CN104003412B - A kind of method utilizing serpentine to carry magnesium white residue to prepare the solid carbon material of lithium silicate high temperature - Google Patents

A kind of method utilizing serpentine to carry magnesium white residue to prepare the solid carbon material of lithium silicate high temperature Download PDF

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Publication number
CN104003412B
CN104003412B CN201410270711.0A CN201410270711A CN104003412B CN 104003412 B CN104003412 B CN 104003412B CN 201410270711 A CN201410270711 A CN 201410270711A CN 104003412 B CN104003412 B CN 104003412B
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high temperature
serpentine
white residue
magnesium
temperature
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CN104003412A (en
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郑水林
狄永浩
牛保军
邹佳运
吴琼
刘翔
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China University of Mining and Technology Beijing CUMTB
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China University of Mining and Technology Beijing CUMTB
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Abstract

Utilize serpentine to carry magnesium white residue and prepare the method that lithium silicate high temperature consolidates carbon material, its technical scheme is as follows: (1) carries magnesium white residue for silicon source with serpentine, and choosing monohydrate lithium hydroxide is that high temperature solid state reaction is carried out in lithium source; (2) mol ratio (by both siliceous lithium atom molar ratio computings) of material controls in 1:4 ~ 4.2, and the calcining temperature of mixture in High Temperature Furnaces Heating Apparatus controls at 480 DEG C ~ 550 DEG C, and calcination time controls at 0.5 ~ 1.5h.Institute of the present invention prepared material is at CO 2to CO in atmosphere 2absorptive capacity is 15% ~ 30%, and maximum adsorption, maximum desorption rate all can reach more than 8%/min, and material is CO after three high temperature adsorption desorption circulations 2the relative initial value conservation rate of absorptive capacity is more than 85%.The raw materials used cheapness of the present invention, technique are simple, preparation process temperature is low, clean environment firendly, and prepared material can be used for CO in the high-temperature flue gas such as fossil fired power plant 2trapping and recovery.

Description

A kind of method utilizing serpentine to carry magnesium white residue to prepare the solid carbon material of lithium silicate high temperature
Technical field
The present invention relates to and a kind of carry magnesium white residue for raw material with serpentine and prepare lithium silicate type high temperature CO 2the method of collecting material, belongs to serpentine resource comprehensive utilization and the solid carbon of high temperature and energy-saving and emission-reduction field.
Background technology
Serpentine carry magnesium white residue be at present to serpentine resource (comprising the asbestos tailings for main component with serpentine) deep processing to fully utilize the main intermediate product of one of gained in the multiple valuable element processes such as magnesium contained by it, silicon, iron, nickel, serpentine through suitable treatment process (acidleach or salt molten after water logging) be extracted most magnesia component after remaining residue, the relatively handled serpentine material quantity accounting of its output usually can up to 40% ~ 50%, and the efficiency utilization direct relation that serpentine carries magnesium white residue the high-efficiency comprehensive utilization of serpentine resource.
Serpentine carries magnesium white residue with unformed silicon-dioxide for main chemical compositions, simultaneously containing a small amount of component such as magnesium oxide, calcium oxide, ferric oxide, according to the difference of serpentine complete processing, carries contained SiO in magnesium white residue 2content can from 55% ~ 95% change, and its specific surface area can reach 100 ~ 300m usually 2/ g is a kind of Silicon-rich product with bigger serface, high reaction activity.The composition and structure feature utilizing serpentine to carry magnesium white residue is added environmentally conscious materials lithium silicate that the preparation of suitable lithium source has a high added value and effectively can be overcome serpentine in the past and put forward the not high drawback of magnesium white residue utilising efficiency, thus directly can drive the high-efficiency comprehensive utilization of serpentine resource, and incidentally gather in the crops certain environmental benefit.
Along with highlighting of Global Greenhouse Effect, reduce CO 2discharge become one of most important technological line of reply climate warming.The solid carbon material of lithium silicate high temperature not only has at high temperature to CO as the solid carbon material of a kind of Efficient high-temperature emerging in recent years 2good absorption adaptability, also has larger CO 2absorptive capacity, faster adsorption/desorption speed and good cyclic regeneration, therefore at numerous CO 2show one's talent in high-temp solid absorption agent, the CO under the hot environments such as fossil fired power plant stack gas and vehicle exhaust can be widely used in 2trapping is significant to reduction of discharging.
The many factors that the synthesis that lithium silicate high temperature consolidates carbon material relates to, generally mainly contains selection two aspects of material choice and synthesis technique.Wherein, the selection of synthesis material generally includes again the selection in silicon source and the selection in lithium source; Synthesis technique aspect at present main with high temperature process heat technique for prevailing technology, but also have the process integration of sol-gel, saturated liquid phase impregnating and high temperature solid-state method.Researchists more both domestic and external once had corresponding research to the synthesis of the solid carbon material of lithium silicate high temperature, but great majority research be with chemical pure or slightly through the silicon-dioxide, tetraethoxy etc. of processing for silicon source, or with relatively inexpensive but non-renewable siliceous nonmetalliferous ore if diatomite, zeolite etc. are silicon source, report current in the selection in lithium source is also main mainly with Quilonum Retard, lithium nitrate, and the synthesis temperature of material is mostly more than 600 DEG C.Generally speaking, at present the solid carbon material preparation method of the lithium silicate high temperature of report exists that raw materials cost is higher, materials synthesis energy consumption is high mostly, and building-up reactions itself also has CO 2or the drawback that other dusty gass are discharged.
China has to compose and deposits abundant serpentine mineral resource and the huge asbestos tailings resource of accumulating amount, the comprehensive development and utilization of these resources especially as the asbestos tailings of secondary resource is extremely urgent, fully utilize the multiple valuable elements such as magnesium contained by it, silicon, iron, nickel and also prove the only way which must be passed, therefore, at present and followingly quite grow serpentine in one period and carry the source that magnesium white residue will have abundance.Up to now, there is not yet and carry magnesium white residue for raw material is to prepare the report of the patent of invention, Research Literature etc. of the solid carbon material of lithium silicate high temperature with serpentine.
Summary of the invention
Technical problem to be solved by this invention is to provide one can at high temperature efficient absorption CO 2the preparation method of the solid carbon material of lithium silicate high temperature, it carries magnesium white residue (carrying magnesium white residue containing asbestos tailings) for raw material with serpentine, add monohydrate lithium hydroxide and do lithium source, not only reduce preparation cost and the reaction process energy consumption of lithium silicate material, ensure that the building-up reactions not greenhouse gases of release new and dusty gas itself, the efficiency utilization also carrying magnesium white residue for serpentine opens new way.
Technical scheme of the present invention is: serpentine is carried magnesium white residue or carry magnesium white residue and monohydrate lithium hydroxide through the pretreated serpentine of corresponding technique and mix than fully by necessarily measuring, material after mixing is placed in high temperature reaction stove, under certain calcining temperature, calcine certain hour, after reaction terminates, namely obtain the solid carbon material of lithium silicate high temperature.
Concrete technology parameter of the present invention is:
Serpentine carries magnesium white residue and monohydrate lithium hydroxide is prepared burden by silicon lithium mol ratio 1:4 ~ 4.2, and the calcining temperature of mixture in High Temperature Furnaces Heating Apparatus is 480 DEG C ~ 550 DEG C, and calcination time is 0.5h ~ 1.5h.
The main reaction of preparation process is as follows:
Made lithium silicate material is to CO 2high temperature absorptive character test: the lithium silicate material being prepared gained by above method is placed in thermogravimetric analyzer, and passes to CO 2atmosphere, carries out CO in the temperature range of 400 DEG C ~ 800 DEG C 2high temperature absorption cycle is tested, and index of correlation test result is: CO 2absorptive capacity is 15% ~ 30%; Adsorption temp interval is 500 DEG C ~ 720 DEG C, and efficient adsorption temperature range is 670 DEG C ~ 710 DEG C; Desorption temperature interval is more than 720 DEG C, and efficient desorption temperature interval is 745 DEG C ~ 755 DEG C; Maximum adsorption, maximum desorption rate all reach more than 8%/min; Material after the circulation of three high temperature adsorption desorptions its to CO 2absorptive capacity compare the initial absorption capacity conservation rate of material more than 85%.
Material is through repeatedly CO 2after adsorption desorption circulation, it is to CO 2absorptive capacity conservation rate calculated by formula 1:
A=(C ÷ B) × 100%(formula 1)
In formula 1, the concrete meaning of each letter is as follows: A---absorptive capacity conservation rate; B---material absorbs CO for the first time 2time the absorptive capacity value that obtains; C---material is through repeatedly CO 2after adsorption desorption circulation, it is to CO 2absorptive capacity value.
Positively effect of the present invention: (1) the present invention carries magnesium white residue for raw material with the intermediate product serpentine of the serpentine of the cheapness Industrial Solid Waste asbestos tailings of main component (comprise with serpentine be) processing and utilization, makes the preparation cost of the solid carbon material of lithium silicate high temperature relatively low; Material preparation temperature controls below 550 DEG C, and calcination time controls within 1.5h, makes preparation process energy consumption lower; Choosing monohydrate lithium hydroxide is lithium source, makes whole synthetic reaction process by product be water, can not increase any pollution newly to environment.
(2) the solid carbon material of the lithium silicate high temperature synthesized by the present invention has high temperature adsorption, desorption rate faster, adsorption and desorption balance can be reached in the short period of time, and there is good cyclic regeneration performance, can be used for CO in the high-temperature flue gas such as fossil fired power plant 2separation and trapping, reduce carbon emission to reach, reclaim carbon resource, relax the effect of Greenhouse effect.
(3) the present invention is that the efficiency utilization that serpentine carries magnesium white residue opens a new way, is conducive to the high-efficiency comprehensive utilization promoting serpentine resource (asbestos tailings containing taking serpentine as main component).
Embodiment
Technical scheme of the present invention and effect is further illustrated below in conjunction with example.
Embodiment one: take serpentine and carry magnesium white residue (carrying magnesium technique gained through acidleach by serpentine) 25g, according to the SiO carried in magnesium white residue 2content (actual numerical value is 76.29%) takes the monohydrate lithium hydroxide (actual numerical value is 53.4g) of respective amount by silicon lithium atom mol ratio 1:4, and the two is even by the abundant blending dispersion of homogenizer; Mixture being placed in High Temperature Furnaces Heating Apparatus, at 500 DEG C, calcining 1h, take out after product cooling, slightly namely obtaining the solid carbon material powder of lithium silicate high temperature through breaing up.Obtained lithium silicate powder is placed in thermogravimetric analyzer, passes to CO 2atmosphere, monitoring instrument temperature rise rate 10 DEG C/min, control temperature scope is room temperature ~ 800 DEG C, carries out CO 2high temperature adsorption, desorption test; Test result display material starts CO about 500 DEG C time 2absorb, start significantly to accelerate CO after 670 DEG C 2absorption, to CO 698 DEG C time 2uptake rate reach maximum, up to 10.51%/min, when 710 DEG C, material is to CO 2absorption reach capacity, when its absorptive capacity is 26.72%, 751 DEG C, material is to CO 2desorption rate reach maximum, reach 8.33%/min, desorption is tending towards complete substantially after about 780 DEG C; In the temperature range of 400 DEG C ~ 800 DEG C, CO is carried out to material 2the performance test of high temperature absorption cycle, test result display after the circulation of three high temperature adsorption desorptions material to CO 2absorptive capacity is 23%, and calculating absorbed capability retention after three high temperature adsorption desorptions circulate by formula 1 is 86%.
Embodiment two: take serpentine and carry magnesium white residue (by snake halite method roasting-flooding magnesium technique gained) 25g, carries out the acidleach process of appropriateness, gets filter residue and dry and break up after filtration to it; According to the SiO in gained filter residue 2content (actual numerical value is 80.51%) takes the monohydrate lithium hydroxide (actual numerical value is 57.8g) of respective amount by silicon lithium atom mol ratio 1:4.1, and the two is even by the abundant blending dispersion of homogenizer; Mixture being placed in High Temperature Furnaces Heating Apparatus, at 550 DEG C, calcining 50min, take out after product cooling, slightly namely obtaining the solid carbon material powder of lithium silicate high temperature through breaing up.Obtained lithium silicate powder is placed in thermogravimetric analyzer, passes to CO 2atmosphere, monitoring instrument temperature rise rate 10 DEG C/min, control temperature scope is room temperature ~ 800 DEG C, carries out CO 2high temperature adsorption, desorption test; Test result display material starts CO about 520 DEG C time 2absorb, start significantly to accelerate CO after 680 DEG C 2absorption, to CO 710 DEG C time 2uptake rate reach maximum, up to 10.20%/min, when 722 DEG C, material is to CO 2absorption reach capacity, when its absorptive capacity is 21.88%, 748 DEG C, material is to CO 2desorption rate reach maximum, reach 9.49%/min, desorption is tending towards complete substantially after about 780 DEG C; In the temperature range of 400 DEG C ~ 800 DEG C, CO is carried out to material 2the performance test of high temperature absorption cycle, test result display after the circulation of three high temperature adsorption desorptions material to CO 2absorptive capacity is 19%, and calculating absorbed capability retention after three high temperature adsorption desorptions circulate by formula 1 is 87%.

Claims (2)

1. utilize serpentine to carry magnesium white residue and prepare the method that lithium silicate high temperature consolidates carbon material, it is characterized in that its processing step is as follows:
(1) serpentine is carried magnesium white residue or the serpentine after acid etching and carry magnesium white residue and monohydrate lithium hydroxide by silicon lithium mol ratio 1:4 ~ 4.2 batching and mixing;
(2) by step (1) mixture in High Temperature Furnaces Heating Apparatus in 480 DEG C ~ 550 DEG C temperature lower calcination 0.5h ~ 1.5h, namely obtain the solid carbon material of lithium silicate high temperature;
The feature of the solid carbon material of the lithium silicate high temperature adopting aforesaid method and processing step to prepare is: CO 2absorptive capacity 15% ~ 30%; Interval 500 DEG C ~ 720 DEG C of adsorption temp, efficient adsorption temperature range 670 DEG C ~ 710 DEG C; Desorption temperature interval is more than 720 DEG C, interval 745 DEG C ~ 755 DEG C of efficient desorption temperature; Maximum adsorption, maximum desorption rate all reach more than 8%/min; Material is CO after three high temperature adsorption desorption circulations 2absorptive capacity conservation rate is more than 85%.
2. a kind of method utilizing serpentine to carry magnesium white residue to prepare the solid carbon material of lithium silicate high temperature according to claim 1, it is characterized in that, described serpentine is carried magnesium white residue and is comprised serpentine and be that the asbestos tailings of main component is carried gained residue after extracting magnesium and serpentine after magnesium technique through acidleach and melted gained residue after extracting magnesium after roasting-flooding magnesium technique through salt with serpentine.
CN201410270711.0A 2014-06-18 2014-06-18 A kind of method utilizing serpentine to carry magnesium white residue to prepare the solid carbon material of lithium silicate high temperature Expired - Fee Related CN104003412B (en)

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CN102241516A (en) * 2010-05-13 2011-11-16 中国科学院上海硅酸盐研究所 Method for preparing Li4SiO4 ceramic powder by water-based sol-gel process
CN102826561A (en) * 2012-09-14 2012-12-19 合肥国轩高科动力能源有限公司 Method for synthesizing lithium silicate with rick husk serving as raw material

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