WO2020040325A1

WO2020040325A1 - Carbon dioxide storage cement composition using carbon dioxide captured by-product, and method for producing same

Info

Publication number: WO2020040325A1
Application number: PCT/KR2018/009669
Authority: WO
Inventors: 김병환; 박상준; 강현진
Original assignee: (주)대우건설; (주)노빌
Priority date: 2018-08-20
Filing date: 2018-08-22
Publication date: 2020-02-27
Also published as: KR101932508B1

Abstract

The present invention relates to a cement composition and a method for producing same, and specifically, to a carbon dioxide storage cement composition using a carbon dioxide captured by-product and a method for producing same, wherein: a carbon dioxide captured by-product is produced by capturing carbon dioxide by reacting an exhaust gas discharged from cement production equipment with an absorbent solution in which calcium hydroxide (Ca(OH)₂) and an alkaline admixture are mixed; and an additive is added to the carbon captured by-product and the resultant by-product is dried into a powdery form, and then mixed into cement to produce a carbon dioxide storage cement.

Description

Carbon dioxide storage cement composition and manufacturing method using carbon dioxide capture by-product

The present invention relates to a cement composition and a manufacturing method, and in particular, the exhaust gas discharged from a cement manufacturing facility is reacted with an absorbent solution containing calcium hydroxide (Ca (OH) ₂ ) and an alkali admixture to collect carbon dioxide to collect carbon dioxide by-products. The present invention relates to a carbon dioxide storage cement composition and a manufacturing method using a carbon dioxide capture by-product for producing, mixing the additives, drying them in powder form, and then mixing them with cement to prepare carbon dioxide storage cement.

Meanwhile, with the development of the industry, the problem of global warming due to the increase in the concentration of carbon dioxide in the air is emerging. The biggest cause of the increase in the concentration of carbon dioxide in the atmosphere is the coal, petroleum, and liquefied natural gas used in the energy industry. The use of fossil fuels.

From the early 19th century, when the industrialization began, the concentration of greenhouse gases such as carbon dioxide (CO ₂ ), methane (CH ₄ ), hydrogen sulfide (H ₂ S) and carbonyl sulfide (COS) increased in the atmosphere, and rapidly increased since the mid-20th century. It was.

As global warming patterns are accelerating due to the increase of these greenhouse gases, regulations on emission and treatment are becoming more stringent. The United Nations Conference on Environment and Development in Rio, Brazil, in June 1992 has increased international attention to global warming. Developed countries, including the United States and Japan, have decided to reduce global greenhouse gas emissions by 5.2% in 2010 compared to 1990. International agreements are being made on ways to reduce acid gases, including agreements. In particular, the separation of carbon dioxide, which makes up about 80% of the greenhouse gases that cause global warming, has emerged as an important issue.

Techniques for suppressing carbon dioxide emissions include energy saving technologies for reducing emissions, separation recovery technologies of emitted carbon dioxide, technologies for using or immobilizing carbon dioxide, and renewable energy technologies that do not emit carbon dioxide.

Carbon dioxide separation recovery techniques studied so far have been proposed as a realistic alternative, such as absorption method, adsorption method, membrane separation method, deep cooling method. In particular, the absorption method is easy to process a large amount of gas, and is suitable for low concentration gas separation, which is easy to apply to most industries and power plants, and is currently in commercial operation.

In addition, a technology for obtaining carbon dioxide capture by-products such as calcium carbonate (CaCO ₃ ), which is an expensive raw material, is obtained as a by-product by collecting carbon dioxide from the exhaust gas, removing carbon dioxide, and reacting the absorbent with the exhaust gas. And registered in Korean Patent Registration Publication No. 10-1322370.

However, these carbon dioxide capture by-products are limited in their use and are required to be applied to various fields, and in order to obtain and utilize the carbon dioxide capture by-products, a separate dehydration, drying, and powdering process is required to increase manufacturing costs. There is a problem.

As a technology for solving this problem, a method and apparatus for manufacturing cement using carbon dioxide, which is Korean Patent Application Publication No. 10-2015-0120714, has been disclosed.

The method and apparatus for producing cement using carbon dioxide include saturating calcium hydroxide (Ca (OH) 2) in water to produce an aqueous calcium hydroxide solution, and injecting carbon dioxide (CO 2) into the aqueous calcium hydroxide solution to cause a carbonation reaction to cause calcium carbonate (CaCO 3). And producing a cement by applying a sol-gel method to silicon oxide (SiO 2), aluminum oxide (Al 2 O 3) and calcium carbonate.

However, the cement produced by such a method and apparatus for producing cement using carbon dioxide has a relatively weak compressive strength.

(Patent Document 01) Korean Patent Registration Publication No. 10-1322370

(Patent Document 02) Republic of Korea Patent Publication No. 10-2015-0120714

The present invention is to solve the above problems, by reacting the exhaust gas discharged from the cement manufacturing equipment with the absorbent liquid mixed with calcium hydroxide (Ca (OH) ₂ ) and alkali admixture to capture carbon dioxide to produce carbon dioxide capture by-products It is an object of the present invention to provide a carbon dioxide storage cement composition and a manufacturing method using a carbon dioxide capture by-product to mix the additives and to dry the powder form and then mix into cement to produce carbon dioxide storage cement.

Features of the present invention for achieving the above object,

A capture process of supplying the discharge gas discharged from the cement manufacturing facility to a reaction column in which an absorption liquid containing calcium hydroxide (Ca (OH) ₂ ) and an alkali admixture is stored to collect carbon dioxide to produce carbon dioxide collection by-products; An additive input process of injecting the sludge-type carbon dioxide capture by-products and additives produced and precipitated in the reaction tower in a microwave dryer; A drying process of drying the carbon dioxide collection byproduct into which the additive is added by using the microwave in the microwave dryer and discharging the byproduct in a powder form; And a cement manufacturing process for preparing carbon dioxide storage cement by mixing dried dry carbon dioxide by-products 5-15 wt% and 85-95 wt% of portland cement.

Here, the additive is mixed in 0.1 to 1.0% by weight based on the weight of carbon dioxide capture by-products.

Here, the additive is 1 to 5% by weight of carbon nanotubes in powder form as a strength reinforcing agent to improve cement strength, and liquid polyethylene as a grinding aid to improve the degree of powder by increasing the grinding efficiency of carbon dioxide capture by-products. Mix 95 to 99% by weight glycol (PEG).

Here, the carbon nanotubes have a purity of 95% or more, an average diameter of 20 nm, a length of 1 to 25 nm, a metal oxide of 5% or less, a bulk density of 0.03 to 0.05 g / cm 3, and a specific surface area of 150 to 250 m 2 / g.

Here, the dried carbon dioxide capture by-product has a powder degree of 6,000 m 2 / g or more.

Here, the reaction tower is installed in plurality or two or more in series or in parallel so that the reaction is made continuously.

Here, the microwave dryer includes a semi-cylindrical housing having an inlet formed on an upper surface of one side, and an exhaust port and an outlet formed on the upper and lower sides of the microwave dryer; A screw installed horizontally in the longitudinal direction of the enclosure to move and grind the sludge-type carbon dioxide collection by-products introduced through the inlet; And a microwave generator installed on an outer surface of the enclosure and generating microwaves to irradiate the interior of the enclosure to dry sludge-containing carbon dioxide by-products.

Another feature of the invention,

It is characterized by the carbon dioxide storage cement using the carbon dioxide capture by-product prepared by the method for producing a carbon dioxide storage cement composition using the carbon dioxide capture by-product.

According to the carbon dioxide storage cement composition and the manufacturing method using the carbon dioxide capture by-product of the present invention configured as described above, the exhaust gas discharged from the cement manufacturing equipment reacts with the absorbent liquid mixed with calcium hydroxide (Ca (OH) ₂ ) and an alkali admixture To collect carbon dioxide contained in the exhaust gas by capturing carbon dioxide by-products, and to prepare carbon dioxide storage cement by mixing carbon dioxide-collecting by-products produced by collecting carbon dioxide into cement to make carbon dioxide storage permanently. have.

1 is a process chart for explaining a carbon dioxide storage cement composition manufacturing method using a carbon dioxide capture by-product according to the present invention.

Figure 2 is a conceptual diagram showing the configuration of a carbon dioxide storage cement composition manufacturing apparatus using a carbon dioxide capture by-product according to the present invention.

Hereinafter, a carbon dioxide storage cement composition manufacturing method using a carbon dioxide capture by-product according to the present invention according to the present invention will be described in detail with reference to the accompanying drawings.

In the following description of the present invention, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the subject matter of the present invention, the detailed description thereof will be omitted. Terms to be described later are terms defined in consideration of functions in the present invention, and may be changed according to intentions or customs of users or operators. Therefore, the definition should be made based on the contents throughout the specification.

1 is a process chart illustrating a method for manufacturing a carbon dioxide storage cement composition using a carbon dioxide capture by-product according to the present invention, Figure 2 is a conceptual diagram showing the configuration of a carbon dioxide storage cement composition manufacturing apparatus using a carbon dioxide capture by-product according to the present invention.

1 and 2, the carbon dioxide storage cement composition manufacturing method using the carbon dioxide capture by-product according to the present invention is a capture step (S10), additive addition step (S20), drying step (S30) and cement manufacturing process ( S40).

<< collection process -S10 >>

First, the exhaust gas discharged from the cement manufacturing facility is supplied to the reaction tower 10 in which the absorbent solution containing calcium hydroxide (Ca (OH) ₂ ) and an alkali admixture is stored to collect carbon dioxide to produce carbon dioxide capture by-products. In this case, two or more reaction towers 10 are installed in series or in parallel so that the reaction is continuously performed. The alkali admixture is sodium hydroxide (NaOH), magnesium hydroxide (Mg (OH) 2), or the like. . In addition, the reaction tower 10 has an air diffuser (11) installed at the lower end of the inside to form a fine air droplets of the exhaust gas to facilitate the contact between the carbon dioxide and the absorbent liquid, and an underwater stirrer (13) installed inside the agitator to agitate the absorbent liquid. ) Is installed. In the drawings, reference numeral F denotes a blowing fan, P denotes a pump, and S denotes a chimney.

<< additive addition process-S20 >>

Then, the carbon dioxide by-products and the additives of the sludge-type sludge produced and precipitated in the reaction tower 10 are introduced into the microwave dryer 20.

The additive is mixed in an amount of 0.1 to 1.0% by weight based on the weight of carbon dioxide by-products, 1 to 5% by weight of carbon nanotubes in powder form as a strength reinforcing agent to improve cement strength, and the efficiency of grinding carbon dioxide by-products. It is a mixture of 95 to 99% by weight of liquid polyethylene glycol (PEG) as a grinding aid to increase the powder degree by increasing the powder. In this case, when the carbon nanotubes are mixed at less than 1% by weight, the compressive strength is lowered. When the carbon nanotubes are mixed at an amount of more than 5% by weight, the cost is increased, and polyethylene glycol is mixed at less than 95% by weight. If there is a disadvantage in that the pulverization efficiency is lowered and the powder degree is lowered, the strength is relatively lowered when it is mixed in excess of 99% by weight.

In addition, the carbon nanotubes have characteristics of 95% purity or more, average diameter of 20 nm, length of 1-25 nm, metal oxide of 5% or less, bulk density of 0.03 to 0.05 g / cm 3 and specific surface area of 150 to 250 m 2 / g. desirable.

Subsequently, the microwave dryer 20 has a semi-cylindrical enclosure 21 and an enclosure 21 having an inlet 21a formed at one upper surface thereof, and having an exhaust port 21b and an outlet 21c formed at the upper and lower sides of the microwave dryer 20. Is installed horizontally in the longitudinal direction is installed on the screw 23 and the outer surface of the housing 21 to move and crush the sludge-type carbon dioxide capture by-product injected through the inlet (21a), and generates a microwave 21 A plurality of microwave generators 25 are irradiated inside to dry the sludge-type carbon dioxide capture by-products.

In addition, the microwave dryer 20 may be introduced into the dielectric heating element in the form of beads together, it is also possible to shorten the drying time by introducing hot air into the inside. In this case, the dielectric heating element is alumina (Al ₂ O ₃ ), silicon carbide (SiC), zirconia (ZrO ₂ ) prepared by combining aluminum or zirconium or carbon single or mixed with silicon to create a high temperature environment It is a high dielectric constant ceramic material.

<< drying process-S30 >>

In the microwave dryer 20, the carbon dioxide capture by-product into which the additive is added is dried using microwaves to discharge carbon dioxide capture by-products having a powder degree of 6,000 m 2 / g or more. At this time, when the powder is less than 6,000 m 2 / g there is a problem that the strength does not occur.

<< cement manufacturing process-S40 >>

Finally, carbon dioxide storage cement is prepared by mixing 5-15 wt% of dried carbon dioxide by-products and 85-95 wt% of Portland cement. At this time, when the carbon dioxide capture by-products are mixed at less than 5% by weight, the compressive strength is relatively high, but does not contribute significantly to reduction of carbon dioxide, and when mixed in excess of 15% by weight, the compressive strength is deteriorated.

Hereinafter, the features of the present invention will be described in more detail with reference to the embodiments of the present invention. However, the present invention is not limited to the following examples.

Example 1

The composition ratio of the additive of Example 1 is 99% by weight polyethylene glycol, 1% by weight carbon nanotubes.

<< Example 2 >>

The composition ratio of the additive of Example 2 is 97% by weight polyethylene glycol, 3% by weight carbon nanotubes.

<< Example 3 >>

The composition ratio of the additive of Example 2 is 95% by weight polyethylene glycol, 5% by weight carbon nanotubes.

In all the composition ratios of Examples 1 to 3, the fluidity was 180 to 200 mm, and the compressive strength was expressed low before 7 days, but the strength was greatly increased thereafter.

As those skilled in the art would realize, the described embodiments may be modified in various ways, all without departing from the spirit or scope of the present invention. It is to be understood, however, that the present invention is not limited to the specific forms referred to in the description, but rather includes all modifications, equivalents, and substitutions within the spirit and scope of the invention as defined by the appended claims. Should be.

10: reaction tower 20: microwave dryer

21: enclosure 23: screw

25: microwave generator

Claims

A capture process of supplying the discharge gas discharged from the cement manufacturing facility to a reaction column in which an absorption liquid containing calcium hydroxide (Ca (OH) 2 ) and an alkali admixture is stored to collect carbon dioxide to produce carbon dioxide collection by-products;

An additive feeding step of injecting the sludge-type carbon dioxide capture by-products and additives produced and precipitated in the reaction tower in a microwave dryer;

A drying process of drying the carbon dioxide capture byproduct into which the additive is added by using the microwave in the microwave dryer and discharging the byproduct in a powder form; And

Method for producing a carbon dioxide storage cement composition using a carbon dioxide capture by-product comprising the cement manufacturing process for producing a carbon dioxide storage cement by mixing the dried carbon dioxide capture by-product 5-15% by weight and 85-95% by weight of Portland cement.
The method of claim 1,

The additive,

Method for producing a carbon dioxide storage cement composition using a carbon dioxide capture by-product, characterized in that the mixture by 0.1 to 1.0% by weight relative to the carbon dioxide capture by-product weight.
The method of claim 2,

The additive,

1 to 5% by weight of powdered carbon nanotubes as a strength reinforcing agent to improve cement strength, and 95 to 99 liquid polyethylene glycol (PEG) as a grinding aid to improve the powder level by increasing the grinding efficiency of carbon dioxide capture by-products. Method for producing a carbon dioxide storage cement composition using a carbon dioxide capture by-product, characterized in that for mixing by weight%.
The method of claim 3, wherein

The carbon nanotubes,

Carbon dioxide using carbon dioxide capture by-products, characterized by a purity of at least 95%, an average diameter of 20 nm, a length of 1-25 nm, a metal oxide of 5% or less, a bulk density of 0.03 to 0.05 g / cm 3, and a specific surface area of 150 to 250 m 2 / g. Method for preparing storage cement composition.
The method of claim 1,

The dried carbon dioxide capture by-products,

Method for producing a carbon dioxide storage cement composition using a carbon dioxide capture by-product, characterized in that the powder degree is 6,000 m2 / g or more.
The method of claim 1,

The reaction tower,

Method for producing a carbon dioxide storage cement composition using a carbon dioxide capture by-product, characterized in that a plurality of two or more in series or in parallel to be installed in a continuous reaction.
The method of claim 1,

The microwave dryer,

A semi-cylindrical housing having an inlet formed on one side of the upper surface, and an exhaust port and an outlet formed on the upper and lower sides of the other side;

A screw installed horizontally in the longitudinal direction of the enclosure to move and grind the sludge-type carbon dioxide collection by-products introduced through the inlet; And

The method of manufacturing a carbon dioxide storage cement composition using a carbon dioxide capture by-product, which is installed on an outer surface of the enclosure and comprises a microwave generator for generating microwaves and irradiating the inside of the enclosure to dry the sludge-type carbon dioxide capture by-products.
Carbon dioxide storage cement using the carbon dioxide capture by-product prepared by the method for producing a carbon dioxide storage cement composition using the carbon dioxide capture by-product of claim 1.