KR101915468B1 - Cement kilns for fluorinated gas treatment and the method using the same - Google Patents

Abstract

The present invention relates to a rotary kiln capable of simultaneously processing fluoride gas while producing a cement additive in a cement kiln and a flame gas The present invention relates to a method for treating a cement, and a method for reforming a preheater system, a rotary kiln, or a cooler so as to inject a fluorine gas and a hydrogen source during a cement firing process, Fluorine can be used as a material for synthesizing clinker, which can treat a large amount of fluorine gas and can produce cement additives at the same time, resulting in an eco-friendly and economical effect.

Description

TECHNICAL FIELD [0001] The present invention relates to a cement burning facility for treating a fluoride gas, and a method for treating a fluoride gas using the same. [0002] Cement kiln for flue gas treatment,

The present invention relates to a device and a method for processing a fluoride gas, in particular cement and prepared cement additives in the firing equipment at the same time, non-carbon dioxide (non-CO ₂₎ A rotary kiln furnace capable of treating a fluorinated gas such as a greenhouse gas, and a fluorine gas treating method.

Global warming is a phenomenon in which the average temperature on the surface of the earth rises, causing various problems such as changing ecosystems in the ground or water, rising sea level, and changing the coastline. One of the causes of this warming is the increase of greenhouse gases caused by the use of fossil fuels and the destruction of forests, and it is now becoming a global problem as well as Korea. Greenhouse gases are carbon dioxide is typically, in addition to methane (CH _4), nitrous oxide (N ₂ O) and hydrogen fluorocarbons (HFCs), perfluorocarbons fluoride gas such as (PFCs), hexafluoride wherein (SF6) is a greenhouse effect It is known as the causing gas. So far, the development of greenhouse gas reduction technologies has been carried out with the largest amount of CO2 emissions. However, non-CO ₂ GHGs have a lower total emission than CO 2, but their contribution to greenhouse effect is very high.

Non-CO ₂ HFCs, PFCs, and SF ₆ gases, which are fluorinated gases in greenhouse gases, are the gases that are mainly emitted from semiconductor processes, and contribute to the greenhouse effect. As a method of treating such fluorinated gas, various technologies such as combustion, thermal distillation, chemical / catalytic distillation, and plasma distillation have been researched and developed. However, in general, fluorinated gas discharged from a semiconductor or LCD process, in which fluorinated gas is heavily used, is produced at a high unit discharge amount and a very low concentration (about 300 to 1000 ppm) There is a problem that energy is consumed, and there is a problem that the size of the processing apparatus is inevitable.

Korean Patent No. 461758 discloses a method for treating a large capacity of a perfluorocompound gas and a method for treating the apparatus, and discloses a catalyst for decomposing and decomposing a perfluorinated compound and a method for decomposing and decomposing a perfluorinated compound in a waste gas using the same. However, since this catalyst contains other substances and particles besides the perfluorinated compound, there is a problem that the catalytic activity is rapidly lowered.

Korean Patent Laid-Open Publication No. 2001-0049466 relates to a method for treating perfluorocarbon gas, and discloses a method for treating a gas containing perfluorocarbon by plasma. However, it is heated and decomposed by the plasma. The plasma decomposition can decompose the perfluorocarbon efficiently at a low temperature, but it is difficult to treat the perfluorocarbon in a large amount and the electricity cost is high.

Therefore, it is necessary to overcome the limitation of the treatment of non-CO ₂ greenhouse gas and fluorinated gas, and to provide economic high-value-added technology.

(0001) Korea Patent No. 461758 (0002) Korean Laid-Open Patent Publication No. 2001-0049466

The present invention relates to a method of treating fluorinated gas which has been devised in order to solve all the problems of the prior art described above, and more particularly, to a rotary kiln used in a cement manufacturing process to complete a resource recycling cycle by recycling fluorinated gas To provide a fluorinated gas processing apparatus capable of simultaneously processing a fluorinated gas and producing a cement raw material.

In order to solve the above-described problems, the present inventors have developed a firing apparatus for decomposing fluorine gas at a high temperature generated during the process, and using a cement firing process requiring fluorine.

In the cement calcination process, the fluorine gas is decomposed by modifying the preheater system, the rotary kiln, or the cooler so as to inject fluoride gas such as non-CO ₂ greenhouse gas into the high temperature generated during the process By using the decomposed fluorine as a material for synthesizing clinker, it is possible to treat a large amount of fluorine gas and simultaneously produce cement additives, thereby bringing about an eco-friendly and economical effect.

Fig. 1 is a conceptual diagram showing the flow of cement calcination facility, cement raw material, fuel and air of the present invention.
Fig. 2 is a conceptual diagram showing the flow of the burner and the fuel, the fluorinated gas, and the air provided in the rotary kiln of the present invention.
3 is a conceptual diagram showing the flow of the cooler, the clinker, the fluorinated gas and the air of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. Prior to the detailed description of the present invention, terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms. Therefore, the embodiments described in this specification and the configurations shown in the drawings are merely the most preferred embodiments of the present invention and do not represent all the technical ideas of the present invention. Therefore, It is to be understood that equivalents and modifications are possible.

The cement manufacturing process is divided into a mining process for extracting limestone as a raw material, a crushing process for crushing mined limestone lumps, a mixing process for mixing crushed limestone to reduce quality dispersion, a raw material for crushing mixed limestone together with other additives in powder form A crushing process, a preheating process in which raw material is heated to a middle temperature to cause calcination to 90%, a calcination process in which a raw material is heated at a high temperature to cause various chemical reactions and physical reactions to produce a clinker, A cooling process for cooling, a grinding process for finishing the cement by further adding gypsum to the clinker, and the like.

The term 'cement calcination facility' as used in the present invention is a concept including a preheater system, a rotary kiln and a cooler for conducting the preheating process, the calcining process and the cooling process.

The limestone collected in the mining process and the additive to be added include CaCO ₃ , SiO ₂ , Al ₂ O ₃ , Fe ₂ O ₃ , MgCO ₃ , K ₂ O, Na ₂ O and the like. , Cu, Mg, Zn, Hg, Ca, Cd, and / or Cl. In addition, the preheating process is carried out at a temperature of 300 to 850 ° C for each preheating step, and is used for burning in a calciner included in the preheater system, such as bituminous coal, LPG, bunker C oil, WDF, waste oil, waste synthetic resin, Sludge and the like can be used. The sintering process is carried out at a temperature of 1,450 to 2,000 DEG C, and bituminous coal, LPG, and / or Bunker C oil may be used for combustion in the burner provided in the rotary kiln. On the other hand, calcium fluoride (CaF ₂ ), which is fluorine-bonded to pyrolytic cement raw material, is also used as an admixture and mineralizer which are a raw material for cement production. The fluorine (F) source is used as a mineralizer to lower the liquid production temperature, which is essential for mineral formation in the production of cement clinker, and the mineralizer serves to lower the firing temperature in the production stage of cement clinker. This is essential for the clinker firing process, which consumes the most energy in the cement production process.

The cement calcination facility of the present invention is capable of treating and utilizing fluorinated gas, and it can decompose fluorinated gas and use decomposed fluorine as a material for synthesizing clinker. In one embodiment, the fluorinated gas can be a non-CO ₂ greenhouse gas, such as perfluorocarbon (PFC), hydrogen fluoride (HFC), as well as chlorofluorocarbon (CFC), nitrogen fluoride It can be used as the fluorine source of the cement calcination facility of the invention. For example, perfluorocarbon (PFC) is specifically, _{CF 4, CHF 3, CH 2} F 2, C 2 F 4, C 2 F 6 of carbon and fluorine are bonded _{compound, C 3 F 6, C 3} F 8, C ₄ F ₈ , C ₄ F _10, and the like. Hydrogen fluoride (HFC) includes HFC-134-a, HFC-152-a, HFC-32 and HFC-125.

Fig. 1 is a conceptual diagram showing the flow of cement calcination facility, cement raw material, fuel and air of the present invention. The 'cement calcining facility' in the embodiment of the present invention includes a precalciner 31 for preheating cement raw material 10 supplied from a raw material feeder and increasing decarbonation reaction in which carbon dioxide is liberated in the raw material A preheater system 30; A raw material passed through the preheater system is introduced into an inlet and fired in a clinker 100 to be carried out as an outlet, and a burner provided at a position opposed to the inlet for firing, A rotary kiln 40 for generating a flame in the direction of the charging port 50; And the clinker injected from the kiln is cooled by a plurality of air injecting parts (21) according to the moving step, and all the air injected into the first air injecting part (25) adjacent to the kiln is sucked into the take- And a cooler 60 having an airflow partition plate and a partition wall for inducing the air flow to the outside. The air sucked into the kiln is discharged to the air outlet 20 through the kiln and the preheater system.

In one embodiment of the present invention, a fuel 12 such as bituminous coal, LPG, Bunker C oil, etc. is supplied to the calciner and the burner through the fuel grinder 14 or the fuel distributor. In addition, the preheater system, rotary kiln or cooler may have feeds (3, 4, 5) for supplying a source of hydrogen and fluoride gas, the preheater system and the rotary kiln being hermetically connected, The cooler is also sealed. Fluorine (F) in which fluorine gas has been decomposed can simply act to corrode inside the firing equipment or other materials. Therefore, it is necessary to supply a hydrogen source that easily bonds with fluorine. The source of hydrogen is at least one selected from H ₂ O, H ₂ , and CH ₄ and prevents the smooth decomposition of the fluorinated gas and the recombination of the decomposed fluorine (F). These materials contain hydrogen atoms and react with F to produce HF, which is relatively easy to convert, and leads to the following chemical reaction with quicklime.

CaO + 2HF -> CaF ₂ + H ₂ O + heat

Therefore, fluorite can be easily produced by the injection of hydrogen source, and the generated heat can compensate the heat used for the endothermic process for decomposing the fluorinated gas to a certain extent, thereby stably maintaining the thermal environment inside the rotary kiln .

2 is a conceptual diagram showing the flow of fuel, fluorinated gas and air through the burner provided in the rotary kiln of the present invention and the burner. According to an embodiment of the present invention, the hydrogen source and the fluorinated gas supply unit 4 provided in the rotary kiln 40 are connected to the burner 50 provided in the kiln by the fluorine gas injection unit 200 and the hydrogen source injection unit 300). The fuel 12 supplied to the burner 50 in the embodiment of the present invention includes the bypass passage 58 of the swirling air and flows through the outside air blower 27 and the blower fan 26 A jet air 54 and a swirling air 56 are supplied and include a bypass path portion 57 of the inside and outside air. The burner generates a flame 52 by a high-temperature injector 51 positioned at a front end, and causes fluorine gas and hydrogen source to be injected into the center of the flame. In an embodiment of the present invention, the injection ports of the fluorinated gas injection unit 200 and the hydrogen source injection unit 300 are protruded toward the hot injection unit 51 so that the injection may occur at the center of the flame.

3 is a conceptual diagram showing the flow of the cooler, the clinker, the fluorinated gas and the air of the present invention. According to an embodiment of the present invention, the hydrogen source and the fluorinated gas supply unit 5 provided in the cooler 60 are located in the first air injection unit 25 of the cooler. The hydrogen source and the fluorinated gas injected from the fluorinated gas injecting unit 400 and the hydrogen source injecting unit 500 located in the first air injecting unit are injected into the kiln (Not shown) for guiding the air flow 22 so as to be sucked into the outflow port of the air outlet 22. In an embodiment of the present invention, an air flow partition plate 65 and a partition wall are installed to assist in the process of sucking the entire amount of the air into the kiln along the air flow 22. [ The partition plate according to an embodiment of the present invention is installed on the upper surface of the inside of the cooler so as to induce the air flow but not interfere with the flow 101 of the clinker 100. The air injected from the plurality of air injecting units 21 provided in the cooler to the air injecting unit located far from the first air injecting unit 25 is cooled by the clinker 100 and then exhausted to the air exhausting pipe 23 The air injected into the air injection unit located at the center can be discharged to the preheating tower addition pipe 24 after cooling the clinker 100.

The hydrogen source and the fluorinated gas supply unit 3 provided in the preheater system 30 according to an embodiment of the present invention are located in the calcination furnace 31 of FIG. In this case, since the thermal energy of the calcining furnace 31 may not be enough to decompose the fluorinated gas, a plasma generating part (not shown) for supplying thermal energy may be provided in the preheater system including the calcining furnace 31.

Also, in case that the temperature inside the rotary kiln 40 is not sufficiently high enough to supply heat energy sufficient to decompose the fluorinated gas, the plasma generator for supplying thermal energy may be provided in the rotary kiln 40 as well. With such a complementary arrangement, it is possible to decompose fluorine gas reliably and promote the generation of hydrofluoric acid (HF). The plasma generating part for supplying thermal energy to the kiln may be installed at a low pressure in the inlet of the fluorinated gas. In an embodiment of the present invention, the plasma generator may be installed in the cooler 60 to supply thermal energy for decomposing fluorine gas supplied to the cooler.

The present invention discloses a method for treating fluorinated gas using a cement firing facility for the fluorinated gas treatment. The preheating step of preheating the cement raw material supplied from the raw material feeder in the preheater system equipped with a precalciner; A step of charging and discharging a raw material passed through the preheater system in a rotary kiln provided with a burner into an inlet and burning a clinker with combustion heat of the burner to carry it out to an outlet; And a plurality of cooling air injection units, wherein all of the air injected into the first air injection unit adjacent to the kiln is introduced into the kiln in a cooler having an airflow partition plate so as to be sucked into the kiln, Wherein the preheating step, the expelling step, or the cooling step may include a supply step of supplying a source of hydrogen and fluorinated gas.

The hydrogen source according to an embodiment of the present invention is at least one selected from H ₂ O, H ₂ , and CH ₄ . According to the method of treating the fluorine gas, the decomposed fluorine (F) may recombine with hydrogen to promote the generation of hydrofluoric acid (HF).

The hydrogen source and the fluoride gas according to one embodiment of the present invention The supplying step may be included in the preheating step so that the fluorine gas and the hydrogen source may be injected through the fluorine gas injecting part and the hydrogen source injecting part provided in the calciner of the preheater system. According to another embodiment of the present invention, the hydrogen source and the fluoride gas In the supplying step, the fluorine gas and the hydrogen source may be injected through the fluorine gas spraying part and the hydrogen source spraying part included in the burner of the rotary kiln included in the firing and extracting step. In another embodiment of the present invention, The hydrogen source and the fluorinated gas supply step may be included in the cooling step so that the fluorinated gas and the hydrogen source may be injected through the fluorinated gas injection part and the hydrogen source injection part provided in the first air injection part of the cooler.

In one embodiment of the present invention, the preheating step may further include the step of supplying thermal energy to the plasma generator for supplying thermal energy to the preheater system. This is because the heat of the preheater system itself can not be sufficiently supplied by the temperature, and the fluorine gas may not be pyrolyzed. In another embodiment of the present invention, the firing and unloading step may further include supplying thermal energy in the plasma generator for supplying thermal energy provided in the rotary kiln, wherein thermal energy sufficient for thermal decomposition of fluorine gas is not supplied even in the rotary kiln It is prepared in case it does not. In another embodiment of the present invention, the cooling step further includes the step of supplying heat energy in the plasma generator for supplying thermal energy to the cooler. Because the chiller is likely not to have enough heat, it may be necessary to provide thermal energy through the plasma.

While the invention has been shown and described with reference to certain preferred embodiments thereof, it should be understood that various changes and modifications may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. .

All technical terms used in the present invention are used in the sense that they are generally understood by those of ordinary skill in the relevant field of the present invention unless otherwise defined. The contents of all publications referred to herein are incorporated herein by reference.

1. Cement burning plant 10. Cement raw material
12. Fuel 14. Fuel crusher
20. Air outlet 22. Air flow
23. Air exhaust pipe 24. Preheating column addition pipe
25. First Air Inlet 30. Preheater System
31. Caldron 40. Rotating kiln
50. Burner 52. Flame
60. Cooler 65. Air flow partition plate
66. Partition wall 100. Clinker
200, 400. Fluorinated gas spraying part 300, 500. Spray source spraying part

Claims (16)

With cement burning facility for fluorinated gas treatment,
The firing apparatus includes:
A preheater system for preheating cement raw material supplied from a raw material feeder;
A raw material passing through the preheater system is introduced into an inlet, and is fired in a clinker to be taken out to an outlet. In the burner provided at a position facing the inlet for firing, A rotary kiln for generating a flame in a direction; And
And a cooler for cooling the clinker supplied from the kiln to a plurality of air injection units according to a moving step,
The preheater system, rotary kiln or cooler has a supply part for supplying a source of hydrogen and fluorine gas,
Wherein the preheater system and the rotary kiln are sealingly connected, the rotary kiln and the cooler are also sealed,
The preheater system may further include a plasma generator for supplying thermal energy,
The fluorinated gas may be at least one selected from the group consisting of perfluorocarbon (PFC), hydrofluorocarbon (HFC), and chlorofluorocarbon (CFC)
Cement burning facility for fluorinated gas treatment.
The method according to claim 1,
Wherein the hydrogen source is at least one selected from H ₂ O, H ₂ , and CH ₄ ,
Cement burning facility for fluorinated gas treatment.
The method according to claim 1,
The supply unit is provided in the preheater system,
Wherein the furnace constituting the preheater system comprises a fluorinated gas spraying part and a hydrogen source spraying part,
Cement burning facility for fluorinated gas treatment.
The method according to claim 1,
The supply portion is provided in the rotary kiln,
Wherein the burner of the rotary kiln comprises a fluorinated gas spraying part and a hydrogen source spraying part,
Cement burning facility for fluorinated gas treatment.
The method according to claim 1,
Wherein the supply unit is provided in the cooler,
Wherein the first air injection unit adjacent to the kiln on the cooler includes a fluorinated gas injection unit and a hydrogen source injection unit,
Cement burning facility for fluorinated gas treatment.
delete The method according to claim 1,
Wherein the rotary kiln further comprises a plasma generator for supplying thermal energy,
Cement burning facility for fluorinated gas treatment.
The method according to claim 1,
Wherein the cooler further comprises a plasma generating part for supplying thermal energy,
Cement burning facility for fluorinated gas treatment.
As a method for treating fluorinated gas using a cement burning facility,
The preheating step of preheating the cement raw material supplied from the feeder in the preheater system;
A firing step of feeding a raw material passed through the preheater system in a rotary kiln provided with a burner into an inlet and firing a clinker with combustion heat of the burner to carry it out to an outlet; And
And a cooling step of cooling the clinker supplied from the kiln in the cooling step according to the moving step, the cooling step including a plurality of cooling air injection units,
Wherein the preheating step, the exporting step, or the cooling step includes a supply step of supplying a source of hydrogen and fluorinated gas,
Wherein the preheating step further comprises the step of supplying thermal energy in a plasma generating part for supplying thermal energy provided in the preheater system,
A Method of Treatment of Fluoride Gas Using Cement Firing System.
10. The method of claim 9,
Wherein the hydrogen source is at least one selected from H ₂ O, H ₂ , and CH ₄ ,
A Method of Treatment of Fluoride Gas Using Cement Firing System.
10. The method of claim 9,
The supplying step is included in the preheating step,
Wherein the fluorine gas and the hydrogen source are injected through the fluorine gas injection part and the hydrogen source injection part provided in the calciner constituting the preheater system,
A Method of Treatment of Fluoride Gas Using Cement Firing System.
10. The method of claim 9,
Wherein the supplying step is included in the firing and unloading step,
Wherein the fluorine gas and the hydrogen source are injected through the fluorine gas spraying part and the hydrogen source spraying part provided in the burner of the rotary kiln,
A Method of Treatment of Fluoride Gas Using Cement Firing System.
10. The method of claim 9,
Wherein the supplying step is included in the cooling step,
Wherein the fluorine gas and the hydrogen source are injected through the fluorine gas injection part and the hydrogen source injection part provided in the first air injection part adjacent to the kiln on the cooler,
A Method of Treatment of Fluoride Gas Using Cement Firing System.
delete 10. The method of claim 9,
Wherein the firing and unloading step further comprises supplying thermal energy in a plasma generator for supplying thermal energy to the rotary kiln,
A Method of Treatment of Fluoride Gas Using Cement Firing System.
10. The method of claim 9,
Wherein the cooling step further comprises the step of supplying thermal energy in a plasma generator for supplying thermal energy to the cooler,
A Method of Treatment of Fluoride Gas Using Cement Firing System.

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