CN103408043B - Method for preparing high-purity magnesium oxide with serpentine as raw material - Google Patents
Method for preparing high-purity magnesium oxide with serpentine as raw material Download PDFInfo
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- CN103408043B CN103408043B CN201310351492.4A CN201310351492A CN103408043B CN 103408043 B CN103408043 B CN 103408043B CN 201310351492 A CN201310351492 A CN 201310351492A CN 103408043 B CN103408043 B CN 103408043B
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Abstract
The invention relates to a method for preparing high-purity magnesium oxide with serpentine as a raw material. The method specifically comprises the steps that: (1) serpentine is crushed, and is activated by calcining; (2) 50wt% of hydrochloric acid is added to the calcined and activated mineral powder for carrying out acid leaching; heating, refluxing, and stirring are carried out; pump filtration is carried out, and a filtrate is collected; (3) ammonium bicarbonate is added and a pH value is regulated to 8-9; the mixture is settled and aged for 10-30min; pump filtration is carried out, and filtrate is collected; and (4) ammonium bicarbonate is continued to be added into the filtrate, until no precipitate is formed; a reaction is carried out under a temperature of 10-30 DEG C, such that basic magnesium carbonate can be obtained; bake-drying and pyrolysis are carried out, such that high-purity magnesium oxide is obtained. The method provided by the invention has the advantages of simple process, low cost, and suitability for industrialized productions. With the calcining activation method, difficulty for removing iron ions and a small amount of calcium component from a high-content magnesium salt of a traditional chemical purification method is solved. Leaching rate of magnesium oxide in serpentine can be higher than 93.53%, and magnesium oxide purity can be higher than 99.78wt%.
Description
Technical field
The present invention relates to a kind of magnesian preparation method, being specifically related to a kind of take antigorite as the method that high-purity magnesium oxide prepared by raw material.
Background technology
Serpentine is the alteration product of peridotites, and be a kind of general name of moisture rich magnesium silicate mineral, its general formula is Mg
3si
2o
5(OH)
4, its structure is the 1:1 type layer silicate mineral that silicon-oxy tetrahedron and oxyhydrogen magnesium octahedron are combined into.Lizardite is divided into, antigorite and chrysotile by its internal structured layer shape.In antigorite, magnesian content is generally more than 36%, and China's antigorite Mineral resources are very abundant, and there is Donghai Area, Jiangsu in the mining area found, county, Yichang etc. are had a rest in Anhui, and each mining area antigorite reserves is all more than 500,000,000 tons.
Magnesium oxide, as a kind of important inorganic chemical product, is mainly used in refractory materials and extracting metals magnesium, also for paper pulp, material of construction, fertilizer, rubber etc.Experiment shows, when content of magnesia is greater than 98%, its thermal conductivity is higher than aluminum oxide 1 times, dissipation loss only has 1/10 of aluminum oxide, there is corrosion resistant performance simultaneously, it can also be used as the various pottery such as silicon oxide and aluminum oxide, sintering aid, stablizer and various electronic material subsidiary material, also can be used as rubber, special additive in plastics industry, but at present, the magnesium oxide that China produces is the content magnesium oxide that is less than 96% mainly, the requirement of high quality refractory materials can not be met, therefore the production of China's high-purity magnesium oxide is almost a blank, be badly in need of development research.
Magnesian producing mainly with seawater or magnesite is that raw material extracts magnesium oxide at present, but prepare highly purified magnesium oxide mainly to extract from seawater, from seawater, extract magnesium oxide need make precipitation agent to remove impurity with a large amount of soda ash, extract magnesian purity higher, the purity of soda ash used is also higher, and cost is also higher.
Containing the silicon-dioxide of more than 34% in antigorite ore deposit, the magnesium oxide of more than 36%, the ferric oxide of more than 8%, also have calcium oxide and other a small amount of component of about 0.7% in addition, be a kind of of great value mineral wealth, wherein the content of magnesium oxide and silicon-dioxide has all exceeded 1/3 of ore gross weight, if these antigorites suitably can be processed, not only can solve the problem that above-mentioned refuse is piled up, can also broad-spectrum magnesium oxide etc. be obtained.
Chinese patent 88109734.9, proposing with serpentine is the method for raw material production magnesiumcarbonate/or magnesium oxide and porous silica, the method is first after 400 ~ 800 DEG C are calcined 2 ~ 4 hours, be separated with after mineral acid treatment again, this patent considers the possibility containing high efficiente callback magnesium magnesium leach liquor from serpentine, but these techniques are considered not to the leaching yield of magnesium, especially under simple normal temperature and pressure, valuable metal in silicate is difficult to leach, inherently cause the leaching effect of the metal target such as magnesium undesirable, Mg in this patent
2+leaching yield can only reach more than 85%, and above-mentioned patent adopts sulfuric acid as solvent extraction, can generate calcium sulfate precipitation thing, causes breeze to decompose not exclusively, and the silica gel formed also is difficult to be separated.
Chinese patent 89106821.X, proposes the comprehensive utilization process of serpentine tailing, and this technique is in N-process, and adopt milk of lime as neutralizing agent, this makes a large amount of calcium oxide mix in magnesium chloride solution while deironing, Ca in magnesium oxide
2+content weighs one of topmost index of quality product, and on carbonation process, it is the same that the method and traditional rhombspar method produce method of magnesium oxide, adopts CO
2two step method, implements calcium completely, magnesium is separated that to be proved be impossible in carbonation process, and to there is operation long for this method in addition, and the rate of recovery is low, and the chloride ion contamination washed away is serious.
Summary of the invention
The object of the invention is to for being that high-purity magnesium oxide the deficiencies in the prior art prepared by raw material with antigorite, providing a kind of with low cost, being easy to suitability for industrialized production, and leaching yield and all very high preparation method of purity.
To achieve these goals, the technical solution used in the present invention is as follows:
Take antigorite as the method that high-purity magnesium oxide prepared by raw material, comprise the following steps:
1) antigorite is pulverized, then calcining and activating;
2) hydrochloric acid that the breeze after calcining and activating adds 50wt% carries out acidleach, heats, refluxes and stir, collected by suction filtrate;
3) bicarbonate of ammonia adjust ph is added to 8 ~ 9, still aging 10 ~ 30min, collected by suction filtrate;
4) filtrate continuation adds bicarbonate of ammonia and generates to sediment-free, and at 10 ~ 30 DEG C, reaction can obtain magnesium basic carbonate, dries, pyrolysis, obtains high-purity magnesium oxide.
By such scheme, the granularity that in step 1), antigorite is pulverized is 200 orders.
By such scheme, in step 1), the temperature of calcining and activating is 400 ~ 900 DEG C, and calcination time is 60min ~ 180min.
By such scheme, step 2) in acidleach temperature be 20 ~ 70 DEG C, leaching time is 20 ~ 90min, and solid-to-liquid ratio (quality of breeze and the volume ratio of hydrochloric acid, g/mL) is 1:2.5 ~ 12.5.
By such scheme, in step 4), pyrolysis temperature is 700 ~ 850 DEG C, and pyrolysis time is 2 ~ 4h.
First original ore powder is carried out calcining and activating and leaches with acid by the present invention's employing, its immanent cause is that the crystalline structure densification of antigorite itself is regular, and with crystal water in molecule, without calcining just with adding row relax, acid is infiltrated lattice and destroyed is very difficult, experiment finds directly to be soaked in water untreated breeze, and pH value is 6 ~ 7; And after high-temperature calcination, antigorite crystal will discharge crystal water, and make original fine and close regular structure become loose, experiment finds the breeze through calcining and activating to be soaked in water, pH becomes 8 ~ 9, so advantageously in leaching out by magnesium oxide wherein with acid; The method of this calcining and activating original ore powder can improve magnesian leaching rate, is also the key point preparing high purity magnesium oxide simultaneously.
Adopt hydrochloric acid to extract as solvent, there will not be and make raw ore generation throw out cause breeze to decompose incomplete problem, thus make Mg
2+leaching rate higher, and adopt add precipitation agent bicarbonate of ammonia in containing the filtrate of impurity and the technological method that refilters of still aging for some time, foreign ion can be made to assemble and to grow into macrobead precipitation, make the effect of removal of impurities fine, thus obtain more highly purified MgO.Raw ore will be calcined 2 hours at 800 DEG C by prior art, and the present invention only need can reach identical effect for 1 hour 400 DEG C of calcinings; The present invention not only can make Mg
2+leaching yield reach more than 93.53%, and the purity of the MgO produced out can up to 99.78wt%, and the purity that leaching yield of the prior art can only reach more than 85%, MgO also can only reach 96.92wt%.
Beneficial effect of the present invention:
1) technique is simple, and cost is low, is suitable for suitability for industrialized production, and the utilization for antigorite opens new approach.
2) calcining and activating method of the present invention solves the difficulty in the past removing iron ion and a small amount of calcium component in chemical purification from high-content magnesium salts.
3) the present invention can make magnesian leaching yield in antigorite reach more than 93.3%.
4) the magnesium oxide purity that the present invention produces can reach more than 97.36wt%.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of antigorite of the present invention after differing temps calcining.
Fig. 2 is the XRD figure spectrum of MgO prepared by the embodiment of the present invention 2.
Fig. 3 is the SEM photo of MgO prepared by the embodiment of the present invention 2, and scale is 3um.
Fig. 4 is the SEM photo of MgO prepared by the embodiment of the present invention 2, and scale is 500nm.
Embodiment
Following embodiment is the further explaination to the technology of the present invention content, not as limiting the scope of the invention.
XRD figure spectrum is surveyed after the retort furnace being milled to 200 object antigorite breezes and being placed in respectively 400 DEG C, 500 DEG C, 600 DEG C, 700 DEG C, 800 DEG C and 900 DEG C is calcined 60min.As shown in Figure 1, have antigorite and clinochlore to the main component that it carries out the known raw ore of material phase analysis, wherein antigorite accounts for 60wt%-70wt%, and clinochlore accounts for 30wt%-40wt%; Calcining temperature is 400 DEG C, 500 DEG C, any noticeable change is not had when 600 DEG C, when calcining temperature reaches 700 DEG C, sample strength significantly reduces, this just means that the structure of antigorite changes metamict into gradually from crystal state, and when calcining temperature reaches 900 DEG C, antigorite crystal destrengthening, is converted into new thing phase.
Embodiment 1
After the retort furnace being milled to 200 object antigorite breezes and being placed in 900 DEG C is calcined 60min, take the hydrochloric acid that 20g adds 200mL50wt%, return stirring 50min at 60 DEG C, after completion of the reaction collected by suction filtrate, filtrate is for containing Ca
2+, Fe
3+deng the magnesium salt solution of foreign ion, at room temperature in filtrate, add NH
4hCO
3, regulate pH to 8, still aging 20min, waiting precipitation to assemble for removing suction filtration again after macrobead precipitation, suction filtration is removed in precipitation washing several times, to reduce the Mg that throw out adsorbs as far as possible
2+, filtrate is heated in the water-bath of 25 DEG C, and add NH gradually in filtrate
4hCO
3, finally can obtain magnesium basic carbonate solid, the magnesium basic carbonate of oven dry be put into the retort furnace pyrolysis 3h of 800 DEG C, obtain high-purity magnesium oxide.
Detect that the leaching yield of MgO can reach 93.78% with atomic absorption spectrophotometer, the MgO purity produced out can reach 99.78wt%.
Embodiment 2
The retort furnace being milled to 200 object antigorite breezes and being placed in 800 DEG C is calcined 60min, get the antigorite breeze that 20g crosses through above-mentioned calcining and activating, add the hydrochloric acid of 200mL50wt% again, return stirring 50min under water-bath 60 DEG C of heating conditions, other step and processing condition are with embodiment 1, can produce and obtain leaching yield and reach 93.53%, purity reaches the MgO of 99.76%.
Done X-ray diffraction to the MgO prepared, experiment condition is Cu target K alpha-ray, Ni filter plate, wavelength 0.15406nm, pipe pressure 40KV, and scanning speed is 0.05 °/s, and sweep interval is 5 °-70 °; The peak of XRD figure spectrum signature shown in accompanying drawing 2 is consistent with magnesian characteristic peak, and this shows that by the product obtained by the method be magnesium oxide, and does not have remaining impurity peaks to occur, the purity of sample is high.
Magnesium oxide product prepared by the present embodiment detects through SEM, sees shown in accompanying drawing 3,4, and the magnesium oxide prepared is the irregular spherical products that sheet is reunited, and particle diameter ratio is more even.
Embodiment 3:
The retort furnace being milled to 200 object antigorite breezes and being placed in 700 DEG C is calcined 120min, get the antigorite breeze that 20g crosses through above-mentioned calcining and activating, add the hydrochloric acid of 200mL50wt% again, 20min is stirred under 20 DEG C of conditions, collected by suction filtrate after completion of the reaction, at room temperature adds NH in filtrate
4hCO
3, regulate pH to 9, still aging 10min, waiting precipitation to assemble for removing suction filtration again after macrobead precipitation, filtrate being heated in the water-bath of 10 DEG C, and add NH gradually in filtrate
4hCO
3, finally can obtain magnesium basic carbonate solid, the magnesium basic carbonate of oven dry be put into the retort furnace pyrolysis 2h of 700 DEG C.
Produce and obtain leaching yield and reach 93.4%, purity reaches the MgO of 98.39wt%.
Embodiment 4:
The retort furnace being milled to 200 object antigorite breezes and being placed in 600 DEG C is calcined 180min, get the antigorite breeze that 20g crosses through above-mentioned calcining and activating, add the hydrochloric acid of 200mL50wt% again, return stirring 90min under water-bath 70 DEG C of heating conditions, collected by suction filtrate after completion of the reaction, at room temperature adds NH in filtrate
4hCO
3, regulate pH to 8, still aging 30min, waiting precipitation to assemble for removing suction filtration again after macrobead precipitation, filtrate being heated in the water-bath of 30 DEG C, and add NH gradually in filtrate
4hCO
3, finally can obtain magnesium basic carbonate solid, the magnesium basic carbonate of oven dry be put into the retort furnace pyrolysis 4h of 850 DEG C
Can produce and obtain leaching yield and reach 95.2%, purity reaches the MgO of 99.78wt%.
Embodiment 5:
The retort furnace being milled to 200 object antigorite breezes and being placed in 500 DEG C is calcined 60min, get the antigorite breeze that 20g crosses through above-mentioned calcining and activating, add the hydrochloric acid of 250mL50wt% again, return stirring 50min under water-bath 60 DEG C of heating conditions, other step and processing condition are with embodiment 1, can produce and obtain MgO leaching yield and reach 94.2%, purity reaches the MgO of 99.18wt%.
Embodiment 6:
The retort furnace being milled to 200 object antigorite breezes and being placed in 400 DEG C is calcined 60min, get the antigorite breeze that 20g crosses through above-mentioned calcining and activating, add the hydrochloric acid of 50mL50wt% again, return stirring 50min under water-bath 60 DEG C of heating conditions, other step and processing condition are with embodiment 1, can produce and obtain leaching yield and reach 93.3%, purity reaches the MgO of 97.36wt%.
Claims (1)
1. be the method that high-purity magnesium oxide prepared by raw material with antigorite, it is characterized in that comprising the following steps:
1) antigorite being crushed to granularity is 200 orders, then calcining and activating; The temperature of calcining and activating is 400 ~ 900 DEG C, and calcination time is 60min ~ 180min;
2) hydrochloric acid that the breeze after calcining and activating adds 50wt% carries out acidleach, heats, refluxes and stir, collected by suction filtrate; Wherein, acidleach temperature is 20 ~ 70 DEG C, and leaching time is 20 ~ 90min, and solid-to-liquid ratio is 1:2.5 ~ 12.5g/mL;
3) bicarbonate of ammonia adjust ph is added to 8 ~ 9, still aging 10 ~ 30min, collected by suction filtrate;
4) filtrate continuation adds bicarbonate of ammonia and generates to sediment-free, and at 10 ~ 30 DEG C, reaction can obtain magnesium basic carbonate, dries, 700 ~ 850 DEG C of pyrolysis 2 ~ 4h, obtains high-purity magnesium oxide.
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| US10563314B2 (en) | 2014-07-18 | 2020-02-18 | Alliance Magnésium Inc. | Hydrometallurgical process to produce pure magnesium metal and various by-products |
| CN106280279A (en) * | 2016-08-10 | 2017-01-04 | 袁春华 | A kind of preparation method of high heat conduction epoxy molding plastic |
| CN107915242A (en) * | 2017-05-30 | 2018-04-17 | 张旭 | Asbestos tailings prepare method of magnesium oxide |
| CN107188239B (en) * | 2017-07-19 | 2019-12-17 | 中国地质大学（武汉） | method for extracting iron element from serpentine magnesium extraction residue and preparing ferric oxide |
| CN110028089A (en) * | 2019-03-18 | 2019-07-19 | 辽宁工程技术大学 | A kind of serpentine tailing prepares method of magnesium oxide |
| CN115818678A (en) * | 2022-07-18 | 2023-03-21 | 陕西天宝矿业有限公司 | Production process of high-quality light magnesium carbonate and light magnesium oxide |
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| "活化酸浸蛇纹石提取镁的实验研究";曾颖等;《矿冶工程》;20060430;第26卷(第2期);第57-60页 * |
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