CN103408043A - 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
- Publication number
- CN103408043A CN103408043A CN2013103514924A CN201310351492A CN103408043A CN 103408043 A CN103408043 A CN 103408043A CN 2013103514924 A CN2013103514924 A CN 2013103514924A CN 201310351492 A CN201310351492 A CN 201310351492A CN 103408043 A CN103408043 A CN 103408043A
- Authority
- CN
- China
- Prior art keywords
- magnesium oxide
- antigorite
- raw material
- purity
- calcining
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
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, be specifically related to a kind ofly take antigorite and prepare the method for high-purity magnesium oxide as raw material.
Background technology
Serpentine is the alteration product of peridotites, is a kind of general name of moisture rich magnesium silicate mineral, and 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.By its internal structured layer shape, be divided into lizardite, antigorite and chrysotile.In antigorite magnesian content is generally more than 36%, and China's antigorite Mineral resources are very abundant, and there are Donghai Area, Jiangsu, Anhui have a rest county, Yichang etc. in the mining area of having found, 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 ratio aluminum oxide is high 1 times, dissipation loss only has 1/10 of aluminum oxide, has simultaneously corrosion resistant performance, it can also be as various potteries such as silicon oxide and aluminum oxide, sintering aid, stablizer and various electronic material subsidiary material, also can be used as rubber, special additive on plastics industry, but at present, the magnesium oxide that China produces is mainly the magnesium oxide that content is less than 96%, can not meet the requirement of high quality refractory materials, therefore the production of China's high-purity magnesium oxide is almost a blank, be badly in need of development research.
It is at present magnesian that to produce mainly with seawater or magnesite be that raw material extracts magnesium oxide, but prepare highly purified magnesium oxide mainly from seawater, extracting, from seawater, extracting 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.
In the antigorite ore deposit, contain the silicon-dioxide more than 34%, magnesium oxide more than 36%, ferric oxide more than 8%, also have in addition calcium oxide and other a small amount of component of 0.7% left and right, be a kind of of great value mineral wealth, wherein the content of magnesium oxide and silicon-dioxide has all surpassed 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 obtain broad-spectrum magnesium oxide etc.
Chinese patent 88109734.9, propose to take serpentine and be raw material production magnesiumcarbonate/or the method for magnesium oxide and porous silica, the method is first after 400～800 ℃ are calcined 2～4 hours, again with after mineral acid treatment, separating, this patent has considered to contain from serpentine the possibility of high efficiente callback magnesium the magnesium leach liquor, but these techniques are considered not the leaching yield of magnesium, especially under simple normal temperature and pressure, valuable metal in silicate is difficult to leach, must 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 the calcium sulfate precipitation thing, cause breeze to decompose not exclusively, and the silica gel formed also is difficult to separate.
Chinese patent 89106821.X, proposed the comprehensive utilization process of serpentine tailing, and this technique, in N-process, adopts milk of lime as neutralizing agent, and this makes a large amount of calcium oxide mix in magnesium chloride solution in deironing, Ca in magnesium oxide
2+Content is to weigh one of topmost index of quality product, and on carbonation process, it is the same that the method is produced method of magnesium oxide with traditional rhombspar method, adopts CO
2Two step method, implement calcium, magnesium fully and separate that to be proved be impossible in carbonation process, this method exists operation long 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 take antigorite as raw material prepares the high-purity magnesium oxide the deficiencies in the prior art, provides a kind of with low cost, is easy to suitability for industrialized production, and leaching yield and purity very high preparation method all.
To achieve these goals, the technical solution used in the present invention is as follows:
A kind ofly take antigorite as raw material prepares the method for high-purity magnesium oxide, comprise the following steps:
1) antigorite is pulverized, then calcining and activating;
2) breeze after calcining and activating adds the hydrochloric acid of 50wt% to carry out acidleach, heats, refluxes and stir, and suction filtration is collected filtrate;
3) add bicarbonate of ammonia to regulate pH value to 8～9, still aging 10～30min, suction filtration is collected filtrate;
4) filtrate continuation adds bicarbonate of ammonia to sediment-free and generates, and reaction can obtain magnesium basic carbonate under 10～30 ℃, dries, pyrolysis, obtains high-purity magnesium oxide.
Press such scheme, the granularity that in step 1), antigorite is pulverized is 200 orders.
Press such scheme, in step 1), the temperature of calcining and activating is 400～900 ℃, and calcination time is 60min～180min.
Press such scheme, step 2) in the acidleach temperature be 20～70 ℃, leaching time is 20～90min, (quality of breeze and the volume ratio of hydrochloric acid g/mL) are 1:2.5～12.5 to solid-to-liquid ratio.
Press such scheme, in step 4), pyrolysis temperature is 700～850 ℃, and pyrolysis time is 2～4h.
At first the present invention's employing is carried out calcining and activating by original ore powder and with acid, is leached, its immanent cause is that the crystalline structure densification of antigorite itself is regular, and in molecule with crystal water, without calcining, just with calculating, processing, acid is infiltrated lattice and is very difficult by its destruction, experiment finds directly to be soaked in water untreated breeze, and the pH value is 6～7; And after high-temperature calcination, the antigorite crystal will discharge crystal water, makes the regular structure of original densification become loose, and experiment is found to be soaked in water through the breeze of calcining and activating, pH becomes 8～9, so more is conducive to acid, magnesium oxide wherein be leached out; The method of this calcining and activating original ore powder can improve magnesian leaching rate, is also the key point of preparing high purity magnesium oxide simultaneously.
Adopt hydrochloric acid to extract as solvent, not there will be and make raw ore generation throw out cause breeze to decompose incomplete problem, thereby make Mg
2+Leaching rate higher, and adopt in containing the filtrate of impurity, add the technological method that precipitation agent bicarbonate of ammonia still aging for some time refilter, can grow into the macrobead precipitation so that foreign ion is assembled, make the effect of removal of impurities fine, thereby obtained more highly purified MgO.Prior art will be calcined raw ore 2 hours at 800 ℃, and the present invention only need can reach identical effect in 1 hour 400 ℃ of calcinings; The present invention not only can be so that Mg
2+Leaching yield reach more than 93.53%, and the purity of the MgO produced out can be up to 99.78wt%, leaching yield of the prior art can only reach more than 85%, the purity of 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, for new approach has been opened up in the utilization of antigorite.
2) calcining and activating method of the present invention has solved in the past in chemical purification from the high-content magnesium salts, removing the difficulty of iron ion and a small amount of calcium component.
3) the present invention can make magnesian leaching yield in antigorite reach more than 93.3%.
4) the magnesium oxide purity produced of the present invention is to more than 97.36wt%.
The accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of antigorite of the present invention after the differing temps calcining.
Fig. 2 is the XRD figure spectrum of the MgO of the embodiment of the present invention 2 preparations.
Fig. 3 is the SEM photo of the MgO of the embodiment of the present invention 2 preparations, and scale is 3um.
Fig. 4 is the SEM photo of the MgO of the embodiment of the present invention 2 preparations, 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.
After being milled to 200 purpose antigorite breezes and being placed in respectively the retort furnace calcining 60min of 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃ and 900 ℃, survey the XRD figure spectrum.As shown in Figure 1, its main component of carrying out material phase analysis raw ore as can be known is had to antigorite and clinochlore, wherein antigorite accounts for 60wt%-70wt%, and clinochlore accounts for 30wt%-40wt%; Calcining temperature is 400 ℃, 500 ℃, in the time of 600 ℃, there is no any noticeable change, sample strength significantly reduces when calcining temperature reaches 700 ℃, this structure that just means antigorite changes metamict into gradually from crystal state, and when calcining temperature reached 900 ℃, antigorite crystal destrengthening, be converted into new phase.
Embodiment 1
After being milled to 200 purpose antigorite breezes and being placed in the retort furnace calcining 60min of 900 ℃, take the hydrochloric acid that 20g adds 200mL50wt%, in 60 ℃ of lower return stirring 50min, suction filtration is collected filtrate after completion of the reaction, and 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, regulating pH to 8, still aging 20min, wait precipitation to assemble for after the macrobead precipitation, removing suction filtration again, will precipitate washing and remove suction filtration several times, to reduce the Mg adsorbed on throw out as far as possible
2+, filtrate is heated in the water-bath of 25 ℃, and add gradually NH in filtrate
4HCO
3, finally can obtain the magnesium basic carbonate solid, the magnesium basic carbonate of oven dry is put into to the retort furnace pyrolysis 3h of 800 ℃, obtain high-purity magnesium oxide.
The leaching yield that detects MgO with atomic absorption spectrophotometer can reach 93.78%, and the MgO purity of producing out is to 99.78wt%.
Embodiment 2
The retort furnace that is milled to 200 purpose antigorite breezes and is placed in 800 ℃ is calcined to 60min, get the antigorite breeze that 20g crosses through above-mentioned calcining and activating, the hydrochloric acid that adds again 200mL50wt%, return stirring 50min under 60 ℃ of heating conditions of water-bath, other step and processing condition are with embodiment 1, can produce and obtain leaching yield and reach 93.53%, purity reaches 99.76% MgO.
The MgO prepared has been done to X-ray diffraction, and experiment condition is Cu target K alpha-ray, the Ni filter plate, and wavelength 0.15406nm, pipe is pressed 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 prepared product of 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 of preparing is the irregular spherical products that sheet is reunited and formed, and particle diameter ratio is more even.
Embodiment 3:
The retort furnace that is milled to 200 purpose antigorite breezes and is placed in 700 ℃ is calcined to 120min, get the antigorite breeze that 20g crosses through above-mentioned calcining and activating, the hydrochloric acid that adds again 200mL50wt%, under 20 ℃ of conditions, stir 20min, suction filtration is collected filtrate after completion of the reaction, at room temperature in filtrate, adds NH
4HCO
3, regulating pH to 9, still aging 10min, wait precipitation to assemble for after the macrobead precipitation, removing suction filtration again, filtrate heated in the water-bath of 10 ℃, and add gradually NH in filtrate
4HCO
3, finally can obtain the magnesium basic carbonate solid, the magnesium basic carbonate of oven dry is put into to the retort furnace pyrolysis 2h of 700 ℃.
Produce and obtain leaching yield and reach 93.4%, purity reaches the MgO of 98.39wt%.
Embodiment 4:
The retort furnace that is milled to 200 purpose antigorite breezes and is placed in 600 ℃ is calcined to 180min, get the antigorite breeze that 20g crosses through above-mentioned calcining and activating, the hydrochloric acid that adds again 200mL50wt%, return stirring 90min under 70 ℃ of heating conditions of water-bath, suction filtration is collected filtrate after completion of the reaction, at room temperature in filtrate, adds NH
4HCO
3, regulating pH to 8, still aging 30min, wait precipitation to assemble for after the macrobead precipitation, removing suction filtration again, filtrate heated in the water-bath of 30 ℃, and add gradually NH in filtrate
4HCO
3, finally can obtain the magnesium basic carbonate solid, the magnesium basic carbonate of oven dry is put into to the retort furnace pyrolysis 4h of 850 ℃
Can produce and obtain leaching yield and reach 95.2%,, purity reaches the MgO of 99.78wt%.
Embodiment 5:
The retort furnace that is milled to 200 purpose antigorite breezes and is placed in 500 ℃ is calcined to 60min, get the antigorite breeze that 20g crosses through above-mentioned calcining and activating, the hydrochloric acid that adds again 250mL50wt%, return stirring 50min under 60 ℃ of heating conditions of water-bath, other step and processing condition are with embodiment 1, can produce and obtain the MgO leaching yield and reach 94.2%, purity reaches the MgO of 99.18wt%.
Embodiment 6:
The retort furnace that is milled to 200 purpose antigorite breezes and is placed in 400 ℃ is calcined to 60min, get the antigorite breeze that 20g crosses through above-mentioned calcining and activating, the hydrochloric acid that adds again 50mL50wt%, return stirring 50min under 60 ℃ of heating conditions of water-bath, 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 (5)
1. take antigorite as raw material prepares the method for high-purity magnesium oxide for one kind, it is characterized in that comprising the following steps:
1) antigorite is pulverized, then calcining and activating;
2) breeze after calcining and activating adds the hydrochloric acid of 50wt% to carry out acidleach, heats, refluxes and stir, and suction filtration is collected filtrate;
3) add bicarbonate of ammonia to regulate pH value to 8～9, still aging 10～30min, suction filtration is collected filtrate;
4) filtrate continuation adds bicarbonate of ammonia to sediment-free and generates, and reaction can obtain magnesium basic carbonate under 10～30 ℃, dries, pyrolysis, obtains high-purity magnesium oxide.
2. take as described in claim 1 antigorite as raw material prepares the method for high-purity magnesium oxide, it is characterized in that the granularity that in step 1), antigorite is pulverized is 200 orders.
3. the antigorite of take as described in claim 1 prepares the method for high-purity magnesium oxide as raw material, and the temperature that it is characterized in that calcining and activating in step 1) is 400～900 ℃, and calcination time is 60min～180min.
4. take as described in claim 1 antigorite as raw material prepares the method for high-purity magnesium oxide, it is characterized in that step 2) in the acidleach temperature be 20～70 ℃, leaching time is 20～90min, solid-to-liquid ratio is 1:2.5～12.5.
5. take as described in claim 1 antigorite as raw material prepares the method for high-purity magnesium oxide, it is characterized in that in step 4), pyrolysis temperature is 700～850 ℃, pyrolysis time is 2～4h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310351492.4A CN103408043B (en) | 2013-08-13 | 2013-08-13 | Method for preparing high-purity magnesium oxide with serpentine as raw material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310351492.4A CN103408043B (en) | 2013-08-13 | 2013-08-13 | Method for preparing high-purity magnesium oxide with serpentine as raw material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103408043A true CN103408043A (en) | 2013-11-27 |
| CN103408043B CN103408043B (en) | 2015-05-13 |
Family
ID=49601104
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310351492.4A Expired - Fee Related CN103408043B (en) | 2013-08-13 | 2013-08-13 | Method for preparing high-purity magnesium oxide with serpentine as raw material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103408043B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106280279A (en) * | 2016-08-10 | 2017-01-04 | 袁春华 | A kind of preparation method of high heat conduction epoxy molding plastic |
| KR20170041701A (en) * | 2014-07-18 | 2017-04-17 | 알리앙스 마그네슘 | Hydrometallurgical process to produce pure magnesium metal and various by-products |
| CN107188239A (en) * | 2017-07-19 | 2017-09-22 | 中国地质大学（武汉） | A kind of method extracted ferro element from Serpentine ore residue after extracting magnesium and prepare iron oxide |
| CN107915242A (en) * | 2017-05-30 | 2018-04-17 | 张旭 | Asbestos tailings prepare method of magnesium 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 |
-
2013
- 2013-08-13 CN CN201310351492.4A patent/CN103408043B/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| 曾颖等: ""活化酸浸蛇纹石提取镁的实验研究"", 《矿冶工程》 * |
| 雷绍民等: ""碳铵法从蛇纹石中提取轻质氧化镁研究"", 《中国矿业》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170041701A (en) * | 2014-07-18 | 2017-04-17 | 알리앙스 마그네슘 | Hydrometallurgical process to produce pure magnesium metal and various by-products |
| US10563314B2 (en) | 2014-07-18 | 2020-02-18 | Alliance Magnésium Inc. | Hydrometallurgical process to produce pure magnesium metal and various by-products |
| KR102413985B1 (en) | 2014-07-18 | 2022-06-27 | 알리앙스 마그네슘 | 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 |
| CN107188239A (en) * | 2017-07-19 | 2017-09-22 | 中国地质大学（武汉） | A kind of method extracted ferro element from Serpentine ore residue after extracting magnesium and prepare iron 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103408043B (en) | 2015-05-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103408043B (en) | Method for preparing high-purity magnesium oxide with serpentine as raw material | |
| CN104016393B (en) | A kind of by dolomite for light calcium carbonate and method of magnesium oxide | |
| CN109777960B (en) | Method for separating and recovering lithium and aluminum from fly ash | |
| CN100584764C (en) | Method for reclaiming ferric oxide from coal ash and coal gangue | |
| CN102923742B (en) | Method for comprehensively extracting aluminum and lithium from coal ash | |
| CN102923743B (en) | Technical method for comprehensively extracting aluminum and lithium from coal ash through acid process | |
| CN103101935B (en) | Method for preparing lithium carbonate from coal ash | |
| CN103738986B (en) | A kind of dolomite calcination water-soluble separating calcium and magnesium produce the method for magnesium hydroxide and calcium carbonate | |
| CN102602966B (en) | Method for separating magnesium and lithium in salt lake brine and preparing lithium carbonate | |
| CN104445313B (en) | Method for extracting aluminum oxide from fly ash by acid-base combination | |
| CN1252295C (en) | Method of preparing high purity magnesiun sand using salt lake bischofite as raw material | |
| CN102897810A (en) | Method for producing aluminum oxide by using fly ash | |
| Yang et al. | Extraction of alumina from alumina rich coal gangue by a hydro-chemical process | |
| CN108295856B (en) | Method for preparing methane dry reforming bimetallic catalyst from fly ash silicon extraction residues | |
| CN109052446B (en) | Method for preparing calcium-aluminum hydrotalcite by using industrial waste residues as raw materials | |
| CN109505003B (en) | Method for preparing calcium sulfate whiskers by stainless steel slag wet microwave leaching | |
| CN113104871B (en) | Method for preparing magnalium hydrotalcite from magnesite | |
| CN113562770B (en) | Method for recycling iron and sodium resources in red mud in gradient manner and fully utilizing tailings | |
| CN101880772B (en) | Method for recycling magnesium from magnesium-containing waste solution | |
| CN113896214B (en) | Method for preparing high-purity lithium carbonate by adsorbing and carbonizing lithium sulfate solution | |
| WO2018040703A1 (en) | Method for preparing high-purity flame-retardant magnesium hydroxide by recovery from heavy-metal sludge | |
| CN109336154A (en) | A method of using coal ash for manufacturing for crystalline sulfuric acid aluminium | |
| CN109354045A (en) | A method of lithium carbonate is prepared using dirty mother liquor is steamed | |
| CN115072749A (en) | Method for extracting lithium from spodumene without slag | |
| CN103214011A (en) | Boric sludge comprehensive utilization method for preparing nanometer magnesia and nanocrystalline iron oxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150513 Termination date: 20160813 |