CN101020577A - CO2 mineralizing process - Google Patents

CO2 mineralizing process Download PDF

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Publication number
CN101020577A
CN101020577A CNA2007100513106A CN200710051310A CN101020577A CN 101020577 A CN101020577 A CN 101020577A CN A2007100513106 A CNA2007100513106 A CN A2007100513106A CN 200710051310 A CN200710051310 A CN 200710051310A CN 101020577 A CN101020577 A CN 101020577A
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reaction
magnesium
distilled water
mineralizing
temperature
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张军营
赵永椿
王志亮
潘霞
宴恒
郑楚光
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Huazhong University of Science and Technology
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Huazhong University of Science and Technology
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Abstract

The CO2 mineralizing process includes the steps of: grinding silicate mineral of natural calcium and magnesium into powder, mixing with the mixed solution of sodium bicarbonate and sodium chloride or distilled water in a reaction kettle, filling CO2 gas to the reaction kettle to 3-12 MPa and reaction at 100-250 deg.c via stirring for 30-90 min to produce carbonate and realize the permanent storage of CO2. The present invention adopts rich natural silicate and can realize large scale CO2 treatment.

Description

A kind of method of CO 2 mineralizing
Technical field
The present invention relates to a kind of method, particularly use the silicate minerals of calcic, magnesium and the method that the carbonic acid gas direct reaction generates carbonate minerals CO 2 mineralizing.
Background technology
In Combustion Source Environmental Pollution and Control research field, after numerous pollutents such as sulfurous gas, oxynitride, particulate matter, toxic trace elements, the influence that " Greenhouse effect " of carbonic acid gas cause for the environment of human survival has caused worldwide extensive concern.World energy sources mechanism once asserted, to the global environment that is fit to human living produce the most direct influence no more than Atmospheric Carbon Dioxide content.The reality of Global warming is just constantly sounded the alarm to the countries in the world people, and nearly 50 years climate warming mainly is a large amount of CO that used the fossil oil discharging by the mankind 2The warming effect of isothermal chamber gas causes.CO 2The Greenhouse effect that produce have become the whole world problem of focus the most, and international community just controls the action that greenhouse gas emissions were taked repeatedly politics and technical elements.
The carbonic acid gas scheme of burying that adopts in the world mainly contains at present: bury the ocean, geology is buried, plant is consolidated carbon etc.The ocean is buried and limited by the region, the solid carbon of plant needs the long time just can demonstrate effect again, geology is buried and is not obviously had above problem, and geology buries a part of carbonic acid gas is transferred in the solid mineral, can realize forever burying of carbonic acid gas.Scholar CO is as calculated arranged 2Energy state than the low 400kJ/mol of carbon, and the energy state of carbonate compares CO 2Also to hang down 60--180kJ/mol, think that the final steady state of carbon atom is not to be present in CO 2In, but be present in the carbonate.So, researchers begin one's study with the mode that forms carbonate (mainly being magnesiumcarbonate, lime carbonate) catch, storing carbon dioxide.This measure The key factor is that positively charged ion---calcium, the magnesium ion that generates lime carbonate, magnesiumcarbonate will be arranged.
People such as Lackner have at first proposed based on muriatic carbonation reaction.CO 2Following reaction takes place with silicate ore:
2HCl+1/3Mg 3Si 2O 5(OH) 4→MgCl 2+5/3H 2O+2/3SiO 2
2HCl+1/2Mg 2SiO 4→MgCl 2+H 2O+1/2SiO 2
MgCl 2+H 2O→Mg(OH)Cl+HCl
2Mg(OH)Cl→Mg(OH) 2+MgCl 2
Mg(OH) 2+CO 2→H 2O+MgCO 3
Experimental result is presented under the high temperature of 50 normal atmosphere and 600 ℃, and the carbonation reaction degree can reach 99% in 30 minutes.And they also find can effectively reduce reaction pressure by reducing the mineral grain particle diameter.But the impurity in the rock can cause the chlorine damage consumption with the chlorion reaction, and also there are shortcomings such as operational difficulty, process complexity and energy consumption height in this method.Although Lackner claim from the reaction liberated heat can offset a part of energy consumption, how to collect and utilize heat of reaction still research in the middle of.People such as Zevenhoven have studied dry method carbonatation process technology.They adopt peridotites and mixed gas (N 2/ CO 285%/15%) reaction at high temperature.But experimental result is unsatisfactory.
It is multiple to utilize sorbent material to come the method for absorbing carbon dioxide to have, and is reported by a plurality of patents and document, and wherein Japanese scholar has described the method for utilizing lithium silicate to come absorbing carbon dioxide in detail in Chinese patents 00108881.5, and this lithium silicate can be used general formula Li xSi yO zRepresent that x wherein, y, z satisfy the integer that x+4y-2z=0 requires, the content x of lithium preferably is at least 4 in the general formula.Obviously, this lithium silicate can't be taken from natural mineral, and it need prepare through special and complicated technology, has higher preparation cost and cycle.And that the silicate ore of the calcic that the present invention studied, magnesium can be taken from fully is natural, need not adopt complicated technology to carry out artificial preparation.Utilize the lithium silicate absorbing carbon dioxide to belong to the separation of carbonic acid gas in essence, lithium silicate can also use as carbon dioxide absorber after release of carbon dioxide again, thereby can't carry out permanent isolation storage to carbonic acid gas, and the present invention has overcome above shortcoming, at isolated high-pureness carbon dioxide, utilize natural silicate ore to realize the permanent storage of carbonic acid gas.The calcium of mentioning in the Japanese Patent, magnesium ion belong to the ancillary component of sorbent material, are used to improve the uptake rate of carbonic acid gas, and the calcium among the present invention, magnesium ion then are to form stable carbonate ore with carbonic acid gas, realize the permanent sequestration of carbonic acid gas.The required temperature and pressure of carbonation reaction of the present invention can be provided by the tail gas of power plant simultaneously, has advantages of high practicability.The present invention creatively to the product after the mineralising in addition utilization, magnesiumcarbonate in the product and lime carbonate can be used for rubber and plastic industry, silicon-dioxide then can be used to prepare the nano level chemical materials.
Though the isolation technique of carbonic acid gas is very ripe at present, how the high-pureness carbon dioxide that obtains after separating is disposed still and is not effectively solved.Mineralizing of the high-pureness carbon dioxide that method of the present invention has been specially adapted to have separated in the power-plant flue gas.
Summary of the invention
The objective of the invention is to overcome the deficiency of above-mentioned prior art, the natural silicate mineral of a kind of calcic, magnesium and the method that the carbonic acid gas direct reaction generates carbonate minerals are provided.
The present invention utilizes the silicate minerals of natural calcium, magnesium, as: serpentine, peridotites, wollastonite etc., react the permanent storage that the stable materials such as carbonate of generation are realized carbonic acid gas under certain condition with carbonic acid gas.The reactional equation general formula is as follows:
(Mg，Ca) xSi yO x+2y+zH 2z+xCO 2→x(Mg，Ca)CO 3+ySiO 2+zH 2O
The silicate minerals institute calcic of above-mentioned said natural calcium, magnesium, the mass percent of magnesium are 15%～40%.Mineralizing of the high-pureness carbon dioxide that method of the present invention has been specially adapted to have separated in the power-plant flue gas.
Method with CO 2 mineralizing of the present invention, its concrete steps are:
1. with silicate ore crushing grinding to the 200 order～500 purpose powder of natural calcium, magnesium;
2. the powder that 1. step is prepared is put into the retort furnace roasting 1～3 hour of 650 ℃ of constant temperature;
3. the mixing solutions for preparing sodium bicarbonate and sodium-chlor (is pressed mass ratio NaHCO 3/ NaCl/ distilled water=1/1～2/5～10) or distilled water as catalytic solution;
4. the mixing solutions or the distilled water that 3. prepare of mineral dust that 2. step is prepared and step mixes, and the mass ratio of ore and reaction soln is 1/10～15, with the mass ratio of distilled water be 1/1～5, put into reactor;
5. in reactor, fill CO 2Gas to pressure is 3MPa～12MPa, temperature of reaction: 100 ℃～250 ℃, stirring reaction 30～90 minutes is promptly realized CO 2 mineralizing.
After reaction was finished, temperature of reaction was reduced to room temperature, and reacting kettle inner pressure can be reduced to normal pressure.Take out material in reactor and after 1～30 hour, get dried sample material at 90 ℃～120 ℃ temperature range inner drying, the quality of weighing is M 1, send into retort furnace and calcine, calcining temperature is 600 ℃～700 ℃, calcination time be 1～3 hour be M to the calcining after product quality of weighing 2Formula by the mineral carbonation reaction conversion ratio: η = 276 × 4.962 × ( M 1 - M 2 ) 54 M 1 + 144 M 2 × 100 % (being applicable to the silicate ore that contains natural magnesium) or η = 40 × ( M 1 - M 2 ) 44 × 0.3 × M 2 × 100 % (being applicable to the silicate ore that contains natural calcium), the mass M before the substitution calcining 1With the mass M after the calcining 2, can calculate the mineral carbonation transformation efficiency is 50%～90%, promptly the silicate ore of 1mol can be converted to the carbonate ore of 0.5mol～0.9mol.
The invention has the advantages that:
1. natural base silicate reserves are abundant, are easy to exploitation, can realize large-scale carbon dioxide treatment.
2. the mineral carbonation product is stable carbonate, non-environmental-pollution and can permanent sequestration of carbon dioxide.
3. the mineral carbonation reaction is thermopositive reaction, has the potentiality of commercial applications.
Relevant emission of carbon-dioxide control or mineralize stores has become the emerging and research field in forward position.CO 2 mineralizing is a kind of method that has the commercial applications potentiality can handle carbonic acid gas on a large scale.
Embodiment
Example 1. is 15% serpentine 1.5 gram crushing grinding to 200 purpose powder with the mass percentage content of magnesium, and with the serpentine sample ore in 650 ℃ of constant temperature calcinings 1 hour, again with sample ore after the roasting and catalytic solution (NaHCO 3: 2.016g, NaCl:2.19g, distilled water: 13.5ml) mix in the reactor that is placed on the reaction under high pressure system, charge into carbonic acid gas, temperature of reaction is 155 ℃, and reaction pressure is 10MPa; Keep the constant reaction of temperature and pressure after 60 minutes, cooling is when treating that system temperature is lower than 85 ℃, lose heart, take out in the reactor residue under 105 ℃ of temperature dry 1 hour, send into retort furnace calcining 2 hours after again will dried residue taking out 1.026 grams, calcining temperature is 650 ℃.The calcining after product is weighed, and the back quality of weighing is 0.941 gram, by the mass M before calcining 1Mass M after (1.026 gram) and the calcining 2(0.941 gram) obtains the mineral carbonation reaction conversion ratio η = 276 × 4.962 × ( M 1 - M 1 ) 54 M 1 + 144 M 2 × 100 % , Transformation efficiency is 58.6% as calculated.
For example, the serpentine of 1mol can absorb the CO of 0.586mol 2Gas, promptly 1 ton serpentine can absorb 0.26 ton CO 2Gas.
Example 2. is 20% serpentine 2.0 gram crushing grinding to 300 purpose powder with the mass percentage content of magnesium, and with the serpentine sample ore in 650 ℃ of constant temperature calcinings 1 hour, again with sample ore after the roasting and catalytic solution (NaHCO 3: 3.024g, NaCl:3.216g, distilled water: 16.5ml) mix in the reactor that is placed on the reaction under high pressure system, charge into carbonic acid gas, temperature of reaction is 120 ℃, and reaction pressure is 12MPa; Keep the constant reaction of temperature and pressure after 60 minutes, cooling is when treating that system temperature is lower than 85 ℃, lose heart, take out in the reactor residue under 105 ℃ of temperature dry 1 hour, send into retort furnace calcining 2 hours after again will dried residue taking out 1.055 grams, calcining temperature is 650 ℃.The calcining after product is weighed, and the back quality of weighing is 0.972 gram, by the mass M before calcining 1Mass M after (1.055 gram) and the calcining 2(0.972 gram) obtains the mineral carbonation reaction conversion ratio η = 276 × 4.962 × ( M 1 - M 2 ) 54 M 1 + 144 M 2 × 100 % , Transformation efficiency is 57.5% as calculated.For example, the serpentine of 1mol can absorb the CO of 0.575mol 2Gas, promptly 1 ton serpentine can absorb 0.253 ton CO 2Gas.
Example 3. is that 35% wollastonite, 10 grams are ground to 400 purpose powder with calcareous amount degree, and with the wollastonite sample ore in 650 ℃ of constant temperature calcinings 2 hours, in volume is to add 40ml first water and 10.0 grams, 400 order wollastonite powder in the reactor of 0.25L, charge into carbonic acid gas, temperature of reaction is 150 ℃, and reaction pressure is 6MPa; Keep the constant reaction of temperature and pressure after 60 minutes, be cooled to room temperature, lose heart, collect resistates in beaker, treat that solution is removed in upper solution clarification hypsokinesis in the beaker, solid transfer to porcelain boat, in drying baker in 105 ℃ dry 24 hours down.After the solid product drying case drying, take out 1.007 grams and at high temperature carry out the calcining and decomposing test, calcination time is 1 hour, and calcining temperature is 700 ℃.The calcining after product is weighed, by the mass M before calcining 1Mass M after (1.007 gram) and the calcining 2(0.738 gram) obtains the mineral carbonation reaction conversion ratio η = 40 × ( M 1 - M 2 ) 44 × 0.3 × M 2 × 100 % , Turnover ratio is 89.5% as calculated.For example, the wollastonite of 1mol can absorb the CO of 0.895mol 2Gas, promptly 1 ton wollastonite can absorb 0.34 ton CO 2Gas.
Example 4. is that 40% wollastonite (12 gram) is ground to 500 purpose powder with the mass percent of calcium, and with the wollastonite sample ore in 650 ℃ of constant temperature calcinings 2 hours, in volume is to add 55ml first water and 12.0 grams, 500 order wollastonite powder in the reactor of 0.25L, charge into carbonic acid gas, temperature of reaction is 200 ℃, and reaction pressure is 4MPa; Keep the constant reaction of temperature and pressure after 60 minutes, be cooled to room temperature, lose heart, collect resistates in beaker, treat that solution is removed in upper solution clarification hypsokinesis in the beaker, solid transfer to porcelain boat, in drying baker in 105 ℃ dry 24 hours down.After the solid product drying case drying, take out 1.004 grams and at high temperature carry out the calcining and decomposing test, calcination time is 1 hour, and calcining temperature is 700 ℃.The calcining after product is weighed, by the mass M before calcining 1Mass M after (1.004 gram) and the calcining 2(0.836 gram) obtains the mineral carbonation reaction conversion ratio η = 40 × ( &Mgr; 1 - &Mgr; 2 ) 44 × 0.3 × &Mgr; 2 × 100 % , Turnover ratio is 60.9% as calculated.For example, the wollastonite of 1mol can absorb the CO of 0.609mol 2Gas, promptly 1 ton wollastonite can absorb 0.23 ton CO 2Gas.

Claims (2)

1. the method for a CO 2 mineralizing is characterized by, and utilizes the silicate minerals of natural calcium, magnesium, generates the permanent storage that stable materials such as carbonate are realized carbonic acid gas with carbon dioxide reaction, and the concrete steps of method are:
1. with silicate ore crushing grinding to the 200 order～500 purpose powder of natural calcium, magnesium;
2. the powder that 1. step is prepared is put into the retort furnace roasting 1～3 hour of 650 ℃ of constant temperature;
3. prepare the mixing solutions of sodium bicarbonate and sodium-chlor or distilled water as catalytic solution;
4. the mixing solutions or the distilled water that 3. prepare of mineral dust that 2. step is prepared and step mixes, and the mass ratio of ore and reaction soln is 1/10～15, with the mass ratio of distilled water be 1/1～5, put into reactor;
5. filling CO2 gas to pressure in reactor is 3MPa～12MPa, temperature of reaction: 100 ℃～250 ℃, stirring reaction 30～90 minutes is promptly realized CO 2 mineralizing.
2. according to the method for the described CO 2 mineralizing of claim 1, the mass percent of the silicate minerals of said natural calcium, magnesium institute calcic, magnesium is 15%～40%;
The mixing solutions of 1. said sodium bicarbonate of step and sodium-chlor is by mass ratio NaHCO 3/ NaCl/ distilled water=1/1～2/5～10 preparations.
CNA2007100513106A 2007-01-19 2007-01-19 CO2 mineralizing process Pending CN101020577A (en)

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101312784B (en) * 2005-11-23 2011-06-22 国际壳牌研究有限公司 A process for separation of carbon dioxide by mineral carbonation
CN102240501A (en) * 2010-05-13 2011-11-16 华南理工大学 Carbon sequestration discharge-reducing method
WO2012028418A1 (en) 2010-09-02 2012-03-08 Novacem Limited Integrated process for producing compositions containing magnesium
CN103415632A (en) * 2010-11-26 2013-11-27 纽卡斯尔创意有限公司 Extraction of alkali metals and/or alkaline earth metals for use in carbon sequestration
CN102137706B (en) * 2008-08-28 2015-09-16 奥瑞凯***技术有限公司 The integrated chemical process improved
CN105477991A (en) * 2015-11-24 2016-04-13 长春工程学院 Method for sealing carbon dioxide and polluting gas in flue gas
CN109621891A (en) * 2018-12-24 2019-04-16 华中科技大学 A kind of lithium base CO2Adsorbent and preparation method thereof
CN113025832A (en) * 2021-03-02 2021-06-25 重庆大学 Nickel extraction and CO mineralization from laterite-nickel ore2Method (2)
CN114634197A (en) * 2022-02-25 2022-06-17 浙江大学 Method for absorbing carbon dioxide by using carbon fixing agent and saline water
CN114751372A (en) * 2022-03-12 2022-07-15 昆明理工大学 Method for fixing carbon dioxide in water-gas shift process by utilizing real-time carbonization of silicate
CN114920245A (en) * 2022-07-04 2022-08-19 重庆大学 Mineralized substance for carbon dioxide sequestration and application thereof

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101312784B (en) * 2005-11-23 2011-06-22 国际壳牌研究有限公司 A process for separation of carbon dioxide by mineral carbonation
CN102137706B (en) * 2008-08-28 2015-09-16 奥瑞凯***技术有限公司 The integrated chemical process improved
CN102240501A (en) * 2010-05-13 2011-11-16 华南理工大学 Carbon sequestration discharge-reducing method
CN102240501B (en) * 2010-05-13 2013-08-28 中山市忠泮节能科技有限公司 Carbon sequestration discharge-reducing method
WO2012028418A1 (en) 2010-09-02 2012-03-08 Novacem Limited Integrated process for producing compositions containing magnesium
CN103415632A (en) * 2010-11-26 2013-11-27 纽卡斯尔创意有限公司 Extraction of alkali metals and/or alkaline earth metals for use in carbon sequestration
CN105477991A (en) * 2015-11-24 2016-04-13 长春工程学院 Method for sealing carbon dioxide and polluting gas in flue gas
CN109621891A (en) * 2018-12-24 2019-04-16 华中科技大学 A kind of lithium base CO2Adsorbent and preparation method thereof
CN113025832A (en) * 2021-03-02 2021-06-25 重庆大学 Nickel extraction and CO mineralization from laterite-nickel ore2Method (2)
CN113025832B (en) * 2021-03-02 2022-07-15 重庆大学 Nickel extraction and CO mineralization from laterite-nickel ore2Method (2)
CN114634197A (en) * 2022-02-25 2022-06-17 浙江大学 Method for absorbing carbon dioxide by using carbon fixing agent and saline water
CN114751372A (en) * 2022-03-12 2022-07-15 昆明理工大学 Method for fixing carbon dioxide in water-gas shift process by utilizing real-time carbonization of silicate
CN114920245A (en) * 2022-07-04 2022-08-19 重庆大学 Mineralized substance for carbon dioxide sequestration and application thereof
CN114920245B (en) * 2022-07-04 2023-10-03 重庆大学 Mineralization for carbon dioxide sequestration and application thereof

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