CN101362048B - Method for absorbing carbon dioxide using carbide mud residue and special carbon dioxide absorber - Google Patents

Method for absorbing carbon dioxide using carbide mud residue and special carbon dioxide absorber Download PDF

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CN101362048B
CN101362048B CN2008101464953A CN200810146495A CN101362048B CN 101362048 B CN101362048 B CN 101362048B CN 2008101464953 A CN2008101464953 A CN 2008101464953A CN 200810146495 A CN200810146495 A CN 200810146495A CN 101362048 B CN101362048 B CN 101362048B
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carbon dioxide
absorption
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calcium carbonate
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CN101362048A (en
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李发修
李发升
李翠萍
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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
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Abstract

The invention discloses a method for making use of carbide slag to absorb and utilize carbon dioxide, and a special carbon dioxide absorber. The method takes the carbide slag as raw material and ammonium formate as a solvent to dissolve calcium hydroxide in the carbide slag to generate calcium formate and ammonia water; after being filtered to remove impurities, the calcium formate and the ammonia water are taken as absorbents to absorb the carbon dioxide in the special carbon dioxide absorber to generate calcium carbonate and ammonium formate; after being cleaned, filtered, dried, cooled and crushed, the calcium carbonate turns into the high-purity calcium carbonate, therefore, the recycling emission reduction of the carbon dioxide is realized.

Description

Absorb the method and the special carbon dioxide absorber of carbon dioxide with carbide slag
Technical field
The present invention relates to a kind ofly absorb the method and the special carbon dioxide absorber of carbon dioxide, directly apply to carbon dioxide renewable resources formula and reduce discharging with carbide slag.
Background technology
Along with industrialized development, the CO2 emissions in the whole world increase year by year, and EI Nino phenomenon frequently takes place, and global temperatures constantly raises, and natural calamity is situation occurred frequently.For tackling this global challenge, scientific and technical personnel invent multiple carbon dioxide discharge-reduction technology, such as, the buried technology of carbon dioxide, the power-saving technology of industrial furnace, new energy technology etc.
But,, still need new approaches, new method in the face of industrial activity huge CO2 emissions like this.
Carbide slag is the industrial solid waste of calcium carbide system acetylene, is strong basicity, relative content 1.83 gram/cubic centimetres, dry density 0.63 gram/cubic centimetre, wet density 1.364 gram/cubic centimetres.One-tenth is grouped into: CaO 63.93%, MgO1.27%, Al 2O 30.5%, Fe 2O 30.95%SiO 27.9%, calcination loss 24.3%.Hence one can see that, and calcium hydroxide is the main component of carbide slag, by Ca (OH) 2+ CO 2→ CaCO 3+ H 2O as can be known, carbide slag can be used as the raw material of absorbing carbon dioxide, renewable resources calcium carbonate, thereby realize the reduction of discharging of carbon dioxide.
Summary of the invention
Technical problem to be solved by this invention provides a kind of method and special carbon dioxide absorber that absorbs carbon dioxide with carbide slag, the carbon dioxide renewable resources is become high-purity calcium carbonate, omit the consumption of lime stone, coke in the calcium carbonate production, and then realize that the renewable resources formula of carbon dioxide reduces discharging.
For addressing the above problem, the present invention is raw material with the carbide slag, with the ammonium formate solution is solvent, calcium hydroxide in the dissolving carbide slag, generate calcium formate and ammoniacal liquor, filter then and dispel silica, di-iron trioxide, alundum (Al, ash impurities, obtain the pure calcium formate and the mixed liquor of ammoniacal liquor.In the absorption unit of dioxide carbon of special use, with calcium formate and ammoniacal liquor is absorbent, the high-pureness carbon dioxide that absorption is collected from industry cellar for storing things stove through purifying, generate calcium carbonate and ammonium formate, terminal point control pH=6.5-7.0, isolated by filtration calcium carbonate and ammonium formate, ammonium formate recycles, calcium carbonate through washing, dehydration, dry, cooling, pulverize and promptly make the purity calcium carbonate that granularity, whiteness, purity meet the GB/T2226-2000 standard.
Special carbon dioxide absorber is a batch reactor, by container part, running part, agitator, carbon dioxide pipe, absorbent liquid feed pipe, product discharge nozzle, and the pH instrument, thermometric instrument is formed.
Container is " tubular ", the bottom is a circular flat bottom, arrange a discharge nozzle on the bottom surface, it between the inwall of container, the outer wall cavity, cavity is used to store heat exchange water, and the water inlet pipe of heat exchange water, outlet pipe are arranged on the outer wall of container, axially arranges 6 baffle plates on the container inner wall symmetrically and evenly, baffle plate is narrow long shaped plate, and adjacent two baffle-panels angles of cut are 60 °.
Running part is made up of decelerator, bearing block, shaft.Bearing block is fixed on container cover central authorities, goes up to be connected with decelerator, links to each other with shaft down.Under motor drives, the rotation of decelerator twisting shaft.
Agitator is the disc turbine agitator, is made up of paddle, disk, axle sleeve.Paddle is connected on the disk, and disk is connected on the axle sleeve, and axle sleeve is fixed on the shaft lower end.
The carbon dioxide pipe, L-shaped, be arranged in the container.Its air inlet is covering, and its vertical component is close to the intersection between baffle plate and the container inner wall, and its horizontal component is on rounded bottom surface, and its gas outlet is below agitator.
Absorbent feed pipe, pH instrument, thermometric instrument are arranged on the spherical cap of container.
Adopt said method and special carbon dioxide absorber, by Ca (OH) 2+ CO 2→ CaCO 3As can be known, but produce 0.44 ton of one ton of purity calcium carbonate absorbing carbon dioxide.Because calcium hydroxide is directed to carbide slag, has omitted CaCO 3→ CO 2+ CaO CaO+H 2O → Ca (OH) 2Process.Therefore omitted the consumption of lime stone, coke.According to the calcium hydroxide raw materials for production norm quota of consumption in conjunction with Ca (OH) 2+ CO 2→ CaCO 3Reaction is calculated as can be known, and one ton of purity calcium carbonate can be saved 0.196 ton in coke (C 〉=80%).By C+O 2→ CO 2As can be known, save 0.196 ton of coke and can reduce 0.77 ton of CO2 emission, absorption and minimizing discharging carbon dioxide add up to 1.21 tons, can save 1.21 tons in lime stone simultaneously.
Record through experiment, make purity calcium carbonate whiteness 94, granularity 125 μ m, testing sieve residue on sieve 0.015%, 45 μ m testing sieve residue on sieve 0.5%, purity 98%, minimum packing density 0.3 gram/cubic centimetre, 10% pH of suspension=6.5～7.0.Observe under 600 times of mineralogical microscopes, calcium carbonate granule is divided into spherical and fibrous.
According to market survey, this purity calcium carbonate can be used as the filler of plastics, rubber, papermaking, can be used for productions such as organic synthesis, metallurgy, glass, coating, can make the remover of sulfur dioxide etc.
At present, spherical calcium carbonate powder market price 300-400 unit/ton, fibrous carbonic acid calcium market price 2000-3000 unit/ton, and the expense of purity calcium carbonate is mainly man-hour, depreciation, maintenance, administration fee etc.
Description of drawings
Fig. 1 is the method flow block diagram that absorbs carbon dioxide with carbide slag.
Fig. 2 is special-purpose absorption unit of dioxide carbon cutaway view.
The specific embodiment
Method with the carbide slag absorbing carbon dioxide shown in Figure 1 comprises the raw material calcium carbide slag, solvent ammonium formate solution and 9 chemical process sections.Dissolution process section 1 is pressed 8: 2 proportion ingredients to the ammonium formate solution of 25% concentration and carbide slag, add from the dissolving tank charging aperture, 25 ℃ of stirring and dissolving temperature, rotating speed 100r/min, 40 minutes time, then the calcium hydroxide in the ammonium formate dissolving carbide slag generates calcium formate and ammoniacal liquor, open the discharging opening valve, compound is entered filter enter the first filtering technique section 2, silica in the carbide slag after filtration, di-iron trioxide, alundum (Al, ash impurities by the filter membrane detention in filter, calcium formate solution and ammoniacal liquor see through filter membrane and are pressed in the special carbon dioxide absorber by compression pump, industry is stored carbon dioxide that fire grate puts through collecting, purification is condensed into 80% high-pureness carbon dioxide gas, carbon dioxide pipe by absorption unit of dioxide carbon is pressed into absorber and enters carbon dioxide absorption process section 3,25-35 ℃ of absorption reaction temperature, partial pressure of carbon dioxide 0.01-0.05MPa, calcium formate absorbing carbon dioxide under the ammoniacal liquor effect then, generate calcium carbonate and ammonium formate, absorption reaction terminal point control pH=6.5-7.0, open discharge nozzle, compound is entered filter enter the second filtering technique section 4, separate calcium carbonate and ammonium formate solution, ammonium formate solution recycles, calcium carbonate enters washing process section 5, enter the 3rd filtering technique section 6 after washing with water, calcium carbonate is with after washings separate, enter drying process section 7,105 ℃ of baking temperatures, enter process for cooling section 8 afterwards and be cooled to room temperature, enter disintegrating process section 9 afterwards, pulverize with pulverizer, calcium carbonate granule 125 μ m testing sieve residue on sieves≤0.015%, 45 μ m testing sieve residue on sieve≤0.50% through pulverizing.
Shown in Figure 2: special-purpose absorption unit of dioxide carbon is by running part (11,12,13) agitator 14, container part (1,3,4,5,6,15,16,17), carbon dioxide pipe 7, absorbent feed pipe 8, product discharge nozzle 2, pH instrument 9, thermometric instrument 10 is formed.
During use, adjust the diameter of belt pulley 12, speed of agitator is adjusted at 300-1000r/min, open heat exchange water water inlet pipe 6, water is filled with cavity 5, from absorbent feed pipe 8, put into absorbent liquid, liquid level and container diameter are suitable, open carbon dioxide pipe 7, send into carbon dioxide, partial pressure of carbon dioxide 0.01-0.05MPa, about purity 80%, then carbon dioxide sprays to the agitator 14 of rotation from the nozzle of air inlet pipe end, the agitator 14 of rotation is directly smashed the carbon dioxide air pocket, simultaneously, owing to existing negative pressure to form air pocket, air pocket is with agitator 14 rotations the time, at gas dorsad for the mixing arm of rotation, liquid, Gu three-phase is used to be fractured into tiny bubble under the mental power function, after these carbon dioxide tiny bubbles are got rid of by impeller, flow to gas zones with absorption liquid, enlarge carbon dioxide and the contact area that absorbs liquid by this, thereby guaranteed the abundant absorption of absorption liquid carbon dioxide, and under the effect of baffle plate 17, the carbon dioxide minute bubbles seethe up and down with liquid, prolong the time of contact of carbon dioxide and absorption liquid, thereby strengthen absorption process.Reaction temperature 25-35 ℃, when thermometric instrument 10 temperature indicative exceed this number range, open heat exchange water outlet pipe 16, adjust the pressure and the water temperature of heat exchange water, thus the control reaction temperature.When pH instrument 9 showed pH=6.5-7.0, absorption process finished, and the closing carbon dioxide absorber is opened discharge nozzle 2 blowings.

Claims (1)

1. one kind absorbs the method for carbon dioxide with carbide slag, by dissolution process section, the first filtering technique section, absorption technique section, the second filtering technique section, washing process section, the 3rd filtering technique section, drying process section, the process for cooling section, the disintegrating process section is formed, and it is characterized in that: described dissolution process section is a solvent with the ammonium formate solution, with the carbide slag is raw material, calcium hydroxide in the dissolving carbide slag generates calcium formate and ammoniacal liquor, reaction equation: Ca (OH) 2+ 2HCOONH 4→ (HCOO) 2Ca+2NH 3H 2O; The described first filtering technique section has been dispeled and has been mixed in calcium formate and middle silica, di-iron trioxide, alundum (Al, the soot impurity of ammoniacal liquor; Described absorption technique section is an absorbent with calcium formate and ammoniacal liquor, and absorbing carbon dioxide generates calcium carbonate and ammonium formate, absorption technique is finished in the absorption unit of dioxide carbon of special use, reaction temperature t=25-35 ℃, absorption reaction terminal point control pH=6.5-7.0, reaction equation: (HCOO) 2Ca+2NH 3H 2O+CO 2→ CaCO 3+ 2HCOONH 4+ H 2O; The described second filtering technique section is separated calcium carbonate and ammonium formate solution; Described washing process section washes calcium carbonate with water; Described the 3rd filtering technique section is separated calcium carbonate and water; The drying process section is at 105 ℃ of dry calcium carbonate; The process for cooling section is cooled to room temperature; Described disintegrating process section, calcium carbonate granule 125 μ m testing sieve residue on sieves≤0.015%, 45 μ m testing sieve residue on sieve≤0.50% through pulverizing; Special-purpose absorption unit of dioxide carbon comprises by belt pulley (12), bearing block (11), shaft (13) is formed running part, by circular flat bottom (1), outer wall (3), inwall (4), cavity (5), container cover (15), heat exchange water water inlet pipe (6), heat exchange water outlet pipe (16), the container part that baffle plate (17) is formed, agitator (14), carbon dioxide pipe (7), absorbent liquid feed pipe (8), product discharge nozzle (2), pH instrument (9), thermometric instrument (10), bearing block (11) is fixed on gross weight belt wheel (12) in the container cover central authorities, connects shaft (13) down; Described container bottom is circular flat bottom (1), container cover (15) is spherical, be cavity (5) between outer wall (3) and the inwall (4), store heat exchange water in the cavity (5), circular flat bottom (1), outer wall (3), inwall (4) is formed three-dimensional cylindrical container, outer wall (3) is gone up and is arranged a heat exchange water water inlet pipe (6), a heat exchange water outlet pipe (16), be used for regulating the pressure and temperature of the water that enters cavity (5), the required temperature of control absorption reaction, axially arrange 6 long narrow shape baffle plates (17) on the inwall (4) symmetrically and evenly, the angle of cut of adjacent screen is 60 °, baffle plate (17) can make the carbon dioxide and the absorption liquid that are subjected to turning effort do flowing of seething up and down like this, prolong the time of contact of carbon dioxide and absorption liquid, described carbon dioxide pipe (7), L-shaped being arranged in the container, its inlet end is in the top of container cover (15), its vertical component is close to the intersection between baffle plate (17) and the inwall (4), its horizontal component is on circular flat bottom (1), and its air nozzle is in agitator (14) below; Absorbent liquid feed pipe (8) is positioned on the container cover (15), product discharge nozzle (2) is positioned at below the circular flat bottom (1), pH instrument (9) is positioned on the container cover (15), be used for absorption process is carried out master control, thermometric instrument (10) is positioned on the container cover (15), is used to indicate the absorption reaction temperature; Agitator (14) is the disc turbine agitator, be fixed on shaft (13) lower end, by the carbon dioxide of rotation dispersion, increase the contact area of carbon dioxide and absorption liquid with shaft (13) rotation, promote abundant absorption carbon dioxide by its below ejection.
CN2008101464953A 2008-09-02 2008-09-02 Method for absorbing carbon dioxide using carbide mud residue and special carbon dioxide absorber Expired - Fee Related CN101362048B (en)

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Cited By (1)

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US9902652B2 (en) 2014-04-23 2018-02-27 Calera Corporation Methods and systems for utilizing carbide lime or slag

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CN103446867B (en) * 2013-08-28 2015-02-25 东北大学 Method for preparing calcium carbonate and recycling CO by collecting and mineralizing CO2 in aluminum electrolysis flue gas
CN103446868B (en) * 2013-08-28 2015-02-25 东北大学 Device for preparing calcium carbonate and recycling CO by collecting and mineralizing CO2 in aluminum electrolysis flue gas
CN103691283A (en) * 2013-12-24 2014-04-02 中南大学 Method for fixing carbon dioxide in industrial smoke
CN104387255B (en) * 2014-11-11 2017-01-25 湖北瑞富阳化工科技有限公司 Preparation method of calcium formate
CN106219586A (en) * 2016-08-02 2016-12-14 王延军 A kind of be raw material production nanometer grade calcium carbonate with carbide slag device and method
CN107744716B (en) * 2017-11-15 2019-09-06 山东大学 The hollow compound CO of shell-type carbide slag2Absorbent and its synthetic method and application
CN115443252A (en) 2020-02-25 2022-12-06 艾瑞莱克公司 Method and system for treating lime to form vaterite
GB2613474A (en) 2020-06-30 2023-06-07 Arelac Inc Methods and systems for forming vaterite from calcined limestone using electric kiln
CN115228278B (en) * 2022-07-19 2024-04-30 天津中材工程研究中心有限公司 PH value regulated calcium carbonate for accelerating mineralization and absorption of CO in flue gas2Systems and methods of (1)

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