CN102001693B - Process for preparing light magnesium oxide and calcium carbonate powder by utilizing dolomite acid method - Google Patents

Process for preparing light magnesium oxide and calcium carbonate powder by utilizing dolomite acid method Download PDF

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CN102001693B
CN102001693B CN2010105776468A CN201010577646A CN102001693B CN 102001693 B CN102001693 B CN 102001693B CN 2010105776468 A CN2010105776468 A CN 2010105776468A CN 201010577646 A CN201010577646 A CN 201010577646A CN 102001693 B CN102001693 B CN 102001693B
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calcium carbonate
ammonia
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姚文贵
姜晓谦
马鸿文
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HAOQINGFIREWOOD (BEIJING) TECHNOLOGY Co Ltd
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Abstract

The invention relates to a process for preparing light magnesium oxide and calcium carbonate powder by utilizing a dolomite acid method, which comprises: dolomite is crushed and pulverized into powder; the powder is dissolved by utilizing hydrochloric acid to be prepared into a solution with key components of MgCl2 and CaCl2; the pH value is adjusted, the ions of Fe3<+>, Al3<+> and the like in the solution are eliminated, and the solution becomes a pure MgCl2 and CaCl2 solution; ammonia is introduced into the solution to react so that Mg2<+> is converted into Mg(OH)2 precipitations, and the light magnesium oxide powder is prepared through filtering, washing, drying and calcining; the filtrate is prepared into calcium carbonate crystals through continuous ammonia introduction and carbonization; and the calcium carbonate crystals are dried to prepare the light calcium carbonate powder. The process has the advantages that the design is reasonable; the energy consumption is low; the purities of the prepared light magnesium oxide and the calcium carbonate are above 98%; the resource utilization ratio of the dolomite is larger than 95%; and the process is worthy of being popularized and implemented.

Description

The scud acid system prepares the technology of light magnesium oxide and calcium carbonate powder
Technical field
The present invention relates to the technology that a kind of scud acid system prepares light magnesium oxide and calcium carbonate powder.
Background technology
Scud is a kind of more common carbonatite, and the essential mineral composition is a rhombspar.The explored scud stock number in the whole world reaches about more than 50,000,000,000 tons, and Chinese fine scud reserves surpass 4,000,000,000 tons, spread all over provinces and regions such as Liaoning, Hebei, Shanxi, Sichuan, Hunan, Hubei, Henan, Shaanxi, Jilin, Jiangsu.
Light magnesium oxide is a kind of important industrial inorganic salt product, can be used for making the filler as polishing agent, tackiness agent, paint and paper such as pottery, enamel, fire-clay crucible and refractory brick; Also be used for industries such as glass, dyestuff, phenoplast.Therefore, light magnesium oxide is that magnesium compound is most important applications one of product the most widely in the product.
Light calcium carbonate also is a kind of important mineral filler, is widely used in industries such as rubber, plastics, coating, papermaking, building.China's light calcium carbonate demand is bigger, and the product requirement quality is higher.
At present; China concentrates on industries such as metallurgy, chemical industry, building materials and agricultural to dolomitic utilization; Be mainly used in and produce MAGNESIUM METAL 99, magnesium compound, magnesite refractory, magnesium gelatinous material, Production of Ceramics raw material etc., but production process exist energy consumption high, shortcomings such as certain environmental pollution, waste sludge discharge amount are big are arranged.
Summary of the invention
The object of the present invention is to provide a kind of scud acid system to prepare the technology of light magnesium oxide and calcium carbonate powder.The present invention makes full use of Natural manganese dioxide and the quicklime in the scud, makes high value-added product.The energy consumption of this technological process is low, is convenient to implement to promote.
For realizing above-mentioned purpose, the present invention takes following technical scheme:
A kind of scud acid system prepares the technology of light magnesium oxide and calcium carbonate powder, and employing scud is raw material, comprises following preparation section:
(1), raw materials pretreatment operation: the scud fragmentation is become the scud powder with ball milling;
(2), scud acid dissolves operation: by HCl and rhombspar mol ratio is 2～2.1, and it is to dissolve in 25%～30% the hydrochloric acid soln that the scud powder is joined mass percent, obtains containing Ca after the filtration 2+, Mg 2+, Fe 3+, Al 3+, Fe 2+And Cl -Isoionic solution, wherein, Ca 2+And Mg 2+Concentration is 1～2mol/L;
(3), removal of impurities operation: contain Ca what operation (2) obtained 2+, Mg 2+, Fe 3+, Al 3+, Fe 2+And Cl -In the isoionic solution, press Fe 2+With the NaClO mol ratio be 1: (2～4) add NaClO solution, feed ammonia then, and regulating pH value is 5～7, and through filtration, the filtrating that obtains is the purified MgCl of containing 2And CaCl 2Solution, filter cake is Fe (OH) 3And Al (OH) 3Deposition emits as solid slag;
(4), in the heavy magnesium operation of ammonia process: to the purified MgCl that contains 2And CaCl 2Solution in feed ammonia, at 40～70 ℃ of following reaction 1～3h, wherein, ammonia and MgCl 2Mol ratio is (2.5～3): 1, and through filtering, filter cake obtains magnesium hydrate precipitate through washing drying again; Filtrating is for containing NH 4 +, Ca 2+, Mg 2+, Cl -And OH -Solution;
(5), Marinco H calcination process: dried Marinco H is calcined 1-2h down at 600～800 ℃, promptly make the light magnesium oxide goods;
(6), calcium carbonate powder production technique: will contain NH 4 +, Ca 2+, Mg 2+, Cl -, OH -Solution at room temperature feed ammonia, maintenance solution is pH>=7.5, uses percent by volume greater than 40% CO again 2Carbonization, carbonization time are at 45～90min, and the filter cake after the filtration is ZG 301, through washing, drying, promptly make light calcium carbonate powder goods again.
Prepare in the technology of light magnesium oxide and calcium carbonate powder, at scud acid system of the present invention in step
(1) in, fragmentation becomes the rhombspar powder below 200 orders with ball milling, and promptly the particle diameter of scud powder is less than 74 μ m.
Prepare in the technology of light magnesium oxide and calcium carbonate powder, at scud acid system of the present invention in step
(6) in, filtrate filtered is the ammonium chloride solution that contains small amount of calcium, mg ion, becomes ammonia chloride crystal through evaporation concentration, and this ammonia chloride crystal obtains hydrogenchloride and ammonia through decomposition, and wherein, hydrogenchloride returns step
(2) recycle in the operation is dissolved in scud acid; Ammonia returns recycle in the calcium carbonate powder production technique of the heavy magnesium operation of ammonia process and/or step (6) of removal of impurities operation, step (4) of step (3).
Advantage of the present invention is:
The technological design that scud acid system of the present invention prepares light magnesium oxide and calcium carbonate powder is reasonable, and energy consumption is low, and light magnesium oxide that makes and lime carbonate purity are all more than 98%, and the scud resource utilization is worth carrying out promotion and implementation greater than 95%.
Description of drawings
Fig. 1 is the technology process flow figure that scud acid system of the present invention prepares light magnesium oxide and calcium carbonate powder.
Embodiment
Scud acid system of the present invention prepares the technology of light magnesium oxide and calcium carbonate powder, and employing scud is raw material, and production process comprises that the acid of raw materials pretreatment, scud is dissolved, removal of impurities, the heavy magnesium of ammonia process, Marinco H calcining and lime carbonate preparation section.
Behind the broken ball milling of scud, it is joined massfraction is to dissolve in 25%～30% the hydrochloric acid soln.Get supernatant liquid, add little amount of N aClO solution, feed ammonia then and regulate the pH value between 5～7,, obtain purified MgCl through filtering 2, CaCl 2Solution.To wherein feeding ammonia, react 1～3h again, through filtering, filter cake obtains magnesium hydrate precipitate through washing, drying; Deposition obtains the light magnesium oxide powder product through calcining; Filtrating obtains the light calcium carbonate powder product through logical ammonia, carbonization, filtration, washing, drying.
Prepare in the technology of light magnesium oxide and calcium carbonate powder at scud acid system of the present invention, in the described raw materials pretreatment operation, after the scud fragmentation, below ball milling to 200 order, promptly the particle diameter of scud powder is less than below the 74 μ m.
Prepare in the technology of light magnesium oxide and calcium carbonate powder at scud acid system of the present invention, the acid of described scud is dissolved in the operation, and it is to dissolve in 25%～30% the hydrochloric acid soln that dolomite rock powder is joined massfraction, obtains containing Ca after the filtration 2+, Mg 2+, Fe 3+, Al 3+, Fe 2+, Cl -Isoionic solution.Solution gets into the removal of impurities operation.
Prepare in the technology of light magnesium oxide and calcium carbonate powder at scud acid system of the present invention, described removal of impurities operation comprises by Fe 2+With the NaClO mol ratio be 1: (2～4) add NaClO solution, feed ammonia then and regulate pH value between 5～7, through filtration, obtain purified MgCl 2, CaCl 2Solution.Solution gets into the heavy magnesium operation of ammonia process.
Prepare in the technology of light magnesium oxide and calcium carbonate powder at scud acid system of the present invention, in the heavy magnesium operation of described ammonia process, Ca in the solution 2+, Mg 2+Concentration to wherein feeding ammonia, is down reacted 1～3h at 40～70 ℃ at 1～2mol/L, and through filtering, filter cake obtains magnesium hydrate precipitate through washing, drying again; Filtrating is for containing NH 4 +, Ca 2+, Mg 2+, Cl -, OH -Solution, get into the lime carbonate preparation section.
Prepare in the technology of light magnesium oxide and calcium carbonate powder at scud acid system of the present invention, described Marinco H calcination process, magnesium hydrate precipitate is calcined 1～2h under 600～800 ℃, promptly make light magnesium oxide powder goods.
Prepare in the technology of light magnesium oxide and calcium carbonate powder at scud acid system of the present invention, described lime carbonate production technique comprises at room temperature feeding ammonia and volume(tric)fraction greater than 40% CO with containing calcium solution 2, obtain ZG 301, through washing, drying, promptly make light calcium carbonate powder goods again.
Prepare in the technology of light magnesium oxide and calcium carbonate powder at scud acid system of the present invention, remaining filtrating being contains the ammonium chloride solution of small amount of calcium, mg ion, can become ammonia chloride crystal through evaporation concentration.Ammonia chloride crystal can decompose preparation hydrogenchloride and ammonia, returns the hydrolysis procedure recycle.
Scud acid system of the present invention prepares the technology of light magnesium oxide and calcium carbonate powder, comprises mainly that the acid of raw materials pretreatment, scud is dissolved, removal of impurities, the heavy magnesium of ammonia process, Marinco H calcining and lime carbonate preparation section.Its typical process flow is as shown in Figure 1.As shown in Figure 1, the scud powder joined in the hydrochloric acid dissolve, obtaining filtrating after the filtration is to contain Ca 2+, Mg 2+, Fe 3+, Al 3+, Cl -Deng solution; Filter cake is a small amount of residue.Containing Ca 2+, Mg 2+, Fe 3+, Al 3+, Cl -In solution, add NaClO and feed NH 3, after the filtration, the filter cake that obtains is for containing Fe (OH) 3And Al (OH) 3Waste residue; Filtrating is for containing Ca 2+, Mg 2+, Cl -Solution.To containing Ca 2+, Mg 2+, Cl -Feed NH in the solution 3, after the filtration, filter cake is Mg (OH) 2Deposition; Filtrating is for containing Ca 2+, Cl -, NH 4 +, OH -Solution.Mg (OH) 2Deposition obtains magnesium oxide powder and H through calcining 2O; Containing Ca 2+, Cl -, NH 4 +, OH -Feed NH in the solution 3, and use CO 2Carbonization after the filtration, obtains calcium carbonate powder and NH 4Cl solution.
Experimental raw: certain place of production scud ore sample (LD-09), the chemical composition analysis result sees table 1.
Chemical composition analysis result (the w of table 1 rhombspar ore (LD-09) B/ %)
Figure BSA00000377038900041
(1) scud through broken ball milling, be sized to granularity＜74 μ m, take by weighing 100g, join the 268g massfraction and be in 30% the hydrochloric acid soln and dissolve, obtain containing Ca 2+, Mg 2+, Fe 3+, Al 3+, Fe 2+, Cl -Isoionic solution and a small amount of waste residue.The X-ray powder diffraction analytical results shows that the main thing of waste residue is silicon-dioxide mutually.
(2) to containing Ca 2+, Mg 2+, Fe 3+, Al 3+, Fe 2+, Cl -Add 2mL9wt%NaClO solution in the isoionic solution, feed ammonia then and regulate the pH value between 5～7,, obtain the purified MgCl of containing through filtering 2, CaCl 2Solution, the small amount of solid waste residue of discharging is mainly Fe (OH) 3And Al (OH) 3Deposition.
(3) to the purified MgCl that contains 2, CaCl 2Solution in feed ammonia, at 40～70 ℃ of following reaction 1.5～2.5h, wherein, ammonia and MgCl 2Mol ratio is 3: 1; Through filtering, filter cake obtains about 28g magnesium hydrate precipitate through washing, drying again; Filtrating is for containing NH 4 +, Ca 2+, Mg 2+, Cl -, OH -Solution.
(4) above-mentioned Marinco H is calcined 1-2h down at 800 ℃, make the about 19g of light magnesium oxide product.Its chemical composition analysis result and the chemical industry standard HG/T 2573-2006 of the People's Republic of China contrast is visible, and the product properties index meets light magnesium oxide Industrial products industry acceptable end product standard.
In the present embodiment, the chemical composition analysis result of prepared light magnesium oxide powder sees table 2.
Chemical composition analysis result (the w of table 2 light magnesium oxide goods B/ %)
Figure BSA00000377038900042
(5) calcium solution that contains that makes in (3) is at room temperature fed ammonia maintenance solution alkalescence, use the CO of concentration again greater than 40vt% 2Gas carbonization, carbonization time are 1h, through filtering, washing, obtain the about 37g of light calcium carbonate.Its chemical composition analysis result and the chemical industry standard HG/T 2567-2006 of the People's Republic of China contrast is visible, and product properties meets industrial active precipitated chalk industry acceptable end product standard.In the present embodiment, the chemical composition analysis result of prepared light calcium carbonate powder sees table 3.
Chemical composition analysis result (the w of table 3 light calcium carbonate goods B/ %)
Figure BSA00000377038900051

Claims (3)

1. a scud acid system prepares the technology of light magnesium oxide and calcium carbonate powder, it is characterized in that employing scud is raw material, comprises following preparation section:
(1), raw materials pretreatment operation: the scud fragmentation is become the scud powder with ball milling;
(2), scud acid dissolves operation: by HCl and rhombspar mol ratio is 2～2.1, and it is to dissolve in 25%～30% the hydrochloric acid soln that the scud powder is joined mass percent, obtains containing Ca after the filtration 2+, Mg 2+, Fe 3+, Al 3+, Fe 2+And Cl -Ion solution, wherein, Ca 2+And Mg 2+Concentration is 1～2mol/L;
(3), removal of impurities operation: contain Ca what operation (2) obtained 2+, Mg 2+, Fe 3+, Al 3+, Fe 2+And Cl -In the ion solution, press Fe 2+With the NaClO mol ratio be 1: (2～4) add NaClO solution, feed ammonia then, and regulating pH value is 5～7, and through filtration, the filtrating that obtains is the purified MgCl of containing 2And CaCl 2Solution, filter cake is Fe (OH) 3And Al (OH) 3Deposition emits as solid slag;
(4), in the heavy magnesium operation of ammonia process: to the purified MgCl that contains 2And CaCl 2Solution in feed ammonia, at 40～70 ℃ of following reaction 1～3h, wherein, ammonia and MgCl 2Mol ratio is (2.5～3): 1, and through filtering, filter cake obtains magnesium hydrate precipitate through washing drying again; Filtrating is for containing NH 4 +, Ca 2+, Mg 2+, Cl -And OH -Solution;
(5), Marinco H calcination process: dried Marinco H is calcined 1-2h down at 600～800 ℃, promptly make the light magnesium oxide goods;
(6), calcium carbonate powder production technique: will contain NH 4 +, Ca 2+, Mg 2+, Cl -, OH -Solution at room temperature feed ammonia, maintenance solution is pH>=7.5, uses percent by volume greater than 40% CO again 2Carbonization, carbonization time are at 45～90min, and the filter cake after the filtration is ZG 301, through washing, drying, promptly make light calcium carbonate powder goods again.
2. scud acid system as claimed in claim 1 prepares the technology of light magnesium oxide and calcium carbonate powder, it is characterized in that, in step (1), fragmentation becomes the rhombspar powder below 200 orders with ball milling, and promptly the particle diameter of scud powder is less than 74 μ m.
3. scud acid system as claimed in claim 1 prepares the technology of light magnesium oxide and calcium carbonate powder; It is characterized in that in step (6), filtrate filtered is the ammonium chloride solution that contains small amount of calcium, mg ion; Become ammonia chloride crystal through evaporation concentration; This ammonia chloride crystal obtains hydrogenchloride and ammonia through decomposition, and wherein, recycle in the operation is dissolved in the scud acid that hydrogenchloride returns step (2); Ammonia returns recycle in the calcium carbonate powder production technique of the heavy magnesium operation of ammonia process and/or step (6) of removal of impurities operation, step (4) of step (3).
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CN102225775A (en) * 2011-05-13 2011-10-26 河北科技大学 Process for producing magnesium hydroxide and calcium carbonate by dolomite conversion method
CN102730734B (en) * 2012-06-18 2015-05-20 佛山市松宝电子功能材料有限公司 Purification method for calcium carbonate
UA103292C2 (en) * 2013-04-10 2013-09-25 Валерій Іванович Семеній Process for processing of solid wastes of chemical treatment of sodium chloride brines at production of sodium chloride
CN104386728B (en) * 2014-11-05 2016-10-05 北京化工大学 A kind of method that acidolysis lime stone prepares homogeneous phase nanometer aragonite calcium carbonate
CN104611763A (en) * 2014-12-25 2015-05-13 武汉工程大学 Technology of using phosphate tailing as raw material to produce in-situ modified nano-magnesium hydroxide whisker
CN107032384B (en) * 2017-06-05 2019-02-22 中南大学 A method of separating and recovering calcium and magnesium from Calcium magnesium minerals
CN109437606A (en) * 2018-12-20 2019-03-08 五邑大学 A kind of preparation method of flake nano magnesium oxide powder
CN109809442B (en) * 2018-12-28 2023-11-17 西安科技大学 System and method for producing magnesium hydroxide and light calcium carbonate by purifying ash in calcium carbide furnace

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