CN1024565C - Comprechensive utilization of serpentine tailings - Google Patents
Comprechensive utilization of serpentine tailings Download PDFInfo
- Publication number
- CN1024565C CN1024565C CN89106821A CN89106821A CN1024565C CN 1024565 C CN1024565 C CN 1024565C CN 89106821 A CN89106821 A CN 89106821A CN 89106821 A CN89106821 A CN 89106821A CN 1024565 C CN1024565 C CN 1024565C
- Authority
- CN
- China
- Prior art keywords
- magnesium
- liter
- ion concentration
- operation steps
- mole
- 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.)
- Expired - Fee Related
Links
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 title claims description 24
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 46
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 35
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 31
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 20
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011777 magnesium Substances 0.000 claims abstract description 19
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 19
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 claims abstract description 17
- 229910000022 magnesium bicarbonate Inorganic materials 0.000 claims abstract description 17
- 239000002370 magnesium bicarbonate Substances 0.000 claims abstract description 17
- 235000014824 magnesium bicarbonate Nutrition 0.000 claims abstract description 17
- 238000002386 leaching Methods 0.000 claims abstract description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 3
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 3
- 239000004571 lime Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 21
- 239000000920 calcium hydroxide Substances 0.000 claims description 18
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 18
- 239000000839 emulsion Substances 0.000 claims description 18
- 238000000197 pyrolysis Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000001556 precipitation Methods 0.000 claims description 15
- 238000003763 carbonization Methods 0.000 claims description 13
- 239000004816 latex Substances 0.000 claims description 13
- 229920000126 latex Polymers 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 12
- 239000006228 supernatant Substances 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- 239000002244 precipitate Substances 0.000 claims description 11
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 10
- 239000001095 magnesium carbonate Substances 0.000 claims description 7
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 7
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 7
- 229960001708 magnesium carbonate Drugs 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 239000004575 stone Substances 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 235000011089 carbon dioxide Nutrition 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000005255 carburizing Methods 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 16
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract description 13
- 239000002253 acid Substances 0.000 abstract description 12
- 239000012535 impurity Substances 0.000 abstract description 10
- 229910052742 iron Inorganic materials 0.000 abstract description 8
- 239000011575 calcium Substances 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052791 calcium Inorganic materials 0.000 abstract description 5
- 239000001569 carbon dioxide Substances 0.000 abstract description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 3
- 239000011707 mineral Substances 0.000 abstract description 3
- 238000013459 approach Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 238000010000 carbonizing Methods 0.000 abstract 1
- 230000001276 controlling effect Effects 0.000 abstract 1
- 239000006071 cream Substances 0.000 abstract 1
- 238000005194 fractionation Methods 0.000 abstract 1
- 235000011167 hydrochloric acid Nutrition 0.000 abstract 1
- 239000000395 magnesium oxide Substances 0.000 description 24
- 239000000706 filtrate Substances 0.000 description 21
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 17
- 239000000047 product Substances 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 8
- 238000000967 suction filtration Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- 230000009466 transformation Effects 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 241000370738 Chlorion Species 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 description 4
- 239000000347 magnesium hydroxide Substances 0.000 description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- -1 aluminum ion Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- KVEAILYLMGOETO-UHFFFAOYSA-H dicalcium magnesium diphosphate Chemical compound P(=O)([O-])([O-])[O-].[Mg+2].[Ca+2].[Ca+2].P(=O)([O-])([O-])[O-] KVEAILYLMGOETO-UHFFFAOYSA-H 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical class [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000002686 phosphate fertilizer Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
Landscapes
- Manufacture And Refinement Of Metals (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The present invention provides an integrative utilization technology of ophiolite ores, which has the following steps: leaching mineral powders using 5 to 9% of hydrochloric acids with 1: 2.2 to 2.6 of acid consumption; adopting a fractionation technology; regulating ph using lime cream to separate iron and other impurities; carbonizing and separating calcium and magnesium using carbon dioxide; heating and decomposing magnesium bicarbonate at a temperature of 102 DEG C under the condition of controlling a certain chlorine ion concentration, and preparing iron oxide red, calcium carbonate and light magnesia from the ophiolite. The quality of the light magnesia prepared by the present invention accords with an HG1-324-77 speciality product standard, and provides an approach having industrial production values for legitimately utilizing the ophiolite ores.
Description
The present invention relates to produce magnesian production technique with serpentine tailing.
China contains abundant serpentine mineral resource, and reserves are above 500,000,000 tons.Year about 200-300 of produced quantity is ten thousand tons/year at present, mainly as the raw material of calcium, magnesium, phosphate fertilizer.In the process of exploitation serpentine ore, produce a large amount of serpentine rubbles, the granularity majority is less than 2-3 centimetre, abandons as refuse.This depleted rubble, this paper is referred to as mine tailing, accounts for 50% of serpentine produced quantity, not only causes the wasting of resources, and piles up because of refuse, occupies the place and forms pollution.This mine tailing stone contains the silicon-dioxide more than 39%, the magnesium oxide more than 34%, and about 8% ferric oxide also has about 2% calcium oxide and other small number of groups branches in addition, is a kind of of great value mineral wealth.
Romania patent R081088 once proposed to leach magnesium oxide with 20% hydrochloric acid leaching method from serpentine, and regulated pH with magnesium hydroxide, removed the impurity in the magnesium chloride solution, and the hydrolysis magnesium chloride is produced magnesium oxide then.But this method acid consumption is big, and the acid-utilising rate is low, the product cost height, and it is unreasonable economically to recycle this waste with it.
The object of the present invention is to provide a kind of production cost low, with serpentine tailing production technique of getting light magnesium oxide made of stones.
The production technique that light magnesium oxide is produced in the present invention's proposition is a kind of preferred method with low cost.Present method is: it is 120-200 purpose breeze that the serpentine tailing stone flour is broken into granularity, and adding concentration is 5-9%(weight) hydrochloric acid, both weight ratios that feeds intake are 1: 4.15～8.84, are heated to 102 ℃ and carry out constant volume dissolving, leaching time is 50-60 minute.Component such as the magnesium in the serpentine breeze, calcium, iron, aluminium, manganese and hydrochloric acid reaction generate muriate and are dissolved.Leach liquor separates with the leaching slag after filtration.The pure hydrochloric acid weight (this paper claims acid consumption) that leaching unit weight magnesium oxide is consumed is 2.2-2.6.The hydrochloric acid that in the ore of equivalent, adds the equal-volume different concns respectively, the size of its acid consumption different with the concentration of hydrochloric acid (seeing Table 1):
The relation of table 1 concentration of hydrochloric acid and acid consumption
Concentration of hydrochloric acid %(weight) 569 12
Acid consumption (gram) 2.92 2.31 2.87 3.14
Preferred concentration of hydrochloric acid is a 5.5-6.5%(weight).The pH value of leach liquor should be controlled at 1.5-2.0 when leaching stopped, the utilization ratio height of acid this moment, and the alkali of consumption is minimum during next step regulator solution pH value, and product cost is minimum, and can reduce the unnecessary impurity of introduction and to the pollution of environment.
The leach liquor oxidizer changes into ferric ion to ferrous ion, and the used oxygenant of the present invention is hydrogen peroxide or chlorinated lime.Then slowly regulate the pH of leach liquor with the milk of lime that contains calcium hydroxide 100-200 grams per liter, the fineness requirement of milk of lime is at the 100-200 order, so that accurately control the pH value of solution, can certainly regulate the pH value with other alkaline matters, the pH=5-9 of control leach liquor.In serpentine ore, except that silicon-dioxide and calcium, iron aluminium is major impurity, and they produce sedimentary pH and see Table 2 in solution:
Table 2 iron, aluminum ion generate sedimentary pH in solution
Fe Al Fe, Al ionic concn
mol/l
Begin to precipitate pH value 2.7 3.7 0.01
Precipitate complete pH value 3.7 4.7 10
-5
Therefore the pH of solution the best is 7-8 when separation of iron, aluminium.This moment, a large amount of precipitation of iron ions was separated out, and throw out can further be processed into red iron oxide, and impurity such as aluminium, manganese also are removed simultaneously.
Remove the supernatant liquor behind the impurity such as iron aluminium manganese, continue to add the pH=11-13.5 of milk of lime regulator solution again.Magnesium chloride when pH value of solution=11 in the solution begins to generate magnesium hydrate precipitate, and magnesium hydrate precipitate is more complete during pH=12.4, and in therefore separating in this step, the preferred pH value of solution is controlled at 12.5-13 and is advisable.Magnesium (in magnesium oxide) in the solution all changes into magnesium hydrate precipitate more than 99% at this moment, and magnesium ion concentration has so just been made said magnesium latex emulsion less than 10 moles every liter in the supernatant liquor.
Abandoning supernatant washes throw out with water, with the chlorion in the disgorging, makes the chlorine ion concentration in the precipitation slurry drop to every liter of 0.03-0.4 mole.Chlorine ion concentration is all influential to carbonization and pyrolytic process, the chlorine ion concentration height, the transformation efficiency that generates Magnesium hydrogen carbonate in the carbonization also raises, the pyrolysis rate when but the chlorine ion concentration height can obviously reduce the Magnesium hydrogen carbonate pyrolysis again, so must take into account the influence of chlorine ion concentration to carbonization and pyrolytic process, best chlorine ion concentration is controlled at every liter of 0.01-0.1 mole.
The slurry of flush away chlorion is sent into carbonating tower, under normal pressure, carry out carbonization with carbonic acid gas, precipitate the calcium hydroxide and the carbon dioxide reaction that carry in the slurry this moment and generate precipitation of calcium carbonate, magnesium hydroxide then becomes the Magnesium hydrogen carbonate of solubility and retains in the solution, when pH=8-10, carbonization stops, and realized the separation of calcium, magnesium ion.Temperature of reaction in the carburizing reagent is 25-30 ℃, and control carbon dioxide flow the 1-4 liter/minute, preferably get the 1-2 liter/minute, this moment, the utilization ratio of carbonic acid gas was higher, during carbonization in the magnesium latex emulsion chlorine ion concentration be controlled at every liter of 0.01-0.1 mole, the transformation efficiency that magnesium hydroxide reaction this moment generates Magnesium hydrogen carbonate can reach 85-90%(in MgO).Separate after filtration, the content of lime carbonate more than 94% in the gained throw out, with currently known methods further processing treatment obtain calcene.
Magnesium hydrogen carbonate filtrate is sent into the thermal degradation device, and at 70-102 ℃ of thermal degradation 15-30 minute, this moment, Magnesium hydrogen carbonate can change into magnesiumcarbonate and basic carbonate magnesium precipitate under the normal pressure, and the chlorine ion concentration in the solution is influential to the thermolysis of Magnesium hydrogen carbonate.Chlorine ion concentration raises, and the pyrolysis rate of Magnesium hydrogen carbonate obviously descends, and when chlorine ion concentration during more than or equal to 0.4 mole every liter, can not obtain magnesiumcarbonate, and when chlorine ion concentration was lower than 0.01 mole every liter, pyrolysis rate (in MgO) can reach more than 95%.(seeing Table 3)
The relation of table 3 pyrolysis rate and chlorine ion concentration
Chlorine ion concentration (every liter of mole) 0.011 0.06 0.1 0.27 0.4
Pyrolysis rate %(weight) 93.0 86.5 75.0 65.0 0
Therefore chlorine ion concentration should be less than 0.01 mole every liter in the solution.
Above-mentioned pyrogenous origin precipitation, after filtration, after the washing, with currently known methods under normal pressure calcination 20-30 minute, calcination temperature was 700-900 ℃, can obtain high-quality light magnesium oxide, quality product meets HGI-324-77 select quality standard-required (seeing Table 4).
Table four light magnesium oxide product analysis result
This product of project HGI-324-77
Superfine standard
Content of magnesia, % 〉=95 98.21
Calcination loss, %≤3 0.72
Calcium oxide content, %≤1.0 0.81
Hydrochloric acid insoluble substance content, %≤0.1 0.019
Chloride content (in CL) %≤0.07 0.061
Sulphate content (SO meter) %≤0.2 0.047
Molysite content (in Fe) %≤0.05 0.03
Manganese salts contg (in Mn) %≤0.003 0.0028
Screenings, the %(40 hole/centimetre)≤0.005 0.004
(80 holes/centimetre)≤0.1 0.007
Look specific volume milliliter/gram 〉=7 8.23
1 the invention will be further described in conjunction with the accompanying drawings more below.
Accompanying drawing 1 is a process flow diagram of the present invention.
1 is hydrochloric acid leaching in the accompanying drawing 1, use 5-9%(weight) hydrochloric acid leaching 120-200 order serpentine breeze, isolate take silica to main solid recrement, the leachate that contains magnesium chloride is delivered to and is carried out first step impurity in 2 and separate, regulate leachate pH=7-8 with milk of lime, separating ferrum is removed aluminium simultaneously, a small amount of impurity such as manganese, the 3rd, produce magnesium latex emulsion, the filtrate of from 2, telling, continue to add milk of lime and make pH value of solution=12.5-13, the magnesium in the solution all changes into magnesium hydrate precipitate, makes said magnesium latex emulsion, 4 are the separation of second step impurity, wash sediment with water, mainly remove the chlorion in the magnesium latex emulsion, make chlorine ion concentration every liter of 0.01-0.1 mole. 5 is that calcium, magnesium separate, and makes calcium hydroxide change into precipitation of calcium carbonate with carbon dioxide, and magnesium hydroxide then changes into magnesium bicarbonate and stays in the solution. 6 for magnesium bicarbonate adds thermal decomposition Formed acid magnesium or basic magnesium carbonate at 102 ℃, and chlorine ion concentration should be less than 0.01 mole every liter in the pyrolysis liquid. 7 precipitate and separate, the solid of separation is magnesium carbonate and basic magnesium carbonate, is sent to 8 calcinations after washing with water and obtains light magnesium oxide. The 9th, produce calcene with 5 isolated calcium carbonate. The 10th, produce iron oxide red from 2 isolated iron hydroxides. The 11st, from the 1 solid recrement production of silica white that separates.
Use the present invention's recyclable special light magnesium oxide more than a ton from 7-8 ton serpentine tailing powder, 300 kilograms of iron oxide reds, 150 kilograms of calcium carbonate and one ton of left and right sides silica.
Advantage of the present invention is clearly, this technology is passed through step by step removing impurities, can obtain simultaneously light magnesium oxide from serpentine tailing stone, the valuable product more than three kinds such as iron oxide red and calcium carbonate, magnesian utilization rate reaches about 50% in the mine tailing, the leaching unit weight It is 2.2-2.6 that amount magnesia consumes the pure hydrochloric acid amount. The present invention can make the serpentine tailing resource more than 35% again obtain utilizing, and finds an approach that has industrial production to be worth for rationally utilizing serpentine and mine tailing thereof. This method is with low cost, and equipment is simple, and investment cost is few, has obvious economic benefit and social benefit.
Further specify the present invention with several examples more below, but be not confined to this several example ranges.
Example 1
With 120 order serpentine breezes 40 gram, in the 1000 milliliter of three hole flask of packing into, add 5%(weight) 230 milliliters of hydrochloric acid, the composition %(weight of breeze) be: 39.52%SiO
2, 34.18%MgO, 1.64%CaO, 5.74%Fe
2O
3, 2.75%FeO, 2.42%Al
2O
3With 0.10%MnO etc., loss on ignition is 13.04%.
On three hole bottles, settle straight run condenser, thermometer and agitator, constantly stir down, kept 50 minutes, after stopping to heat, add 100 milliliters in water at 90 ℃, cooling, suction filtration, filtrate pH=1.5-2, the acid consumption of leaching MgO is 2.6, filter cake is SiO
2, can be used as the raw material of producing white carbon black.
Filtrate is got in above-mentioned acidleach, contains in 1000 ml beakers, adds 7%(weight) H
2O
25 milliliters, under constantly stirring, add and contain effective Ca(OH)
2The milk of lime of 200 grams per liters makes the pH=7 of filtrate.Suction filtration, wash the thick product of red iron oxide about 4 the gram.
In above-mentioned filtrate, continue to add milk of lime, and constantly stir, make pH=13, standing demix, abandoning supernatant, precipitation be with clear water flush away chlorion repeatedly, makes in the supernatant liquor chlorine ion concentration less than 0.03 mole every liter.
With the above-mentioned magnesium oxide slurry that contains, add water and be made into the magnesium latex emulsion that contains the MgO8 grams per liter, chlorine ion concentration is 0.01 mole every liter, packs in 1000 milliliter of three hole flask, feeds CO under normal pressure
2, flow is 1.2 liters/minute, and temperature is 26 ℃, when emulsion pH=8, stops carbonization, and the transformation efficiency of MgO is 89%, and the separating obtained precipitation of suction filtration is lime carbonate, and content is the raw material of producing calcene about 94%.
Above-mentioned filtrate is packed in 1000 ml beakers, and the chlorine ion concentration of filtrate was 0.01 mole every liter, 102 ℃ of heating 20 minutes, the pyrolysis rate of Magnesium hydrogen carbonate is 93%, and pyrogenous origin magnesiumcarbonate and basic carbonate magnesium precipitate separate through suction filtration, and wash with water several times, will precipitate the immigration retort furnace then, 800 ℃ of calcinations 30 minutes, obtain about 4.8 grams of high purity light magnesium oxide, product contains MgO 98.43%, muriate 0.06%, molysite 0.03%, vitriol 0.05%, loss on ignition 0.77%.Meet the superfine standard of HGI-324-77.
Example 2
The composition content of breeze is identical with example 1, get 200 order serpentine breezes, 40 grams, in the 1000ml three hole flasks of packing into, add 6%(weight) the HCL230 milliliter, install 102 ℃ of little boiling with example 1, constantly stir, kept 60 minutes, after stopping to heat, add 100 milliliters in water, cooling back suction filtration, filtrate pH=1.5-2.0, the acid consumption of leaching MgO is 2.4.
The same with example 1, in leach liquor, add 7%(weight) H
2O
23 milliliters, under constantly stirring, add and contain effective Ca(OH)
2The milk of lime of 200 grams per liters makes the pH=7.5 of filtrate, and filtering separation gets about 4 grams of the thick matter product of red iron oxide.
Continue to add milk of lime in above-mentioned filtrate, constantly stir, make pH=12.5, behind the standing demix, abandoning supernatant washes with water and makes in the supernatant liquor chlorine ion concentration less than 0.03 mole every liter.
Above-mentioned emulsion is added water be made into the magnesium latex emulsion that contains MgO 10 grams per liters, chlorine ion concentration is 0.01 mole every liter, feeds CO with example 1
2, flow is 1.5 liters/minute, stops carbonization when emulsion pH=8, the transformation efficiency of MgO is 89%, obtains precipitation of calcium carbonate, contains CaCO
394%.
Filtrate is carried out pyrolysis at 102 ℃, the chlorine ion concentration of pyrolysis liquid is less than 0.003 mole every liter, heated 18 minutes, the pyrolysis rate of Magnesium hydrogen carbonate is 96%, isolate throw out, will be deposited in 900 ℃ of heating 25 minutes, get about 5 grams of high purity light magnesium oxide, product contains MgO 98.2%, CaO0.81%, muriate 0.061%, molysite 0.03%, vitriol 0.047%, loss on ignition 0.72%.
Example 3
With example 1 device, get 160 order serpentine breezes, 40 grams, add 9%(weight) the HCL230 milliliter, and 102 ℃ of little heating 55 minutes of boiling, after stopping to heat, add 100 milliliters in water, cooling back suction filtration, filtrate pH=1.5-2.0, the acid consumption of leaching MgO is 2.9.
With the example 1 the same 7%(weight that in leach liquor, adds) H
2O
23 milliliters, add the pH=7.8 that milk of lime makes filtrate, filtering separation gets about 4 grams of red iron oxide raw product, continues to add milk of lime, makes the pH=13.5 of filtrate, standing demix, abandoning supernatant, and wash precipitation with water.
Add water and be made into the magnesium latex emulsion that contains MgO 11 grams per liters, chlorine ion concentration is 0.27 mole every liter, feeds CO with example 1
2, flow is 2 liters/minute, and 28 ℃ of temperature stop carbonization when emulsion pH=8, and the transformation efficiency of MgO is 90%, filtering separation, getting calcium carbonate content is 94%.
Filtrate is carried out pyrolysis at 102 ℃, and the chlorine ion concentration of pyrolysis liquid is 0.27 mole every liter, heats 20 minutes, and the pyrolysis rate of Magnesium hydrogen carbonate is 65%.Filtering separation, throw out get about 3.4 grams of high purity light magnesium oxide 800 ℃ of heating 20 minutes, and quality product meets the superfine standard of HGI-324-77.
Example 4
With example 1 device, get 180 order serpentine breezes, 40 grams, add 7.5%(weight) the HCL230 milliliter, and 102 ℃ of heating 60 minutes, after stopping to heat, add 100 milliliters in water, cooling back suction filtration, filtrate pH=1.5-2.0, the acid consumption of leaching MgO is 2.8, filter cake is SiO
2, be available as the white carbon black raw material, add 7%(weight in the filtrate) H
2O
23 milliliters, add the pH=8 that milk of lime makes filtrate, filtering separation gets about 4 grams of coarse iron oxide goods, continues to add milk of lime, makes the pH=12.5 of filtrate, standing demix, abandoning supernatant, and wash precipitation with water.
Add water and be made into the magnesium latex emulsion that contains MgO 12 grams per liters, chlorine ion concentration is 0.06 mole every liter, feeds CO with example 1
2, flow is 2.5 liters/minute, and temperature is 25 ℃, stops carbonization when emulsion pH=8, and the transformation efficiency of MgO is 90%, filtering separation, getting calcium carbonate content is 94%.
Filtrate is carried out pyrolysis at 102 ℃, and the chlorine ion concentration of pyrolysis liquid is 0.06 mole every liter, heats 18 minutes, the pyrolysis rate of Magnesium hydrogen carbonate is 86%, filtering separation, and throw out was 850 ℃ of heating 30 minutes, get about 4.4 grams of high purity light magnesium oxide, quality product meets the HGI-324-77 standard.
Claims (8)
1, a kind ofly produce the method for light magnesium oxide, it is characterized in that this method has following steps from serpentine tailing:
(a) ophiruid stone mine tailing is with 5-9% (weight) hydrochloric acid, and be 1 in the weight ratio of breeze and hydrochloric acid: 4.15-8.84, leaching temperature leach under 102 ℃ of conditions, the pH=1.5-2.0 of leach liquor, filtering separation then during the leaching termination;
(b) in leach liquor, add oxygenant earlier, then the pH with milk of lime adjusting leach liquor is 5-9, sediment separate out;
(c) in supernatant liquor, continue to add milk of lime, control pH is 12.5-13.0, makes magnesium latex emulsion;
(d) magnesium latex emulsion washes with water through the settlement separate throw out that goes out, and chlorine ion concentration is every liter of a 0.03-0.4 mole in the control precipitation slurry;
(e) the precipitation slip after washing is under normal pressure, the flow of carbonic acid gas be the 1-2 liter/minute, carbonization temperature is carbonization under 25-30 ℃ the condition, carburizing reagent terminal point pH is 8-10, separates and removes precipitation of calcium carbonate;
(f) containing the supernatant liquor of Magnesium hydrogen carbonate, is under 70-102 ℃ in temperature, pyrolysis 15-30 minute, obtains magnesiumcarbonate and basic carbonate magnesium precipitate;
(g) 700-900 ℃ of calcination precipitation, make light magnesium oxide.
2, in accordance with the method for claim 1, it is characterized in that the middle concentration of hydrochloric acid that leaches the serpentine tailing powder of operation steps (a) is a 5.5-6.5%(weight).
3, in accordance with the method for claim 1, the granularity that it is characterized in that used serpentine tailing powder in the operation steps (a) is the 120-200 order.
4, in accordance with the method for claim 1, it is characterized in that said oxygenant is hydrogen peroxide or chlorinated lime in the operation steps (b).
5, in accordance with the method for claim 1, it is characterized in that control pH value of solution=7-8 in the operation steps (b).
6, in accordance with the method for claim 1, it is characterized in that chlorine is 0.01～0.1 mole every liter from concentration in the middle control of operation steps (d) the magnesium latex emulsion precipitation slurry.
7, according to the described production method of claim 1, when it is characterized in that in the operation steps (e) carbonization in the magnesium latex emulsion chlorine ion concentration be 0.01～0.1 mole every liter.
8, according to right 1 described production method, it is characterized in that in the operation steps (f), contain chlorine ion concentration in the Magnesium hydrogen carbonate supernatant liquor less than 0.01 mole every liter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN89106821A CN1024565C (en) | 1989-09-20 | 1989-09-20 | Comprechensive utilization of serpentine tailings |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN89106821A CN1024565C (en) | 1989-09-20 | 1989-09-20 | Comprechensive utilization of serpentine tailings |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1050411A CN1050411A (en) | 1991-04-03 |
| CN1024565C true CN1024565C (en) | 1994-05-18 |
Family
ID=4856895
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN89106821A Expired - Fee Related CN1024565C (en) | 1989-09-20 | 1989-09-20 | Comprechensive utilization of serpentine tailings |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1024565C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024201239A1 (en) * | 2023-03-24 | 2024-10-03 | Salamander Magnesium International Limited | Extraction process |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1048647C (en) * | 1994-02-25 | 2000-01-26 | 黄军梁 | Method for prepn. of filter aid using asbestos tailing |
| CN100404422C (en) * | 2006-12-01 | 2008-07-23 | 河北科技大学 | A kind of method of low-temperature pyrolysis heavy magnesium water to prepare basic magnesium carbonate and co-production magnesium silicate |
| CN101929121B (en) * | 2009-06-26 | 2012-05-30 | 中国矿业大学(北京) | A method of comprehensively utilizing serpentine acid leaching residue to fill modified road asphalt |
| CN101607721B (en) * | 2009-07-23 | 2011-06-08 | 宜昌弘林华镁矿业投资有限公司 | Method for preparing highly pure magnesium hydroxide and magnesium hexa-silicate by using olivine tailing mine |
| DK2322581T3 (en) * | 2009-11-03 | 2015-12-07 | Omya Int Ag | A process for the preparation of hydromagnesite |
| US9061920B2 (en) | 2009-11-10 | 2015-06-23 | Omya International Ag | Precipitated magnesium carbonate |
| CN104108732A (en) * | 2013-04-19 | 2014-10-22 | 西峡宏泰镁橄榄石有限公司 | Method for utilizing waste forsterite mineral powder to prepare high-purity magnesium oxide |
| CA2968005C (en) * | 2014-11-18 | 2021-11-02 | Alliance Magnesium Inc. | Process to produce magnesium compounds, and various by-products using sulfuric acid in a hcl recovery loop |
| CN104891951B (en) * | 2015-05-19 | 2017-04-12 | 河北工程大学 | A method of extracting a silicon-magnesium-aluminum composite insulating material from asbestos tailings |
| US11401168B2 (en) * | 2016-07-27 | 2022-08-02 | Institut National De La Recherche Scientifique | Production of low carbon footprint magnesia |
| CN106673025A (en) * | 2016-11-18 | 2017-05-17 | 江苏仁欣环保科技有限公司 | Technological method for producing magnesium hydroxide by utilization of magnesium-containing wastewater generated by laterite nickel ore wet-process |
| CN108793490A (en) * | 2018-06-07 | 2018-11-13 | 合肥市东方美捷分子材料技术有限公司 | A method of removing water body ammonia nitrogen using tailing |
| CN113247864B (en) * | 2021-05-24 | 2022-11-15 | 中国成达工程有限公司 | Automatic continuous production system and method for calcium-process bleaching powder fine chlorination unit |
-
1989
- 1989-09-20 CN CN89106821A patent/CN1024565C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024201239A1 (en) * | 2023-03-24 | 2024-10-03 | Salamander Magnesium International Limited | Extraction process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1050411A (en) | 1991-04-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1024565C (en) | Comprechensive utilization of serpentine tailings | |
| WO2010088863A1 (en) | Method for depositing metal ions | |
| CN104016398B (en) | A kind of method that dilute sulfuric acid utilized in industrial wastewater produces sulfate | |
| AU8820798A (en) | A method for isolation and production of magnesium metal, magnesium chloride, magnesite and magnesium based products | |
| CN101058852A (en) | Multistage counter current acid leaching process containing nickel serpentine ore | |
| CN101519219A (en) | Manufacturing process for light magnesium carbonate | |
| CN1384214A (en) | A method for producing rare earth chloride by carbon reduction roasting of mixed rare earth concentrate | |
| CN107879367A (en) | A kind of red mud Comprehensive utilization method | |
| GB2099410A (en) | Treatment for aluminous materials | |
| CN1683569A (en) | Process for decomposing bactnaesite by hydrochloric acid method | |
| CN112520777A (en) | Process for preparing calcium chloride by using byproduct hydrochloric acid slag water of titanium white | |
| CN101760638B (en) | Method for recovering magnesium from magnesium sulfate solution | |
| CN1422808A (en) | Method for preparing light magnesium oxide and white carbon black from ophiolite and recovering ammonia sulfate | |
| CN1280099A (en) | Technology for producing alumina via high alumina to silica ratio sintering process | |
| CN1863732A (en) | Treatment method of waste sulfuric acid containing iron | |
| CN1033081C (en) | Method for extracting light magnesium carbonate from boron mud | |
| RU2202516C1 (en) | Method of production of aluminum oxide | |
| CN1824607A (en) | Vanadium extraction technology of high aluminium slag | |
| CN102863008B (en) | Method for producing high-purity zinc oxide by ammonia method using low-grade zinc oxide ores | |
| CN102115813A (en) | Comprehensive utilization method for low-grade magnesite | |
| CN1408904A (en) | Process for producing high purity magnesium oxide monocrystal using waste magnesite ore | |
| CN1053412A (en) | The bicarbonate of ammonia neutralisation is produced zinc oxide | |
| CN1442362A (en) | Bayer process stripping additive and its preparation and using method | |
| CN1178860C (en) | Process for preparing barium chloride by chlorating and calcining carbonate-type barium ore | |
| CN1887725A (en) | Method of recovering V2O5 from Bayer process mother liquid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: HANHAI ENTERPRISE ( GROUP ) CO.,LTD. Free format text: FORMER OWNER: JINAN CITY, ZHONGGUORENMINJIEFANGJUN Effective date: 20011112 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20011112 Address after: 816000 Golmud City, Qinghai Province Patentee after: Hanhai enterprise (Group) Co., Ltd. Address before: No. 217 Inn South Road, Ji'nan, Shandong Patentee before: Jinan Medical College of P. L. A. |
|
| C15 | Extension of patent right duration from 15 to 20 years for appl. with date before 31.12.1992 and still valid on 11.12.2001 (patent law change 1993) | ||
| OR01 | Other related matters | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |