CN100575262C - A kind of method for preparing ultra-fine calcium oxide from dolomite - Google Patents

A kind of method for preparing ultra-fine calcium oxide from dolomite Download PDF

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CN100575262C
CN100575262C CN200810063043A CN200810063043A CN100575262C CN 100575262 C CN100575262 C CN 100575262C CN 200810063043 A CN200810063043 A CN 200810063043A CN 200810063043 A CN200810063043 A CN 200810063043A CN 100575262 C CN100575262 C CN 100575262C
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dolomite
calcium oxide
ultra
powder
fine calcium
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CN101318681A (en
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叶瑛
陈雪刚
吕双双
夏枚生
张路
姚志通
李秀悌
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Zhejiang University ZJU
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Zhejiang University ZJU
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Abstract

The invention discloses a kind of method for preparing ultra-fine calcium oxide from dolomite.Dolomite has extremely abundant standing stock in China, and its main component is that chemical general formula is MgCa (CO 3) 2Rhombspar.By simple several steps: at first dolomite calcined powder and the reaction of dolomite acidizing fluid are realized that calcium magnesium separates; Drip alkaline solution in the calcium chloride solution that obtains then after calcium magnesium separates, the calcium hydroxide particulate of acquisition obtains having active ultra-fine calcium oxide powder after calcining.Ultra-fine calcium oxide has a wide range of applications in fields such as fire retardant, sorbent material, weighting agents.The method for preparing ultra-fine calcium oxide that the present invention proposes, its technical process is simple, and facility investment is few, running cost is cheap, the calcium oxide purity that makes is more than 90%, and obtains to have the super fine magnesium hydroxide powder of economic worth simultaneously, is a cost-effective method for preparing ultra-fine calcium oxide.

Description

A kind of method for preparing ultra-fine calcium oxide from dolomite
Technical field
The present invention relates to the preparation method of compound, relate in particular to a kind of method for preparing ultra-fine calcium oxide from dolomite.
Background technology
Dolomite is calcium magnesium resource important on the earth, in China extremely abundant standing stock is arranged.But the dolomitic development and use degree of China is very low at present, and raw ore is only sold in most of mine.
Ultra-fine CaO has very strong adsorptive power owing to have high-specific surface area, high reactivity, has been used to the high-concentration fluorine-contained waste water of replacing lime breast solution-treated at present, and mercury in the adsorbable processing waste water and mercury chloride etc.Because CaO low price, abundant raw materials also generally are used as the sulphur-fixing agent in the desulfurization technology, but effective elimination H 2S and COS.It high adsorption capacity that possesses, low preparation cost, longly recycle the life-span and good antiwear characteristics makes it to become preferred elevated temperature CO 2Remove agent.As soil release agent, the flue gas that produces is burned in adsorbable treating refuse through activatory CaO.
Calcium oxide still is a kind of broad-spectrum weighting agent.In corundum pouring material, behind the doping CaO, can significantly improve its strength retention and heat-shock resistance.Add CaO in the flying dust, can effectively reduce the content of flying dust leach liquor heavyweight vehicle metal trace elements A s, Se and Cr.CaO and other oxide Ms gO, Al 2O 3, SiO 2When forming devitrified glass, the increase of CaO content can promote the sintering densification of microcrystalline glass powder, and increases the specific inductivity and the thermal expansivity of sample.At 10NiO-NiFe 2O 4Doping The addition of C aO in the composite ceramics can increase the density and the radial shrinkage ratio of pottery, and promotes the growth of ceramic crystalline grain.The adding of CaO auxiliary agent can strengthen Ni/Al 2O 3Activity of such catalysts and anti-carbon deposit performance.Be filled in the polyethylene through the calcium oxide after the surface treatment, can greatly strengthen its mechanical property, and have light degradation property preferably.One of solid base catalyst that ultra-fine CaO is still commonly used has high reactivity, catalyst life is long and advantage such as cheap, is applied in the multiple organic synthesis.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of method for preparing ultra-fine calcium oxide from dolomite is provided.
It comprises the steps:
1) with the abundant broken dolomite powder of 100 grams, calcined 3~8 hours in 900~1600 ℃ of stoves, obtain dolomite calcining product, its chemical structure of general formula is (Mg, Ca) O;
2) with the abundant broken dolomite powder of 100~150 grams, join in the hydrochloric acid soln of 1~4 liter of 0.5~2mol/L, stirring reaction 0.5~3 hour, the elimination undissolved residue obtains the dolomite acidizing fluid;
3) dolomite is calcined in the deionized water that product joins 30~90 ℃ of 200~1000mL and carried out digestion process; Remove residue, add the dolomite acidizing fluid, stirring reaction 0.5~3 hour, centrifugation, washing, the solid phase oven dry obtains the super fine magnesium hydroxide powder;
4) in above-mentioned parting liquid, slowly splash into the alkaline solution of 0.5~5 liter of 0.4~4N, and add 0.5~5 the gram dispersion agent, in 50~90 ℃ of water-baths, reacted 0.5~5 hour, centrifugation, washing, solid product oven dry, in 600~900 ℃ of stoves, calcined 2~8 hours, cooling obtains the ultra-fine calcium oxide powder.
Described dolomite is natural output rock, and its essential mineral composition is a rhombspar, and chemical structure of general formula is CaMg (CO 3) 2Ultra-fine calcium oxide is that median size is the CaO powder of 10~500nm.Alkaline solution is one or more in NaOH, KOH, urea or the ammonia soln.Dispersion agent is one or more in tripoly phosphate sodium STPP, polyoxyethylene glycol, citric acid or the Sodium dodecylbenzene sulfonate.
The method for preparing ultra-fine calcium oxide from dolomite that the present invention proposes is starting material with natural dolomite, and cheap, its preparation technology's flow process is very simple, and equipment investment cost is low, produces waste liquid in process of production hardly, helps environment protection.The calcium oxide powder particle homogeneous that makes, median size has advantages such as high-specific surface area, high reactivity, high-temperature stable between 10~500nm, be with a wide range of applications in fields such as weighting agent, fire retardant, sorbent materials.
Embodiment
Advantages such as that ultra-fine calcium oxide has is high temperature resistant, high adsorption capacity, high reactivity have been widely used as sulphur-fixing agent, CO at present 2Removing the weighting agent of materials such as agent, pottery, the catalyzer of organic synthesis etc., is a kind of purposes inorganic powder very widely.
The present invention proposes and a kind ofly prepare the method for ultra-fine calcium oxide from dolomite, its preparation technology's flow process is simple, low production cost.Embodiment may further comprise the steps:
The first step of preparation is to get the fully broken dolomite of 100 grams, calcines 3~8 hours in 900~1600 ℃ of stoves, and dolomite is progressively sloughed CO in the calcination process 2, forming chemical structure of general formula is that (Mg, the Ca) dolomite calcined powder of O wherein contains a small amount of SiO 2, Fe 2O 3, Al 2O 3Etc. less important component.
MgCa(CO 3) 2→MgO+CaO+2CO 2
Other gets the fully broken dolomite of 100~150 grams, joins in the hydrochloric acid soln of 1~4 liter of 0.5~2mol/L, and stirring reaction 0.5~3 hour behind the elimination undissolved residue, obtains with MgCl 2And CaCl 2It is main dolomite acidizing fluid; Ca, Mg constituent content are slightly more than the calcium-magnesium content in the dolomite calcined powder in the acidizing fluid.
MgCa(CO 3) 2+4HCl→MgCl 2+CaCl 2+2H 2O+2CO 2
Second step of preparation is dolomite calcined powder to be joined in the deionized water of 30~90 ℃ of 200~1000mL carry out digestion process; Forging CaO in the powder and MgO reacts in warm water and becomes Mg (OH) 2And Ca (OH) 2After removing residue, in Digestive system, add dolomite acidizing fluid, stirring reaction 0.5~3 hour; According to reaction: Ca (OH) 2+ MgCl 2→ CaCl 2+ Mg (OH) 2The reaction Gibbs function become, Δ G=-94.85KJ/mol, this reaction can spontaneously be carried out at normal temperatures.Calcium-magnesium content in the acidizing fluid is more than the content in the dolomite calcined powder, thereby guaranteed that this reaction can finish more completely.After finishing, reaction obtains the suspension of magnesium hydroxide and calcium chloride.
MgO+CaO+H 2O→Mg(OH) 2+Ca(OH) 2
Ca(OH) 2+MgCl 2→CaCl 2+Mg(OH) 2
The 3rd step of preparation is the suspension eccentric cleaning that will obtain, and obtains the super fine magnesium hydroxide powder after the solid phase oven dry; In clear liquid, slowly splash into the alkaline solution of 0.5~5 liter of 0.4~4N, and add 0.5~5 gram dispersion agent, be reflected in 50~90 ℃ of water-baths and carried out 0.5~5 hour.The drop rate of control alkaline solution can evenly precipitate calcium hydroxide slowly in the reaction process; The effect of dispersion agent is to make to produce repulsive force between the particulate, and forms layer protecting film at microparticle surfaces, thereby reduces the reunion between the particle.
Ca 2++2OH -→Ca(OH) 2
The precipitation that obtains was calcined 2~8 hours in 600~900 ℃ of stoves after centrifugal, cleaning, oven dry, and superfine calcium hydroxide powder is decomposed into CaO, promptly gets the ultra-fine calcium oxide powder after the cooling.
Further specify the present invention below in conjunction with embodiment.
Embodiment 1:
1) with the abundant broken dolomite powder of 100 grams, calcining is 8 hours in 900 ℃ of stoves, obtains dolomite calcining product, and its chemical structure of general formula is (Mg, Ca) O;
2) with the abundant broken dolomite powder of 100 grams, join in the hydrochloric acid soln of 1 liter of 2mol/L, stirring reaction 3 hours, the elimination undissolved residue obtains the dolomite acidizing fluid;
3) dolomite is calcined in the deionized water that product joins 30 ℃ of 1000mL and carried out digestion process; Remove residue, add the dolomite acidizing fluid, stirring reaction 0.5 hour, centrifugation, washing, the solid phase oven dry obtains the super fine magnesium hydroxide powder;
4) slowly splash into the NaOH solution of 5 liters of 0.4N in above-mentioned parting liquid, and add 0.5 gram polyoxyethylene glycol, reaction is 0.5 hour in 90 ℃ of water-baths, centrifugation, washing, solid product oven dry, calcining is 8 hours in 600 ℃ of stoves, and cooling obtains the ultra-fine calcium oxide powder.
Embodiment 2:
1) with the abundant broken dolomite powder of 100 grams, calcining is 3 hours in 1600 ℃ of stoves, obtains dolomite calcining product, and its chemical structure of general formula is (Mg, Ca) O;
2) with the abundant broken dolomite powder of 150 grams, join in the hydrochloric acid soln of 4 liters of 0.5mol/L, stirring reaction 0.5 hour, the elimination undissolved residue obtains the dolomite acidizing fluid;
3) dolomite is calcined in the deionized water that product joins 90 ℃ of 200mL and carried out digestion process; Remove residue, add the dolomite acidizing fluid, stirring reaction 3 hours, centrifugation, washing, the solid phase oven dry obtains the super fine magnesium hydroxide powder;
4) slowly splash into the KOH solution of 0.5 liter of 4N in above-mentioned parting liquid, and add 5 gram citric acids, reaction is 5 hours in 50 ℃ of water-baths, centrifugation, washing, solid product oven dry, and calcining is 2 hours in 900 ℃ of stoves, and cooling obtains the ultra-fine calcium oxide powder.
Embodiment 3:
1) with the abundant broken dolomite powder of 100 grams, calcining is 6 hours in 1200 ℃ of stoves, obtains dolomite calcining product, and its chemical structure of general formula is (Mg, Ca) O;
2) with the abundant broken dolomite powder of 120 grams, join in the hydrochloric acid soln of 2 liters of 1mol/L, stirring reaction 1 hour, the elimination undissolved residue obtains the dolomite acidizing fluid;
3) dolomite is calcined in the deionized water that product joins 50 ℃ of 500mL and carried out digestion process; Remove residue, add the dolomite acidizing fluid, stirring reaction 2 hours, centrifugation, washing, the solid phase oven dry obtains the super fine magnesium hydroxide powder;
4) slowly splash into the urea soln of 2 liters of 2N in above-mentioned parting liquid, and add 3 gram Sodium dodecylbenzene sulfonatees, reaction is 2 hours in 70 ℃ of water-baths, centrifugation, washing, solid product oven dry, calcining is 6 hours in 700 ℃ of stoves, and cooling obtains the ultra-fine calcium oxide powder.
Embodiment 4:
1) with the abundant broken dolomite powder of 100 grams, calcining is 5 hours in 1400 ℃ of stoves, obtains dolomite calcining product, and its chemical structure of general formula is (Mg, Ca) O;
2) with the abundant broken dolomite powder of 140 grams, join in the hydrochloric acid soln of 3 liters of 0.7mol/L, stirring reaction 2 hours, the elimination undissolved residue obtains the dolomite acidizing fluid;
3) dolomite is calcined in the deionized water that product joins 70 ℃ of 800mL and carried out digestion process; Remove residue, add the dolomite acidizing fluid, stirring reaction 1 hour, centrifugation, washing, the solid phase oven dry obtains the super fine magnesium hydroxide powder;
4) slowly splash into the ammonia soln of 3 liters of 1N in above-mentioned parting liquid, and add 1 gram tripoly phosphate sodium STPP, reaction is 3 hours in 80 ℃ of water-baths, centrifugation, washing, solid product oven dry, and calcining is 4 hours in 800 ℃ of stoves, and cooling obtains the ultra-fine calcium oxide powder.

Claims (5)

1. one kind prepares the method for ultra-fine calcium oxide from dolomite, it is characterized in that comprising the steps:
1) with the abundant broken dolomite powder of 100 grams, in 900~1600 ℃ of stoves, calcined 3~8 hours, obtain dolomite calcining product;
2) with the abundant broken dolomite powder of 100~150 grams, join in the hydrochloric acid soln of 1~4 liter of 0.5~2mol/L, stirring reaction 0.5~3 hour, the elimination undissolved residue obtains the dolomite acidizing fluid;
3) dolomite is calcined in the deionized water that product joins 30~90 ℃ of 200~1000mL and carried out digestion process; Remove residue, add the dolomite acidizing fluid, stirring reaction 0.5~3 hour, centrifugation, washing, the solid phase oven dry obtains the super fine magnesium hydroxide powder;
4) in above-mentioned parting liquid, slowly splash into the alkaline solution of 0.5~5 liter of 0.4~4N, and add 0.5~5 the gram dispersion agent, in 50~90 ℃ of water-baths, reacted 0.5~5 hour, centrifugation, washing, solid product oven dry, in 600~900 ℃ of stoves, calcined 2~8 hours, cooling obtains the ultra-fine calcium oxide powder.
2. according to claim 1ly a kind ofly prepare the method for ultra-fine calcium oxide from dolomite, it is characterized in that described dolomite is natural output rock, its essential mineral composition is a rhombspar.
3. according to claim 1ly a kind ofly prepare the method for ultra-fine calcium oxide, it is characterized in that described ultra-fine calcium oxide is that median size is the CaO powder of 10~500nm from dolomite.
4. according to claim 1ly a kind ofly prepare the method for ultra-fine calcium oxide, it is characterized in that described alkaline solution is one or more in NaOH, KOH, urea or the ammonia soln from dolomite.
5. according to claim 1ly a kind ofly prepare the method for ultra-fine calcium oxide, it is characterized in that described dispersion agent is one or more in tripoly phosphate sodium STPP, polyoxyethylene glycol, citric acid or the Sodium dodecylbenzene sulfonate from dolomite.
CN200810063043A 2008-07-08 2008-07-08 A kind of method for preparing ultra-fine calcium oxide from dolomite Expired - Fee Related CN100575262C (en)

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CN103058243B (en) * 2012-12-31 2015-05-27 杭州师范大学 Nanometer calcium oxide and application thereof
CN104016393B (en) * 2014-06-12 2016-01-06 合肥工业大学 A kind of by dolomite for light calcium carbonate and method of magnesium oxide
CN104402251B (en) * 2014-10-10 2016-09-14 韩秀峰 The production technology of a kind of construction material HOMACA and application process
CN109384255A (en) * 2018-11-30 2019-02-26 武汉科技大学 A kind of calcium oxide spherolite and preparation method thereof
CN110422865A (en) * 2019-08-13 2019-11-08 浙江钙科机械设备有限公司 A kind of aerated bricks calcium oxide production technology
CN112705155B (en) * 2019-10-25 2022-11-04 中国石油化工股份有限公司 Adsorbent for removing carbonyl sulfide, preparation method and application thereof
CN113173717A (en) * 2021-05-20 2021-07-27 江西福得利碳酸钙业有限责任公司 Calcium oxide production process and preparation device thereof

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