KR102040118B1 - Greenhouse gas emission management system according to using fluorine-containing gas raw materials in cement production process - Google Patents

Abstract

In the present invention, in the greenhouse gas emission management system in the cement kiln system, the operation plan of the cement kiln system, daily / monthly / yearly purchase amount and injection amount of fluorine-containing gas, data input information and measurement analysis management information input module; In the cement kiln system, the fluorine-containing gas injection amount, temperature and emissions from the measuring device in real time while the pre-decomposed fluorine-containing gas and quicklime (CaO) react to perform the fluorine immobilization process; Temperature of the system; And a management module for receiving and managing temperature measurement values of the reactants. In the management module, the greenhouse gas emission calculation module for calculating the emission of the fluorine-containing gas by using the greenhouse gas emission calculation method based on the input measured value; And a control module for controlling the temperature of the fluorine-containing gas, the temperature of the system, or the temperature of the reactant according to the discharge of the fluorine-containing gas.

Description

Greenhouse gas emission management system according to using fluorine-containing gas raw materials in cement production process

The present invention relates to a greenhouse gas emission control system according to the use of fluorine-containing gas raw material in the cement production process, and more particularly to a greenhouse gas emission management system according to the use of fluorine-containing gas raw material in the cement kiln system.

Matters concerning the calculation and reporting certification of GHG emissions in the domestic emission trading system are set out in the Guidelines on Reporting and Certification of Emissions from Greenhouse Gas Emission Trading Scheme (hereinafter referred to as “Guide to Greenhouse Gas Emission Reporting and Certification”). To follow. According to Article 11 (Calculation Methods and Application Criteria of Emissions, etc.) of 「Greenhouse Gas Emissions Reporting and Certification Guide」, detailed management methods and calculation criteria for GHG emissions, etc. are based on 'Appendix 6'. In the case of GHG emission activities that do not provide a method for estimating GHG emissions, the allocation target company has developed its own estimation method to calculate GHG emissions.

SF _{6, which} is used as a raw material for the manufacture of subsidiary materials in the cement production process, is a greenhouse gas substance with a high GWP and is subject to national emissions and emissions trading system. SF ₆ is finally immobilized as a product (cement) through a continuous reaction process such as SF ₆ injection, plasma decomposition (S, F), cement subsidiary material immobilization (CaSO ₄ , CaF ₂ ), etc. in a kiln. There is a possibility of greenhouse gas (SF ₆ ) emissions if ₆ is undecomposed or immobilized. Therefore, in the process of manufacturing SF ₆ and simultaneously treating SF ₆ in a cement firing facility, a method for calculating greenhouse gas (SF ₆ ) emissions is required. However, the GHG Emission Reporting and Certification Guideline does not currently provide a formula for estimating greenhouse gas emissions from the use of SF ₆ raw materials in the cement production process.

Accordingly, the present invention provides a methodology for calculating greenhouse gas emissions through process analysis and emission calculation method analysis for the use of fluorine-containing gas (SF ₆ ) raw materials in cement kiln systems, and through continuous and systematic monitoring of the monitoring items presented therein. To provide a system for managing greenhouse gas emissions.

According to an embodiment of the present invention for solving the above problems, a data input module for receiving an operation plan, a daily / monthly / yearly purchase amount and injection amount of fluorine-containing gas, a measurement device information and measurement analysis management information of a cement kiln system; In the cement kiln system, the fluorine-containing gas injection amount, temperature and emissions from the measuring device in real time while the pre-decomposed fluorine-containing gas and quicklime (CaO) react to perform the fluorine immobilization process; System temperature; And a management module for receiving and managing reactant temperature measurements. In the management module, the greenhouse gas emission calculation module for calculating the emission of the fluorine-containing gas by using the greenhouse gas emission calculation method based on the input measured value; And a control module for controlling the temperature of the fluorine-containing gas, the temperature of the system, or the temperature of the reactant according to the emission of the fluorine-containing gas.

In one embodiment of the present invention, the GHG emission calculation method is the amount of fluorine-containing gas is fixed to CaO in the cement kiln by subtracting the amount of fluorine-containing gas discharged from the cement kiln from the input fluorine-containing gas injection amount It includes the step of determining.

In one embodiment of the present invention, the fluorine-containing gas includes SF ₆ , in the high temperature kiln the SF ₆ is previously decomposed and fixed with the following reaction formula CaO.

(1) 2CaO + 2SO ₄ → 2CaSO ₄ + O ₂

(2) CaO + 2HF → CaF ₂ + H ₂ O

In one embodiment of the present invention, the GHG emission calculation method is represented by the following equation.

E _i = Q _i x (1-DR _i )

And consumption (ton) of the formula E _i is SF ₆ (i) greenhouse gas emissions (tGHG) and, Q _i is SF ₆ (i) of,

DR _i is the decomposition rate (fixed rate) of SF ₆ (i) consumed, which is a prime number between 0 and 1, and is calculated by DR _i = (Q _i -R _i ) / Q _i , Q _i is the consumption (ton) of the SF _{6 (i),} R i is the amount (ton) of the SF ₆ (i) to be discharged through the discharge port.

In the above formula, i means fluorine-containing gas, that is SF ₆ .

In one embodiment of the invention, in the cement kiln, the injected SF ₆ is pyrolyzed and then reacted with the CaO to immobilize.

In one embodiment of the present invention, the pyrolysis is performed by supplying a heat source of 1,000 ° C. or more generated during cement firing.

In one embodiment of the present invention, thermal energy may be additionally supplied from the plasma generator.

In one embodiment of the present invention, the temperature of the CaO is 700 ~ 2,000 ℃, the temperature of the fluorine-containing gas is adjusted to 1,000 ~ 5,000 ℃.

In an embodiment of the present disclosure, the method may further include generating and reporting online a greenhouse gas emission status report including the calculated greenhouse gas emissions.

In one embodiment of the invention, the fluorine-containing gas injection amount, temperature and discharge rate in real time; Temperature of the system; Temperature of the reactants; And it may further include a display module for visualizing the greenhouse gas emissions.

According to the present invention, in the process of processing a fluorine-containing gas while simultaneously producing a cement subsidiary material in a cement firing facility, it is possible to continuously and systematically manage greenhouse gas emissions through calculation of greenhouse gas emissions.

When the greenhouse gas emission management system of the present invention is commercialized and stabilized, SF ₆ generated from all over the country is supplied to the cement production process, so that resource recycling and resource recovery are environmentally friendly without any occurrence of F ₂ , HF, SOx, etc. Can be done.

The present invention can enable the continuous acquisition of carbon credits through continuous and systematic reduction of greenhouse gas emissions.

1 is a view showing a greenhouse gas emission management system according to an embodiment of the present invention.
2 is a flowchart illustrating a method for managing greenhouse gas emissions according to an embodiment of the present invention.
3 is a flow chart of the overall process of cement production.
4 and 5 schematically illustrate the cement firing process.

Hereinafter, the greenhouse gas emission management system of the present invention will be described in detail with reference to the accompanying drawings.

1 is a view showing a greenhouse gas emission management system according to an embodiment of the present invention.

Referring to FIG. 1, the system of the present invention receives data of an operation plan of a cement kiln system 20, a daily / monthly / yearly fluorine-containing gas (SF ₆ ) purchase amount and injection amount, measuring device information, and measurement analysis management information. In the input module 11 and the cement kiln system 20, the pre-decomposed fluorine-containing gas (SF ₆ ) and quicklime (CaO) react with each other to carry out the fluorine immobilization process, while injecting the fluorine-containing gas from the measuring device in real time, and the temperature. And emissions; Temperature of the system; And a management module 12 that receives and manages a temperature measurement value of the reactant, and the management module 12 discharges the fluorine-containing gas SF ₆ using a greenhouse gas emission calculation method based on the input measurement value. And a control module 14 for controlling the temperature of the fluorine-containing gas, the temperature of the system, or the temperature of the reactant according to the emission of the fluorine-containing gas SF ₆ . .

2 is a flowchart illustrating a method for managing greenhouse gas emissions according to an embodiment of the present invention.

First, in the operation and management planning stage, the cement kiln system operation plan, daily / monthly / yearly SF ₆ purchase amount and injection amount, measuring instrument information and measurement analysis management information are inputted to the data input module. Cement kiln refers to a kiln for firing cement raw materials mixed and crushed at an appropriate ratio. According to Article 11 of the Guidelines on Reporting and Certification of GHG Emissions Trading Scheme, allocated entities are required to monitor the plan, including an overview of the emission activities, the reporting facilities, the GHGs reported, the methodology for calculating emissions, and the management criteria for each parameter. In order to do this, the cement kiln system operation plan, daily / monthly / yearly SF ₆ purchase amount and injection amount, measuring instrument information and measurement analysis management information are inputted into the data input module.

The greenhouse gas to be reported in the present invention is a fluorine-based greenhouse gas, specifically, HFCs, PFCs, SF ₆ and the like. Fluorine-based greenhouse gases are used during the product production process in the chemical and electrical industries, but are consumed for various purposes, such as the filling of produced equipment. In particular, SF ₆ is mainly needed (consumed) in the heavy electric equipment industry and the electrical and electronics industry, and SF ₆ is expected to be in constant demand since there are no replacement items right now. As SF ₆ prices are on the decline, the business of reusing recovered and refined waste SF ₆ gas is likely to weaken competitiveness and increase consumption of SF ₆ .

Subsequently, in the operation of the SF ₆ treatment / fixation process, the plasma generated HF gas and SF ₆ previously decomposed in the cement process kiln are chemically reacted with reactant quicklime (CaO), which is a useful material in the cement process, CaF ₂ ( Mineralizer) and CaSO ₄ (delay agent). 4 and 5 schematically illustrate the cement firing process. At this time, the fluorine-containing gas injection amount, temperature and discharge amount from the measuring device in real time; Temperature of cement kiln; And temperature measurement values of the reactants are received and input into the management module.

In one embodiment of the present invention, to improve the pre-heater system, a rotary kiln, or the cooler to inject SF ₆ and a source of hydrogen in the process of progress of cement sintering step, and decomposing the heat SF ₆ occurring in the cement sintering process The decomposed S and F can be used as a material for clinker synthesis, and a large amount of SF ₆ was used as a raw material.

As a heat source for converting SF ₆ into HF in advance, a heat source of 1,000 ° C. or more generated during the cement firing process is used. In addition, heat energy may be additionally supplied through the plasma generator.

When SF ₆ is introduced as a raw material, it is thermally decomposed into sulfur (S) source and fluorine (F) source by plasma, which is immobilized with calcium sulfate (CaSO ₄ ) and calcium fluoride (CaF ₂ ) by reacting with CaO present in the cement kiln. (See FIGS. 4 and 5).

Sulfur (S) through SF ₆ pyrolysis combines with oxygen contained in excess air to form SO ₄ (sulfonate), and SO ₄ reacts with CaO (quick lime) to form CaSO ₄ , which contains active material and chemical admixture If you mix it into fine powder, it becomes cement.

S + ₂ O ₂ → SO ₄

2CaO + 2SO ₄ → 2CaSO ₄ + O ₂

In the case of fluorine (F) through SF ₆ pyrolysis, it is necessary to supply hydrogen sources (H ₂ O, H _2, etc.) because it may act to corrode other materials, and the hydrogen atoms included in these hydrogen sources are It reacts to make HF which is converted relatively easily, and reacts with CaO (quick lime) to induce the following chemical reaction.

H ₂ + F ₂ → 2HF

CaO + 2HF → CaF ₂ + H ₂ O + heat

CaSO ₄ , also known as gypsum, can be used as a admixture to promote hydration of cement. CaF ₂ serves to lower the firing temperature in the production of cement clinker. The CaF ₂ produced by immobilization can reduce the firing temperature of limestone decarbonated by about 100 ~ 200 ℃, thus saving energy. Therefore, CaF ₂ produced by immobilization is essential in the clinker firing process, which accounts for the most energy consumption in the cement production process.

The cement kiln contains a large amount of quicklime (CaO), a material capable of immobilizing S and F decomposed from SF ₆ , and less than 2% of free lime (f-CaO) after firing. It is desirable to exist

The quicklime (CaO) temperature of the reactant raw material is preferably 700 to 2,000 ° C, and the temperature of the fluorine-containing gas is controlled to 1,000 to 5,000 ° C. If it is in the above range can be permanently immobilized with 100% CaF ₂ and CaSO ₄ , it is possible to produce cement without a separate treatment.

GHG emissions are calculated based on the measured values input from the management module.

The present inventors examined the feasibility of the decomposition rate (low coefficient) estimation method presented in the similar methodology to which the greenhouse gas reduction technology is applied as the method of calculating the greenhouse gas emissions. As a result, it was confirmed that unprocessed process gas emissions could be regarded as undecomposed (unfixed) SF ₆ emissions.

In one embodiment of the present invention, the GHG emission calculation method is represented by the following equation.

E _i = Q _i x (1-DR _i )

And consumption (ton) of the formula E _i is SF ₆ (i) greenhouse gas emissions (tGHG) and, Q _i is SF ₆ (i) of,

DR _i is the decomposition rate (fixed rate) of SF ₆ (i) consumed, which is a prime number between 0 and 1, and is calculated by DR _i = (Q _i -R _i ) / Q _i , Q _i is the consumption (ton) of the SF _{6 (i),} R i is the amount (ton) of the SF ₆ (i) to be discharged through the discharge port.

The parameter Q _i in the activity data of the GHG emission estimation formula is a measure of the amount of SF ₆ consumed in the process. The emission factor (parameter DR _i of the fixation (distribution rate) is the rate at which SF ₆ consumed is not released to the atmosphere but is immobilized (decomposed). The consumption of SF ₆ (Q _i ) is measured just before it enters the kiln. The amount of SF ₆ (R _i ) released after the use of raw materials in the cement production process is measured immediately after SF ₆ is discharged from the kiln outlet.

The formula for calculating the greenhouse gas emission is to apply the concept of 1-degradation rate when consumed by input into a process (discharge facility) or decomposed (destructive) through an abatement system. In the process of the present invention, SF ₆ is used as an auxiliary material. Hence, SF ₆ is primarily decomposed using a high temperature heat source (plasma) and immobilized (CaSO ₄ , CaF ₂ ) as a subsidiary material. Therefore, the method of estimating the decomposition rate (decomposition coefficient) applied in the case of decomposition (destruction) treatment through abatement system was applied. The (inflow-emission) / inflow concept is applied to the calculation of the failure rate (or decomposition coefficient).

The GHG emission formula is a method of estimating GHG emissions when SF ₆ input for cement production can be released to the atmosphere without being immobilized (ie, undecomposed / unfixed) as the final product. ) And the amount of SF ₆ emitted can be measured and analyzed.

In an embodiment of the present disclosure, the method may further include generating and reporting online a greenhouse gas emission status report including the calculated greenhouse gas emissions. The GHG emission status report may be used as data for determining whether the GHG reduction target amount is met. In addition, as greenhouse gas reduction information, it can be used as a basis for generating a carbon credit.

In one embodiment of the present invention, the amount of fluorine-containing gas injection, temperature and emissions, preferably in real time; Temperature of the system; Temperature of the reactants; And it may further include a display module for visualizing the greenhouse gas emissions.

In the present invention, the term module refers to a unit for processing a specific function or operation, which may be implemented by hardware or software or a combination of hardware and software.

Claims (10)

In the greenhouse gas emission management system in the cement kiln system,
A data input module for receiving an operation plan of the cement kiln system, a daily / monthly / yearly purchase amount and injection amount of fluorine-containing gas, measuring device information, and measurement analysis management information;
In the cement kiln system, the fluorine-containing gas injection amount, temperature and emissions from the measuring device in real time while the pre-decomposed fluorine-containing gas and quicklime (CaO) react to perform the fluorine immobilization process; Temperature of the system; And a management module for receiving and managing temperature measurement values of the reactants.
In the management module, the greenhouse gas emission calculation module for calculating the emission of the fluorine-containing gas by using the greenhouse gas emission calculation method based on the input measured value; And
It includes a control module for controlling the temperature of the fluorine-containing gas, the temperature of the system or the temperature of the reactant according to the discharge of the fluorine-containing gas,
The greenhouse gas emission calculation method is a greenhouse gas emission management system, characterized in that expressed by the following equation:
E _i = Q _i x (1-DR _i )
And consumption (ton) of the formula E _i is SF ₆ (i) greenhouse gas emissions (tGHG) and, Q _i is SF ₆ (i) of,
DR _i is the decomposition rate (fixed rate) of SF ₆ (i) consumed, which is a prime number between 0 and 1, and is calculated by DR _i = (Q _i -R _i ) / Q _i , Q _i is the consumption (ton) of the SF _{6 (i),} R i is the amount (ton) of the SF ₆ (i) to be discharged through the discharge port. The method of claim 1,
The GHG emission estimating method includes determining a value obtained by subtracting the amount of fluorine-containing gas discharged from the cement kiln from the input amount of fluorine-containing gas injected into a fixed amount of fluorine-containing gas to CaO in the cement kiln. Greenhouse gas emission management system. The method according to claim 1 or 2,
The fluorine-containing gas after being comprises a SF _6, SF ₆ in a cement kiln is pre-decomposition converted to HF, a greenhouse gas which is characterized in that the fixing in response to the above reaction scheme CaO emission control system:
(1) 2CaO + 2SO ₄ → 2CaSO ₄ + O ₂
(2) CaO + 2HF → CaF ₂ + H ₂ O delete The method of claim 3,
In the cement kiln, the injected SF ₆ is pyrolyzed and then reacted with the CaO to be immobilized. The method of claim 5,
The pyrolysis is a greenhouse gas emission management system, characterized in that proceeding by supplying a heat source of 1,000 ℃ or more generated during the cement firing process. The method of claim 6,
Greenhouse gas emission management system, characterized in that the thermal energy is additionally supplied from the plasma generating unit. The method of claim 1,
The temperature of the CaO is 700 ~ 2,000 ℃, the temperature of the fluorine-containing gas is characterized in that the greenhouse gas emissions management system is controlled to 1,000 ~ 5,000 ℃. The method of claim 1,
The GHG emission management system further comprising the step of generating a GHG emission status report including the calculated GHG emissions and reporting online. The method of claim 1,
Fluorine-containing gas dosage, temperature and emissions in real time; Temperature of the system; Temperature of the reactants; And a display module for visualizing the greenhouse gas emissions.

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