WO2014175478A1

WO2014175478A1 - Apparatus for separating and collecting co2 having deoxidation apparatus

Info

Publication number: WO2014175478A1
Application number: PCT/KR2013/003516
Authority: WO
Inventors: 백일현; 박기태; 유정균
Original assignee: 한국에너지기술연구원
Priority date: 2013-04-24
Filing date: 2013-04-24
Publication date: 2014-10-30
Also published as: KR20140126956A; KR101485952B1

Abstract

Provided is a process for removing oxygen contained in a flue gas before the flue gas reaches an absorption tower so that the oxygen is not absorbed simultaneously when CO₂ is absorbed by an amine-based absorbent at the absorption tower, so as to solve a CO₂ absorbent degradation phenomenon. The apparatus for separating and collecting CO₂ and the processing method, according to the present invention, remove dissolved oxygen in a flue gas through a catalyst combustion apparatus. Accordingly, dissolved oxygen is removed before the flue gas reaches the absorption tower, thereby preventing oxidative effect of an absorbent and solving the degradation phenomenon caused by the oxidative effect.

Description

【Specification】

[Name of invention]

CO2 Separation and Recovery System with Oxygen Removal Device

[Technical Field]

<1> The present invention relates to a carbon dioxide separation and recovery apparatus having a oxygen removal device capable of preventing deterioration of the absorbent by removing residual oxygen contained in the flue gas before entering the absorption tower for carbon dioxide separation recovery and its process method It is about.

Background Art

<2> Carbon Dioxide Capture & Storage (CCS) technology is a technology that isolates carbon dioxide from the atmosphere from carbon dioxide sources such as power plants, steel and cement plants due to the use of fossil fuels.

<3>

<4> Among the CCS technologies, carbon dioxide capture technology is a core technology that accounts for 70 to 80% of the total cost. Postcombustion technology, pre-combustion technology, and oxy-oxygen combustion technology (Oxy) Ⅰ fuel combustion technology) (the latest development status of carbon dioxide capture technology Chang-Keun Lee, Industrial Chemistry Prospect, Vol. 12, No. 1, 2009).

<5>

<6> Postcombustion technology is a technique for absorbing or reacting carbon dioxide (C0 ₂ ) from fossil fuel combustion in various solvents and precombustion technology is used for combustion. The separation of carbon dioxide before is carried out by gasifying fossil fuels such as coal to convert it to C0 ₂ and hydrogen, and then to separate carbon dioxide (C0 ₂ ) from carbon dioxide (C0 ₂ ) / hydrogen () mixed gas. It is a technique for easily capturing carbon dioxide (C0 ₂ ) in exhaust gas by combusting or burning a mixed gas. In addition, Oxy-fuel combustion technology is a technology that facilitates the capture of carbon dioxide (C0 ₂ ) by burning only using oxygen instead of air when burning fossil fuel. Post-combustion capture is the most widely used of the above techniques.

<7>

<8> Post combustion capture technology, which captures carbon dioxide contained in flue gas after combustion, uses a method of absorbing, regenerating, and separating carbon dioxide using an absorbent. The main research directions are focused on improvement of absorbent performance and process improvement. This technology is already operating wet absorption technology and dry adsorption technology to supply carbon dioxide necessary for urea fertilizer production, automatic welding, carbonated drinks, etc., and the efficiency of wet absorption technology is high.

<9>

<10> The representative process of the wet absorption technology is a capture process using an amine-based absorbent, which is a technology that has secured the technical reliability applied in the reforming process of the petrochemical process, but it is applied to the flue gas which is a combustion flue gas containing various pollutants. Application requires improvements in absorbent performance and process. The process using an amine-based absorbent is a chemical absorption process using an alkanolamine in which an amine and a hydroxyl group are bonded to an alkyl group as an absorbent to regenerate an absorption tower that selectively absorbs carbon dioxide from an inlet gas and an absorber that absorbs carbon dioxide. It is composed of stripping tower (heating regeneration tower) and auxiliary equipment.

<11>

Mono ethanol amine (MEA), the most widely used amine absorbent, provides the cause of acidic carbon dioxide and acid-base neutralization reactions in alkaline aqueous solutions formed by unshared electrons of amine groups. (carbamate or bicarbonate) is decomposed and regenerated at about 110 to 130 ^° C. In addition, depending on the structure, the amine absorbent may include DEA (diethanol amine), TEA (tr iethanolamine), MDEA (methyldi ethanol amine), DIPA (di iso-propanolamine) and AMP (2-amino-2-methyl-l-propanol). Idol has a lot of difference in absorption capacity and absorption rate of carbon dioxide according to the structural characteristics.

<13>

<14> The most important design factors in the separation process using a wet absorbent include the carbon dioxide removal efficiency and speed of the absorbent. However, the absorbent selection is also an important design variable as the stability of device absorption and deterioration of the absorbent. Must be taken into account. Compared to other absorbents, amine-based compounds have better reaction properties with carbon dioxide under atmospheric pressure and atmospheric pressure, so that carbon dioxide, which is present in low concentrations in the exhaust gas discharged in large volumes, is separated from the atmospheric pressure at 40 to 50 ^° C in silver. Although it shows the efficiency of oxygen, it has the problem that the absorption of carbon dioxide decreases as Oxidative Degradat ion reacts with oxygen in the presence of oxygen.

<15> That is, one of the factors causing the deterioration of the absorbent is mainly generated by reacting with the absorbent because oxygen (0 ₂ ) remaining in the exhaust gas remains in the aqueous solution without some of the excess oxygen supplied to the combustor being burned. This is referred to as the oxidative degradation phenomenon of the absorbent (degradation characteristics of the carbon dioxide absorbent, Junhan Kim et al. 2, Theories and Applications of Chem. Eng., 2007, Vol. 13, No. 2).

<17>

In order to prevent the deterioration caused by the wet carbon dioxide recovery separation process, a lot of research is being conducted, and mainly a deterioration inhibitor (ethylenediamine tetraacetic acid,

Ethylenedi amine tetraacet icacid, etc.) is used. In this case, other additives must be used, but additives added to prevent deterioration may incur additional operating costs and induce side effects in the entire absorption process. In order to solve this problem, a process of removing oxygen (Korean Patent 1038674) before absorbing carbon dioxide and the like before reaching a stripping column that undergoes a heat regeneration process has also been attempted. However, after residual oxygen reacts with the absorbent, oxidative degradation occurs already. Therefore, it is necessary to fundamentally block the absorbent deterioration by blocking the absorbent and oxygen beforehand.

<19>

[Detailed Description of the Invention]

[Technical problem]

In order to solve the degradation of the carbon dioxide absorbent, a process of removing oxygen contained in the flue gas before reaching the absorption tower is performed so that oxygen is not absorbed simultaneously when carbon dioxide (C0 ₂ ) is absorbed by the amine-based absorbent in the absorption tower. To provide.

Technical Solution

In order to solve the above object, the present inventors have found that flue gas is the selective catalytic reduction

Before reaching the (SCR) device, the present inventors have found that the oxygen elimination effect can be maximized by passing a catalytic combustor which removes oxygen through catalytic combustion in flue gas containing carbon dioxide and oxygen, thereby completing the present invention. .

<22>

The present invention provides a catalytic combustor for removing oxygen through catalytic combustion in a flue gas containing carbon dioxide and oxygen; An optional catalytic reduction (SCR) device for removing NOx of flue gas that has passed through the catalytic combustor; An electrostatic precipitator (EP) for removing dust of the flue gas passing through the selective catalytic reduction device; Flue gas desulfurization to remove SOx of flue gas passed through the electrostatic precipitator (EP) (FGD: Flue gas desulfuriation) device; A temperature dropping device for lowering the temperature of the flue gas passing through the flue gas desulfurization device (DCC: Direct Contacting Cooler); The flue gas and the amine-based absorber passed through the temperature lowering device is supplied, the supplied amine-based absorber absorbs carbon dioxide contained in the exhaust gas to produce a saturated carbon dioxide absorbent, the gas component unreacted with the amine-based absorber Absorption tower to discharge the; And a stripping column for separating the carbon dioxide saturated absorbent into carbon dioxide and an absorbent to regenerate the amine-based absorbent.

<24>

In the present invention, the catalyst in the catalytic burner is platinum (Pt), rhodium (Rh), palladium

Provided is a carbon dioxide separation and recovery apparatus having an oxygen removal apparatus using an oxidation catalyst selected from the group consisting of (Pd).

<26>

The present invention also provides a catalytic combustor, at least one selected from the group consisting of methane, ethane propane, butane, pentane nucleus, heptane, octane, nonane, decane, undecane, and dodecane as hydrocarbons. To provide a carbon dioxide separation recovery device having an oxygen removal device.

<28>

The present invention also provides a carbon dioxide separation and recovery apparatus having an oxygen removal device using a regeneration method of directly heating and engraving a ceramic having a large surface area.

<30>

The present invention also provides a catalytic combustion apparatus comprising an SCR reactor activated by flue gas introduced into the reactor without reheating, and a reducing agent supply line for supplying NH ₃ into the SCR reactor, wherein the activation temperature of the catalyst is Provided is a carbon dioxide separation recovery device having an oxygen removal device, which is set ^at 320 ^° C.

<32>

In the present invention, the flue gas desulfurization apparatus uses a wet method, and absorbs so ₂ in the gaseous phase by using an absorbent of water or an alkaline solution to dehydrate the alkaline components, reactions, and sludge produced. Disclosed is a carbon dioxide separation rare water device having an oxygen removal device.

<34> The present invention also provides a carbon dioxide separation and recovery apparatus having an oxygen removal device, wherein the temperature dropping device lowers the temperature of the flue gas discharged from the flue gas desulfurization device to 40 to 45 ^° C. do.

<36>

The present invention also provides a carbon dioxide separation and recovery apparatus having an oxygen removal device using an amine absorbent used in the absorption tower.

<38>

The present invention also provides the amine absorbent is MEA (Monoethanol amine),

From the group consisting of DGA (Diglycolamine), MDEA (N-Methyldiethanolamine), DEA (Diethanol amine), TEA (Tr iethanolamine), AMP (2 'Amino 2-methyl 1-propanol), PZ (Piperazine), DIPA (Diisopropanolamine) Provided is a carbon dioxide separation recovery device having an oxygen removal device, which is at least one selected.

Advantageous Effects

The carbon dioxide separation and recovery apparatus including the oxygen removing device and the process method thereof according to the present invention remove dissolved oxygen in the flue gas through a catalytic combustion device. Accordingly, the dissolved oxygen is removed before the flue gas reaches the absorption tower to prevent oxidation of the absorbent and to solve the degradation caused by the oxidation.

[Brief Description of Drawings]

1 is a process conceptual diagram showing a carbon dioxide separation recovery process provided with an oxygen removing device of the present invention.

2 is a conceptual diagram showing a catalytic combustion reaction.

[Form for implementation of invention]

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to FIGS. 1 to 2 so that those skilled in the art can easily practice the present invention.

1 is a process conceptual diagram illustrating a carbon dioxide separation recovery process including an oxygen removing device.

The carbon dioxide separation and recovery apparatus including the oxygen removal device includes a combustor (1), a catalytic combustion device (2), a selective reduction catalyst device (3), an electrostatic precipitator (4), a flue gas desulfurization device (5), and The descent apparatus 6, the absorption tower 7, and the stripping tower 8.

The combustor 1 is combusted by injecting fossil fuels such as liquefied petroleum gas (LPG), liquefied natural gas (LNG), petroleum and coal and air containing excess oxygen to burn the combustion. The resulting by-products of fly ash, carbon dioxide (C0 ₂ ), nitrogen oxides (NOx), sulfur oxides (SOx), carbon monoxide (CO) and unburned carbon (HC) are generated with heat and are not reacted with nitrogen ( N ₂ ) and oxygen (0 ₂ ) remain.

In an embodiment of the present invention, fly ash, which is a dust generated when incineration of coal dust as coal as a raw material of about 1,400 to l, 50 (rc), is directly discharged from the combustor.

The flue gas from which the fly ash is removed includes 0 ₂ , N ₂ , which does not participate in the combustion reaction, and combustion byproducts C0 ₂ , N0 ₂ , NO, NOx, SOx, CO, HC, and the like. Is discharged and fed to the catalytic combustion device (2).

The catalytic combustion apparatus 2 performs a process of reacting incomplete combustion gas such as CO and NO with residual oxygen.

CO and NO contained in the flue gas are reacted with 0 _{2 which} does not participate in combustion in the catalytic combustor and thus NO + (1/2) 0 ₂ → N0 ₂ , CO + (1/2) 0 ₂ → C0 ₂ , 4HC + 50 ₂ → 2H ₂ 0 + 4C0 ₂ is converted from the catalytic combustor with the non-banung components N ₂ , NOx, SOx, C0 ₂ and supplied to the selective catalytic reduction apparatus (3). In the process of NO + (1/2) 0 ₂ → N0 ₂ , unbanung NOx components remain, and the unreacted NOx components are also discharged together with other gas components and supplied to the selective catalytic reduction apparatus 3.

In addition, a combustion agent may be further injected into the catalytic combustor to remove residual oxygen. In one embodiment of the present invention, hydrocarbons such as methane, ethane, propane, butane, pentane, nuclear coal, heptane, octane, nonane, decane, undecane, dodecane, and the like are injected into the combustor.

The selective catalytic reduction apparatus 3 removes NOx remaining in the flue gas.

In an embodiment of the present invention, the selective catalytic reduction apparatus 3 selectively reduces NOx in flue gas to nitrogen and water vapor by ammonia reaction while simultaneously passing flue gas and ammonia (NH ₃ ) reducing agent in the catalyst layer. The reaction scheme is as follows.

<53> 4N0 + 4NH ₃ + 0 ₂ → 4N ₂ + 6H ₂ 0

<54> 2N0 ₂ + 4NH ₃ + 0 ₂ → 3N ₂ + 6H ₂ 0

In one embodiment of the present invention, the catalyst is a flue gas supplied inside without reheating. SCR reactor activated by the, and a reducing agent supply line for supplying N¾ into the SCR reactor, the activation temperature of the catalyst is set to less than 320 ^° C.

The dust contained in the flue gas from which NOx has been removed through the selective reduction catalyst device 3 is removed through the electrostatic precipitator 4. In one embodiment of the present invention, the electrostatic precipitator 4 separates the dust in the flue gas by moving it to the wall surface of the apparatus by using an electrostatic force.

Flue gas from which dust has been removed through the electrostatic precipitator 4 is supplied to the flue gas desulfurization apparatus 5. The flue gas desulfurization apparatus 5 removes SOx contained in the exhaust gas after combustion by using the principles of absorption, adsorption, oxidation, reduction, and the like. In one embodiment of the present invention, the flue gas desulfurization apparatus (5) uses a wet method, and absorbs SO ₂ in the gaseous phase by using an absorbent of water or an alkaline solution to dehydrate the alkaline components, reactions and fish sludge. It is a device for treatment and disposal or for the production of marketable by-products such as gypsum.

Through the flue gas desulfurization apparatus (5), the flue gas from which SOx is removed is supplied to the silver degassing apparatus. The temperature drop device lowers the temperature so that the carbon dioxide contained in the flue gas can be absorbed by the amine-based absorbent. In one embodiment of the present invention, the silver lowering device 6 is to drop the temperature of the flue gas of 55 to 60 ° C from which the SOx discharged from the flue gas desulfurization apparatus 5 is removed to 40 to 45 ^° C. give.

<59>

The temperature reduced flue gas and the absorbent are supplied to the absorption tower (7). In one embodiment of the present invention, the absorbent supplied absorbs carbon dioxide contained in the mixed gas to produce a saturated carbon dioxide absorbent, and discharges the absorbent and uncoated gas components.

In one embodiment of the present invention, the absorbent used in the absorption tower 7 uses an amine heat absorber, and the absorbent is ME Monoethanol amine, DGA (Diglycolamine), MDEA (N-Me t hy). At least one selected from the group consisting of 1 diet hano 1 am i ne), DEACDiethanol amine), Triethanolamine (TEA), AMP (2—Amino 2—methyl 1-propanol), and PZ (Piperazine), DIPA (Diisopropanolamine) Use.

The carbon dioxide saturated absorbent removed by discharging the gas component unreacted with the absorbent is preheated through a heat exchanger and then supplied to the stripping column 8. The carbon dioxide supplied to the stripping column (8) is caused by the saturated energy absorbed by the thermal energy generated by the reboiler below the stripping column. The carbon dioxide is stripped off and the absorbent is regenerated and fed back to the absorption tower (7).

2 is a conceptual diagram showing a reaction of a catalytic combustion device.

In one embodiment of the present invention, the catalytic combustion device 2 uses a regeneration method of directly heating and cooling a ceramic having a large surface area.

In addition, in one embodiment of the present invention, after forcibly supplying flue gas discharged from the combustor 1 into the catalytic combustion device 2 using a press-fit blower (not shown), the catalytic combustion device 2 The flue gas supplied inside is preheated to a temperature close to the combustion chamber temperature by the heat storage material 30 at the inlet side of the catalytic combustion device 2. The preheated flue gas is oxidized and decomposed in a completely burned silver 750 to 80 CTC by an auxiliary burner 10 in the combustion chamber and treated as a harmless and odorless gas. The treated flue gas passes through the heat storage material 50 on the outlet side, and heats waste heat of high temperature to the heat storage material and is sensed to a predetermined temperature, and then enters the selective reduction catalyst device 3 through the exhaust pipe 40.

In one embodiment of the present invention, the catalyst 20 used in the catalytic combustion device 2 is used by supporting platinum (Pt), rhodium (Rd) and palladium (Pd). In the catalytic combustion device (2), metals of platinum and palladium are used as a catalyst for converting carbon monoxide (CO) into carbon dioxide (C0 ₂ ) and hydrocarbons (HC) into carbon dioxide (C0 ₂ ) and water (¾0). Rhodium is NO (NOx)

It is used as a catalyst to promote reaction to reduce to N ₂ .

In one embodiment of the present invention, the heat storage material is to use the waste heat of the flue gas as much as possible, and to use it for preheating the flue gas, and to maximize the recovery of the waste heat, without using a heat exchanger, a ceramic having a large surface area Direct heating and cooling heat storage

Use the regeneration method. Subsequent carbon dioxide absorption process by oxidizing the remaining toxic gases carbon monoxide, hydrocarbons and incompletely oxidized nitrogen oxides into a safe gas and removing residual oxygen at the same time through the catalytic combustion reaction occurring in the catalytic combustor (2) It can have the effect of not containing oxygen.

<68>

<69> [Description of the Sign]

1. Combustor 2. Catalytic combustion device

3. Selective Reduction Catalyst Apparatus 4. Electrostatic Precipitator

5. Flue gas desulfurization device 6. Temperature dropping device

7. Absorption tower 7. Extraction tower

10. Auxiliary Burners 20. Catalysts 30. Heat storage inlet 40. Exhaust pipe

50. Outer heat storage material

Claims

[Range of request]

[Claim 11

Catalytic combustion apparatus for removing oxygen through catalytic combustion in flue gas containing carbon dioxide and oxygen;

A selective catalytic reduction (SCR) device for removing NOx of the flue gas passing through the catalytic burner;

An electrostatic precipitator (EP: Electrostatic Precipitator) which removes dust of the flue gas which has passed through the selective catalytic reduction apparatus;

Flue gas desulfuriation (FGD) apparatus for removing SOx of flue gas passing through the electrostatic precipitator (EP: Electrostatic Precipitator);

A temperature dropping device (DCC: Direct Contacting Cooler) for lowering the degree of silver in the flue gas passing through the flue gas desulfurization device;

The flue gas and the amine-based absorber passed through the temperature lowering device is supplied and the supplied amine-based absorber absorbs carbon dioxide contained in the exhaust gas to produce a saturated carbon dioxide absorber, and discharges the amine-based absorber and uncomfortable gas components. Absorption tower; And

And a stripping column for separating the carbon dioxide saturated absorbent into carbon dioxide and an absorbent to regenerate the amine-based absorbent.

Carbon Dioxide Separation and Recovery Device with Oxygen Removal Device.

[Claim 2]

The method of claim 1,

In the catalytic burner, the catalyst is selected from the group consisting of platinum (Pt), rhodium (Rh) and palladium (Pd),

CO2 Separation and Recovery System with Oxygen Removal Device.

[Claim 3]

The method of claim 1,

The catalytic combustor, which uses one or more selected from the group consisting of hydrocarbons methane, ethane, propane, butane, pentane, nuclear coal, heptane, octane, nonane, decane, undecane, and dodecane as a combustor,

CO2 Separation and Recovery System with Oxygen Removal Device.

[Claim 4]

The method of claim 1, 촉매 the catalytic combustion device is a heat storage for directly heating and engraving a ceramic having a large surface area

using regeneration method,

CO2 Separation and Recovery System with Oxygen Removal Device.

[Claim 5]

The method of claim 4,

The catalytic combustor includes an SCR reactor activated by flue gas introduced into the reactor without reheating, and a reducing agent supply line for supplying NH ₃ into the SCR reactor, wherein the activation temperature of the catalyst is less than 320 ^° C.,

Carbon Dioxide Separation and Recovery Device with Oxygen Removal Device.

[Claim 6]

The method of claim 1,

The flue gas desulfurization apparatus uses a wet method, and absorbs SO ₂ in the gaseous phase by using an absorber of water or an alkaline solution to dehydrate and dissolve the alkaline component and the produced sludge.

CO2 Separation and Recovery System with Oxygen Removal Device

[Claim 7]

The method of claim 1,

The temperature drop device is to drop the silver of the flue gas discharged from the flue gas desulfurization device to 40 to 45 ^° C,

Carbon dioxide separation recovery device having an oxygen removal device.

[Claim 8]

The method of claim 1,

The absorbent used in the absorption tower uses an amine-based absorbent,

Carbon Dioxide Separation and Recovery Device with Oxygen Removal Device.

[Claim 9]

The method of claim 1,

The sorbents are Monoethanolamine (MEA), Diglycolamine (DGA), N-Methyldiethanolamine (MDEA), Diethanolamine (DEA), Triethanolamine (TEA), 2-½ino 2 一 methyl 1-propanol (AMP), Piperazine (PZ), DIPA (Di isopropanolamine) is one or more selected from the group consisting of

Carbon dioxide separation recovery device having an oxygen removal device.