CN101935059B - Clean preparation method for basic magnesium carbonate - Google Patents
Clean preparation method for basic magnesium carbonate Download PDFInfo
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- CN101935059B CN101935059B CN2010102962510A CN201010296251A CN101935059B CN 101935059 B CN101935059 B CN 101935059B CN 2010102962510 A CN2010102962510 A CN 2010102962510A CN 201010296251 A CN201010296251 A CN 201010296251A CN 101935059 B CN101935059 B CN 101935059B
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Abstract
The invention relates to a clean preparation method for basic magnesium carbonate, which prepares the basic magnesium carbonate by taking natural mineral brucite or synthesized magnesium hydroxide as raw materials and by performing the atom economic reaction of the raw material and CO2. All atoms in the raw materials participate in the reaction, and a target product is generated; the economical efficiency of the atoms is 100 percent; and thus, the reaction is a typical atom economic reaction. A reaction process avoids using raw materials such as dolomite, magnesite or brine, and sodium carbonate which are usually used by the conventional synthesis method, so that a product has no impurities, the pure product can be directly obtained without drying, a washing link is removed, a great amount of water source is saved, and the environment is protected.
Description
Technical field
The present invention relates to a kind of is raw material with brucite or synthetic Marinco H, and the cleaning procedure of employing atomic economy reaction prepares the method for magnesium basic carbonate, belongs to the preparation field of ceramic.
Technical background
Magnesium basic carbonate is that chemical constitution is the mixture of magnesiumcarbonate and Marinco H, and its molecular formula is xMgCO
3YMg (OH)
2ZH
2O, wherein the value of x is between 3-5, and y is approximately 1, and the value of z slightly changes with the change of working condition between 0-8.Magnesium basic carbonate is a kind of important inorganic magnesium compound material; Except that raw material as preparation highly-purity magnesite, magnesium salts series product; Also can be used as additive and the modifying agent of the special agent of rubber, medicine, insulating material, dentistry, high glass, food and various Chemicals etc., application prospect is very wide.
The method for preparing magnesium basic carbonate comprises ore method, coprecipitation method and other feedstock production methods etc.The traditional method desired raw material is many, and utilization ratio is low, and the preparation method generally can produce greenhouse gases CO
2, be not easy to recycling.Contain excessive foreign ion such as Cl in the product simultaneously
-, NH
4 +, HCO
3 -Deng, need to wash with big water gaging, water resources is caused serious waste.Therefore, atom economyization and environmentally friendly magnesium basic carbonate preparation technology are the targets that people pursue always.
Rhombspar carborization in the ore method and magnesite carborization are the earliest, also to be the most widely used method for preparing magnesium basic carbonate in the industry.These two kinds of methods are that rhombspar or magnesite are mixed with coal, and calcination in rotary kiln or shaft furnace makes calcination ore deposit and water become muddy and carries out carbonization with stack gas, then through at room temperature Mg (HCO
3)
2Solution is blown and is obtained MgCO
33H
2O is converted into magnesium basic carbonate or Natural manganese dioxide then.Document (Hu Qingfu etc. the rhombspar carborization is produced two magnesium, one calcium economic scale. inorganic chemicals industry .1999; 31 (6); 21-22.) reported and used the concrete steps of this method and the blending ratio of condition such as ore and coal etc. that this method production cost is higher, and technical process is long, the difficult control of quality product; The wastage of material phenomenon is serious, and reaction can produce greenhouse gases CO in addition
2, do not belong to the reaction of atom economy type.
Magnesia double decomposition in the ore method also is the very common method for preparing magnesium basic carbonate.This method be with magnesia, sulfuric acid, hydrogen-carbonate by being raw material, carry out acidolysis reaction, replacement(metathesis)reaction, pyrolytic reaction, make the product magnesium basic carbonate through operations such as filtrations, washing, dehydration, drying, pulverizing again.Document (Wang Baoxin. bischofite prepares the technical study of high-quality magnesium basic carbonate. Beijing: Postgraduate School, Chinese Academy of Sciences's Master's thesis; 2007) reported this method concrete steps, and the sub product sulfate of ammoniac that proposes this method can be used as nitrogenous fertilizer and sell, compare other two kinds of ore methods; By product to producing has had better utilised; But will use strong acid in raw materials used, therefore serious to equipment corrosion, production unit requires very high.
Coprecipitation method is to mix with carbon ammonium or soda ash with bittern, carries out replacement(metathesis)reaction, pyrolytic reaction, makes the product magnesium basic carbonate through operations such as filtration, washing, dehydration, drying, pulverizing again.Document (Chen Shoude. the study on the synthesis of food grade magnesium basic carbonate. periodical .2008 during chemical industry, 22 (3): 32-33) described the method that use bittern and soda ash prepare magnesium basic carbonate, this method technical process is simple, constant product quality, but owing to introduce Na in the reaction
+, Cl
-Etc. a large amount of ions, removal of impurities is comparatively complicated, need a large amount of deionized water wash, and production environment is relatively poor.Also relate to a series of problems such as recovery, environmental pollution of ammonia when using the carbon ammonium.
Other methods that prepare magnesium basic carbonate mainly contain industrial sulphuric acid magnesium method and refining Marinco H method.Document (Zhang Wengen. refining magnesium basic carbonate novel process. new technology novel process .1999, (3): mention 37-38.), industrial sulphuric acid magnesium method is with rough sal epsom of technical grade and Na
2S mixes, and again through acidifying, filtration, is total to thermal response with soda ash solution again and obtains the final product magnesium basic carbonate; Document (Yuan Chunhua etc. the application of magnesium basic carbonate and compound method. salt lake research .2005; 13 (2): mention 40-44.); The Marinco H method is that refining Marinco H is dissolved in the deionized water in proportion, the control solution temperature, and control reaction end pH value is between 7.5～9.0; With deionized water wash back oven dry several times, pulverizing, obtain the product magnesium basic carbonate.At present these two kinds of preparing methods are because the factor of aspects such as raw material, experiment condition, experimental installation and can't realize large-scale industrial production, just use as the problem of theoretical investigation or when the prepared in laboratory therefore basically.Wherein the former has solved emission greenhouse gas CO in the traditional method
2Problem, but still need massive laundering to wash; The latter not only can absorb CO
2, and only need simple washing to get final product, but this method need be controlled pH value, CO in the reaction
2Straying quatity, and to prepare feed hydrogen Natural manganese dioxide earlier, its operating procedure is comparatively complicated, higher to equipment requirements, production cost is higher.
Brucite is a kind of natural crystal, and staple is Mg (OH)
2, its magnesium content is arranged in numerous magnesia mineral and is occupied the umber one.Brucite is abundant at China's reserves, but only it is carried out using after the elementary processing at present, and added value of product is low, and narrow in application range fails to be utilized effectively, significant wastage Mineral resources.Therefore brucite is carried out high-value-use, develop new derived product with high added value, significant.
Summary of the invention
The clean method for preparing that the purpose of this invention is to provide a kind of magnesium basic carbonate, this method with the natural mineral brucite are or synthetic Marinco H raw material, with CO
2Prepare magnesium basic carbonate through atomic economy reaction.
Technical scheme of the present invention is: earlier natural brucite or synthetic Marinco H are mixed and grind to form the slurries of certain particle size with water, feed CO then
2Gas, single step reaction prepares magnesium basic carbonate, and its reaction equation is following:
xMg(OH)
2+yCO
2+zH
2O→Mg
x(OH)
2x-y(CO
3)
y·zH
2O
Various atoms in the raw material are all participated in reaction and have been generated title product or water molecules, no coupling product production in the process, and product just can carry out drying without washing and obtain pure product, has practiced thrift water resources greatly, has protected environment.
The concrete preparation process of magnesium basic carbonate of the present invention is following:
Steps A: adding quality to granularity in less than the natural mineral brucite of 500 μ m or synthetic Marinco H be its 6.7-33.3 deionized water doubly, and mixing being placed on colloidal mill or grinding in ball grinder, makes its granularity less than 50 μ m;
Step B: the slurries that steps A is obtained place autoclave, impose the CO of 0.08-1.0Mpa to it
2Gaseous tension, and be warming up to 50-180 ℃, reaction was taken out product after 0.5-20 hour under agitation condition, and in 50-180 ℃ time dry 1-10 hour, obtaining particle diameter was micron-sized magnesium basic carbonate after the direct centrifuging.
The invention has the beneficial effects as follows: only used brucite or synthetic Marinco H and CO in the reaction process
2, not using other raw materials such as rhombspar, bittern, soda ash, all raw materials are all participated in reaction and are generated title product, and Atom economy is 100%, belongs to typical atomic economy reaction.Do not contain any by product in the reaction product, can directly carry out drying and obtain product, practiced thrift water resources greatly, protected environment.
Description of drawings
Fig. 1 is the XRD spectra of embodiment 1 gained magnesium basic carbonate;
Fig. 2 is the FT-IR spectrogram of embodiment 2 gained magnesium basic carbonates;
Fig. 3 is the SEM spectrogram of embodiment 2 gained magnesium basic carbonates;
Fig. 4 is the differential thermal-thermogravimetric analysis figure of the magnesium basic carbonate of 2 of embodiment.
Embodiment
Embodiment 1:
The natural mineral brucite of the about 400 μ m of 46.7g particle diameter is mixed with the 731.6g deionized water; Obtain the 0.8L solid content and be 6% brucite slurries, grind 20min, make its particle diameter less than 45 μ m with colloidal mill; Place autoclave then, feed the CO of 0.35Mpa
2Pressure is warming up to 170 ℃ under agitation condition, reacted 5 hours, stops ventilation and heating, and with the product spinning that obtains, directly in 50 ℃ of dryings 10 hours, obtaining particle diameter was micron-sized magnesium basic carbonate after the cooling.
Adopting day XRD-6000 type X-ray powder diffraction appearance of island proper Tianjin company that sample is carried out crystalline structure characterizes.Fig. 1 is the XRD spectra of embodiment 1 gained sample; As can be seen from the figure, the characteristic peak in the standard magnesium basic carbonate XRD spectra comprises that 2 θ=9.6 °, about 13.8 °, 15.2 °, the 30.8 ° peaks of locating all have to appear; Each characteristic diffraction peak peak shape point is alarmmed, and the interpret sample crystalline structure is complete.
Embodiment 2:
The natural mineral brucite of the about 200 μ m of 46.7g particle diameter is mixed with the 731.6g deionized water; Obtain the 0.8L solid content and be 6% brucite slurries, use ball mill grinding 15min, make its particle diameter less than 10 μ m; Place autoclave then, feed the CO of 0.78Mpa
2Pressure is warming up to 100 ℃ under agitation condition, reacted 3 hours, stops ventilation and heating, and with the product spinning that obtains, directly in 160 ℃ of dryings 2 hours, obtaining particle diameter was micron-sized magnesium basic carbonate after the cooling.
Adopt the German Bruker Vector22 of company type Fourier transformation infrared spectrometer that sample is carried out qualitative analysis.Fourier transform spectrum (FT-IR) spectrogram by embodiment 2 gained samples is as shown in Figure 2, wherein 3450cm
-1With near 3513cm
-1Vibration peak be by H
2O molecule and OH
-Ionic is flexible to be caused with flexural vibration, shows and contains crystal water or OH in the product
-1360cm
-1About spectrum peak ownership be CO
3 2-The vibration peak of C-O, these absorption peaks all are consistent with the magnesium basic carbonate characteristic peak, and the inclusion-free peak.
Adopt the German ZEISS Supra55 of company type sem (SEM) observing samples surface topography.Fig. 3 is the SEM photograph of the sample of embodiment 2 preparations, and is visible by figure, and the magnesium basic carbonate that makes is that sheet structure is piled up the ball-like structure crystal that forms.
The material that adopts Beijing permanent scientific instrument HCT-2 of factory type differential thermal-thermogravimetric analyzer to measure product is formed, and Fig. 4 is the differential thermal-thermogravimetric analysis figure of embodiment 2 preparation products.Can calculate Mg in the product (OH) according to each flex point coordinate among the figure
2, MgCO
3With H
2The ratio of O is 5: 4: 6.
Adopt the size of the Mastersizer2000 type laser particle analyzer measure sample of Britain Ma Erwen company.The product size scope that under the reaction conditions that the present invention relates to, obtains is not waited to 10 μ m by 2 μ m, all belongs to micron order.
Can infer tentatively that through above-mentioned sign the product chemical constitution formula that obtains is: Mg
9(OH)
10(CO
3)
46H
2O.
Embodiment 3:
The synthetic Marinco H of the about 10 μ m of 24.5g particle diameter is mixed with the 790.4g deionized water; Obtain the 0.8L solid content and be 3% magnesium hydroxide slurry, grind 15min, make its particle diameter less than 0.5 μ m with colloidal mill; Place autoclave then, feed the CO of 0.35Mpa
2Pressure is warming up to 60 ℃ under agitation condition, reacted 5 hours, stops ventilation and heating, and with the product spinning that obtains, directly in 80 ℃ of dryings 8 hours, obtaining particle diameter was micron-sized magnesium basic carbonate after the cooling.
Embodiment 4:
The synthetic Marinco H of the about 2.7 μ m of 103.5g particle diameter is mixed with 759.3g water, obtain the 0.8L solid content and be 12% magnesium hydroxide slurry, grind 15min, make its particle diameter, place autoclave then, feed the CO of 0.55Mpa less than 20 μ m with colloidal mill
2Pressure is warming up to 120 ℃ under agitation condition, reacted 3 hours, stops ventilation and heating, and with the product spinning that obtains, directly in 120 ℃ of dryings 5 hours, obtaining particle diameter was micron-sized magnesium basic carbonate after the cooling.
Claims (1)
1. the clean method for preparing of a magnesium basic carbonate is characterized in that, its concrete preparation method is following:
Steps A: adding quality to granularity in less than the natural mineral brucite of 500 μ m or synthetic Marinco H be its 6.7-33.3 deionized water doubly, and mixing being placed on colloidal mill or grinding in ball grinder, makes its granularity less than 50 μ m;
Step B: the slurries that steps A is obtained place autoclave, impose the CO of 0.08-1.0MPa to it
2Gaseous tension, and be warming up to 50-180 ℃, reaction was taken out product after 0.5-20 hour under agitation condition, and in 50-180 ℃ time dry 1-10 hour, obtaining particle diameter was micron-sized magnesium basic carbonate after the direct centrifuging.
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| CN2010102962510A CN101935059B (en) | 2010-09-29 | 2010-09-29 | Clean preparation method for basic magnesium carbonate |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102275959B (en) * | 2011-07-18 | 2013-07-03 | 内蒙古昶泰资源循环再生利用科技开发有限责任公司 | Process for producing high-purity basic magnesium carbonate from dolomite |
| CN103011210B (en) * | 2012-12-11 | 2014-06-04 | 清华大学 | Method for preparing and synthesizing magnesium carbonate from magnesium chloride and carbon dioxide |
| CN104386717B (en) * | 2014-11-17 | 2016-04-20 | 山东航通工贸有限公司 | A kind of method preparing high purity magnesium hydroxide fire retardant |
| CN104495884B (en) * | 2014-11-21 | 2016-11-30 | 河北科技大学 | basic magnesium carbonate and preparation method thereof |
| CN105755297B (en) * | 2014-12-19 | 2018-09-04 | 中国科学院过程工程研究所 | A kind of method that high pressure carbonization carries magnesium |
| CN110446685B (en) * | 2017-01-25 | 2022-09-06 | 南洋理工大学 | Concrete mixture based on reinforced reactive magnesia cement |
| CN108147438B (en) * | 2017-12-25 | 2023-09-19 | 河北镁神科技股份有限公司 | Slurry combined bed reaction device for producing basic magnesium carbonate and application method thereof |
| CN109110790B (en) * | 2018-11-05 | 2020-12-22 | 河北镁神科技股份有限公司 | Preparation process of anti-skid magnesium carbonate block |
| CN109437258B (en) * | 2018-12-05 | 2021-02-26 | 河北镁神科技股份有限公司 | Preparation method of magnesium oxide powder special for heat-conducting plastic |
| CN113264751A (en) * | 2021-05-24 | 2021-08-17 | 北京科技大学 | Porous material using magnesium solid carbon product as raw material and preparation method thereof |
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| CN1680192A (en) * | 2004-04-07 | 2005-10-12 | 田玉海 | Production of light magnesium carbonate or light magnesium oxide |
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|---|---|---|---|---|
| CN1680192A (en) * | 2004-04-07 | 2005-10-12 | 田玉海 | Production of light magnesium carbonate or light magnesium oxide |
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