体）、メルヴィナイト等のカルシウムマグネシウムシリケート等も共存してよく、γ－Ｃ２Ｓと共存した場合には炭酸ガス固定化材として有効に作用する。一方、β－Ｃ２Ｓと共存した場合には、炭酸ガス固定化材としての性能を発揮できない。 In the present invention, in addition to the above-mentioned γ-C 2 S, tricalcium silicate (3CaO.SiO 2 ), monocalcium silicate (α-wollastonite), rankinite, melilite (gehlenite-akermanite solid solution), melvinite, etc. Calcium magnesium silicate and the like may also coexist, and when they coexist with γ-C 2 S, they act effectively as a carbon dioxide fixing material. On the other hand, when it coexists with β-C 2 S, it cannot exhibit its performance as a carbon dioxide gas fixing material.
γ－Ｃ２Ｓは、製造時にダスティングと呼ばれる粉化現象をともなうため、他の化合物に比べて粉砕に要するエネルギーが少なく、長期にわたって炭酸ガス固定化効果が大きいことから、カーボンネガティブな炭酸ガス固定化材として好適である。 Since γ-C 2 S is accompanied by a powdering phenomenon called dusting during production, it requires less energy to grind compared to other compounds, and has a large carbon dioxide fixation effect over a long period of time, so it is a carbon negative carbon dioxide gas. Suitable as a fixing material.
炭酸ガス固定化材中のγ－Ｃ２Ｓの含有量は、２５質量％以上であることが好ましく、４０質量％以上であることがより好ましい。
炭酸ガス固定化材中のγ－Ｃ２Ｓやβ－Ｃ２Ｓ等の同定には、粉末Ｘ線回折（ＸＲＤ）を用いることができる。その同定結果に基づいて、リートベルト法によりγ－Ｃ２Ｓやβ－Ｃ２Ｓ等を定量することができる。
The content of γ-C 2 S in the carbon dioxide fixing material is preferably 25% by mass or more, more preferably 40% by mass or more.
Powder X-ray diffraction (XRD) can be used to identify γ-C 2 S, β-C 2 S, etc. in the carbon dioxide fixing material. Based on the identification results, γ-C 2 S, β-C 2 S, etc. can be quantified by the Rietveld method.
上記のような炭酸ガス固定化材は、内部を還元雰囲気とした電気炉内で、ＣａＯ源とＳｉＯ２源と含む原料に熱処理を施す製造方法により得られる。 The carbon dioxide fixing material as described above is obtained by a manufacturing method in which a raw material containing a CaO source and a SiO 2 source is subjected to heat treatment in an electric furnace with a reducing atmosphere inside.
還元雰囲気とは、大気のガス組成の酸素濃度よりも低いガス組成を意味し、酸素濃度は１０体積％以下が好ましく、５体積％以下がより好ましい。このような状態にするためには、電気炉内にＣＯガス等還元ガスを含ませることが有効であり、窒素雰囲気中でＣＯガス濃度を１～１０体積％程度とすることが好ましい。 A reducing atmosphere means a gas composition lower than the oxygen concentration of the atmospheric gas composition, and the oxygen concentration is preferably 10% by volume or less, more preferably 5% by volume or less. In order to achieve such a state, it is effective to include a reducing gas such as CO gas in the electric furnace, and it is preferable to set the CO gas concentration to about 1 to 10% by volume in a nitrogen atmosphere.
電気炉としては、雰囲気を還元雰囲気にできるものであれば特に限定されず、公知のものを使用することができる。ＣＯ２排出量の低減効果の観点から、使用する電極には、カーボン電極を用いることが好ましい。また同様の観点から、炉体にカーボンを用いることが好ましい。 The electric furnace is not particularly limited as long as it can create a reducing atmosphere, and any known electric furnace can be used. From the viewpoint of the effect of reducing CO 2 emissions, it is preferable to use a carbon electrode as the electrode to be used. Also, from the same viewpoint, it is preferable to use carbon for the furnace body.
ＣａＯ源とＳｉＯ２源とを含む原料としては、化学組成としてＣａＯを含むＣａＯ原料とＳｉＯ２を含むＳｉＯ２原料のそれぞれを混合した混合物、化学組成として、ＣａＯ及びＳｉＯ２の両者を含む原料、これらの混合原料等が挙げられる。
原料の配合割合は、γ－Ｃ２Ｓが生成するような割合となるように調整することが好ましい。
A raw material containing a CaO source and a SiO 2 source includes a mixture of a CaO raw material containing CaO and a SiO 2 raw material containing SiO 2 as a chemical composition, a raw material containing both CaO and SiO 2 as a chemical composition, Mixed raw materials of these may be mentioned.
The blending ratio of the raw materials is preferably adjusted to such a ratio that γ-C 2 S is produced.
ＣａＯ原料としては、例えば、石灰石等の炭酸カルシウム、消石灰等の水酸化カルシウム等が挙げられる。ＳｉＯ２原料としては、例えば、ケイ石や粘土等が挙げられる。 Examples of the CaO raw material include calcium carbonate such as limestone, and calcium hydroxide such as slaked lime. Examples of the SiO 2 raw material include silica stone and clay.
本実施形態では、既述の原料として、工業原料を用いてもよいが、産業副産物を用いることもできる。産業副産物としては、副生水酸化カルシウム、廃コンクリート塊から発生する微粉末、鉄鋼スラグ、シリカフュームやフライアッシュに代表されるような産業副産物として発生する様々なシリカ質ダスト等が挙げられ、これらは工業原料の一部又は全部に置き換えて使用することができる。
以下、産業副産物について例示する。
In this embodiment, industrial raw materials may be used as the raw materials described above, but industrial by-products may also be used. Industrial by-products include by-product calcium hydroxide, fine powder generated from waste concrete lumps, steel slag, various siliceous dusts generated as industrial by-products such as silica fume and fly ash, etc. It can be used to replace part or all of industrial raw materials.
Examples of industrial by-products are given below.
（副生水酸化カルシウム）
本実施形態に係る副生水酸化カルシウム（副生消石灰ともいう）とは、産業副産物として発生する水酸化カルシウムを総称するものである。例えば、カルシウムカーバイドからアセチレンを生成する工程で副生する水酸化カルシウムが挙げられる。副生水酸化カルシウムは、例えば、水酸化カルシウムの純度が９５％程度で、不純物を５％以下の範囲で含む。
(By-product calcium hydroxide)
By-product calcium hydroxide (also referred to as by-product slaked lime) according to the present embodiment is a general term for calcium hydroxide generated as an industrial by-product. For example, calcium hydroxide is a by-product in the process of producing acetylene from calcium carbide. For example, the by-product calcium hydroxide has a purity of about 95% and contains impurities in a range of 5% or less.
（フライアッシュ）
本実施形態に係るフライアッシュとは、火力発電所から発生する副産物であり、石炭灰やフライアッシュを総称するものである。本発明では、未燃カーボン量が多く、有効利用が難しいとされる石炭灰も利用可能である。
(fly ash)
The fly ash according to this embodiment is a byproduct generated from a thermal power plant, and is a general term for coal ash and fly ash. In the present invention, coal ash, which has a large amount of unburned carbon and is difficult to utilize effectively, can also be used.
（鉄鋼スラグ）
本実施形態に係る鉄鋼スラグとは、高炉スラグ（水砕スラグ、徐冷スラグ）、転炉スラグ、電気炉スラグ、ステンレススラグを総称するものである。高炉スラグとは、高炉で銑鉄を生産する際に発生する副産物であり、水で急冷してガラス化した高炉水砕スラグや、徐冷されて結晶化した高炉徐冷スラグがある。転炉スラグとは、高炉で得た銑鉄を精錬する転炉工程で発生する副産物である。電気炉スラグとは、スクラップを集めて電炉で還元し、鉄を得る際に発生するスラグを総称するものであり、電気炉酸化期スラグや電気炉還元期スラグがある。ステンレススラグとは、ステンレス鋼を生産する際に発生するスラグを総称するものである。本実施形態では、いずれも利用可能である。
(steel slag)
The steel slag according to this embodiment is a general term for blast furnace slag (granulated slag, slowly cooled slag), converter slag, electric furnace slag, and stainless steel slag. Blast furnace slag is a byproduct generated when producing pig iron in a blast furnace, and includes granulated blast furnace slag, which is quenched with water and vitrified, and slow-cooled blast furnace slag, which is slowly cooled and crystallized. Converter slag is a byproduct generated in the converter process, which refines pig iron obtained in a blast furnace. Electric furnace slag is a general term for slag generated when scrap is collected and reduced in an electric furnace to obtain iron, and includes electric furnace oxidation stage slag and electric furnace reduction stage slag. Stainless steel slag is a general term for slag generated during the production of stainless steel. In this embodiment, both can be used.
本実施形態では、ＣａＯ源とＳｉＯ２源とを含む原料が産業副産物であり、強熱減量で補正した乾物ベースでの不純物量が５％以上でもγ型のダイカルシウムシリケートを得ることができる。不純物の増加により、共存化合物が増えていくものの（γ型のダイカルシウムシリケートの純度は下がるものの）、不純物が２０％程度でも、γ型のダイカルシウムシリケートを生成させることができる。この化合物の生成により、ダスティングを誘発させ、粉化させることができる。粉化することで比表面積が高くなり、ＣＯ２吸収材料として有用となる。同一の化学成分であっても、γ型のダイカルシウムシリケートを生成しない場合（β型のダイカルシウムシリケートが生成する場合）には、粉化が起こらす、塊状となるため、ＣＯ２吸収材料としては有用ではない。不純物としては、例えば、酸化物標記した化学成分として、Ｆｅ２Ｏ３、Ａｌ２Ｏ３、ＭｇＯ、ＴｉＯ２、Ｎａ２Ｏ、Ｋ２Ｏ、ＭｎＯ、ＳＯ３の少なくともいずれかが挙げられる。 In this embodiment, the raw material containing the CaO source and the SiO 2 source is an industrial by-product, and it is possible to obtain γ-type dicalcium silicate even if the amount of impurities on a dry matter basis corrected by loss on ignition is 5% or more. Although the number of coexisting compounds increases with an increase in impurities (although the purity of γ-type dicalcium silicate decreases), γ-type dicalcium silicate can be produced even with impurities of about 20%. The formation of this compound can induce dusting and cause powdering. Powdering increases the specific surface area, making it useful as a CO 2 absorption material. Even if the chemical components are the same, if γ-type dicalcium silicate is not produced (β-type dicalcium silicate is produced), powdering occurs and the product becomes lumpy, so it cannot be used as a CO 2 absorption material. is not useful. Examples of impurities include at least one of Fe 2 O 3 , Al 2 O 3 , MgO, TiO 2 , Na 2 O, K 2 O, MnO, and SO 3 as chemical components labeled as oxides.
乾物ベースでの上記不純物は合計で、５～３０％であることが好ましい。乾物ベースは、強熱減量（L.O.I.：Loss on ignition）で補正することができる。具体的には、強熱減量を差し引いた質量を１００とした時の相対値として表す。
また、強熱減量で補正した乾物ベースでのＣａＯ含有量は、生産性及びカーボンネガティブの観点から、３０～７０％であることが好ましく、４０～６０％であることがより好ましい。
The total amount of the above impurities on a dry matter basis is preferably 5 to 30%. The dry matter basis can be corrected for loss on ignition (LOI). Specifically, it is expressed as a relative value when the mass after subtracting the loss on ignition is taken as 100.
Further, the CaO content on a dry matter basis corrected by loss on ignition is preferably 30 to 70%, more preferably 40 to 60%, from the viewpoint of productivity and carbon negative.
本実施形態では、原料を電炉に投入し、加熱処理により溶融し、排出・冷却することでＣＯ２吸収材料を製造することができる。原料は混合粉砕等の原料調製をする必要はなく、計量だけ済ませて、電炉に投入すればよい。溶融して液相反応させるため、原料を細かく粉砕する必要がない。 In this embodiment, the CO 2 absorbing material can be manufactured by charging raw materials into an electric furnace, melting them by heat treatment, and discharging and cooling them. There is no need to prepare the raw materials by mixing and pulverizing them, just measure them and put them into the electric furnace. Because it is melted and subjected to a liquid phase reaction, there is no need to finely grind the raw materials.
粉状の原料がある場合には、発塵防止や加熱時の吹き上げ防止の観点から、造粒やブリケット化した後、電炉に投入することもできる。 If powdered raw materials are available, they can be granulated or briquettered and then fed into an electric furnace in order to prevent dust generation and blow-up during heating.
熱処理温度は、１４００～１８００℃の範囲が好ましく、１５００～１７００℃がより好ましい。溶融後、一定時間反応させ、炉内から溶融物を流し出して冷却する。冷却は超急冷以外であればよく、特に限定されないが、徐冷することが好ましい。 The heat treatment temperature is preferably in the range of 1400 to 1800°C, more preferably 1500 to 1700°C. After melting, the reactor is allowed to react for a certain period of time, and the molten material is poured out of the furnace and cooled. Cooling may be performed by any method other than ultra-rapid cooling, and is not particularly limited, but slow cooling is preferred.
前述の原料を、電気炉内で熱処理してカーボンネガティブな炭酸ガス固定化材を製造するにあたり、再生可能エネルギーを用いて電気炉を操業することができる。これによって、ＣＯ２吸収材料を製造する際のＣＯ２排出量原単位をより低減することができる。 In producing a carbon-negative carbon dioxide gas fixing material by heat-treating the above-mentioned raw materials in an electric furnace, the electric furnace can be operated using renewable energy. This makes it possible to further reduce the CO 2 emissions per unit of production when producing the CO 2 absorbing material.
再生可能エネルギーは、水力発電、太陽光発電、風力発電、バイオマス発電、地熱発電等が利用可能である。特に、水力発電、太陽光発電、風力発電を選定することが好ましい。再生可能エネルギーを使用することにより、エネルギー由来のＣＯ２排出量を削減できる。 Renewable energies include hydroelectric power, solar power, wind power, biomass power, and geothermal power. In particular, it is preferable to select hydroelectric power generation, solar power generation, and wind power generation. By using renewable energy, energy-derived CO 2 emissions can be reduced.
以下、実施例によって本発明を具体的に説明するが、本発明はこれらの実施例によって限定されるものではない。 Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.
［実施例１］
表１に示す原料を用いて、表２に示す配合原料を調製した。表２の配合原料を、ロータリーキルンによる熱処理及び電気炉による熱処理を行って、生成化合物をＸＲＤで、ダスティングの有無を目視で確認するとともに、ＣＯ２吸収量を評価した。結果を表３に記載した。
[Example 1]
Using the raw materials shown in Table 1, the blended raw materials shown in Table 2 were prepared. The blended raw materials in Table 2 were heat treated in a rotary kiln and in an electric furnace, and the resulting compounds were visually confirmed by XRD for the presence or absence of dusting, and the amount of CO 2 absorbed was evaluated. The results are listed in Table 3.
ロータリーキルンによる熱処理：デンカ（株）のキルンを用いた。原料調製では、ボールミルを用いて原料を平均粒径で１５μｍ程度に混合粉砕した。焼成温度はバーナーの焼点温度で管理し、１４５０～１５００℃で行った。 Heat treatment using a rotary kiln: A kiln manufactured by Denka Co., Ltd. was used. In raw material preparation, the raw materials were mixed and ground to an average particle size of about 15 μm using a ball mill. The firing temperature was controlled by the burning point temperature of the burner, and was 1450 to 1500°C.
電気炉による熱処理：デンカ(株)の青海工場内の電気炉を用いた。原料調製のための混合粉砕処理は行わなかった。溶融温度は１６５０℃とした。なお、操業にはカーボン電極とカーボンの炉体を用いた。定常運転になってからの排ガス組成を測定した。ガス組成は、窒素８０体積％、酸素が１０体積％、Ｈ２Ｏが７体積％、ＣＯが２体積％であった。 Heat treatment using an electric furnace: An electric furnace at Denka Co., Ltd.'s Omi factory was used. Mixing and pulverizing treatment for raw material preparation was not performed. The melting temperature was 1650°C. A carbon electrode and a carbon furnace body were used for the operation. The exhaust gas composition was measured after steady operation. The gas composition was 80% by volume of nitrogen, 10% by volume of oxygen, 7% by volume of H 2 O, and 2% by volume of CO.
上記表中のＣＨは副生消石灰、ＦＡはフライアッシュ、ＢＦＳは高炉水砕スラグ、ＬＯＩは１０００℃で強熱した際の減量（質量％）、不純物の総量は、酸化物標記した化学成分として、Ｆｅ２Ｏ３、Ａｌ２Ｏ３、ＭｇＯ、ＴｉＯ２、Ｎａ２Ｏ、Ｋ２Ｏ、ＭｎＯ、ＳＯ３の総和とした。
なお、各不純物の割合は、ＪＩＳ Ｒ ５２０２により求めた。
In the above table, CH is byproduct slaked lime, FA is fly ash, BFS is granulated blast furnace slag, LOI is weight loss when ignited at 1000℃ (mass%), and the total amount of impurities is as a chemical component labeled as oxide. , Fe 2 O 3 , Al 2 O 3 , MgO, TiO 2 , Na 2 O, K 2 O, MnO, and SO 3 .
Note that the proportion of each impurity was determined according to JIS R 5202.
・ダスティングの有無と物状：９０μｍ通過率が５０％以上である場合をダスティング有りとし、５０％未満の場合をダスティング無しとした。また、物状は、製造後の生成物の形態を目視により評価した。
・ＣＯ２吸収量：それぞれで得られた製造物を、炭酸ガス濃度５％、温度３０℃、及び相対湿度６０％の空気中で７日間炭酸化させた際の二酸化炭素吸収量を求めた。なお、この際、炭酸化処理を行う前の試料が二酸化炭素を含んでいる場合があることを考慮し、下記の式により、ＣＯ２吸収量を算出した。
（ＣＯ２吸収量）＝（炭酸化処理後の試料の二酸化炭素量）－（炭酸化処理前の試料の二酸化炭素量）
なお、上記式の二酸化炭素量は無機の全炭素分析（クーロマチック－Ｃ）によって求めた。
- Presence or absence of dusting and physical condition: Dusting was considered to be present when the 90 μm passing rate was 50% or more, and dusting was considered to be present when it was less than 50%. In addition, the physical condition of the product was evaluated by visual observation of the form of the product after production.
- CO 2 absorption amount: The carbon dioxide absorption amount was determined when the products obtained in each case were carbonated in air at a carbon dioxide concentration of 5%, a temperature of 30° C., and a relative humidity of 60% for 7 days. At this time, taking into consideration that the sample before carbonation treatment may contain carbon dioxide, the amount of CO 2 absorbed was calculated using the following formula.
( CO2 absorption amount) = (amount of carbon dioxide in the sample after carbonation treatment) - (amount of carbon dioxide in the sample before carbonation treatment)
The amount of carbon dioxide in the above formula was determined by inorganic total carbon analysis (Coulomatic-C).
本実施例によれば、不純物が２０％前後と非常に多い条件でもγ-Ｃ２Ｓが生成し、粉状の活性の高いＣＯ２吸収材料が得られる。従来のキルン法では、γ-Ｃ２Ｓは生成せず、小石状のクリンカーとなり、ＣＯ２吸収能力が小さいものであった。
ここで、メリライトとは、ゲーレナイトとアケルマナイトの固溶体である。
According to this example, γ-C 2 S is generated even under conditions where the impurity content is very high, around 20%, and a highly active powdered CO 2 absorbing material can be obtained. In the conventional kiln method, γ-C 2 S was not produced, resulting in pebble-like clinker with low CO 2 absorption capacity.
Here, melilite is a solid solution of gehlenite and akermanite.
［実施例２］
ＣＯ２吸収材料の製造にかかるＣＯ２排出量原単位を算出した。表２に示す配合原料１を用いて、ロータリーキルンによる熱処理及び電気炉による熱処理の比較検討を行った。結果を表３に記載した。
[Example 2]
The CO 2 emissions per unit of production of the CO 2 absorbing material was calculated. Using the raw material 1 shown in Table 2, a comparative study was conducted between heat treatment using a rotary kiln and heat treatment using an electric furnace. The results are listed in Table 3.
ロータリーキルンによる熱処理：デンカ株式会社のキルンを用い、買電により操業。（i）原料調製、（ii）造粒、（iii）焼成、（iv）冷却の手順で製造した。まず、（i）原料調製では、ボールミルを用いて原料を平均粒径で１５μｍ程度に混合粉砕した。固相反応を進行させるために原料を細かく粉砕する必要があるためである。この際、電力を消費した。（ii）造粒工程でも電力を消費した。（iii）焼成工程では電力及び燃料を消費した。焼成はバーナーの焼点温度で管理し、１４５０℃～１５００℃で行った。（iv）冷却工程では電力を消費した。 Heat treatment using a rotary kiln: A Denka Co., Ltd. kiln is used and is operated using purchased electricity. It was manufactured using the following steps: (i) raw material preparation, (ii) granulation, (iii) calcination, and (iv) cooling. First, in (i) raw material preparation, the raw materials were mixed and ground using a ball mill to an average particle size of about 15 μm. This is because the raw materials need to be finely pulverized in order to advance the solid phase reaction. At this time, electricity was consumed. (ii) The granulation process also consumed electricity. (iii) The firing process consumed electricity and fuel. Firing was controlled by the burning point temperature of the burner, and was carried out at 1450°C to 1500°C. (iv) The cooling process consumed electricity.
デンカ株式会社青海工場内の電気炉を用い、水力発電由来の電力（再生可能エネルギー）で操業。（i）原料投入、（ii）加熱溶融処理、（iii）排出・冷却の手順で製造した。電炉法では、キルン法と異なり、原料調製のための混合粉砕処理は不要である。これは溶融して液相反応させるためである。（i）～（iii）の手順で電力を消費した。１６５０℃で溶融した。なお、操業にはカーボン電極とカーボンの炉体を適用しており、これら炭材の損耗を調べてＣＯ２排出量に換算した。 It is operated using electricity derived from hydroelectric power (renewable energy) using an electric furnace in Denka Co., Ltd.'s Omi factory. It was manufactured using the following steps: (i) raw material input, (ii) heating and melting treatment, and (iii) discharge and cooling. Unlike the kiln method, the electric furnace method does not require mixing and pulverizing treatment for raw material preparation. This is to melt and cause a liquid phase reaction. Power was consumed in steps (i) to (iii). It melted at 1650°C. In addition, carbon electrodes and a carbon furnace body were used in the operation, and the wear and tear of these carbon materials was investigated and converted into CO 2 emissions.
ここで、それぞれのＣＯ２排出量原単位は次の数字を使用した。
電力：０．４０７ｋｇＣＯ２／ｋＷｈ、ただし、再生可能エネルギーは無視した。
燃料：３．０３ｋｇＣＯ２／Ｌ
炭材：損耗量に３．６６７を乗じて、Ｃ（モル質量：１２）からＣＯ２（モル質量：４４）に換算した。
Here, the following numbers were used for each CO 2 emission unit.
Electric power: 0.407 kgCO 2 /kWh, however, renewable energy was ignored.
Fuel: 3.03kgCO2 /L
Carbon material: The amount of loss was multiplied by 3.667 to convert from C (molar mass: 12) to CO 2 (molar mass: 44).
本実施例によれば、ＣＯ２吸収材料を製造する際のＣＯ２排出量原単位を２２ｋｇＣＯ２／ｔと、著しく小さくすることができる。従来法のキルン法も、セメントを製造する場合と比べると小さい値であるものの、本実施例と比較すると１桁大きい値となっている。
According to this example, the CO 2 emission unit when producing the CO 2 absorbing material can be significantly reduced to 22 kg CO 2 /t. Although the conventional kiln method also has a smaller value compared to the case of producing cement, the value is one order of magnitude larger than that of this example.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01148735A (en) * | 1987-12-04 | 1989-06-12 | Nippon Steel Corp | Method for manufacturing binder by slag modification |
| JP2004027238A (en) * | 1994-02-24 | 2004-01-29 | Nippon Kayaku Co Ltd | Marking composition, molded product, and marking method |
| JP5914492B2 (en) * | 2011-08-25 | 2016-05-11 | デンカ株式会社 | Method for producing γ-2CaO · SiO 2 |
| JP2021093895A (en) * | 2019-12-06 | 2021-06-17 | ダニエリ オートメーション ソシエタ ペル アチオニ | Plant for melting and/or heating metal material, and method of supplying power to the same |
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- 2023-08-01 CN CN202380056673.6A patent/CN119630480A/en active Pending
- 2023-08-01 WO PCT/JP2023/028185 patent/WO2024029544A1/en not_active Ceased
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01148735A (en) * | 1987-12-04 | 1989-06-12 | Nippon Steel Corp | Method for manufacturing binder by slag modification |
| JP2004027238A (en) * | 1994-02-24 | 2004-01-29 | Nippon Kayaku Co Ltd | Marking composition, molded product, and marking method |
| JP5914492B2 (en) * | 2011-08-25 | 2016-05-11 | デンカ株式会社 | Method for producing γ-2CaO · SiO 2 |
| JP2021093895A (en) * | 2019-12-06 | 2021-06-17 | ダニエリ オートメーション ソシエタ ペル アチオニ | Plant for melting and/or heating metal material, and method of supplying power to the same |
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