CN106882831A - A kind of method that organic amine industrial gypsum system fixes carbon dioxide - Google Patents
A kind of method that organic amine industrial gypsum system fixes carbon dioxide Download PDFInfo
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- CN106882831A CN106882831A CN201710164904.1A CN201710164904A CN106882831A CN 106882831 A CN106882831 A CN 106882831A CN 201710164904 A CN201710164904 A CN 201710164904A CN 106882831 A CN106882831 A CN 106882831A
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- organic amine
- industrial gypsum
- carbon dioxide
- amine
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
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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
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/10—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
Abstract
The present invention relates to a kind of utilization of waste as resource, reduction of greenhouse gas discharge and application technology as the second resource, and in particular to a kind of method that organic amine industrial gypsum system fixes carbon dioxide.Organic amine and industrial gypsum are mixed and made into suspension slurry, CO is contained to being introduced in slurries2Simulated flue gas, occur carbonation reaction.Product is calcium carbonate and organic amine sulfate.The former can be used for the exploitation of the industrial products such as precipitated calcium carbonate, and the latter can realize the regeneration of absorbing liquid by methods such as electrodialysis.Compared with traditional ammonia industrial gypsum carbon sequestration system, the present invention build organic amine industrial gypsum carbon sequestration system ensure carbon sequestration efficiency on the premise of, with low stain, reproducible advantage.
Description
Technical background
The present invention relates to a kind of utilization of waste as resource, reduction of greenhouse gas discharge and application technology as the second resource, and in particular to
The method that a kind of organic amine-industrial gypsum system fixes carbon dioxide.
Background technology
With continuing to develop for China's thermoelectricity, phosphate fertilizer and other relevant industries, the output and heap of industry by-product gypsum are high-volume
Sharply increase.To, the t of ardealite annual emissions about 7,000 ten thousand, the t of accumulation volume of cargo in storage about 300,000,000, the annual emissions of desulfurated plaster in 2014
About 75,500,000 t, the t of accumulation volume of cargo in storage about 1.3 hundred million.The bulk deposition of industry by-product gypsum, a large amount of spaces are not only taken up, while also
Severe contamination soil, destroys ecological environment.The comprehensive utilization of industry by-product gypsum can not only turn waste into wealth, and realize resources circulation
Utilize, also help transformation Industrial Economic Development mode.But at present, China's industry by-product gypsum year comprehensive utilization ratio is still below
Less than 50%.The method of main some industrial gypsums comprehensive utilization is still for use as cement retarder and production Thistle board
It is main, but this market segment is influenceed larger by China's natural gypsum rich reserves.Other industrial gypsums comprehensively utilize new method
Calcium carbonate and ammonium sulfate etc. are prepared including being used as soil conditioner, coproduction, but need to consider the latent of heavy metal as soil conditioner
In influence.
In recent years, carbon dioxide is fixed using ammonia-industrial gypsum mixed system（It is carbonated）, while co-producing calcium carbonate and
The method of ammonium sulfate is proposed by various countries researcher.Industrial gypsum absorbs CO2Carbonate treatment, has both reached CO2Seal purpose up for safekeeping,
The pollution problem that a large amount of gypsum are piled up is solved again, is a kind of strategy of doulbe-sides' victory.Industrial gypsum is generally with calcium sulphate dihydrate
（CaSO4·2H2O）Form exist, purity about between 80%-95%, one of product calcium carbonate after carbonation reaction
（CaCO3）Can be used directly, and another product ammonium sulfate is then chemical fertilizer primary raw material.The technique have carbon sequestration, change give up into
Various advantages such as treasured, recycling.Chinese Academy of Sciences's Zhao's turbulent waves etc. proposes the aqueous solution of the ardealite in ammonia, and pressurize CO2Gas condition
Under realize the carbonate treatment process of ardealite, transformation efficiency reached 97% in 5 minutes.Bao Weijun etc. is proposed in ammonia
In medium system, the ardealite that is produced with chemical industry, fluorite, the calcium base such as desuifurized of desulfurated plaster and steel industry are consolidated
Body discarded object is the carbonating process of raw material, and using high temperature, high pressure tactics reinforcing conversion ratio.Sichuan University professor Zhu Jiahua carries
Selexol process gas-fertilizer-chlor-alkali Poly-generation circulation technology is gone out, conversion processing has been carried out to ardealite using industrial flue waste gas
Production ammonium sulfate.Sun Zhiguo etc. then constitutes new system and fixes CO using humate and desulfurated plaster2, coproduction precipitated calcium carbonate etc.
Chemical products.Spain C á rdenas-Escudero etc., by the use of NaOH as medium, absorbs CO under normal temperature, condition of normal pressure2
To calcium carbonate and sodium sulphate.Amin etc. is in high temperature（200℃）Autoclave in attempted using titanium gypsum be raw material, prepare
The experiment of calcium carbonate.Products therefrom purity, yield are relatively low.South Korea Wonbaek etc. is respectively adopted two-step method, one-step method by desulfurization stone
Cream is converted into calcium carbonate calcite crystal and ammonium sulfate, and there is desulfurated plaster preferably reaction to live under as a result finding normal temperature and pressure
Property, but pure calcite content is relatively low（5% or so）.Simultaneously the volatility of ammonia and putting for reaction itself are considered in one-step method
Thermal characteristics, reaction temperature should be less than 20 DEG C.
In summary, using industrial gypsum（Such as ardealite, desulfurated plaster even titanium gypsum）As calcium source, in different medium
（Such as ammonia, NaOH, humic acid）It is middle to absorb fixed CO2By widely studied both at home and abroad.Situation wherein with ammonia as main medium compared with
For universal, carbonate treatment effect and economy reach industrial applications degree.But, the volatile feature of ammonia, and sulphur
The sour ammonium market demand instability limit further applying for the technology.
The content of the invention
Present invention use boiling point is higher, reproducible organic amine, substitutes low boiling, the ammonia of high pollution as medium, and
Itself and industrial gypsum are mixed with new carbon sequestration system, its carbon sequestration efficiency high, product is calcium carbonate and reproducible organic amine
Sulfate, really realizes that the green resourceization of industrial gypsum is utilized.
The purpose of the present invention is achieved through the following technical solutions：Organic amine and industrial gypsum are mixed and made into suspension
Slurries, CO is contained to being introduced in slurries2Simulation tail（Cigarette）, there is carbonation reaction in gas.Product is calcium carbonate and organic amine sulfuric acid
Salt.The former can be used for the exploitation of the industrial products such as precipitated calcium carbonate, and the latter can realize the regeneration of absorbing liquid by methods such as electrodialysis.
The method that a kind of organic amine of the present invention-industrial gypsum system fixes carbon dioxide, comprises the following steps that：
（1）Configuration quality concentration is stored in retort for 6 ~ 10% organic amine aqueous solution, heats and keep retort temperature, excellent
Elect 40 ~ 80 DEG C as.
（2）The industrial gypsum powder of the mass of organic amine aqueous solution 10 ~ 30% is added, is stirred, mixed pulp.
（3）To being passed through CO in retort2Volume content is 15 ~ 100% simulated flue gas.
（4）After 15 ~ 60min of reaction, the filtering of reacted gained solid product is rinsed, drying can obtain calcium carbonate product.
After above-mentioned reaction, gained filtrate can be used for Ion-exchange.
Described organic amine is mainly organic alcohol amine, including MEA, diethanol amine, triethanolamine, diisopropanolamine (DIPA),
One or more mixing in N methyldiethanol amine.
In the method for the fixed carbon dioxide of the present invention, replace ammonia as medium from organic amine, organic alcohol amine boiling point is high
In ammonia, it is ensured that organic amine-industrial gypsum system carbon sequestration efficiency reaches more than 95%, and one of product is the carbonic acid with added value
Calcium, can be used to prepare the industrial products such as precipitated calcium carbonate, it can also be used to desulfurizing agent；Another product is organic amine sulfate, can
Regenerated by electrodialytic technique and continued on for absorption system.The technology it is useless control useless comprehensive utilization while, it is to avoid ammonia
As the secondary pollution problem of medium, recycling for absorbing liquid is realized.
Brief description of the drawings
Fig. 1 is conversion ratio of the industrial gypsum in different organic amine media in the present invention；
Fig. 2 is the XRD that the embodiment of the present invention is obtained product calcium carbonate.
Specific embodiment
Present invention process is described in further detail below by different organic amines-industrial gypsum system implementation case.
Case study on implementation 1：
Configuration quality concentration be 6% aqueous monoethanolamine 5L in retort, be warming up to 40 DEG C.Add desulfurated plaster powder
0.5kg.Stirring keeps slurries to suspend, while to being bubbled into CO in retort2Volume content is 15% simulated flue gas.Reaction
After 60min, desulfurated plaster conversion ratio is up to 97.8%.By the filtering of reacted slurries, dried for 60 DEG C after solid portion is rinsed.Filtrate
Dissociated with electrodialytic technique, and triethanolamine and sulfuric acid are obtained with OH- combination regeneration.
Case study on implementation 2：
Configuration quality concentration be 8% diethanol amine aqueous solution 5L in retort, be warming up to 60 DEG C.Add desulfurated plaster powder
1.5kg.Stirring keeps slurries to suspend, while to being bubbled into CO in retort2Volume content is 60% simulated flue gas.Reaction
After 30min, desulfurated plaster conversion ratio is up to 97.8%.By the filtering of reacted slurries, dried for 60 DEG C after solid portion is rinsed.Filtrate
Dissociated with electrodialytic technique, and triethanolamine and sulfuric acid are obtained with OH- combination regeneration.
Case study on implementation 3：
Configuration quality concentration be 10% triethanolamine aqueous solution 5L in retort, be warming up to 80 DEG C.Add ardealite powder
1.0kg.Stirring keeps slurries to suspend, while to being bubbled into CO in retort2The simulated flue gas of volume content 100%.Reaction
After 15min, ardealite conversion ratio is up to 97.8%.By the filtering of reacted slurries, dried for 60 DEG C after solid portion is rinsed.Filtrate is used
Electrodialytic technique is dissociated, and obtains triethanolamine and sulfuric acid with OH- combination regeneration.
Case study on implementation 4：
Using with the identical method of case study on implementation 1, its difference is, prepares diisopropanolamine (DIPA) that mass concentration is 6% as reaction
Medium.
Case study on implementation 5：
Using with the identical method of case study on implementation 1, its difference is, prepares the N methyldiethanol amine that mass concentration is 10% and makees
It is reaction medium.
Case study on implementation 6：
Using with the identical method of case study on implementation 1, its difference is, prepares MEA and diethanol amine that mass concentration is 6%
Mixed solution as reaction medium.
Case study on implementation 7：
Using with the identical method of case study on implementation 1, its difference is, prepares triethanolamine, diisopropanol that mass concentration is 10%
The mixed solution of amine and N methyldiethanol amine is used as reaction medium.
Claims (2)
1. the method that a kind of organic amine-industrial gypsum system fixes carbon dioxide, it is characterised in that comprise the following steps that：
（1）Configuration quality concentration is stored in retort for 6 ~ 10% organic amine aqueous solution, heats and keep retort temperature 40
~80℃；
（2）According to organic amine aqueous solution quality 10 ~ 30% add industrial gypsum powder, stirring, mixed pulp；
（3）To being passed through CO in retort2Volume content is 15 ~ 100% flue gas；
（4）After 15 ~ 60min of reaction, the filtering of reacted gained solid product is rinsed, drying can obtain calcium carbonate product.
2. the method for fixed carbon dioxide according to claim 1, it is characterised in that described organic amine is Organic Alcohol
Mix for one or more in amine, including MEA, diethanol amine, triethanolamine, diisopropanolamine (DIPA), N methyldiethanol amine
Close.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710164904.1A CN106882831B (en) | 2017-03-20 | 2017-03-20 | The method that a kind of organic amine-industrial gypsum system fixes carbon dioxide |
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| CN201710164904.1A CN106882831B (en) | 2017-03-20 | 2017-03-20 | The method that a kind of organic amine-industrial gypsum system fixes carbon dioxide |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113149055A (en) * | 2021-05-27 | 2021-07-23 | 湖南西林环保材料有限公司 | Method for preparing calcium carbonate and sulfate by using industrial desulfurized gypsum |
| CN113998724A (en) * | 2021-11-29 | 2022-02-01 | 南京工程学院 | One-step method for fixing carbon by gypsum and regulating and controlling particle size of product |
| CN114684839A (en) * | 2022-03-07 | 2022-07-01 | 南京工程学院 | Method for grading, mineralizing and carbon-fixing industrial by-product gypsum and gradient utilization of products |
| CN114870586A (en) * | 2022-04-15 | 2022-08-09 | 呼和浩特蒙祥环保科技有限公司 | Carbon dioxide curing method |
| CN114931853A (en) * | 2022-07-26 | 2022-08-23 | 苏州博纽强新材料科技有限公司 | Trapping CO in cement kiln flue gas 2 Method for synergistically preparing low-carbon cement and obtained product |
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| CN103539187A (en) * | 2013-10-22 | 2014-01-29 | 山东大学 | Indirect process of preparing light calcium carbonate based on medium strengthening |
| CN105523571A (en) * | 2014-10-22 | 2016-04-27 | 中国石油化工股份有限公司 | Method for processing mineralized organic amine and resource utilization used after carbon dioxide capture |
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| CN103539187A (en) * | 2013-10-22 | 2014-01-29 | 山东大学 | Indirect process of preparing light calcium carbonate based on medium strengthening |
| CN105523571A (en) * | 2014-10-22 | 2016-04-27 | 中国石油化工股份有限公司 | Method for processing mineralized organic amine and resource utilization used after carbon dioxide capture |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113149055A (en) * | 2021-05-27 | 2021-07-23 | 湖南西林环保材料有限公司 | Method for preparing calcium carbonate and sulfate by using industrial desulfurized gypsum |
| CN113998724A (en) * | 2021-11-29 | 2022-02-01 | 南京工程学院 | One-step method for fixing carbon by gypsum and regulating and controlling particle size of product |
| CN114684839A (en) * | 2022-03-07 | 2022-07-01 | 南京工程学院 | Method for grading, mineralizing and carbon-fixing industrial by-product gypsum and gradient utilization of products |
| CN114684839B (en) * | 2022-03-07 | 2024-03-22 | 南京工程学院 | Hierarchical mineralization carbon fixation and product cascade utilization method for industrial byproduct gypsum |
| CN114870586A (en) * | 2022-04-15 | 2022-08-09 | 呼和浩特蒙祥环保科技有限公司 | Carbon dioxide curing method |
| CN114931853A (en) * | 2022-07-26 | 2022-08-23 | 苏州博纽强新材料科技有限公司 | Trapping CO in cement kiln flue gas 2 Method for synergistically preparing low-carbon cement and obtained product |
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| CN106882831B (en) | 2018-05-08 |
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