CN102580468A - Method for implementing trapping and separation of CO2 in flue gas by adopting magnesium-based absorbent - Google Patents

Method for implementing trapping and separation of CO2 in flue gas by adopting magnesium-based absorbent Download PDF

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Publication number
CN102580468A
CN102580468A CN2012100186105A CN201210018610A CN102580468A CN 102580468 A CN102580468 A CN 102580468A CN 2012100186105 A CN2012100186105 A CN 2012100186105A CN 201210018610 A CN201210018610 A CN 201210018610A CN 102580468 A CN102580468 A CN 102580468A
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flue gas
absorbent
mgo
solid
trapping
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CN102580468B (en
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张军
卢伟伟
时清亮
宋帮才
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Henan University of Science and Technology
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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
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • 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
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

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Abstract

The invention discloses a method for implementing trapping and separation of CO2 in flue gas by adopting a magnesium-based absorbent and relates to a CO2 trapping and separation technology. According to the invention, Mg(OH)2 suspension is used as the absorbent for CO2 in the flue gas; compared with the existing CO2 trapping capacity, the CO2 trapping capacity of the method is finally greatly improved by controlling conditions of a suitable solid-to-liquid ratio of the suspension, a ratio of the absorbent to the flue gas and the like; and a food-grade CO2 product with high purity is also obtained. The method disclosed by the invention has strong CO2 trapping capacity, simple process, low trapping agent regeneration cost and strong technical applicability.

Description

A kind of employing magnesium base absorbant is realized CO in the flue gas 2Capture and the method for separating
Technical field
The present invention relates to CO 2Capture and isolation technics, specifically be that a kind of employing magnesium base absorbant is realized CO in the flue gas 2Capture and the method for separating.
Background technology
In recent years, global warming has become the focal issue that international community pays special attention to, and greenhouse gases are CO particularly 2A large amount of dischargings are principal elements of climate warming, control and reduce CO 2Discharging is the urgent task that human society faces.Occupying an important position in industry at China's coal electricity, iron and steel, chemical industry, petrochemical industry and cement industry, also is energy resource consumption and CO simultaneously 2So the important industry of discharging is about CO 2Trapping technique mainly is to carry out to above industry, and according to the technical foundation and the applicability of trapping system, engineering circle is usually with CO 2Trapping system is divided into following four kinds: capture before the burning back captures, burns, oxygen-enriched combustion technology and chemical chain burning technology.
The CO that is developing energetically at present 2Trapping technique mainly contains 3 kinds, chemical solvent absorption method, absorption method and membrane separation process.Wherein with the research of chemical solvent absorption method at most, this method occupies CO 2The market of capture 70%; Also be considered to most economical feasible; The absorbent that is used to collecting carbonic anhydride has ammoniacal liquor, NaOH, one-level hydramine (MEA), secondary hydramine (DEA, DIPA) and tertiary alcohol amine (MDEA) etc., forms a kind of CO that contains behind carbon dioxide and the amine absorbent generation chemical reaction 2Compound, temperature be 100 ℃～140 ℃ and than the slightly high pressure condition of standard atmospheric pressure under compound decomposition, amine absorber is regenerated, and isolates adsorbent and highly purified CO 2, but this method is owing to carry out needing in the regenerative process to consume a large amount of energy at absorbent, simultaneously because the CO of alcamines material 2Trapping ability is lower, complex process, equipment investment are bigger, so the CO of pure amine absorption process 2The capture cost is higher.
Summary of the invention
In order to reduce CO in the prior art 2Separation with capture cost, simplify technical process, the present invention provides a kind of employing magnesium base absorbant to realize CO in the flue gas 2Capture and the method for separating.
In order to achieve the above object, technical scheme of the present invention is achieved in that a kind of employing magnesium base absorbant realizes CO in the flue gas 2Capture and the method for separating comprise following step:
(1), MgO is mixed with into Mg (OH) with water 2Suspension is as the smoke absorption agent, and the additional proportion of MgO and water makes the mass ratio of solid and liquid in the suspension less than 3.5;
(2), the smoke absorption agent of step (1) preparation and flue gas to be absorbed are passed into the CO that has agitating function respectively 2In the absorber, and control absorbent temperature be 13.5 ℃～50.0 ℃, pH is 8.5～10.2, CO 2The volume ratio of absorber inner absorbent storage and flue gas storage is 1.8～3.5, the CO in the flue gas that feeds in the unit interval 2The smoke absorption agent of amount of substance and feeding in altogether the ratio of amount of substance of magnesium be 0.9～1.0;
(3), post reaction mixture gets into centrifugal separator and carries out Separation of Solid and Liquid, the liquid that obtains is circulated to the preparation section of absorbent as the water circulation use that adds, with the solid MgCO of gained 33H 2The O crystal carries out heat drying to remove physics moisture and chemical moisture wherein under 130 ℃～170 ℃ temperature;
(4), with the solid MgCO that obtains after the drying 3Join and heat in the airtight rotary kiln to realize the regeneration of trapping agent MgO, control rotary kiln temperature obtains MgO solid and CO at 350 ℃～500 ℃ after the heating 2Gas, MgO get into the preparation section of absorbent again, the high-purity CO of gained 2Gas is through after the dust removal process, and the compression of lowering the temperature makes food-class CO 2Product.
The described CO that contains 2The industrial smoke that flue gas is the fire coal that carries out of coal electricity, cement, smelting, chemical industry, fuel oil, combustion gas produced, and other is because the resulting CO that contains of chemical reaction 2Gas.
Described MgO is the magnesia of magnesium-containing mineral calcining gained such as magnesite, dolomite, shepardite or the magnesia that the chemical method preparation gets.
Beneficial effect:
(1), trapping ability is strong.The present invention is with Mg (OH) 2Suspension as absorbent to CO in the flue gas 2Capture, and the mass ratio through solid and liquid in the control suspension, and feed the flue gas of reactor and the conditions such as ratio of absorbent, improved unit mass absorbent absorption CO 2Amount, finally make the present invention to CO 2Trapping ability and existing CO 2Trapping ability is compared and is enhanced.
(2), regeneration cost is low.Only need carry out simple heating to the capture product after dehydrating and decompose the regeneration that can realize trapping agent, reduce the regeneration cost of trapping agent, but also made food-class CO 2Product.
(3), the adaptability of technology is strong.Need not carry out big transformation for industries such as existing coal electricity, cement, smelting, chemical industry and can realize the present invention.
(4), technology is simple, is prone to industrialization.The present invention includes only absorbent preparation, absorbs, and dehydrates, operation such as trapping agent regeneration, and process route is simple, and raw material sources are extensive, and selecting equipment for use all is former on the market, easy realization of industrial production.
Description of drawings
Fig. 1 is the annexation sketch map of device therefor of the present invention.
The specific embodiment
A kind of employing magnesium base absorbant is realized CO in the flue gas 2Capture and the method for separating comprise following step:
(1), MgO is mixed with into Mg (OH) with water 2Suspension is as the smoke absorption agent, and the additional proportion of MgO and water makes the mass ratio of solid and liquid in the suspension less than 3.5;
(2), the smoke absorption agent of step (1) preparation and flue gas to be absorbed are passed into the CO that has agitating function respectively 2In the absorber, and control absorbent temperature be 13.5 ℃～50.0 ℃, pH is 8.5～10.2, CO 2The volume ratio of absorber inner absorbent storage and flue gas storage is 1.8～3.5, the CO in the flue gas that feeds in the unit interval 2The smoke absorption agent of amount of substance and feeding in altogether the ratio of amount of substance of magnesium be 0.9～1.0;
(3), post reaction mixture gets into centrifugal separator and carries out Separation of Solid and Liquid, the liquid that obtains is circulated to the preparation section of absorbent as the water circulation use that adds, with the solid MgCO of gained 33H 2The O crystal carries out heat drying to remove physics moisture and chemical moisture wherein under 130 ℃～170 ℃ temperature;
(4), with the solid MgCO that obtains after the drying 3Join and heat in the airtight rotary kiln to realize the regeneration of trapping agent MgO, control rotary kiln temperature obtains MgO solid and CO at 350 ℃～500 ℃ after the heating 2Gas, MgO get into the preparation section of absorbent again, the high-purity CO of gained 2Gas is through after the dust removal process, and the compression of lowering the temperature makes food-class CO 2Product.
The described CO that contains 2The industrial smoke that flue gas is the fire coal that carries out of coal electricity, cement, smelting, chemical industry, fuel oil, combustion gas produced, and other is because the resulting CO that contains of chemical reaction 2Gas.
Described MgO is the magnesia of magnesium-containing mineral calcining gained such as magnesite, dolomite, shepardite or the magnesia that the chemical method preparation gets.
Embodiment 1
Present embodiment combines 1 pair of technical process further explain of the present invention of accompanying drawing:
MgO is joined in the absorbent preparing device 1, add entry again and prepare Mg (OH) 2Suspension, the solid-to-liquid ratio (mass ratio) of control suspension is 3.5, suspension is delivered to the CO with agitating function by stock pump 2 2In the absorber 3, with the CO the flue gas that feeds from absorber bottom 2Carry out carbonation reaction, the pH value of control absorption system is 10.2, and temperature is 13.5 ℃, CO in the flue gas of feeding absorber 2Amount of substance and absorbent in altogether the ratio of amount of substance of magnesium be 1.0, the absorbent in the absorber and the volume ratio of flue gas are 3.5;
From CO 2The flue gas of the processing that absorber 3 comes out is discharged from the top, and post reaction mixture gets into centrifugal separator 4 and carries out Separation of Solid and Liquid, and the liquid that obtains is circulated to absorbent and prepares the process recycle, the solid MgCO of gained 33H 2The O crystal proceed to drier 5 heat dryings with remove wherein physics moisture and chemical moisture, control temperature be 170 ℃;
Drying removes the MgCO of gained behind the moisture 3Solid gets into heating in the airtight rotary kiln 6, and control rotary kiln temperature is at 500 ℃, and rotating speed is 5r/min; To realize the regeneration of trapping agent MgO; The MgO of regeneration gained gets into absorbent again and prepares workshop section's recycle, improves the utilization rate of trapping agent, the high-purity CO of regeneration gained 2Gas is after deduster 7 dedustings, through CO 2Compressor 8 is delivered to CO after compressing cooling with heat exchanger 9 2High pressure storage tank 10 promptly makes food-class CO 2Product, product purity are 99.98%.
Embodiment 2
MgO is joined in the absorbent preparing device, add entry again and prepare Mg (OH) 2Suspension, the solid-to-liquid ratio (mass ratio) of control suspension is 0, suspension is delivered to the CO with agitating function by stock pump 2In the absorber, with the CO in the flue gas 2Carry out carbonation reaction, the pH value of control absorption system is 8.5, and temperature is 50.0 ℃, CO in the flue gas of feeding absorber 2Amount of substance and absorbent in altogether the ratio of amount of substance of magnesium be 0.9, the absorbent in the absorber and the volume ratio of flue gas are 1.8;
From CO 2The post reaction mixture that absorber comes out gets into centrifugal separator and carries out Separation of Solid and Liquid, and the liquid that obtains is circulated to absorbent and prepares the process recycle, with the solid MgCO of gained 33H 2The O crystal carry out heat drying with remove wherein physics moisture and chemical moisture, control temperature be 130 ℃;
Drying removes the MgCO of gained behind the moisture 3Solid gets in the airtight rotary kiln and heats, and control rotary kiln temperature is at 480 ℃, and rotating speed is 5r/min; To realize the regeneration of trapping agent MgO; The MgO of regeneration gained gets into absorbent again and prepares workshop section's recycle, improves the utilization rate of trapping agent, the high-purity CO of regeneration gained 2Gas is after the deduster dedusting, through CO 2After compressor and the heat exchanger compression cooling, be delivered to CO 2High pressure storage tank promptly makes food-class CO 2Product, product purity are 99.92%.
Embodiment 3
MgO is joined in the absorbent preparing device, add entry again and prepare Mg (OH) 2Suspension, the solid-to-liquid ratio (mass ratio) of control suspension is 2.0, suspension is delivered to the CO with agitating function by stock pump 2In the absorber, with the CO in the flue gas 2Carry out carbonation reaction, the pH value of control absorption system is 9.0, and temperature is 30 ℃, CO in the flue gas of feeding absorber 2Amount of substance and absorbent in altogether the ratio of amount of substance of magnesium be 0.95, the absorbent in the absorber and the volume ratio of flue gas are 3.0 times;
From CO 2The post reaction mixture that absorber comes out gets into centrifugal separator and carries out Separation of Solid and Liquid, and the liquid that obtains is circulated to absorbent and prepares the process recycle, with the solid MgCO of gained 33H 2The O crystal carry out heat drying with remove wherein physics moisture and chemical moisture, control temperature be 150 ℃;
Drying removes the MgCO of gained behind the moisture 3Solid gets in the airtight rotary kiln and heats, and control rotary kiln temperature is at 350 ℃, and rotating speed is 2r/min; To realize the regeneration of trapping agent MgO; The MgO of regeneration gained gets into absorbent again and prepares workshop section's recycle, improves the utilization rate of trapping agent, the high-purity CO of regeneration gained 2Gas is after the deduster dedusting, through CO 2After compressor and the heat exchanger compression cooling, be delivered to CO 2High pressure storage tank promptly makes food-class CO 2Product, product purity are 99.95%.

Claims (2)

1. one kind is adopted the magnesium base absorbant to realize CO in the flue gas 2Capture and the method for separating is characterized in that: comprise following step:
(1), MgO is mixed with into Mg (OH) with water 2Suspension is as the smoke absorption agent, and the additional proportion of MgO and water makes the mass ratio of solid and liquid in the suspension less than 3.5;
(2), the smoke absorption agent of step (1) preparation and flue gas to be absorbed are passed into the CO that has agitating function respectively 2In the absorber, and control absorbent temperature be 13.5 ℃～50.0 ℃, pH is 8.5～10.2, CO 2The volume ratio of absorber inner absorbent storage and flue gas storage is 1.8～3.5, the CO in the flue gas that feeds in the unit interval 2The smoke absorption agent of amount of substance and feeding in altogether the ratio of amount of substance of magnesium be 0.9～1.0;
(3), post reaction mixture gets into centrifugal separator and carries out Separation of Solid and Liquid, the liquid that obtains is circulated to the preparation section of absorbent as the water circulation use that adds, with the solid MgCO of gained 33H 2The O crystal carries out heat drying to remove physics moisture and chemical moisture wherein under 130 ℃～170 ℃ temperature;
(4), with the solid MgCO that obtains after the drying 3Join and heat in the airtight rotary kiln to realize the regeneration of trapping agent MgO, control rotary kiln temperature obtains MgO solid and CO at 350 ℃～500 ℃ after the heating 2Gas, MgO get into the preparation section of absorbent again, the high-purity CO of gained 2Gas is through after the dust removal process, and the compression of lowering the temperature makes food-class CO 2Product.
2. a kind of employing magnesium base absorbant as claimed in claim 1 is realized CO in the flue gas 2Capture and the method for separating is characterized in that: the described CO of containing 2The industrial smoke that flue gas is the fire coal that carries out of coal electricity, cement, smelting, chemical industry, fuel oil, combustion gas produced, and other is because the resulting CO that contains of chemical reaction 2Gas.
CN201210018610.5A 2012-01-20 2012-01-20 Method for implementing trapping and separation of CO2 in flue gas by adopting magnesium-based absorbent Expired - Fee Related CN102580468B (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103212262A (en) * 2013-04-26 2013-07-24 陈坚 Smog gas treatment system and smog gas treatment method
CN105032164A (en) * 2015-07-10 2015-11-11 中国船舶重工集团公司第七一八研究所 Carbon dioxide absorbent taking magnesium oxide as main material and preparation method for carbon dioxide absorbent
CN109790044A (en) * 2016-07-27 2019-05-21 国家科学研究学院 The magnesia of low-carbon emission produces
CN112007946A (en) * 2020-07-28 2020-12-01 南京大学环境规划设计研究院股份公司 Ectopic bioremediation device for pollutants
CN113731155A (en) * 2021-09-29 2021-12-03 大连海事大学 Carbon dioxide emission reduction and utilization device and method for dredging ship

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6046921A (en) * 1983-08-25 1985-03-14 Tokuyama Soda Co Ltd Production of magnesium orthocarbonate
JPH04171042A (en) * 1990-11-05 1992-06-18 Youyuu Tansanengata Nenryo Denchi Hatsuden Syst Gijutsu Kenkyu Kumiai Carbon dioxide absorbent
CN102188893A (en) * 2010-03-09 2011-09-21 北京化工大学 Method for absorbing carbon dioxide in combustion product gases by using magnesium oxide

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6046921A (en) * 1983-08-25 1985-03-14 Tokuyama Soda Co Ltd Production of magnesium orthocarbonate
JPH04171042A (en) * 1990-11-05 1992-06-18 Youyuu Tansanengata Nenryo Denchi Hatsuden Syst Gijutsu Kenkyu Kumiai Carbon dioxide absorbent
CN102188893A (en) * 2010-03-09 2011-09-21 北京化工大学 Method for absorbing carbon dioxide in combustion product gases by using magnesium oxide

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
RANJANI V.SIRIWARDANE ET AL.: "Novel Regenerable Magnesium Hydroxide Sorbents for CO2 Capture at Warm Gas Temperatures", 《INDUSTRIAL & ENGINEERING CHEMISTRY》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103212262A (en) * 2013-04-26 2013-07-24 陈坚 Smog gas treatment system and smog gas treatment method
CN105032164A (en) * 2015-07-10 2015-11-11 中国船舶重工集团公司第七一八研究所 Carbon dioxide absorbent taking magnesium oxide as main material and preparation method for carbon dioxide absorbent
CN109790044A (en) * 2016-07-27 2019-05-21 国家科学研究学院 The magnesia of low-carbon emission produces
CN112007946A (en) * 2020-07-28 2020-12-01 南京大学环境规划设计研究院股份公司 Ectopic bioremediation device for pollutants
CN113731155A (en) * 2021-09-29 2021-12-03 大连海事大学 Carbon dioxide emission reduction and utilization device and method for dredging ship

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