CN1422808A - Method for preparing light magnesium oxide and white carbon black from ophiolite and recovering ammonia sulfate - Google Patents
Method for preparing light magnesium oxide and white carbon black from ophiolite and recovering ammonia sulfate Download PDFInfo
- Publication number
- CN1422808A CN1422808A CN 01131802 CN01131802A CN1422808A CN 1422808 A CN1422808 A CN 1422808A CN 01131802 CN01131802 CN 01131802 CN 01131802 A CN01131802 A CN 01131802A CN 1422808 A CN1422808 A CN 1422808A
- Authority
- CN
- China
- Prior art keywords
- carbonization
- magnesium oxide
- make
- carbon black
- ophiolite
- 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.)
- Pending
Links
Abstract
The invention belongs to deep processing of nonmetal mineral chemial industry, using ophiolite to make light MgO2 and white charcoal black and recovery ammonium sulphate. Immerse the ophiolite in acid, filter and make the filtrate through neutralization, impurity sulphate. Immerse the ophiolite in acid, filter and make the filtrate through neutralization, impurity elimination by oxide, then through carbonization and incineration to get light MgO, make solid SiO2 and caustic soda whose concentration is 30-40% react to get water glass and then make the water glass through two-step acid adjustment to produce white charcoal black, and make the filtrate of basic magnesium carbonate through two-step evaporation to recover ammonium sulphate.
Description
(1) technical field
The invention belongs to the deep processing of a kind of non-metallic minerals chemical industry, produce the method for light magnesium oxide, white carbon black and reclaim(ed) sulfuric acid ammonium specifically with serpentine
(2) background technology
Serpentine is the huge a kind of non-metallic mineral resources of China's reserves, and the parent rock in chrysotile mineral deposit is a serpentine, and the asbestos deposit of China more than 90% is chrysotile, and single serpentine mineral deposit is also arranged.In the asbestos mine, asbestos serpentine after selection by winnowing is abandoned as mine tailing, approximately produces one ton of asbestos and need abandon about 40 tons of serpentine tailings; Only as the additive or the steel-making covering slag of calcium, magnesium, phosphate fertilizer, consumption is limited in single serpentine ore exploitation, and economic worth is very low.The main chemical of serpentine is MgO and SiO
2, wherein MgO content is about 38%, SiO
2Content is about 40%, and crystal water content is about 10%, Fe
2O
3About 8%, remain and be oxide compounds such as Mn, Cr, Al, Ca.In order to enlarge the comprehensive utilization of serpentine, Chinese patent application number: 88109764.9, it is raw material production magnesiumcarbonate/or the method for magnesium oxide and porous silica with the serpentine that publication number: CN1041740A has proposed, this method is at first calcined the snake stone flour 2～4 hours under 400～800 ℃ of conditions, acidleach then.Facts have proved in order to open the interlayer hydroxyl of serpentine, make brucite octahedron (containing the MgO layer) and SiO
2Tetrahedron separates, and adopts calcining method cost height, seriously polluted, and the production line investment is big, and the SiO that generates after calcining
2Active low, for the manufacturing of white carbon black brings difficulty.In addition, the raffinate-sal epsom ammonia solution of this method after with carbonization is heated to ammonia and SO
2The decomposition volatilization temperature reclaimed, be what be difficult to realize in technology, and do not have the critical process-removal of impurities in the serpentine minerals chemical technique.Chinese patent application number: 89106821.X, publication number: CN1050411A has proposed the comprehensive utilization process of serpentine tailing, this process using hydrochloric acid is as solvent extraction, but hydrochloric acid is to the requirement for anticorrosion height of technology, and the villaumite market sale of reclaiming is not prosperous, in N-process, adopt milk of lime as neutralizing agent in addition, this makes a large amount of CaO mix in the magnesium chloride solution in deironing.Ca in light magnesium oxide
++Content is to weigh one of topmost index of quality product.Electromagnetism level magnesium oxide requires CaO＜0.7%.And at carbonation process, it is the same that this method is produced method of magnesium oxide with traditional rhombspar method, adopts CO
2Two step method is implemented calcium, magnesium fully and is separated to be facts have proved it is impossible in carbonation process.This in addition method exists operation long, and the rate of recovery is low, the chloride ion contamination of flush away is serious.Chinese patent application number: 92101146.6, publication number: CN1075936A has proposed method for extracting magnesium oxide from serpentine, this method adopts two step calcination methods, though chemical reaction process is simple, but it is actual because filtration-drying-calcining-water logging-filtration-drying-calcining, energy consumption is big in the production, the cost height.And the light magnesium oxide activity is also low.The SiO that above-described the whole bag of tricks obtains in all not proposing to produce
2How further to be processed into white carbon black with real economy benefit.
(3) summary of the invention
The invention solves above-mentioned problems of the prior art, proposed a kind of method of producing light magnesium oxide, white carbon black and reclaim(ed) sulfuric acid ammonium with serpentine.Its method is as follows:
1. serpentine is ground into 140～220 purpose fine powders, through the magnetic separator magnetic separation, its magneticstrength should be greater than 2800 oersteds, to remove rich greenalite; Then breeze is soaked in water, stir, its solid-to-liquid ratio is 1: 5～1: 10,30～100 minutes time, add the vitriol oil at last slowly, and it is 20～40% that reaction solution stops concentration, and is warming up to 80～100 ℃, the joining day is 0.5～1.5 hour.
2. above-mentioned solution is filtered, solution after the filtration is sal epsom and the mixed solution that is dissolved in other impurity of acid, with concentration be 10～25% magnesia emulsion as neutralizing agent, adding speed is per minute 5% (volume), pH value need be strict controlled between 6～10 during neutralization reaction.Carry out oxidation with hydrogen peroxide again after the neutralization reaction, the hydrogen peroxide add-on is 1: 30～1: 50 of volume ratio;
3. above-mentioned reaction solution after filtration, disgorging (impurity), carry out carbonization then, the concentration of the pure liquid of sal epsom is controlled at 13～25 degree Beaume, carry out carbonization with ammoniacal liquor and bicarbonate of ammonia, the proportioning of ammoniacal liquor and bicarbonate of ammonia is an ammoniacal liquor: bicarbonate of ammonia 3: 1～5: 1 (weight ratio), carbonization temperature are 20～80 ℃, and the time is 30～200 minutes.
4. the magnesium basic carbonate that contains the white crystals body after the carbonization and the solution of ammonium sulfate are emitted, leave standstill slaking in 1～2 hour in storage tank, filter then, the solid drying after the filtration gets magnesium basic carbonate, again with magnesium basic carbonate through calcine light magnesium oxide.
5. the porous silica of step 2 gained is put into reactor, add entry, add concentration then and be 20～40% white liquor, when stirring is warming up to 70～90 ℃, add white residue, its solid-to-liquid ratio is 1: 1～1: 3.5,80～100 ℃ of temperature of reaction are kept in stirring, get final product blowing in 3 hours, above-mentioned reactant is filtered, promptly get purified water glass.
6. add water glass in reactor, after stirring was warming up to 50～60 ℃, adding concentration was 20～30% dilute sulphuric acid, the degree of neutralization that makes reaction solution is 20～45%, stop to add acid then, aging 30～50 minutes, system temperature is risen to 80～90 ℃ again, the dilute sulphuric acid that adds same concentrations, making pH value is 3, and then is warming up to 90～100 ℃ ℃, wears out to get final product blowing in 20～50 minutes, after filtration, washing, drying, promptly get white carbon black.
7. the ammonium sulfate mixed liquor after will filtering evaporates the reclaim(ed) sulfuric acid ammonium, removes to contain (NH in this liquid
4)
2SO
4Also contain part MgCO outward,
3, MgSO
4And Mg (HO)
2Deng, therefore to carry out removal of impurities, MgCO
3, MgSO
4Can remove MgSO by precipitation
4With (NH
4)
2SO
4Form sour ammonium double salt [MgSO
4(NH
4)
2SO
46H
2O] because the crystallization concentration of sour ammonium double salt is less than ammonium sulfate, so during crystallization for the first time, sour ammonium double salt is separated out.It can be used as, and farming is fertile directly to be used; Carry out the evaporation of second step then, purified ammonium sulfate is separated out.
The present invention shows through type approval test and utilizes 4 tons of serpentine ores can get 1 ton of high-quality light magnesium oxide (MgO 〉=98%, CaO≤0.5%, iron≤0.03%), 1.3 tons of white carbon black (specific surface area 160～180m
2/ g) and 4 tons of technical grade ammonium sulfate.Above products obtained therefrom quality is good.Power consumption is few, and environmental pollution is little.
(4) embodiment
The invention will be further described below in conjunction with embodiment:
Embodiment 1
8Kg 200 purpose serpentine breezes through the magnetic separator deironing, are put into the reactor that 40Kg water is housed, heated and stirred 30 minutes then, add 93% vitriol oil 7Kg, adding speed is 10Kg/ hour, temperature is controlled at＜and 100 ℃, left standstill after the reaction 0.5 hour, and filtered.Solution is put into reactor, add NaClO
312g stirred 20 minutes, then the magnesia emulsion was added slowly, make solution reach PH=8.5 and stop, being incubated 1 hour, filter, remove impurity, POV magnesium liquid is added in the reactor, stir, slowly add 20 liters of carbonated aqueous ammonias, stirring and keeping temperature is 60 ℃, is warming up to 70 ℃ after adding, be incubated 1 hour, discharging, washed twice after filtering, the dry basic acid magnesium that gets is put into magnesium basic carbonate the inherent 850 ℃ of calcinings of muffle furnace 0.8 hour then, gets high-quality light magnesium oxide 2.1Kg.Product contains MgO＞97.8%, CaO＜0.5%, molysite 0.05%, and quality meets national standard.
Embodiment 2
Get the serpentine breeze that is same as embodiment 1, produce magnesium sulfate solution by the method for embodiment 1, with magnesium sulfate solution at reactor internal heating to 70 ℃.MgO suspension liquid with 10% is transferred reaction solution PH to 8, and aging 30 minutes, add hydrogen peroxide then, making does not have the oxidation of divalent of oxidation to become ferric iron, stirs 20 minutes.Filter, washing, later step is with embodiment 1.The magnesium oxide that embodiment 2 produces still reaches high-quality product, and the content of molysite lower (＜0.05%), the oxygenant consumption also reduces.
Embodiment 3
With the filtered liquid after embodiment 1 or embodiment 2 carbonizations, be used for the reclaim(ed) sulfuric acid ammonium, get the 5Kg filtered liquid, in vaporizer, evaporate, initial concentration of solution is 10～15 degree Beaume, puts into cooling crystallizer during evaporation concentration to 25～30 degree Beaume, gets the thick product of ammonium magnesium sulfate double salt through centrifugation then.Solution after separating is put into vaporizer continue evaporation, when concentration reaches 30～35 degree Beaume, put into cooling crystallizer, leave standstill centrifugation after 20 minutes, obtain technical grade ammonium sulfate 420g, its quality index is nitrogen content 21.2%, H
2SO
4＜0.05%, iron level 0.006%.
Embodiment 4
White residue among embodiment 1 or the embodiment 2 is used for producing white carbon black.In reactor, add earlier 150 premium on currency, add concentration then and be 20 liters in 38% caustic soda, stir and be warming up to 85 ℃, add white residue (doing) 75Kg,, stirring was kept temperature of reaction 1.5～2.5 hours, then blowing.With reacting liquid filtering, add then in the reactor to stir and be warming up to 55 ℃.Dilute sulphuric acid with 30% adds slowly, the degree of neutralization that makes reaction solution is to stop to add acid at 42% o'clock, aging 30 minutes, system temperature is risen to 85 ℃ again, beginning adds acid for the second time, when the system pH value is 3, stop to add acid, be warming up to 100 ℃, aging 30 minutes, cooling, filtration promptly get product white carbon black 58Kg, after testing SiO
292%, pH value be 6.5, total iron amount＜1000mg/Kg, specific surface area 186m
2/ g.
Claims (7)
- A kind ofly produce the method for light magnesium oxide, white carbon black and reclaim(ed) sulfuric acid ammonium, it is characterized in that with serpentine:With 140～220 purpose serpentine breezes through the magnetic separator magnetic separation, its magneticstrength is removed rich greenalite ore deposit greater than 2800 oersteds, and then carries out the sulfuric acid to leach operation;
- 2. the magnesium sulfate solution after will filtering carries out neutralization reaction earlier, and neutralizing agent is the magnesia emulsion, and concentration is 10～25%, and adding speed is 5%/min (volume).PH value is 6～10, and then carries out oxidation, and its oxygenant is a hydrogen peroxide, removes metal ions such as de-iron, manganese, aluminium, calcium, and the hydrogen peroxide consumption is 1: 30～1: 50 with neutralizer volume ratio;
- 3. to purified MgSO 4Liquid carries out carbonization, and the proportioning that is used for the carbonization ammonium water of carbonization is an ammoniacal liquor: bicarbonate of ammonia=3: 1～5: 1 (weight ratio), carbonization temperature are 20～80 ℃, and the time is 30～200 minutes;
- 4. the filtration of thing liquid, washing, drying after the carbonization are obtained magnesium basic carbonate, obtain light magnesium oxide through calcining;
- 5. it is that the weight ratio of its caustic soda and white residue (doing) is 1: 2～1: 3.5, reacts 2～4 hours, produces water glass in 20～40% the white liquor that the porous silica after acidleach being filtered adds concentration;
- 6. after the water glass stirring being warming up to 50～60 ℃, add 20～30% dilute sulphuric acid, the degree of neutralization that makes reaction solution is 20～45%, system temperature is risen to 80～90 ℃ again, add the dilute sulphuric acid of same concentrations, making pH value is 2～3.5, and then be warming up to 100 ℃, obtain white carbon black;
- 7. the ammonium sulfate mixed liquor after carburizing reagent being filtered divides two steps evaporation reclaim(ed) sulfuric acid ammonium, and it is 30～35 degree Beaume that the first step is evaporated to concentration, and cooling removes double salt [MgSO 4(NH 4) 2SO 46H 2O]; The evaporation once more of second step, purified ammonium sulfate is separated out, thereby obtains (the NH of technical grade 4) 2SO 4Product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01131802 CN1422808A (en) | 2001-11-27 | 2001-11-27 | Method for preparing light magnesium oxide and white carbon black from ophiolite and recovering ammonia sulfate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01131802 CN1422808A (en) | 2001-11-27 | 2001-11-27 | Method for preparing light magnesium oxide and white carbon black from ophiolite and recovering ammonia sulfate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1422808A true CN1422808A (en) | 2003-06-11 |
Family
ID=4670876
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01131802 Pending CN1422808A (en) | 2001-11-27 | 2001-11-27 | Method for preparing light magnesium oxide and white carbon black from ophiolite and recovering ammonia sulfate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1422808A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101497453B (en) * | 2008-01-30 | 2010-08-04 | 中国科学院过程工程研究所 | Method for preparing ammonium magnesium sulfate hexahydrate from giobertite |
| CN102190333A (en) * | 2011-04-12 | 2011-09-21 | 铜陵化学工业集团有限公司 | Method for processing serpentine with titanium white waste acid |
| CN102285674A (en) * | 2010-12-30 | 2011-12-21 | 新疆蓝天伟业科技开发有限公司 | Method for comprehensively utilizing low-grade magnesite |
| CN102491345A (en) * | 2011-12-01 | 2012-06-13 | 安徽安纳达钛业股份有限公司 | Carbonization method for preparing precipitated white carbon black |
| CN103449482A (en) * | 2012-06-01 | 2013-12-18 | 中国科学院过程工程研究所 | Method for preparing magnesium oxide, nickel, cobalt and white carbon black through utilizing serpentine |
| CN109292783A (en) * | 2018-10-31 | 2019-02-01 | 深圳市鑫美威自动化设备有限公司 | One kind containing MgSiO3The method of comprehensive utilization of slag |
| CN112320826A (en) * | 2020-10-29 | 2021-02-05 | 刘峰 | Method for jointly preparing high-purity magnesium oxide and refined ammonium sulfate by using low-grade magnesite |
| CN115991496A (en) * | 2023-02-22 | 2023-04-21 | 西南科技大学 | Preparation method of hydrated magnesium ammonium sulfate |
| CN116253343A (en) * | 2023-05-12 | 2023-06-13 | 中科镁基（北京）科技有限公司 | Utilization method of black talcum |
| CN115991496B (en) * | 2023-02-22 | 2024-04-30 | 西南科技大学 | Preparation method of hydrated magnesium ammonium sulfate |
-
2001
- 2001-11-27 CN CN 01131802 patent/CN1422808A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101497453B (en) * | 2008-01-30 | 2010-08-04 | 中国科学院过程工程研究所 | Method for preparing ammonium magnesium sulfate hexahydrate from giobertite |
| CN102285674A (en) * | 2010-12-30 | 2011-12-21 | 新疆蓝天伟业科技开发有限公司 | Method for comprehensively utilizing low-grade magnesite |
| CN102285674B (en) * | 2010-12-30 | 2013-11-27 | 新疆蓝天伟业科技开发有限公司 | Method for comprehensively utilizing low-grade magnesite |
| CN102190333A (en) * | 2011-04-12 | 2011-09-21 | 铜陵化学工业集团有限公司 | Method for processing serpentine with titanium white waste acid |
| CN102190333B (en) * | 2011-04-12 | 2016-01-06 | 铜陵化学工业集团有限公司 | A kind of method of processing serpentine with titanium white waste acid |
| CN102491345A (en) * | 2011-12-01 | 2012-06-13 | 安徽安纳达钛业股份有限公司 | Carbonization method for preparing precipitated white carbon black |
| CN103449482B (en) * | 2012-06-01 | 2015-12-16 | 中国科学院过程工程研究所 | A kind of method utilizing serpentine to prepare magnesium oxide, nickel, cobalt and white carbon black |
| CN103449482A (en) * | 2012-06-01 | 2013-12-18 | 中国科学院过程工程研究所 | Method for preparing magnesium oxide, nickel, cobalt and white carbon black through utilizing serpentine |
| CN109292783A (en) * | 2018-10-31 | 2019-02-01 | 深圳市鑫美威自动化设备有限公司 | One kind containing MgSiO3The method of comprehensive utilization of slag |
| CN112320826A (en) * | 2020-10-29 | 2021-02-05 | 刘峰 | Method for jointly preparing high-purity magnesium oxide and refined ammonium sulfate by using low-grade magnesite |
| CN115991496A (en) * | 2023-02-22 | 2023-04-21 | 西南科技大学 | Preparation method of hydrated magnesium ammonium sulfate |
| CN115991496B (en) * | 2023-02-22 | 2024-04-30 | 西南科技大学 | Preparation method of hydrated magnesium ammonium sulfate |
| CN116253343A (en) * | 2023-05-12 | 2023-06-13 | 中科镁基（北京）科技有限公司 | Utilization method of black talcum |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102115816B (en) | Comprehensive utilization method for laterite-nickel ore | |
| CN101597698B (en) | Method for extracting vanadium by stone coal through acid leaching | |
| CN101058852A (en) | Multistage counter current acid leaching process containing nickel serpentine ore | |
| CN102002585B (en) | Method for producing vanadium iron with stone-like coal pickle liquor | |
| CN101418379B (en) | Method for extracting nickel and cobalt by enclosed leaching nickel oxide mine | |
| US9512502B2 (en) | Method for producing a high-purity nanometer zinc oxide from low-grade zinc oxide ore by ammonia decarburization | |
| CN102849783B (en) | Production method of high-purity nanometer zinc oxide from low-grade zinc oxide ore by ammonia decarbonization | |
| CN101016581A (en) | Method of synthetically and highly effectively reclaiming nickel and magnesium resource from nickel-containing serpentine | |
| CN114606387A (en) | Wet-process and pyrogenic-process combined comprehensive recovery method for arsenic-alkali residue | |
| CN114737066B (en) | Method for extracting lithium from leaching residues of lithium ores | |
| CN1024565C (en) | Comprechensive utilization of serpentine tailings | |
| CN101760637B (en) | Leaching technology of magnesium-containing ore | |
| CN102828034B (en) | Method for producing high-purity zinc oxide through decarbonization on low-grade zinc oxide ore by adopting ammonia process | |
| CN109988902B (en) | Method for dealkalizing iron-reinforced red mud and separating and recovering iron | |
| CN1422808A (en) | Method for preparing light magnesium oxide and white carbon black from ophiolite and recovering ammonia sulfate | |
| CN106629806A (en) | Method for producing dihydrate gypsum from waste liquid in laterite nickel ore wet process | |
| CN101760638B (en) | Method for recovering magnesium from magnesium sulfate solution | |
| CN108862370A (en) | A method of nano zine oxide being produced under zinc ammonia complexing environment using containing zinc ore crude | |
| CN1166788C (en) | Optimal dissolving method of preparing rare earth fluorochloride material liquid from bastnasite concentrate | |
| CN102863011B (en) | Method of using low-grade zinc oxide ore to produce high-purity nano zinc oxide by means of ammonia process | |
| CN101760643B (en) | Improved method for recovering magnesium from magnesium sulfate solution | |
| CN1059762A (en) | The novel process of V 2 O 5 production by chloric acid chlorination method | |
| CN108866331A (en) | A method of zinc oxide being produced under zinc ammonia complexing environment using containing zinc ore crude | |
| CN102863008B (en) | Method for producing high-purity zinc oxide by ammonia method using low-grade zinc oxide ores | |
| CN110896643B (en) | Method for producing zinc-containing compound or zinc oxide from zinc-containing raw ore through intermediate step of calcium zincate synthesis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |