CN112919468A - Method for recovering carbon dioxide by calcining limestone with oxygen-enriched combustion-supporting effect - Google Patents
Method for recovering carbon dioxide by calcining limestone with oxygen-enriched combustion-supporting effect Download PDFInfo
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- CN112919468A CN112919468A CN202110265076.7A CN202110265076A CN112919468A CN 112919468 A CN112919468 A CN 112919468A CN 202110265076 A CN202110265076 A CN 202110265076A CN 112919468 A CN112919468 A CN 112919468A
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- carbon dioxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2/00—Lime, magnesia or dolomite
- C04B2/02—Lime
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2/00—Lime, magnesia or dolomite
- C04B2/10—Preheating, burning calcining or cooling
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention discloses a method for recovering carbon dioxide by calcining limestone with oxygen-enriched combustion-supporting. And (3) feeding the limestone into a calcining furnace for calcining after crushing and screening to generate quicklime, and crushing the quicklime to prepare a quicklime product. After being gasified, the LNG is mixed with an oxygen-enriched air pipeline and is sent into a calcining furnace for combustion. Gas discharged from the calcining furnace sequentially passes through a heat exchanger for heat exchange, a spray tower for primary dust removal and cooling, a packed tower for absorbing water vapor, then the obtained gas sequentially passes through a low-temperature heat exchanger for heat exchange and cooling, a bag-type dust remover for dust removal and a compressor for multi-stage compression to generate liquid carbon dioxide, and finally gas-liquid separation is carried out to obtain the liquid carbon dioxide with the purity of more than 98%. The method can simultaneously produce high-quality quicklime and liquid carbon dioxide with the purity of more than 98 percent, realizes the liquefaction and separation of carbon dioxide gas and other gases generated by calcining limestone at normal temperature, has simple and continuous system structure, convenient operation, energy consumption saving and is suitable for large-scale continuous production.
Description
Technical Field
The invention relates to the field of comprehensive utilization of inorganic nonmetallic ores, in particular to a method for recovering carbon dioxide by calcining limestone in an oxygen-enriched combustion-supporting manner.
Background
Calcium carbonate is an important inorganic chemical raw material, and has been used for hundreds of years in industrial development. Calcium carbonate is used as a high-quality filler and a white pigment, and is widely applied to filling of composite materials in the fields of chemical industry, metallurgy, building materials, electronics, light industry, medicine, agriculture and the like. The calcium carbonate products are classified into heavy calcium carbonate and light calcium carbonate, wherein the heavy calcium carbonate (called ground calcium carbonate for short) is also called ground calcium carbonate and is prepared by crushing, grinding and grading limestone, calcite, marble, dolomite and the like.
The real value of calcium carbonate application is its deep processed product. The requirements of large-scale, fine, functional and diversified calcium carbonate products enable the calcium carbonate products to develop towards the directions of ultra-fine, ultra-purification, surface modification and compounding at a high speed, so that the calcium carbonate products have the filling function and the reinforcing property. The calcination of calcium carbonate to obtain products such as carbon dioxide and quicklime is one of the important research directions.
Currently, in the comprehensive application of calcium carbonate, the main methods for removing carbon dioxide include a physical absorption method, a chemical absorption method, a pressure swing adsorption method and a membrane method.
1) The physical absorption method includes a cold methanol method, a polyethylene glycol dimethyl ether method and an allyl carbonate method. The physical absorption method needs to be carried out under the condition that the pressure is 2-5 MPa and the temperature is lower, and the solution is regenerated by means of reduced pressure desorption. The method has low energy consumption and low purification degree. The application of the method in a purification process with higher purification degree requirement is yet to be further improved.
2) The chemical absorption method can absorb the carbon dioxide in the gas under the environment of lower pressure, and the degree of removing the carbon dioxide is very high. The currently used chemical absorption method is mainly a hot potash method. The hot potash process is a method for effectively removing carbon dioxide, and its principle is to use a small amount of organic matter or a large amount of inorganic matter as an activator of the hot potassium carbonate process for removing carbon dioxide. However, in the practical application process, the absorbent regeneration process has the disadvantages of complicated operation, unfavorable continuous production, high energy consumption, high investment and the like.
3) Pressure Swing Adsorption (PSA) is a new gas separation process that has emerged in recent years. The process is based on an adsorption unit operation and is generally used for separating and refining certain gases in mixed gases. The adsorption process principle is that the different adsorption forces of the adsorbents on different gases are utilized to selectively adsorb a certain component in a gas mixture, so that the component is separated from other gases. In the process operation process, a plurality of sets of adsorption devices are used in parallel to keep the continuity of the process production; and the energy consumption, the occupied area, the operation cost and the equipment investment cost are higher. Therefore, the application and popularization of the technology are awaited for further improvement of the technology and improvement of the technology.
4) In the membrane method, when a compressed mixed gas free of liquid water and oil flows along the inner cavity of a hollow fiber tube, the partial pressure of each gas is a driving force, namely, the partial pressure difference, formed by the high pressure side (raw material side) and the low pressure side (permeation side) of the hollow fiber tube, and the gas (such as CO2 and H2) with large dissolution coefficient and diffusion coefficient2S) preferentially permeates through the tube wall and the rest of the gas (CH)4) The separation is achieved due to the relative difficulty of permeation, but the price is high, the investment and the recovery are not in direct proportion, and the popularization is difficult.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for recovering carbon dioxide by calcining limestone with oxygen-enriched combustion-supporting, wherein carbon dioxide gas and other impurity gases generated by calcining limestone are efficiently separated by liquefying at normal temperature while producing high-quality quicklime, and liquid carbon dioxide with purity of more than 98% is produced, so that high-quality utilization of carbon dioxide is realized; meanwhile, the method is suitable for large-scale continuous production, and the system has the advantages of simple and continuous structure, convenience in operation and energy consumption saving.
The invention adopts the following technical scheme to solve the technical problems:
a method for recovering carbon dioxide by calcining limestone with oxygen-enriched combustion-supporting comprises the following process steps:
(1) crushing limestone to the particle size of 100-150 mm by a crusher, screening by using a vibrating screen with the aperture of 50mm, recycling undersize as a raw material for making bricks, and feeding oversize into a calcining furnace for calcining;
(2) after being gasified by a gasification device, LNG is mixed with an oxygen-enriched air pipeline and sent to the calcining furnace in the step (1) for combustion;
(3) after the oversize material is calcined in the calcining furnace, crushing the generated quick lime, and cooling to generate a quick lime finished product;
(4) the method comprises the following steps of firstly exchanging heat of flue gas discharged from a calcining furnace through a heat exchanger, primarily cooling and dedusting the flue gas through a spray tower, then sending the flue gas into a packed tower through a fan, adsorbing water vapor in the flue gas by using a molecular sieve as a filler in the packed tower, sending the gas discharged from the packed tower into a low-temperature heat exchanger, reducing the temperature of the gas to 14-16 ℃, removing redundant particulate matters through a bag-type dust remover, finally pre-compressing the gas to 2.5MPa through a compressor, performing multi-stage compression to 5.3MPa, generating liquid carbon dioxide, and separating the liquid carbon dioxide through a gas-liquid separator for recycling and storing.
The oxygen content of the oxygen-enriched air reaches 40-50%.
The filler of the adsorption tower adopts zeolite molecular sieve.
The LNG is provided by a blocking explosion-proof skid-mounted LNG storage tank and then is sent to a gasification device for gasification.
The invention has the advantages that:
the method of the invention realizes the liquefaction of carbon dioxide in the mixed gas at normal temperature while producing high-quality quicklime, adopts the normal-temperature liquefaction method to efficiently separate carbon dioxide gas and other impurity gases generated by calcining limestone, produces liquid carbon dioxide with the purity of more than 98 percent, realizes the high-quality utilization of the carbon dioxide, and provides the liquid carbon dioxide for food or industrial use. The method is suitable for large-scale continuous production, and has the advantages of simple and continuous system structure, convenient operation, energy consumption saving and wide application prospect.
Drawings
FIG. 1 is a process flow diagram of the process of the present invention.
Detailed Description
The following detailed description of the embodiments of the present invention is provided in conjunction with the accompanying drawings and the specific embodiments, but not to limit the scope of the claims of the present invention.
As shown in figure 1, the method for recovering carbon dioxide by calcining limestone with oxygen-enriched combustion-supporting comprises the following process steps:
(1) the method comprises the following steps of (1) crushing limestone by a crusher, feeding the crushed limestone into a hopper, crushing the crushed limestone into particles with the particle size of 100-150 mm by the crusher, and sieving the particles by a vibrating sieve with the sieve hole diameter of 50mm, wherein undersize materials, namely fine slag with the particle size of less than 50mm, are recycled as raw materials for making bricks; the oversize material is mainly limestone raw material with the grain size of 100 mm-150 mm, and the limestone raw material is sent into a calcining furnace by a hoister to be calcined to generate quicklime and carbon dioxide gas, and the chemical equation is as follows:
CaCO3+CH4+2O2→CaO+2CO2+2H2O
(2) after being gasified by the gasification device, the LNG is mixed with oxygen-enriched air and sent to the calcining furnace for combustion.
(3) And after the limestone raw material is calcined in the calcining furnace, the generated quicklime is sent out through a lime discharging machine, is sent to a crusher for crushing through a hoister and a belt conveyor in sequence, and is packaged after being cooled to obtain a finished quicklime product.
(4) The method comprises the following steps of firstly exchanging heat of flue gas discharged from a calcining furnace through a heat exchanger, then primarily cooling and dedusting through a spray tower, then sending the flue gas into a packed tower through a fan, absorbing water vapor in the flue gas by using a molecular sieve as a packing of the packed tower, sending gas discharged from the packed tower into a low-temperature heat exchanger for heat exchange to reduce the temperature of the gas to 14-16 ℃, removing redundant particulate matters through a bag-type dust remover, finally precompressing the gas to 2.5MPa through a primary compressor, and compressing the gas to 2.5MPa through a secondary compressor5.3MPa, and liquid carbon dioxide is generated. Liquid carbon dioxide is separated by a gas-liquid separator and is led into a carbon dioxide storage tank for storage. The invention adopts liquefied natural gas to replace the traditional coal fuel. Compared with the coal fired by the traditional process, the LNG has the advantages of low price, less impurities, environmental friendliness and the like, meets the requirement of clean energy, and has the LNG density of 0.42-0.46 g/cm3In the meantime.
The invention adopts oxygen-enriched air to support combustion, oxygen in an oxygen tank is sent into a pipeline through a fan, the oxygen content of the oxygen-enriched air is increased to 40-50% from the oxygen content of the atmosphere 21%, and then the oxygen-enriched air is mixed with LNG and sent into the calcining furnace for combustion. The method aims to reduce the content of other gases except oxygen in the combustion gas, so that methane can be fully combusted, the combustion efficiency of LNG fuel gas is improved, and the yield of carbon dioxide is improved.
The filler of the packed tower adopts a 5A calcium A type zeolite molecular sieve, has the advantages of high adsorption capacity, strong selectivity, high temperature resistance and the like, and can purify sulfides and nitrides in gas to a certain extent to achieve the aim of environmental protection. The filler has a specification of 100mm multiplied by 50mm, has a structure with pore channels with uniform pore diameters and regularly arranged pores, contains aluminosilicate as a component, and has a bulk density of 400-500 kg/m3And can resist high temperature below 800 ℃.
LNG in the LNG storage tank is supplemented by the blocking explosion-proof skid-mounted LNG filling station and then is supplied to the gasification device for gasification. The blocking explosion-proof skid-mounted LNG filling station has the characteristics of safety, convenience, environmental protection, high maneuverability, high intelligent degree and the like.
The first-stage compressor adopts the existing Z-0.07/170-type 250-type compressor and is of a vertical, two-row, first-stage compression, reciprocating piston type, oil injection lubrication, water cooling and skid-mounted structure. The inlet pressure is 0.1Mpa (G), the exhaust pressure is 2.5MPa (G), and the theoretical exhaust volume is 700N m3H is used as the reference value. The second-stage compressor is a conventional DW-5.16/2.5-250 type compressor, and is of a horizontal type, two-row and four-stage compression type, reciprocating piston type, cylinder oil-free lubrication type, water-cooling type and skid-mounted type structure. Inlet pressure 2.5MPa (G), exhaust pressure 5.3MPa (G), theoretical displacement 1000N m3H is used as the reference value. The pressure of the gas after the secondary compression is up toWhen the pressure is 5.3MPa and the temperature is reduced to below 16 ℃, separating carbon dioxide with the volume ratio of 40% from the compressed gas to obtain liquid carbon dioxide with the purity of 99%.
Claims (4)
1. A method for recovering carbon dioxide by calcining limestone with oxygen-enriched combustion-supporting is characterized by comprising the following process steps:
(1) crushing limestone to the particle size of 100-150 mm by a crusher, screening by using a vibrating screen with the aperture of 50mm, recycling undersize as a raw material for making bricks, and feeding oversize into a calcining furnace for calcining;
(2) after being gasified by a gasification device, LNG is mixed with an oxygen-enriched air pipeline and sent to the calcining furnace in the step (1) for combustion;
(3) after the oversize material is calcined in the calcining furnace, crushing the generated quick lime, and cooling to generate a quick lime finished product;
(4) the method comprises the following steps of firstly exchanging heat of flue gas discharged from a calcining furnace through a heat exchanger, primarily cooling and dedusting the flue gas through a spray tower, then sending the flue gas into a packed tower through a fan, adsorbing water vapor in the flue gas by using a molecular sieve as a filler in the packed tower, sending the gas discharged from the packed tower into a low-temperature heat exchanger, reducing the temperature of the gas to 14-16 ℃, removing redundant particulate matters through a bag-type dust remover, finally pre-compressing the gas to 2.5MPa through a compressor, performing multi-stage compression to 5.3MPa, generating liquid carbon dioxide, and separating the liquid carbon dioxide through a gas-liquid separator for recycling and storing.
2. A method for recovering carbon dioxide from the combustion-supporting calcined limestone with oxygen rich as claimed in claim 1, wherein the oxygen content of the oxygen-rich air is up to 40% -50%.
3. A method for recovering carbon dioxide by calcining limestone with oxygen-enriched combustion-supporting as claimed in claim 1, wherein the packing of the adsorption tower is zeolite molecular sieve.
4. A method for recovering carbon dioxide from limestone through oxygen-enriched combustion-supporting calcination as claimed in claim 1, wherein the LNG is supplied from a barrier explosion-proof skid-mounted LNG storage tank and then sent to a gasification device for gasification.
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Cited By (2)
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| CN113769871A (en) * | 2021-09-15 | 2021-12-10 | 林高兴 | Active lime calcining system |
| CN115520867A (en) * | 2022-09-14 | 2022-12-27 | 首钢京唐钢铁联合有限责任公司 | Method for increasing concentration of carbon dioxide in lime kiln flue gas |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113769871A (en) * | 2021-09-15 | 2021-12-10 | 林高兴 | Active lime calcining system |
| CN115520867A (en) * | 2022-09-14 | 2022-12-27 | 首钢京唐钢铁联合有限责任公司 | Method for increasing concentration of carbon dioxide in lime kiln flue gas |
| CN115520867B (en) * | 2022-09-14 | 2024-02-09 | 首钢京唐钢铁联合有限责任公司 | Method for improving carbon dioxide concentration in lime kiln flue gas |
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