CN103801253A - Method for preparing calcium oxide based CO2 cyclic adsorbing material from steel slag - Google Patents

Method for preparing calcium oxide based CO2 cyclic adsorbing material from steel slag Download PDF

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CN103801253A
CN103801253A CN201410065745.6A CN201410065745A CN103801253A CN 103801253 A CN103801253 A CN 103801253A CN 201410065745 A CN201410065745 A CN 201410065745A CN 103801253 A CN103801253 A CN 103801253A
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calcium oxide
slag
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solution
calcium
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CN103801253B (en
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蒋建国
田思聪
颜枫
李凯敏
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Tsinghua University
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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

Abstract

The invention relates to a method for preparing a calcium oxide based CO2 cyclic adsorbing material from steel slag. The method comprises the steps of mixing the steel slag with an acetic acid solution, stirring at normal temperature and under normal pressure, centrifugally separating a mixed solution obtained by stirring, taking supernate, adding a phosphoric acid solution into the supernate according to the measured concentration of calcium, magnesium, aluminum and iron so as to remove an iron ion precipitate in the supernate, centrifugally separating again, then adding proper amount of aluminum oxide or calcium oxide to regulate the ratio of calcium ions to magnesium ions to aluminum ions in the solution, performing evaporative crystallization on the obtained solution, stoving the obtained crystal substance at 105 DEG C, uniformly grinding a dried sample, then heating up and calcining at constant temperature so as to obtain the adsorbing material. The method can prepare the high performance compound calcium based CO2 cyclic adsorbing material from the cheap, green and sustainable raw material, and effectively solves the problem that natural limestone material has poor capacity in adsorbing CO2 circularly, and the prepared adsorbing material can efficiently gather CO2 in smoke discharged by large-scale industries of steel production, coal-fired power generation and the like in site and at low cost.

Description

One is prepared calcium oxide-based CO take slag as raw material 2the method of circulation absorption material
Technical field
The invention belongs to greenhouse gases collecting carbonic anhydride, utilization and Plugging Technology Applied field, be specifically related to a kind of calcium oxide-based CO for preparing take slag as raw material 2the method of circulation absorption material.
Background technology
Large quantity research shows, the CO being discharged by mankind's activities such as combustion of fossil fuel 2be the primary greenhouse gases that cause Global climate change, it has reached more than 60% to the contribution of Global Greenhouse Effect.At present, the CO in earth atmosphere 2concentration rises to rapidly 380ppm by the 280ppm before the industrial revolution, if CO 2concentration in atmosphere continues to rise to and exceedes 550ppm, just may cause irreversible extensive damage to the mankind's living environment.The energy resource structure of taking as the leading factor with fossil fuel in the world, will continue within the following many decades time.Therefore, CO can be effectively cut down in research and development 2the technology of discharge just seems particularly important.
At present, one is called as the up-to-date CO of the trapping of the carbon ", utilize and seal up for safekeeping " (Carbon Capture, Utilization and Storage, CCUS) 2emission control technique theory has been subject to paying close attention to widely and studying.It refers to by certain technological means CO 2from the higher combustion product gases of its content, trap the high-purity CO obtaining 2gas is preferentially for food processing, chemical fertilizer production, fire-fighting fire extinguishing, and the industry such as plant production, and that redundance is considered is again compressed, transportation and be finally transferred to the technology path that long term storage is carried out in the geological structures such as abandoned well, gas field, colliery layer or ocean.Wherein, CO 2the cost of trapping link is the highest, can reach the 60%-70% of CCUS totle drilling cost.Therefore, efficiently and cheaply CO of exploitation 2trapping technique becomes the focus of CCUS area research.
Lime stone (calcium oxide) Cyclic Calcination method has cheapness, environmental friendliness, CO 2the advantages such as adsorption capacity is large, reaction rate is fast and easy and simple to handle, with other emerging CO such as Activated Zeolite Adsorption, alkali carbonate absorption method and ionic liquid absorption processes 2trapping technique is compared, and is considered to CO after the burning of the tool application prospect that can substitute traditional liquid amine absorption process 2trapping technique.But, natural limestone in Cyclic Calcination process due to high temperature sintering and hole the caused CO that subsides 2the problem that circulation absorption ability declines rapidly, becomes and limits its application and the most important factor developing.Research shows, to doped with Mg O or Al in CaO 2o 3etc. safe graceful temperature (T tammann) higher metal oxide can reach the effect of improving its anti-sintering property, but these modifications CaO adsorbent is conventionally synthetic as raw material take the pure material of calcic, aluminium, magnesium, the cost of precursor material is higher and material synthesis method is complicated.For this reason, find alternative materials more cheap and that have a large capacity and a wide range, and develop easy and simple to handle and be easy to the material preparation method that scale is applied, be applied to CO for modification CaO adsorbent 2trapping has great importance.
Using large Industrial Solid Waste-slag as cheap and green raw material, adopt simple and easy to do synthetic method to prepare efficient oxidation calcium base CO 2circulation absorption material, does not also have related application and research report both at home and abroad.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art, the object of the present invention is to provide a kind of calcium oxide-based CO for preparing take slag as raw material 2the method of circulation absorption material, can be to large-scale CO such as iron and steel production and coal fired power generations 2industrial emission source is realized efficiently and cheaply carbon trapping.
To achieve these goals, the technical solution used in the present invention is:
One is prepared calcium oxide-based CO take slag as raw material 2the method of circulation absorption material, comprises the following steps:
The first step, by slag with 1g:(15～25) solid-to-liquid ratio of mL mixes with acetum, continuous stirring 4～6 hours under normal temperature and pressure conditions,
Second step, carries out centrifugation to the mixed liquor after stirring, and gets supernatant and measures the wherein concentration of calcium, magnesium, aluminium and four kinds of ions of iron, according to measured iron concentration, with Fe:H 3pO 4=1:(1.2～1.6) mol ratio in supernatant, add phosphoric acid solution, mixed liquor was at room temperature stirred after 15～20 minutes, mixed liquor is carried out to centrifugation, get supernatant,
The 3rd step, according to measured calcium, magnesium and aluminium ion concentration, to adding aluminium oxide in supernatant or calcium oxide is adjusted the ratio between calcium in solution, magnesium, aluminium ion, makes Ca 2+with Al 3+mol ratio be (5～9): 1, Ca 2+with Mg 2+mol ratio be greater than 1.5; Gained solution is carried out to rotary evaporation in vacuo crystallization, until solution is by evaporate to dryness,
The 4th step, takes out gained crystal being placed at 105 ℃ and dries 6～8 hours, then by the sample of oven dry after grinding evenly from room temperature homogeneous heating to 800 ℃, calcining at constant temperature 2～4 hours, thus obtain sorbing material.
Preferably, described slag is first crushed to particle diameter and is no more than 1mm before mixing.
Preferably, the mass concentration of described acetum is 20%～30%.
Preferably, the mass concentration of described phosphoric acid solution is 85%.
Preferably, when described rotary evaporation in vacuo crystallization, bath temperature is 70～90 ℃, and rotary speed is 120～150rpm,
Preferably, the described intensification frequency from room temperature homogeneous heating to 800 ℃ is 5 ℃/min.
Compared with prior art, the invention has the beneficial effects as follows:
(1) the simple and easy to do efficient oxidation calcium base CO for preparing is proposed first take large Industrial Solid Waste-slag as cheap green raw material 2the method of circulation absorption material.(2) this material is to CO 2saturated extent of adsorption can reach
Figure BDA0000469894640000031
above, circulation absorption CO 2reach after 30 times its CO 2adsorption capacity decay is no more than 30%, and cyclical stability is the more than 2 times of natural limestone, and its preparation cost is compared existing synthetic calcium oxide-based CO 2circulation absorption material can significantly reduce.
The specific embodiment
Describe embodiments of the present invention in detail below in conjunction with embodiment.
Embodiment 1
One is prepared calcium oxide-based CO take slag as raw material 2the method of circulation absorption material, comprises the following steps:
The first step, is no more than 1mm by slag crushing to particle diameter, get 4g slag and mix with the acetum of mass concentration 30% with the solid-to-liquid ratio of 1g:15mL, under normal temperature and pressure conditions to mixed liquor continuous stirring 6 hours,
Second step, mixed liquor after stirring is carried out to centrifugation, get supernatant and record the wherein concentration of calcium, magnesium, aluminium and four kinds of ions of iron and be respectively 12.8g/L, 5.1g/L, 0.9g/L, 1.9g/L, according to measured iron concentration, with 1mol Fe:1.6mol H 3pO 4mol ratio be 85% phosphoric acid solution 0.38g to adding mass concentration in supernatant, mixed liquor was at room temperature stirred after 15 minutes, mixed liquor is carried out to centrifugation, get supernatant,
The 3rd step according to measured calcium, magnesium and aluminium ion concentration, is added 0.1g aluminium oxide in supernatant, makes Ca in solution 2+with Al 3+mol ratio be 5, gained solution is carried out to rotary evaporation in vacuo crystallization, bath temperature is 80 ℃, rotary speed is 120rpm, until solution is by evaporate to dryness,
The 4th step, takes out gained crystal being placed at 105 ℃ and dries 6 hours, then by the sample of oven dry after grinding evenly from room temperature homogeneous heating (5 ℃/min) to 800 ℃, calcining at constant temperature 2 hours, thus obtain sorbing material.
This material is carried out to carbonating-calcination cycle trapping CO 2performance test, its saturated CO 2adsorbance is 0.46g cO2/ g adsorbent, circulation absorption CO 2reach after 30 times its CO 2adsorption capacity still can reach 0.25g cO2/ g adsorbent, than the CO circulating first 2adsorption capacity only decays 16%, and its cyclical stability is 2.8 times of natural limestone.
Embodiment 2
One is prepared calcium oxide-based CO take slag as raw material 2the method of circulation absorption material, comprises the following steps:
The first step, is no more than 1mm by slag crushing to particle diameter, get 5g slag and mix with the acetum of mass concentration 24% with the solid-to-liquid ratio of 1g:20mL, under normal temperature and pressure conditions to mixed liquor continuous stirring 5 hours,
Second step, mixed liquor after stirring is carried out to centrifugation, get supernatant and record the wherein concentration of calcium, magnesium, aluminium and four kinds of ions of iron and be respectively 12.6g/L, 3.3g/L, 0.3g/L, 6.1g/L, according to measured iron concentration, with 1mol Fe:1.2mol H 3pO 4mol ratio be 85% phosphoric acid solution 1.5g to adding mass concentration in supernatant, mixed liquor was at room temperature stirred after 20 minutes, mixed liquor is carried out to centrifugation, get supernatant,
The 3rd step according to measured calcium, magnesium and aluminium ion concentration, is added 0.12g aluminium oxide in supernatant, makes Ca in solution 2+with Al 3+mol ratio be 9, gained solution is carried out to rotary evaporation in vacuo crystallization, bath temperature is 90 ℃, rotary speed is 150 rpm, until solution is by evaporate to dryness,
The 4th step, takes out gained crystal being placed at 105 ℃ and dries 8 hours, then by the sample of oven dry after grinding evenly from room temperature homogeneous heating (5 ℃/min) to 800 ℃, calcining at constant temperature 3 hours, thus obtain sorbing material.
This material is carried out to carbonating-calcination cycle trapping CO 2performance test, its saturated CO 2adsorbance is 0.53g cO2/ g adsorbent, circulation absorption CO 2reach after 30 times its CO 2adsorption capacity still can reach 0.30g cO2/ g adsorbent, than the CO circulating first 2adsorption capacity only decays 21%, and its cyclical stability is 2.6 times of natural limestone.
Embodiment 3
One is prepared calcium oxide-based CO take slag as raw material 2the method of circulation absorption material, comprises the following steps:
The first step, is no more than 1mm by slag crushing to particle diameter, get 6g slag and mix with the acetum of mass concentration 20% with the solid-to-liquid ratio of 1g:25mL, under normal temperature and pressure conditions to mixed liquor continuous stirring 4 hours,
Second step, mixed liquor after stirring is carried out to centrifugation, get supernatant and record the wherein concentration of calcium, magnesium, aluminium and four kinds of ions of iron and be respectively 11.2g/L, 3.5g/L, 1.4g/L, 4.1g/L, according to measured iron concentration, with 1mol Fe:1.5mol H 3pO 4mol ratio be 85% phosphoric acid solution 1.9g to adding mass concentration in supernatant, mixed liquor was at room temperature stirred after 15 minutes, mixed liquor is carried out to centrifugation, get supernatant,
The 3rd step, carries out rotary evaporation in vacuo crystallization to gained solution, and bath temperature is 70 ℃, and rotary speed is 125rpm, until solution is by evaporate to dryness,
The 4th step, takes out gained crystal being placed at 105 ℃ and dries 7 hours, then by the sample of oven dry after grinding evenly from room temperature homogeneous heating (5 ℃/min) to 800 ℃, calcining at constant temperature 4 hours, thus obtain sorbing material.
This material is carried out to carbonating-calcination cycle trapping CO 2performance test, its saturated CO 2adsorbance is 0.48g cO2/ g adsorbent, circulation absorption CO 2reach after 30 times its CO 2adsorption capacity still can reach 0.27g cO2/ g adsorbent, than the CO circulating first 2adsorption capacity only decays 18%, and its cyclical stability is 2.7 times of natural limestone.

Claims (6)

1. prepare calcium oxide-based CO take slag as raw material for one kind 2the method of circulation absorption material, is characterized in that, comprises the following steps:
The first step, by slag with 1g:(15～25) solid-to-liquid ratio of mL mixes with acetum, continuous stirring 4～6 hours under normal temperature and pressure conditions,
Second step, carries out centrifugation to the mixed liquor after stirring, and gets supernatant and measures the wherein concentration of calcium, magnesium, aluminium and four kinds of ions of iron, according to measured iron concentration, with Fe:H 3pO 4=1:(1.2～1.6) mol ratio in supernatant, add phosphoric acid solution, mixed liquor was at room temperature stirred after 15～20 minutes, mixed liquor is carried out to centrifugation, get supernatant,
The 3rd step, according to measured calcium, magnesium and aluminium ion concentration, to adding aluminium oxide in supernatant or calcium oxide is adjusted the ratio between calcium in solution, magnesium, aluminium ion, makes Ca 2+with Al 3+mol ratio be (5～9): 1, Ca 2+with Mg 2+mol ratio be greater than 1.5; Gained solution is carried out to rotary evaporation in vacuo crystallization, until solution is by evaporate to dryness,
The 4th step, takes out gained crystal being placed at 105 ℃ and dries 6～8 hours, then by the sample of oven dry after grinding evenly from room temperature homogeneous heating to 800 ℃, calcining at constant temperature 2～4 hours, thus obtain sorbing material.
2. according to claim 1ly prepare calcium oxide-based CO take slag as raw material 2the method of circulation absorption material, is characterized in that, described slag is first crushed to particle diameter and is no more than 1mm before mixing.
3. according to claim 1ly prepare calcium oxide-based CO take slag as raw material 2the method of circulation absorption material, is characterized in that, the mass concentration of described acetum is 20%～30%.
4. according to claim 1ly prepare calcium oxide-based CO take slag as raw material 2the method of circulation absorption material, is characterized in that, the mass concentration of described phosphoric acid solution is 85%.
5. according to claim 1ly prepare calcium oxide-based CO take slag as raw material 2the method of circulation absorption material, is characterized in that, when described rotary evaporation in vacuo crystallization, bath temperature is 70～90 ℃, and rotary speed is 120～150rpm.
6. according to claim 1ly prepare calcium oxide-based CO take slag as raw material 2the method of circulation absorption material, is characterized in that, the described intensification frequency from room temperature homogeneous heating to 800 ℃ is 5 ℃/min.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114213146A (en) * 2022-01-18 2022-03-22 中国建筑材料工业地质勘查中心宁夏总队 Preparation and adsorption of CO by using coal slime as raw material2Key technology for paving green building material by using road surface
CN114522522A (en) * 2022-01-29 2022-05-24 武汉理工大学 Has CO2Calcium-aluminum-based solid waste carrier material with efficient circulating and trapping functions and preparation method thereof
CN114832770A (en) * 2022-04-25 2022-08-02 东北大学 Method for preparing calcium-based circulating carbon capturing material by using steel slag

Citations (1)

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CN101828074A (en) * 2007-09-19 2010-09-08 C奎斯特技术有限责任公司 Methods and devices for reducing hazardous air pollutants

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CN101828074A (en) * 2007-09-19 2010-09-08 C奎斯特技术有限责任公司 Methods and devices for reducing hazardous air pollutants
US20120288428A1 (en) * 2007-09-19 2012-11-15 C-Quest Technologies L.L.C. Methods and devices for reducing hazardous air pollutants

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114213146A (en) * 2022-01-18 2022-03-22 中国建筑材料工业地质勘查中心宁夏总队 Preparation and adsorption of CO by using coal slime as raw material2Key technology for paving green building material by using road surface
CN114213146B (en) * 2022-01-18 2023-08-11 中国建筑材料工业地质勘查中心宁夏总队 CO adsorption prepared by using coal slime as raw material 2 Preparation method of green building material paved by pavement
CN114522522A (en) * 2022-01-29 2022-05-24 武汉理工大学 Has CO2Calcium-aluminum-based solid waste carrier material with efficient circulating and trapping functions and preparation method thereof
CN114832770A (en) * 2022-04-25 2022-08-02 东北大学 Method for preparing calcium-based circulating carbon capturing material by using steel slag

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