KR101588728B1 - A Composite of gamma-dicalcium silicate for CO2 capture comprising fly ash of fluidize-bed boiler and manufacturing method thereof - Google Patents

Abstract

Provided is a gamma dicalcium silicate composition for capturing carbon dioxide, which is produced by; forming clinker by mixing ingredients with 15-25 parts by weight of water with respect to 100 parts by weight of the ingredients, wherein the ingredients comprises 35-70 wt% of fluidized-bed boiler fly ash, 25-50 wt% of waste foundry sand powder ground to have the particle size of 1,000-2,000 blaine (cm^2/g), and 5-15 wt% of paper ash powder ground to have the particle size of 1,000-2,000 blaine (cm^2/g), with respect to the total weight of the clinker based on solid; and drying and sintering the same thereafter. In addition, provided is a production method thereof.

Description

TECHNICAL FIELD The present invention relates to a gamma-dicalcium silicate composition for capturing carbon dioxide, which contains fly ash of a fluidized-bed phase boiler, and a method for producing the gamma-dicalcium silicate composition,

The present invention relates to a gamma-calcium silicate material, which is a functional material capable of capturing carbon dioxide and carbon dioxide released from industry, thermal power plants and the like, and more particularly to a gamma-calcium silicate material produced by using a fluidized bed phase boiler fly ash and a foundry sand 0001] The present invention relates to a gamma-dicalcium silicate composition for capturing carbon dioxide having a different crystal form and a method for producing the same.

Carbon dioxide is one of the greenhouse gases known to have the greatest impact on global warming. Therefore, if these CO2 emissions are not controlled, global warming can lead to global environmental disasters. Therefore, flue gas, which is a gas stream generated by the combustion of fossil fuels, syngas produced by gasification of coal, or syngas produced by reforming natural gas, It is a very important task for mankind to remove the carbon dioxide contained in the fuel gas.

Wet chemical scrubbing, adsorption, membrane separation, cryogenic cooling, etc., are the methods of removing carbon dioxide from flue-gases. However, these methods are costly, especially in large- It is difficult to use for recovery.

Another way to remove carbon dioxide from flue-gases is dry chemical scrubbing. This is a technique that uses solids instead of liquid solvents used in wet chemical cleaning. That is, the active component in the solid sorbent and carbon dioxide undergo chemical reaction in the absorption reactor to produce carbonates or bicarbonates, thereby removing carbon dioxide from the gas stream and absorbing the carbon dioxide, which is regenerated by regeneration in the regeneration reactor, It is a technique to use. Such a dry chemical cleaning technique is also referred to as dry regenerable sorbent technology.

The characteristics of dry regeneration absorption technology are that they are low in cost, can be recycled and reused, are excellent in various aspects such as design flexibility, application of environmentally low energy absorption process and high efficiency carbon dioxide absorption (absorbing ability and reactivity). It is a future technology that can sustain growth development compared with technology.

U.S. Patent No. 6,387,337 B1 (Apr. 14, 2002) describes the use of alkali or alkaline earth metal compounds in the temperature range of 93-1,093 ° C (200-2,000 ° F) in a moving-bed reactor for the absorption and regeneration of carbon dioxide And a carbon dioxide recovery method for continuously performing the carbon dioxide recovery method. Here, the absorbent is limited to an absorbent in which an alkali metal or an alkaline earth metal compound is deposited on a support.

However, the above patent has a disadvantage in that the cost of recovering carbon dioxide is high and the environment-friendliness is insufficient.

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made keeping in mind the above problems occurring in the prior art, and it is an object of the present invention to provide a gamma-dicalcium silicate composition for capturing carbon dioxide which can efficiently capture carbon dioxide at low cost and a method for producing the same.

Also, the present invention provides a gamma-dicalcium silicate composition for capturing carbon dioxide which can be produced by utilizing fly ash produced in a fluidized-bed-phase boiler and waste pigments that are discharged in large quantities from a casting factory and discarded, .

The present invention

25 to 50% by weight of a waste powder obtained by pulverizing 35 to 70% by weight of fly ash fly ash and 1,000 to 2,000 blanks of powder (Blaine, cm ² / g) with respect to the total weight of climber on the basis of solid content, Components comprising 5 to 15% by weight of a paper ash powder crushed by 1,000 to 2,000 blances (Blaine, cm ² / g) are mixed with 15 to 25 parts by weight of water based on 100 parts by weight of the components to form a clinker , And drying and firing the obtained gamma-dicalcium silicate composition for carbon dioxide capture.

Further, according to the present invention,

(a) from 25 to 50% by weight of a waste paper pulverized from 35 to 70% by weight of a fluidized bed boiler fly ash and from 1,000 to 2,000 blanks (Blaine, cm < 2 > / g) based on the total weight of climbers, The components including 5 to 15% by weight of the pulverized ash powder of 1,000 to 2,000 blanks (Blaine, cm < 2 > / g) were mixed with 15 to 25 parts by weight of water based on 100 parts by weight of the components to form clinker And drying;

(b) firing the dried clinker in an electric furnace at 1,300 DEG C to 1,450 DEG C; And

and (c) recovering the clinker by cooling the electric furnace after the calcination is completed. The present invention also provides a method for producing a calcium silicate composition for capturing carbon dioxide.

Since the gamma-dicalcium silicate composition for capturing carbon dioxide of the present invention is produced by using fly ash produced in a fluidized bed boiler which is generated in a large amount but has little recycled value, and waste plaster which is discharged in large quantities in a casting factory and discarded, It can make a great contribution to environmental protection.

In addition, since carbon dioxide in the atmosphere can be efficiently captured and carbon dioxide can be captured during the release of carbon dioxide by a capture process, which is one of the carbon dioxide dry regeneration and absorption technologies, it provides an excellent effect for reducing carbon dioxide, It can contribute greatly to the prevention of global warming.

In addition, it is mixed with cement products such as bricks, interlocking, and barrier seams, and exhibits excellent carbon dioxide capturing characteristics, so that it is useful for various fields.

Fig. 1 shows the result of quantitative analysis by the Rietvald method of X-ray of gamma-calcium silicate prepared in Example 1. Fig.
FIG. 2 is a graph showing the results of a powder-x-ray analysis performed to confirm the carbon dioxide capture performance of the gamma-dicalcium silicate compound in Test Example 1. FIG.

The present invention relates to a process for producing a slurry containing 25 to 50% by weight of a waste powder obtained by pulverizing 35 to 70% by weight of fly ash fly ash and 1,000 to 2,000 blanks of powder (Blaine, cm ² / g), based on the total weight of climber, , And 5 to 15% by weight of a pulverized ash powder of 1,000 to 2,000 blances (Blaine, cm ² / g) were mixed with 15 to 25 parts by weight of water based on 100 parts by weight of the components A calcium silicate composition for capturing carbon dioxide, which is produced by molding a clinker, drying and firing.

The fluidized bed boiler fly ash may include 30 to 60 wt% of calcium oxide (CaO) and 30 to 60 wt% of anhydrous gypsum (CaSO ₄ ), more preferably 40 to 50 wt% of burnt lime (CaO) And 40 to 50% by weight of anhydrous gypsum (CaSO ₄ ) may be used.

The waste sand containing silica (SiO ₂ ) in an amount of 60 to 90% by weight, more preferably 70 to 80% by weight may be used.

The paper ash may contain calcium oxide (CaO) in an amount of 70% by weight or more, more preferably 80% by weight or more.

The fluidized-bed phase boiler fly ash contains about 40 wt% or more of quicklime and about 40% or more of anhydrous gypsum in the mineral composition, and can not be used as a replacement material for ordinary ordinary portland cement due to excess quicklime In addition, since the content of anhydrous gypsum is high, it can not be used for the production of ordinary Portland cement.

The present invention provides a method of utilizing the above-described fluidized bed boiler fly ash in a non-recyclable state, and a method of manufacturing the gamma-dicalcium silicate composition for capturing carbon dioxide.

More specifically, the present invention relates to a method of capturing carbon dioxide, which is one of the carbon dioxide-based regeneration absorption technologies, by utilizing a waste fly ash produced in a fluidized-bed boiler in a large amount but having little recycled value, The present invention also provides a gamma-dicalcium silicate composition and a method for producing the gamma-dicalcium silicate composition, which are necessary for capturing carbon dioxide by carbonation at the time of release of carbon dioxide or by capturing process.

The paper ash used in the present invention can be used after being used in a paper mill and incinerated.

The present invention reduces the amount of carbon dioxide, which is a major cause of global warming, by utilizing fly ash generated in a fluidized bed boiler and waste foundry that is discharged in large quantities in a casting factory and discarded, It is very useful in terms of securing.

The gamma-dicalcium silicate composition of the present invention is used in cement products such as bricks, interlocking, and barrier stones to exhibit excellent carbon dioxide capture characteristics, and thus has a very high utilization characteristic.

The method for preparing the gamma-dicalcium silicate composition for capturing carbon dioxide

(a), based on the solid content of the clinker (climker) based on the total weight of the fluidized bed the boiler fly ash 35 to 70% by weight, fineness of 1,000 to 2,000 Blaine (Blaine, cm ² / g) a Waste Foundry Sand powder pulverized into 25 to 50% by weight , And 5 to 15% by weight of pulverized ash powder of 1,000 to 2,000 blances (Blaine, cm ² / g) were mixed with 15 to 25 parts by weight of water based on 100 parts by weight of the components Molding and drying the post clinker;

(b) firing the dried clinker in an electric furnace at 1,300 DEG C to 1,450 DEG C; And

(c) recovering the clinker by cooling the electric furnace after the calcination is completed.

The fluidized bed boiler fly ash may include 30 to 60 wt% of calcium oxide (CaO) and 30 to 60 wt% of anhydrous gypsum (CaSO ₄ ), more preferably 40 to 50 wt% of burnt lime (CaO) And 40 to 50% by weight of anhydrous gypsum (CaSO ₄ ) may be used.

The waste sand containing silica (SiO ₂ ) in an amount of 60 to 90% by weight, more preferably 70 to 80% by weight may be used.

The paper ash preferably contains calcium oxide (CaO) in an amount of 70% by weight or more, more preferably 80% by weight or more.

 The size of the clinker formed in the step (a) may be about 1 mm to 3 mm in diameter. The drying time of the molded clinker is about 0.3 to 3 days in the case of natural drying.

In the step (b), the heating rate of the electric furnace is preferably 1 to 30 ° C / min, more preferably 5 to 15 ° C / min. When the heating rate of the electric furnace is within the above range, gamma is preferable because the yield of calcium silicate production is increased.

In the recycling of the clinker in the step (c), it is preferable that the electric furnace is quenched to a temperature of atmospheric to within a range of from 3 to 30 minutes, more preferably from 10 to 20 minutes, after naturally cooling to 800 to 1,000 ° C. As the quenching method, all methods known in the art can be applied, and particularly, a quenching method in which the wind is strongly blown is preferred. When the electric furnace is cooled in the above manner, gamma is preferable because the yield of calcium silicate production can be increased.

The calcination in the step (c) may be performed for 0.1 to 3 hours, preferably 0.5 to 2 hours.

The method of the present invention may further comprise pulverizing the gamma-dicalcium silicate prepared in the step (c) with powder of 3,000 to 4,000 blances (Blaine, cm ² / g) so that the gamma- Can be obtained. In fact, the gamma-iodine calcium silicate is naturally differentiated into a powdery phase in the atmosphere, but it is also possible to use it by forced grinding as described above.

In the above description, the content of the description of the gamma-dicalcium silicate composition for capturing carbon dioxide can be applied to all of the methods for producing the carbon dioxide-capturing gamma-dicalcium silicate composition, and vice versa.

Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are intended to further illustrate the present invention, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.

Example  1: Gamma for capturing carbon dioxide - The calcium silicate  Preparation of composition

50% by weight of a fluidized bed boiler fly ash containing 45% by weight of calcium oxide (CaO) and 45% by weight of an anhydrous gypsum (CaSO ₄ ) component based on the total weight of climber based on solids; 40% by weight of a waste sand having a silica (SiO ₂ ) content of 75% by weight is pulverized into 1,000 to 2,000 blanks (Blaine, cm ² / g) powder; And 10% by weight of a paper ash powder in which calcium oxide (CaO) was contained in an amount of 90% by weight and which was ground in 1,000-2,000 blanks (Blaine, cm ² / g) Was mixed with 20 parts by weight of water based on 100 parts by weight of the mixed component to prepare a clinker having a diameter of about 1 cm and dried naturally in air for 1 day.

The dried clinker was placed in an electric furnace, heated at a heating rate of 10 캜 / min, and fired at 1, 400 캜 for 1 hour. After waiting until the temperature of the electric furnace was cooled to 900 캜, the electric furnace was quenched for 20 minutes by the rapid quenching method, cooled to the same temperature as the atmospheric temperature, and then the gamma-dicalcium silicate composition The clinker was recovered.

The clinker was pulverized again with 3,500 blanks (Blaine, cm < 2 > / g) to finally prepare a gamma-dicalcium silicate composition.

In order to identify the components of gamma-dicalcium silicate, quantitative analysis of the components by the Rietvald method was performed by X-ray. As a result of quantitative analysis (FIG. 1), it was confirmed that the amount of gamma-di calcium silicate was 80.5% by weight or more based on the total weight.

Test Example  1: gamma- The calcium silicate  Confirming carbon dioxide capture performance of the composition

100 parts by weight of the gamma-dicalcium silicate composition prepared in Example 1 was thoroughly mixed with 7.5 parts by weight of water, and cylindrical specimens having a diameter of 20 mm and a length of 30 mm were produced by a compression press to a density of 1,500 kg / m ³ . The prepared cylindrical specimens were placed in a container saturated with carbon dioxide and cured for 1 day, 14 days, and 28 days. Cured specimens of each age group were analyzed by powder-X-ray (FIG. 2).

As a result of the experiment, it was confirmed that the gamma-dicalcium silicate compound produced by the present invention can carry out the carbon dioxide capturing function by capturing carbon dioxide to generate carbonates.

Claims (7)

25 to 50% by weight of a waste powder obtained by pulverizing 35 to 70% by weight of fly ash fly ash and 1,000 to 2,000 blanks of powder (Blaine, cm ² / g) based on the total weight of the climber on a solid basis, Components comprising 5 to 15% by weight of a paper ash powder crushed by 1,000 to 2,000 blances (Blaine, cm ² / g) are mixed with 15 to 25 parts by weight of water based on 100 parts by weight of the components to form a clinker , Dried and calcined to form a carbon dioxide-capturing gamma-dicalcium silicate composition. The method according to claim 1,
The fluidized bed phase boiler fly ash comprises 30 to 60 wt% of calcium oxide (CaO) and 30 to 60 wt% of anhydrous gypsum (CaSO ₄ ); The Waste Foundry Sand comprises a silica (SiO ₂₎ 60 to 90% by weight, and; Wherein the paper ash comprises 70% or more of calcium oxide (CaO). (a) clinker (climker) based on the total weight of the fluidized bed the boiler fly ash 35 to 70% by weight, fineness of 1,000 to 2,000 Blaine (Blaine, cm ² / g) a Waste Foundry Sand powder 25 to 50% by weight ground to a solid content basis, And 5 to 15% by weight of pulp-paper ash powder pulverized with 1,000 to 2,000 blanks (Blaine, cm ² / g), and shaping and drying the clinker;
(b) firing the dried clinker in an electric furnace at 1,300 DEG C to 1,450 DEG C; And
(c) cooling the electric furnace after the calcination is completed to recover the clinker. < Desc / Clms Page number 19 > [Claim 3]
The fluidized bed phase boiler fly ash comprises 30 to 60 wt% of calcium oxide (CaO) and 30 to 60 wt% of anhydrous gypsum (CaSO ₄ ); The Waste Foundry Sand comprises a silica (SiO ₂₎ 60 to 90% by weight, and; Wherein the paper ash comprises 70 wt% or more of calcium oxide (CaO). [Claim 3]
Wherein the heating rate of the electric furnace is 1 to 30 占 폚 / min during the firing process of the step (b). [Claim 3]
Characterized in that the electric furnace is cooled naturally from 800 ° C. to 1,000 ° C. in the course of recovering the clinker in the step (c), and then quenched to an atmospheric temperature within 3 to 30 minutes thereafter. Gt; The method of claim 3,
The method of claim 1, further comprising pulverizing the gamma-dicalcium silicate prepared in step (c) with powder of 3,000 to 4,000 blances (Blaine, cm ² / g) Gt;

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