CN115228278A - PH value regulation and control calcium carbonate for accelerating mineralization and absorption of CO in flue gas 2 System and method - Google Patents
PH value regulation and control calcium carbonate for accelerating mineralization and absorption of CO in flue gas 2 System and method Download PDFInfo
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- 230000033558 biomineral tissue development Effects 0.000 title claims abstract description 169
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 62
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 37
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 27
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000003546 flue gas Substances 0.000 title claims abstract description 22
- 230000033228 biological regulation Effects 0.000 title description 2
- 239000004568 cement Substances 0.000 claims abstract description 120
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 78
- 238000003756 stirring Methods 0.000 claims abstract description 67
- 239000002912 waste gas Substances 0.000 claims abstract description 66
- 238000003860 storage Methods 0.000 claims abstract description 55
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims abstract description 26
- 239000001632 sodium acetate Substances 0.000 claims abstract description 26
- 235000017281 sodium acetate Nutrition 0.000 claims abstract description 26
- 238000001514 detection method Methods 0.000 claims abstract description 23
- 239000000654 additive Substances 0.000 claims abstract description 19
- 230000000996 additive effect Effects 0.000 claims abstract description 19
- 230000001105 regulatory effect Effects 0.000 claims abstract description 19
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- 238000005261 decarburization Methods 0.000 claims abstract description 6
- 238000007599 discharging Methods 0.000 claims abstract description 5
- 241000537371 Fraxinus caroliniana Species 0.000 claims abstract description 4
- 235000010891 Ptelea trifoliata Nutrition 0.000 claims abstract description 4
- 230000001089 mineralizing effect Effects 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 27
- 238000005070 sampling Methods 0.000 claims description 14
- 238000005262 decarbonization Methods 0.000 claims description 12
- 230000001276 controlling effect Effects 0.000 claims description 11
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 8
- 239000000920 calcium hydroxide Substances 0.000 claims description 8
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 8
- 238000012544 monitoring process Methods 0.000 claims description 4
- YPSVSPBXPRTRQF-UHFFFAOYSA-N calcium;oxygen(2-);hydrate Chemical compound O.[O-2].[Ca+2] YPSVSPBXPRTRQF-UHFFFAOYSA-N 0.000 claims description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 98
- 239000001569 carbon dioxide Substances 0.000 abstract description 49
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 49
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- 241000196324 Embryophyta Species 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract description 5
- 239000002245 particle Substances 0.000 description 11
- 239000000292 calcium oxide Substances 0.000 description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000000428 dust Substances 0.000 description 5
- 239000002910 solid waste Substances 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 230000000740 bleeding effect Effects 0.000 description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000010813 municipal solid waste Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- YLUIKWVQCKSMCF-UHFFFAOYSA-N calcium;magnesium;oxygen(2-) Chemical compound [O-2].[O-2].[Mg+2].[Ca+2] YLUIKWVQCKSMCF-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000029219 regulation of pH Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/80—Semi-solid phase processes, i.e. by using slurries
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
Abstract
The invention discloses a pH value regulated calcium carbonate for accelerating mineralization and absorption of CO in flue gas 2 The system comprises a cement kiln bypass air-discharging ash storage, metering and conveying system, an additive system, a water supply system, a kiln tail waste gas air supply system, a pH online detection system, a stirring mineralization absorption system, a decarburization waste gas air-out system and a mineralized ash conveying system; in the mineralization process, sodium acetate is added, the mass fraction of a sodium acetate aqueous solution is controlled to be 1-3%, water is added into cement kiln bypass air-release ash according to the water-ash ratio of 0.1-0.3 for stirring, the pH value is regulated within the range of 10-11, the size of calcium carbonate crystals generated by reaction is regulated, and the mineralization reaction rate and mineralization absorption amount are accelerated. The invention can realize that the absorption rate of carbon dioxide in kiln tail waste gas reaches more than 30 percent, develops a new way for reducing the emission of carbon dioxide in a cement plant, and has wide practical application and popularization values.
Description
Technical Field
The invention relates to the technical field of reducing carbon dioxide emission in the cement industry, in particular to a method for regulating and controlling pH value to accelerate mineralization and absorption of CO in flue gas by calcium carbonate 2 Systems and methods of (1).
Background
According to statistics, the carbon dioxide discharged by global cement production accounts for 7% of the total carbon dioxide discharge, and the cement industry greatly reduces the carbon dioxide discharge and is expected to reduce the adverse effect on climate warming. The cement industry is also a carbon dioxide emission enlarger in China, and the data show that the annual emission amount of carbon dioxide in China in 2019 is about 100 million tons and accounts for 30 percent of the annual emission amount of carbon dioxide in the world, wherein the annual emission amount of carbon dioxide in the cement industry is about 13.2 million tons and accounts for about 15 percent of the total emission amount of carbon dioxide in industrial enterprises in China, and the carbon dioxide emission reduction task of the cement industry is difficult.
The mineralization absorption of the carbon dioxide has the characteristics of small environmental risk, no need of monitoring and natural long-term stable existence of the generated carbonate, and is expected to become an important mode for carbon dioxide emission reduction and resource utilization. A large amount of solid wastes containing calcium magnesium oxide or hydroxide are discharged every year in China, can be used for mineralizing and absorbing carbon dioxide, and has the advantages of wide sources, large total solid carbon amount, suitability for local materials and the like. Therefore, one of the methods for reducing the carbon dioxide emission in the cement industry is to react the generated carbon dioxide with alkaline materials generated in the cement manufacturing process to form carbonate, so that permanent carbon fixation is realized, and contribution is made to carbon emission reduction in the cement industry.
The cement kiln bypass air-bleed dust-collecting ash is a calcium-containing alkaline material discharged by a bypass air-bleed system in the cement production process. Because the cement kiln is complex in cooperatively disposing garbage, sludge and solid waste components and high in sulfur and chlorine content, a large amount of alkali, chlorine and sulfur elements are released in the cooperative disposing process of the cement kiln and are circularly enriched in the kiln, so that the crust and the blockage in the kiln are easily caused. In order to avoid the cyclic enrichment of alkali, chlorine and sulfur in a kiln system, when the content of sulfur and chlorine in hot raw materials reaches a certain value, a bypass air discharge technology is adopted to discharge a part of flue gas enriched with high-concentration alkali, chlorine and sulfur so as to relieve the problem; the decomposed partial calcium oxide and magnesium oxide and a large amount of alkaline substances are released together with the smoke, so that the bypass air-bleeding dust-collecting ash is a high-alkali high-chlorine material with complex components, and the main utilization mode is to use the dust-collecting ash as a mixed material added into cement in a small amount at present. As the consumption of municipal solid waste, sludge, solid waste and hazardous waste in the cement industry in China is increasing, a large number of cement plants are built into a cooperative disposal system, a bypass air discharge system is gradually standard distribution of a cooperative disposal solid waste cement kiln, the generation amount of dust in the bypass air discharge and collection increases year by year, and the difficulty in comprehensive utilization is increased.
The method for mineralizing and absorbing the carbon dioxide in the kiln tail waste gas discharged by the cement plant by using the bypass air bleeding dust collecting ash of the cement plant is an important way for utilizing the bypass air bleeding dust collecting ash with a high added value, but in the process of absorbing the carbon dioxide in the kiln tail waste gas by using the bypass air bleeding dust collecting ash, the generated calcium carbonate crystals can be deposited on the surfaces of bypass air bleeding dust collecting ash particles, so that the reaction efficiency of mineralizing and absorbing the carbon dioxide is delayed.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a method for regulating and controlling pH value to accelerate mineralization and absorption of CO in flue gas by calcium carbonate 2 Systems and methods of (1).
The invention is realized by that pH value is regulated and controlled, calcium carbonate accelerates mineralization and absorbs CO in flue gas 2 The system comprises a cement kiln bypass air-discharging ash storage, metering and conveying system, an additive system, a water supply system, a kiln tail waste gas air supply system, a pH on-line detection system, a stirring mineralization absorption system, a decarburization waste gas air-out system and a mineralization ash conveying system;
the outlet of the cement kiln bypass air-released ash storage, metering and conveying system is connected with the feed inlet of the stirring mineralization absorption system, the outlet of the additive system is connected with the inlet of the water supply system, the outlet of the water supply system is connected with the water inlet of the stirring mineralization absorption system, the outlet of the kiln tail waste gas air supply system is connected with the air inlet of the stirring mineralization absorption system, the pH on-line detection system is connected with the pH value sampling port of the stirring mineralization absorption system, the air outlet of the stirring mineralization absorption system is connected with the decarburization waste gas air outlet system, and the discharge port of the stirring mineralization absorption system is connected with the mineralization ash conveying system.
Preferably, the cement kiln bypass air-bleeding ash storage, metering and conveying system comprises a cement kiln bypass air-bleeding ash storage bin, an electric gate valve and a screw metering feeder which are sequentially connected, and an outlet of the screw metering feeder is connected with a feeding hole of the stirring mineralization absorption system.
Preferably, the additive system comprises an additive storage bin, a disc feeder and a feeding scraper-trough conveyer which are connected in sequence, and an outlet of the feeding scraper-trough conveyer is connected with an inlet of a water supply system.
Preferably, the water supply system comprises a water storage tank, a metering water pump and a water supply pipeline which are connected in sequence, and an outlet of the water supply pipeline is connected with a water inlet of the stirring mineralization absorption system.
Preferably, the stirring, mineralizing and absorbing system comprises a mineralizing stirrer, and a feed inlet, a water inlet, a pH value sampling port, an air inlet, an air outlet and a discharge port which are arranged on the mineralizing stirrer.
Preferably, the kiln tail waste gas air supply system comprises a centrifugal fan and a kiln tail waste gas air supply pipeline, wherein an inlet of the centrifugal fan is connected with a kiln tail chimney, and an outlet of the centrifugal fan is connected with an air inlet of the stirring mineralization absorption system through the kiln tail waste gas air supply pipeline; the decarbonization waste gas air-out system comprises a decarbonization waste gas air-out pipeline, an air outlet of the stirring mineralization absorption system is connected with an inlet of the decarbonization waste gas air-out pipeline, and an outlet of the decarbonization waste gas air-out pipeline is connected with a kiln tail chimney.
Preferably, the pH on-line detection system comprises a sampling device and a detection device, wherein the sampling device is installed at a pH value sampling port of the mineralization stirrer.
PH value-regulated calcium carbonate-based device for accelerating mineralization and absorption of CO in flue gas 2 The method for mineralizing and absorbing carbon dioxide by using the system comprises the following steps:
s1, adding sodium acetate into a water supply system through an additive system, and controlling the mass fraction of a sodium acetate aqueous solution to be 1-3%;
s2, feeding the cement kiln bypass air-released ash into a stirring mineralization absorption system through a cement kiln bypass air-released ash storage, metering and conveying system, adding water according to the water-ash ratio of 0.1-0.3, and stirring for a certain time to fully hydrate calcium oxide in the cement kiln bypass air-released ash into calcium hydroxide;
s3, leading the mud kiln tail waste gas from a kiln tail chimney by a kiln tail waste gas air supply system, and leading the mud kiln tail waste gas according to 3000-5000Nm 3 Introducing the air quantity of/h into a stirring mineralization absorption system, introducing the tail waste gas of the cement kiln while stirring, mineralizing for 0.5-1.5h, and allowing the bypass air discharging ash of the cement kiln to absorb CO in the tail waste gas of the cement kiln 2 Realizing permanent curing;
s4, in the mineralization process, monitoring the pH value of the materials in the stirring mineralization absorption system in the whole process by using a pH value online detection system, ensuring that the pH value is between 10 and 11, slowly adding cement kiln bypass air-release ash into the stirring mineralization absorption system when the pH value is reduced to be less than 10, and maintaining the pH value of the materials to be between 10 and 11 all the time until the mineralization is finished;
and S5, after mineralization is finished, stopping introducing the tail waste gas of the cement kiln, opening a discharge port of the stirring mineralization absorption system, and conveying the generated mineralized ash to a storage yard or a storage warehouse through a mineralized ash conveying system.
The invention has the advantages and positive effects that:
1. the invention firstly proposes that calcium carbonate is regulated and controlled by pH value to accelerate mineralization and absorb CO in flue gas 2 The technology can accelerate the solidification rate of carbon dioxide, improve the mineralization absorption amount of the carbon dioxide, and has important significance for the carbon dioxide emission reduction practice of a cement plant;
2. in a sodium acetate environment, the pH value is adjusted to be within the range of 10-11, so that the calcium carbonate crystals can be promoted to grow continuously, and carbon dioxide can enter the interior of bypass ash particles through gaps among the calcium carbonate crystals to be mineralized continuously, so that the mineralization rate is accelerated remarkably;
3. the mineralization absorption method is a semidry method, has simple process flow, is environment-friendly, and has no wastewater discharge;
4. the invention provides a new method for accelerating the carbon dioxide mineralization utilization in the cement industry, and opens up a new emission reduction way for the cement industry which is difficult to reduce emission; along with the increase of the demand of replacing fuel and disposing solid waste in the cement industry, the yield of the bypass air-release ash is increased, and the method is suitable for large-area popularization and application and has better popularization and application prospects.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly described below, and it is obvious that the drawings in the description below are some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 shows that pH value-regulated calcium carbonate provided by the embodiment of the invention accelerates mineralization and absorption of CO in flue gas 2 A system flow diagram of (1);
FIG. 2 is a schematic diagram of the mineralization reaction of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
The traditional slurry absorption tower type mineralization process route has a complex flow, needs to consume a large amount of water, and the mineralized materials need to be subjected to filter pressing dehydration, and the filter pressing liquid contains a large amount of salt, so that the high-salinity wastewater which is difficult to treat is obtained. On the basis of a large number of experiments, the inventor develops a semidry mineralization technical route by optimizing the water addition amount, the ventilation amount and the mineralization time, and combines a pH value regulation and control mineralization speed acceleration technology to realize a technical scheme of high mineralization speed, high mineralization degree and simple process flow of bypass air-released ash.
Referring to fig. 1, an embodiment of the present invention provides a method for absorbing CO in flue gas by accelerating mineralization of calcium carbonate with pH regulation 2 The system comprises a cement kiln bypass air-bleeding ash storage, metering and conveying system, an additive system, a water supply system, a kiln tail waste gas air supply system, a pH on-line detection system, a stirring mineralization absorption system, a decarburization waste gas air-out system and a mineralization ash conveying system.
The stirring, mineralizing and absorbing system comprises a mineralizing stirrer, and a feed inlet, a water inlet, a pH value sampling port, an air inlet, an air outlet and a discharge port which are positioned on the mineralizing stirrer.
The cement kiln bypass air-bleeding ash storage, metering and conveying system comprises a cement kiln bypass air-bleeding ash storage bin, an electric gate valve and a screw metering feeder which are sequentially connected, and an outlet of the screw metering feeder is connected with a feed inlet of the mineralizing mixer.
The additive system comprises an additive storage bin, a disc feeder and a feeding scraper-trough conveyer which are sequentially connected, the water supply system comprises a water storage tank, a metering water pump and a water supply pipeline which are sequentially connected, the outlet of the feeding scraper-trough conveyer is connected with the inlet of the water storage tank, and the outlet of the water supply pipeline is connected with the water inlet of the mineralization stirrer.
The pH on-line detection system comprises a sampling device and a detection device, wherein the sampling device is arranged at a pH value sampling port of the mineralization stirrer.
The kiln tail waste gas air supply system comprises a centrifugal fan and a kiln tail waste gas air supply pipeline, wherein the inlet of the centrifugal fan is connected with a kiln tail chimney, and the outlet of the centrifugal fan is connected with the air inlet of the mineralization stirrer through the kiln tail waste gas air supply pipeline; the decarbonization waste gas air-out system comprises a decarbonization waste gas air-out pipeline, an air outlet of the mineralization stirrer is connected with an inlet of the decarbonization waste gas air-out pipeline, and an outlet of the decarbonization waste gas air-out pipeline is connected with a kiln tail chimney.
And the discharge opening of the mineralization stirrer is connected with a mineralization ash conveying system.
PH value-regulated calcium carbonate-based device for accelerating mineralization and absorption of CO in flue gas 2 The method for mineralizing and absorbing carbon dioxide by using the system comprises the following steps:
s1, adding sodium acetate into a water storage tank through an additive system, and controlling the mass fraction of a sodium acetate aqueous solution to be 1-3%;
s2, feeding the cement kiln bypass air-released ash into a mineralizing stirrer through a cement kiln bypass air-released ash storage, metering and conveying system, adding water according to the water-ash ratio of 0.1-0.3, and stirring for 5-10 minutes to fully hydrate calcium oxide in the cement kiln bypass air-released ash into calcium hydroxide;
s3, water is led from a kiln tail chimney to mud kiln tail waste gas by a centrifugal fan, and 3000-5000Nm is adopted 3 Introducing the air quantity of/h into a mineralization stirrer, introducing the cement kiln tail waste gas while stirring, and mineralizing for 0.5-1.5h to ensure that the cement kiln bypass air discharge ash absorbs CO in the cement kiln tail waste gas 2 Realizing permanent curing;
s4, in the mineralization process, monitoring the pH value of the materials in the mineralization stirrer in the whole process by using a pH value online detection system, ensuring that the pH value is between 10 and 11, slowly adding cement kiln bypass air-release ash into the mineralization stirrer when the pH value is reduced to be less than 10, and maintaining the pH value of the materials to be between 10 and 11 all the time until the mineralization is completed;
and S5, after mineralization is finished, stopping leading the tail waste gas of the cement kiln, opening a discharge port of the mineralization stirrer, and conveying the generated mineralized ash to a storage yard or a storage warehouse through a mineralized ash conveying system.
The inventor researches and discovers that the reaction rate of mineralizing and absorbing carbon dioxide by using bypass air-bleeding ash of the cement kiln alone is influenced by the degree of mineralization, and CaCO generated by the reaction is generated along with the increase of the degree of mineralization 3 The particles cover the surfaces of the bypass air-bleeding ash particles, so that carbon dioxide is prevented from further entering the particles to carry out mineralization reaction, and the reaction rate and the reaction degree are limited.
Bypass air-bleeding ash particlesWhen encountering water, the calcium oxide in the water reacts with the water to generate calcium hydroxide, and the calcium hydroxide and CO in the kiln tail waste gas 2 The reaction takes place to form calcium carbonate, see chemical reaction equations (1) and (2).
CaO+H 2 O→Ca(OH) 2 (1)
Ca(OH) 2 +CO 2 →CaCO 3 +H 2 O (2)
With the development of the reaction process, the content of calcium oxide in the bypass air-bleeding ash particles is gradually reduced, the inner core shrinks, calcium hydroxide generated by the reaction of calcium oxide and water covers the outer layer of the particles, the mineralization reaction of carbon dioxide and calcium hydroxide also occurs on the surfaces of the bypass air-bleeding ash particles, and the calcium carbonate particles generated by the reaction are fine and cover the surfaces of the bypass air-bleeding ash particles, so that the entering of carbon dioxide and the process of the mineralization reaction are hindered, as shown in fig. 2.
A large number of experimental researches show that the crystal size of calcium carbonate particles generated by reaction can be increased by introducing a certain amount of sodium acetate as buffer and controlling the pH value of the material to be in the range of 10-11, so that carbon dioxide can penetrate through a calcium carbonate layer to enter a calcium hydroxide layer to continuously carry out mineralization reaction, and the mineralization reaction process and the mineralization absorption amount are accelerated.
To further understand the contents, characteristics and effects of the present invention, the following examples 1-5 and comparative examples 1-3 are listed for detailed description to illustrate the technical effects of the present invention:
the chemical components of the cement kiln bypass air-bleeding ash used in the detection and analysis are firstly shown in the following table 1:
TABLE 1 Cement kiln by-pass air bleed ash chemistry
| L.O.I | SiO 2 | Al 2 O 3 | Fe 2 O 3 | CaO | MgO | K 2 O | Na 2 O | SO 3 | Cl- |
| 10.34 | 10.50 | 3.44 | 1.90 | 48.55 | 1.66 | 14.98 | 0.47 | 1.48 | 7.653 |
The bypass air-bleeding ash theoretically absorbs carbon dioxide amount (%) = CaO content × 44/56=48.55 × 44/56=38.1%.
Example 1
Adding sodium acetate into a water storage tank through an additive system, controlling the mass fraction of a sodium acetate aqueous solution to be 3%, and conveying 1 ton of cement kiln bypass air-released ash into a mineralization stirrer through a cement kiln bypass air-released ash storage, metering and conveying system; then press againstFeeding sodium acetate aqueous solution into a mineralization stirrer according to a water-cement ratio of 0.1, starting the mineralization stirrer to stir for 5 min, and introducing 3000Nm from a kiln tail chimney through a centrifugal fan 3 Introducing the cement kiln tail waste gas into a mineralization stirrer, mineralizing and stirring for 0.5h, detecting the pH value of the material through a pH value online detection system in the mineralization process, and slowly adding cement kiln bypass air-release ash into the mineralization stirrer to maintain the pH value of the material between 10 and 11 all the time until mineralization is finished; and after mineralization is finished, stopping introducing the tail waste gas of the cement kiln and stirring, and conveying the generated mineralized ash into a mineralized ash conveying system through a discharge opening of the mineralized stirrer to a storage yard or a storage warehouse.
Carbon dioxide absorptivity (%) = (weight of mineralized ash after mineralization is finished-weight of air ash discharged by a cement kiln bypass entering the mineralized mixer-weight of water for mineralization)/weight of air ash discharged by a cement kiln bypass entering the mineralized mixer is multiplied by 100%, and the carbon dioxide absorptivity is detected to be 32%.
Example 2
Adding sodium acetate into a water storage tank through an additive system, controlling the mass fraction of a sodium acetate aqueous solution to be 2%, and conveying 1 ton of cement kiln bypass air-released ash into a mineralization stirrer through a cement kiln bypass air-released ash storage, metering and conveying system; then according to the water-cement ratio of 0.2, sending the sodium acetate water solution into a mineralization stirrer through a water supply system, starting the mineralization stirrer to stir for 8 minutes, and then leading 4000Nm from a kiln tail chimney through a centrifugal fan 3 Introducing the cement kiln tail waste gas into a mineralization stirrer, mineralizing and stirring for 1.0h, detecting the pH value of the material through a pH value online detection system in the mineralization process, slowly adding cement kiln bypass discharged ash into the mineralization stirrer, and keeping the pH value of the material between 10 and 11 all the time until the mineralization is finished; and after mineralization is finished, stopping the waste gas and stirring at the tail of the cement kiln, and conveying the generated mineralized ash into a mineralized ash conveying system through a discharge port of a mineralized stirrer to be conveyed to a storage yard or a storage warehouse.
Carbon dioxide absorptivity (%) = (weight of mineralized ash after mineralization is finished-weight of air ash discharged by a cement kiln bypass entering the mineralized mixer-weight of water for mineralization)/weight of air ash discharged by a cement kiln bypass entering the mineralized mixer is multiplied by 100%, and carbon dioxide absorptivity is detected to be 30%.
Example 3
Adding sodium acetate into a water storage tank through an additive system, controlling the mass fraction of a sodium acetate aqueous solution to be 3%, and conveying 1 ton of cement kiln bypass air-released ash into a mineralization stirrer through a cement kiln bypass air-released ash storage, metering and conveying system; then according to the water-cement ratio of 0.3, feeding the sodium acetate aqueous solution into a mineralization stirrer through a water supply system, starting the mineralization stirrer to stir for 10 minutes, and then introducing 5000Nm from a kiln tail chimney through a centrifugal fan 3 Introducing the cement kiln tail waste gas into a mineralization stirrer, mineralizing and stirring for 1.5h, detecting the pH value of the material through a pH value online detection system in the mineralization process, and slowly adding cement kiln bypass air-release ash into the mineralization stirrer to maintain the pH value of the material between 10 and 11 all the time until mineralization is finished; and after mineralization is finished, stopping introducing the water into the tail waste gas of the cement kiln and stirring, and conveying the generated mineralized ash into a mineralized ash conveying system through a discharge opening of the mineralized stirrer to be conveyed to a storage yard or a storage warehouse.
Carbon dioxide absorption (%) = (weight of mineralized ash after mineralization is finished-weight of unmineralized cement kiln bypass air-released ash entering the mineralized stirrer-weight of mineralized water)/weight of cement kiln bypass air-released ash entering the mineralized stirrer is multiplied by 100%, and the absorption rate of carbon dioxide is detected to be 31%.
Comparative example 1
The water for stirring is pure water, and 1 ton of cement kiln bypass air-released ash is sent into a mineralizing mixer through a cement kiln bypass air-released ash storage, metering and conveying system; then according to the water-cement ratio of 0.2, sending the pure water into a mineralization stirrer through a water supply system, starting the mineralization stirrer to stir for 8 minutes, and then leading 4000Nm from a kiln tail chimney through a centrifugal fan 3 Introducing the cement kiln tail waste gas into a mineralization stirrer, mineralizing and stirring for 1.0h, detecting the pH value of the material through a pH value online detection system in the mineralization process, and slowly adding cement kiln bypass air-release ash into the mineralization stirrer to maintain the pH value of the material between 10 and 11 all the time until mineralization is finished; after mineralization is finished, stopping water passing through the waste gas at the tail of the cement kiln and stirring, and leading the generated mineralized ash to pass throughThe discharge opening of the over-mineralization stirrer enters a mineralized ash conveying system and is conveyed to a storage yard or a storage warehouse.
Carbon dioxide absorption rate (%) = (weight of mineralized ash after mineralization is finished-weight of bypass air-blown ash of cement kiln entering into mineralization stirrer and weight of mineralized water)/weight of bypass air-blown ash of cement kiln entering into mineralization stirrer x 100%, and carbon dioxide absorption rate is detected to be 16%.
Comparative example 2
Adding sodium acetate into a water storage tank through an additive system, controlling the mass fraction of a sodium acetate aqueous solution to be 3%, and conveying 1 ton of cement kiln bypass air-released ash into a mineralization stirrer through a cement kiln bypass air-released ash storage, metering and conveying system; then according to the water-cement ratio of 0.2, feeding the sodium acetate aqueous solution into a mineralization stirrer through a water supply system, starting the mineralization stirrer to stir for 8 minutes, and then introducing 4000Nm from a kiln tail chimney through a centrifugal fan 3 Introducing the cement kiln tail waste gas into a mineralization stirrer, mineralizing and stirring for 1.0h, detecting the pH value of the material through a pH value online detection system in the mineralization process, slowly adding cement kiln bypass discharged ash into the mineralization stirrer, and keeping the pH value of the material between 8 and 10 all the time until the mineralization is finished; and after mineralization is finished, stopping introducing the water into the tail waste gas of the cement kiln and stirring, and conveying the generated mineralized ash into a mineralized ash conveying system through a discharge opening of the mineralized stirrer to be conveyed to a storage yard or a storage warehouse.
Carbon dioxide absorptivity (%) = (weight of mineralized ash after mineralization is finished-weight of air ash discharged by a cement kiln bypass entering the mineralized mixer-weight of water for mineralization)/weight of air ash discharged by a cement kiln bypass entering the mineralized mixer is multiplied by 100%, and carbon dioxide absorptivity is detected to be 18%.
Comparative example 3
The water for stirring is pure water, and 1 ton of cement kiln bypass air-released ash is sent into a mineralization stirrer through a cement kiln bypass air-released ash storage, metering and conveying system; then according to the water-cement ratio of 0.2, sending the pure water into a mineralization stirrer through a water supply system, starting the mineralization stirrer to stir for 8 minutes, and then leading 4000Nm from a kiln tail chimney through a centrifugal fan 3 H, introducing the waste gas from the tail of the cement kiln into the mineralized mixture for stirringThe machine is used for mineralizing and stirring for 3.0h, the pH value of the material is detected by a pH value online detection system in the mineralizing process, and the cement kiln bypass air-release ash is slowly added into the mineralizing stirrer to maintain the pH value of the material between 8 and 10 all the time until the mineralizing is finished; and after mineralization is finished, stopping introducing the water into the tail waste gas of the cement kiln and stirring, and conveying the generated mineralized ash into a mineralized ash conveying system through a discharge opening of the mineralized stirrer to be conveyed to a storage yard or a storage warehouse.
Carbon dioxide absorptivity (%) = (weight of mineralized ash after mineralization is finished-weight of air ash discharged by a cement kiln bypass entering the mineralized mixer-weight of water for mineralization)/weight of air ash discharged by a cement kiln bypass entering the mineralized mixer is multiplied by 100%, and the carbon dioxide absorptivity is detected to be 20%.
Comparative example 4
Adding sodium acetate into a water storage tank through an additive system, controlling the mass fraction of a sodium acetate aqueous solution to be 3%, and conveying 1 ton of cement kiln bypass air-released ash into a mineralization stirrer through a cement kiln bypass air-released ash storage, metering and conveying system; then according to the water-cement ratio of 0.2, feeding the sodium acetate aqueous solution into a mineralization stirrer through a water supply system, starting the mineralization stirrer to stir for 8 minutes, and then introducing 4000Nm from a kiln tail chimney through a centrifugal fan 3 Introducing the cement kiln tail waste gas into a mineralization stirrer, mineralizing and stirring for 3.0h, detecting the pH value of the material through a pH value online detection system in the mineralization process, and slowly adding cement kiln bypass air-release ash into the mineralization stirrer to maintain the pH value of the material between 8 and 10 all the time until mineralization is finished; and after mineralization is finished, stopping introducing the water into the tail waste gas of the cement kiln and stirring, and conveying the generated mineralized ash into a mineralized ash conveying system through a discharge opening of the mineralized stirrer to be conveyed to a storage yard or a storage warehouse.
Carbon dioxide absorptivity (%) = (weight of mineralized ash after mineralization is finished-weight of air ash discharged by a cement kiln bypass entering the mineralized mixer-weight of water for mineralization)/weight of air ash discharged by a cement kiln bypass entering the mineralized mixer is multiplied by 100%, and the carbon dioxide absorptivity is detected to be 21%.
Examples 1-3 show that the absorption rate of carbon dioxide in the kiln tail flue gas is over 30 percent and the highest absorption rate reaches 32 percent, the mineralization can be completed within 0.5-1.5 hours, the mineralization rate is high, and the mineralization degree is high by the system and the method provided by the invention; comparative examples 1 to 4 in comparison with example 1, under the same conditions of flue gas, the absorption rate of carbon dioxide could not be improved without using sodium acetate or by prolonging the mineralization time.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (8)
1. PH value-regulated calcium carbonate-based device for accelerating mineralization and absorption of CO in flue gas 2 The system is characterized by comprising a cement kiln bypass air-discharging ash storage, metering and conveying system, an additive system, a water supply system, a kiln tail waste gas air supply system, a pH online detection system, a stirring mineralization absorption system, a decarburization waste gas air outlet system and a mineralized ash conveying system;
the outlet of the cement kiln bypass air-released ash storage, metering and conveying system is connected with the feed inlet of the stirring mineralization absorption system, the outlet of the additive system is connected with the inlet of the water supply system, the outlet of the water supply system is connected with the water inlet of the stirring mineralization absorption system, the outlet of the kiln tail waste gas air supply system is connected with the air inlet of the stirring mineralization absorption system, the pH on-line detection system is connected with the pH value sampling port of the stirring mineralization absorption system, the air outlet of the stirring mineralization absorption system is connected with the decarburization waste gas air outlet system, and the discharge port of the stirring mineralization absorption system is connected with the mineralization ash conveying system.
2. The pH-regulated calcium carbonate according to claim 1 for accelerated mineralization absorption of CO in flue gas 2 Of (2) aThe device is characterized in that the cement kiln bypass air-bleeding ash storage, metering and conveying system comprises a cement kiln bypass air-bleeding ash storage bin, an electric gate valve and a screw metering feeder which are sequentially connected, and an outlet of the screw metering feeder is connected with a feed inlet of the stirring mineralization absorption system.
3. The pH-regulated calcium carbonate according to claim 1 for accelerated mineralization absorption of CO in flue gas 2 The system is characterized by comprising an additive storage bin, a disk feeder and a feeding scraper-trough conveyer which are sequentially connected, wherein the outlet of the feeding scraper-trough conveyer is connected with the inlet of a water supply system.
4. The pH-regulated calcium carbonate according to claim 1 for accelerating mineralization and absorption of CO in flue gas 2 The system is characterized in that the water supply system comprises a water storage tank, a metering water pump and a water supply pipeline which are connected in sequence, and an outlet of the water supply pipeline is connected with a water inlet of the stirring mineralization absorption system.
5. The pH-regulated calcium carbonate according to claim 1 for accelerated mineralization absorption of CO in flue gas 2 The system is characterized in that the stirring, mineralizing and absorbing system comprises a mineralizing stirrer, and a feeding port, a water inlet, a pH value sampling port, an air inlet, an air outlet and a discharging port which are positioned on the mineralizing stirrer.
6. The pH-regulated calcium carbonate according to claim 1 for accelerating mineralization and absorption of CO in flue gas 2 The system is characterized in that the kiln tail waste gas air supply system comprises a centrifugal fan and a kiln tail waste gas air supply pipeline, wherein the inlet of the centrifugal fan is connected with a kiln tail chimney, and the outlet of the centrifugal fan is connected with an air inlet of the stirring, mineralizing and absorbing system through the kiln tail waste gas air supply pipeline; the decarbonization waste gas air-out system comprises a decarbonization waste gas air-out pipeline, an air outlet of the stirring mineralization absorption system is connected with an inlet of the decarbonization waste gas air-out pipeline, and an outlet of the decarbonization waste gas air-out pipeline is connected with a kiln tail chimney.
7. The pH-regulated calcium carbonate according to claim 1 for accelerating mineralization and absorption of CO in flue gas 2 The system is characterized in that the pH on-line detection system comprises a sampling device and a detection device, and the sampling device is arranged at a pH value sampling port of the mineralization stirrer.
8. pH value regulated calcium carbonate based on system of any one of claims 1 to 7 for accelerating mineralization and absorption of CO in flue gas 2 The method is characterized by comprising the following steps:
s1, adding sodium acetate into a water supply system through an additive system, and controlling the mass fraction of a sodium acetate aqueous solution to be 1-3%;
s2, feeding the cement kiln bypass air-released ash into a stirring mineralization absorption system through a cement kiln bypass air-released ash storage, metering and conveying system, adding water according to the water-ash ratio of 0.1-0.3, and stirring for a certain time to fully hydrate calcium oxide in the cement kiln bypass air-released ash into calcium hydroxide;
s3, leading the mud kiln tail waste gas from a kiln tail chimney by a kiln tail waste gas air supply system, and according to 3000-5000Nm 3 The air quantity of per hour is introduced into a stirring, mineralizing and absorbing system, the tail waste gas of the cement kiln is introduced while stirring, and the mineralization is carried out for 0.5 to 1.5 hours, so that the bypass air-release ash of the cement kiln absorbs the CO in the tail waste gas of the cement kiln 2 Realizing permanent curing;
s4, in the mineralization process, monitoring the pH value of the materials in the stirring mineralization absorption system in the whole process by using a pH value online detection system, ensuring that the pH value is between 10 and 11, slowly adding cement kiln bypass air-release ash into the stirring mineralization absorption system when the pH value is reduced to be less than 10, and maintaining the pH value of the materials to be between 10 and 11 all the time until the mineralization is finished;
and S5, after mineralization is finished, stopping leading the tail waste gas of the cement kiln, opening a discharge port of the stirring mineralization absorption system, and transporting the generated mineralized ash to a storage yard or a storage warehouse through a mineralized ash conveying system.
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