CN112194155B - Method for producing high-purity magnesium oxide by brine-carbide slag method - Google Patents
Method for producing high-purity magnesium oxide by brine-carbide slag method Download PDFInfo
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- 239000002893 slag Substances 0.000 title claims abstract description 81
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000000395 magnesium oxide Substances 0.000 title claims abstract description 67
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 55
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- 239000012267 brine Substances 0.000 claims abstract description 56
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 239000012452 mother liquor Substances 0.000 claims abstract description 33
- 239000012065 filter cake Substances 0.000 claims abstract description 26
- 238000005406 washing Methods 0.000 claims abstract description 22
- 239000000839 emulsion Substances 0.000 claims abstract description 19
- 238000001914 filtration Methods 0.000 claims abstract description 18
- 239000012066 reaction slurry Substances 0.000 claims abstract description 17
- 230000032683 aging Effects 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 15
- 238000000746 purification Methods 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001556 precipitation Methods 0.000 claims abstract description 9
- 238000004537 pulping Methods 0.000 claims abstract description 7
- 238000007670 refining Methods 0.000 claims abstract description 7
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 6
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 6
- 238000007865 diluting Methods 0.000 claims abstract description 5
- 238000012544 monitoring process Methods 0.000 claims abstract description 3
- 238000006703 hydration reaction Methods 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 230000000887 hydrating effect Effects 0.000 claims description 17
- 239000002002 slurry Substances 0.000 claims description 17
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 16
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 12
- 239000011777 magnesium Substances 0.000 claims description 12
- 229910052749 magnesium Inorganic materials 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 9
- 239000001110 calcium chloride Substances 0.000 claims description 9
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 9
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 8
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 6
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910001424 calcium ion Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 24
- 229910052742 iron Inorganic materials 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 238000001514 detection method Methods 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 7
- 239000000292 calcium oxide Substances 0.000 description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 7
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 5
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 5
- 239000000347 magnesium hydroxide Substances 0.000 description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 5
- 239000010413 mother solution Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 4
- 235000011941 Tilia x europaea Nutrition 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 4
- 239000000920 calcium hydroxide Substances 0.000 description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000004571 lime Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 239000005997 Calcium carbide Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000010009 beating Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- PPAVUALENQYVKC-UHFFFAOYSA-L disodium chloride hydroxide hydrate Chemical compound O.[Cl-].[Na+].[OH-].[Na+] PPAVUALENQYVKC-UHFFFAOYSA-L 0.000 description 1
- 238000005008 domestic process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- -1 electricity Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000010057 rubber processing Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/02—Magnesia
- C01F5/06—Magnesia by thermal decomposition of magnesium compounds
- C01F5/08—Magnesia by thermal decomposition of magnesium compounds by calcining magnesium hydroxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/14—Magnesium hydroxide
- C01F5/22—Magnesium hydroxide from magnesium compounds with alkali hydroxides or alkaline- earth oxides or hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention provides a method for producing high-purity magnesium oxide by adopting a brine-carbide slag method, which comprises the following steps: s1, pulping and diluting carbide slag with circulating mother liquor or circulating washing water, and then performing cyclone separation and purification to obtain refined carbide slag emulsion; s2, sequentially adding the circulating mother liquor and carbide slag into brine containing soluble magnesium salt for refining to obtain refined brine; s3, adding the refined carbide slag emulsion of S1 into the refined brine of S2, controlling the feeding process to be completed within 20-30 min, reacting for 10-30min at 15-35 ℃, and monitoring the pH value at the end point of the reaction to be 10-11; then carrying out an aging reaction for 2-24 hours; s4, carrying out cyclic operation on the precipitation reaction of the S3 for 5-20 batches, combining the reaction slurry, filtering to obtain cyclic mother liquor and a filter cake, and washing and calcining the filter cake to obtain the high-purity magnesium oxide. The method can obviously reduce the production cost, and the purity meets the high-purity standard; and can be applied to industrial production.
Description
Technical Field
The invention belongs to the technical field of comprehensive utilization of solid wastes, and particularly relates to a method for producing high-purity magnesium oxide by adopting a brine-carbide slag method.
Background
Magnesia is an inorganic oxide and high purity magnesia products have many good properties, such as: excellent alkali resistance and heat conductivity, good chemical activity, etc., and thus are widely used in the fields of ceramics, electricity, plastics and rubber processing, fuel oil and lubricating oil, steel processing, medicine, etc.
At present, the domestic process for producing high-purity magnesium oxide with the purity of more than 99 percent mainly adopts a magnesium hydroxide method, namely a soluble magnesium salt is used as a raw material, ammonia or alkali is used as a precipitator, and a chemical method is adopted to produce the high-purity magnesium oxide, such as a lime-brine method, an ammonium-lime-brine method, a sodium hydroxide-brine method, a barium hydrosulfide-brine method and the like. Wherein, the technology for producing the high-purity magnesium oxide by adopting an ammonium method and a lime method is mature, and the large-scale production can be carried out. However, there are still problems in the production process, such as the storage period of raw materials in the lime process, and the production of high purity magnesium oxide in the ammonium process and other processes has a problem of relatively high cost.
The carbide slag is a byproduct in the PVC production industry, and is industrial waste residue taking calcium carbide (calcium carbide) as a raw material, calcium hydroxide as a main component after acetylene gas is obtained by hydrolysis, and in addition, the carbide slag also contains soluble acetylene, sintered iron, aluminum, silicon compounds, calcium carbonate generated by underfiring, a small amount of organic matters, free carbon of tiny particles and the like. And about 2 tons of carbide slag (calculated by dry weight) are produced as a byproduct of each ton of PVC products, so that the comprehensive utilization of the carbide slag is a problem to be solved urgently in the PVC production industry.
At present, the carbide slag which is a byproduct in the PVC production industry in China is difficult to realize harmless emission, so that the carbide slag is mainly used for producing cement by virtue of comprehensive utilization. However, compared with limestone technology, the technology for producing cement from carbide slag has about 20% higher energy consumption and about 20-25% lower yield. And the carbide slag contains a lot of sulfur, phosphorus, chlorine and other impurities, and the impurities can affect the quality of cement.
The comprehensive utilization of the carbide slag is realized by utilizing the characteristics of the carbide slag, so that a process for producing high-purity magnesium oxide by adopting the carbide slag method to replace the existing lime method is necessary to be developed, good economic benefit can be obtained, and the requirement of environmental protection can be met. Particularly, with the continuous enhancement of environmental protection requirements, lime production is controlled, the price is increased, and the cost advantage of the carbide slag method is further enhanced.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a method for producing high-purity magnesium oxide by adopting a brine-carbide slag method, which can remarkably reduce the production cost and ensure that the purity meets the high-purity standard; and can be applied to industrial production.
In order to achieve the above object, the technical scheme of the present invention is as follows.
A method for producing high-purity magnesium oxide by adopting a brine-carbide slag method comprises the following steps:
s1, pulping and diluting carbide slag with circulating mother liquor or circulating washing water, and then performing cyclone purification to obtain refined carbide slag emulsion;
s2, sequentially adding the circulating mother liquor and carbide slag into brine containing soluble magnesium salt for refining to obtain refined brine;
s3, adding the refined carbide slag emulsion of S1 into the refined brine of S2, controlling the feeding process to be completed within 20-30 min, reacting for 10-30min at 15-35 ℃, and monitoring the pH value at the end point of the reaction to be 10-11; then carrying out an aging reaction for 2-24 hours; the quality of the product is improved through the aging reaction, and the better the quality of the product is along with the extension of the aging time.
S4, carrying out cyclic operation on the precipitation reaction of the S3 for 5-20 batches, combining the reaction slurry, filtering to obtain cyclic mother liquor and a filter cake, and washing and calcining the filter cake to obtain the high-purity magnesium oxide.
Further, the method further comprises the following steps: s5, purifying the magnesium oxide of the S4 by a hydration reaction method; the specific operation of the purification treatment is as follows:
s5.1, preparing a hydrating agent solution with the magnesium content of 0.05-0.2 mol/L;
s5.2, adding high-purity magnesium oxide of S4 into the hydrating agent solution of S5.1, and carrying out hydration reaction at 30-60 ℃; then aging reaction is carried out for 24-48 hours to obtain seed crystal slurry;
s5.3, circularly operating the hydration reaction of the S5.2 for 5-20 batches; mixing the reaction slurry and filtering to obtain circulating mother liquor and filter cake; and washing and calcining the filter cake to obtain the purified high-purity magnesium oxide.
In step S5.1, the hydrating agent solution is obtained by dissolving magnesium chloride and calcium chloride in circulating mother solution or circulating washing water; wherein the concentration of magnesium ions is 0.05-0.2 mol/L, and the concentration of calcium ions is 1mol/L. The addition of magnesium ions and calcium ions helps to control the formation and growth of crystal particles.
Further, in S5.2, the ratio of the magnesium oxide to the hydrating agent solution is 20 to 100g/L.
Further, in S4 and S5.3, the calcination temperature is 700-900 ℃ and the calcination time is 1-2 h.
In S5.2, the hydration reaction time is 30-60 min; and the hydration reaction is followed by cyclone separation and purification.
In S3, seed slurry of S5.2 is added to the purified brine before the purified carbide slag emulsion is added dropwise.
In step S1, the ratio of the carbide slag to the circulating mother liquor or the circulating washing water during pulping is: 1 g/5-10 mL; during cyclone purification, the concentration of the carbide slag slurry is 3-5 wt%.
In step S2, the molar ratio of the calcium chloride in the circulating mother liquor to the magnesium sulfate in the brine is 1.2 to 1.5:1.
in step S2, the pH value of the refined brine is 7.5-8.0.
The invention has the beneficial effects that:
1. the method of the invention purifies carbide slag slurry by adopting a cyclone separation method, thereby removing sinter and calcium carbonate; the circulating mother liquor and the carbide slag are added into the original brine, so that the original brine can be subjected to desulfurization and decarburization treatment; and the magnesium hydroxide generated by the reaction can be used for adsorbing and removing boron, iron and organic matters in the brine; thereby realizing the refining and purification of the refined carbide slag emulsion and brine and being beneficial to improving the purity of magnesium oxide.
2. According to the method, the refined carbide slag emulsion is added into refined brine, the reaction end point is regulated and controlled through the reaction pH value, and the product quality is improved through an aging reaction; the coarse magnesium hydroxide obtained by precipitation reaction contains adsorbed acetylene and free carbon, and is removed by high-temperature calcination after filtration and washing, so that the purity of the magnesium oxide is further improved.
3. The method of the invention can further purify the calcined high-purity magnesia, and the purity of the magnesia is further improved by adding the magnesia into a hydration agent solution containing magnesium for hydration reaction.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The main impurities in carbide slag milk are soluble acetylene and sintered iron, aluminum, silicon compounds and calcium carbonate due to underfiring, as well as small particles of free carbon. Sinter and calcium carbonate can be removed by cyclone separation.
The circulating mother liquor and the carbide slag can be added for desulfurizing and decarbonizing brine.
The chemical reaction formula of brine desulfurization and decarbonization is as follows:
CaCl 2 +MgSO 4 +H 2 O→CaSO 4 2H 2 O↓+MgCl 2
CO 3 2- (or HCO) 3 - )+Ca(OH) 2 →CaCO 3 +H 2 O
Boron, iron and organic matters in the brine are removed by a magnesium hydroxide adsorption method.
The crude magnesium hydroxide obtained by the precipitation reaction contains adsorbed acetylene and free carbon. Is removed by high temperature calcination after filtration and washing.
Example 1
A method for producing high-purity magnesium oxide by adopting a brine-carbide slag method comprises the following steps:
s1, pulping and diluting carbide slag with circulating mother liquor or circulating washing water, and performing cyclone separation to obtain refined carbide slag emulsion;
when beating, the feed liquid ratio of carbide slag to circulating mother liquor or circulating washing water is as follows: 1 g/5-10 mL; during cyclone purification, the concentration of the carbide slag slurry is 3-5 wt%.
And detecting the refined carbide slag emulsion, wherein the concentration of the calcium hydroxide is 0.022mol/L. Wherein, carbide slag is respectively taken from Shanxi Jintai chlor alkali and North chemical industry, and the carbide slag is in paste form, and typical detection results are as follows: drying weight loss: 39%; calcium oxide: 38.5wt%.
S2, sequentially adding the circulating mother liquor and carbide slag into brine containing soluble magnesium salt for refining to obtain refined brine; adjusting the mixing ratio of the brine and the circulating mother liquor according to the magnesium sulfate content in the original brine and the calcium chloride content in the circulating mother liquor, wherein the molar ratio of the calcium chloride to the magnesium sulfate is 1.2-1.5:1; the adding amount of carbide slag is controlled by an acidometer to adjust the pH value of refined brine, wherein the pH value of the refined brine is controlled to be about 7.5-8.
And detecting refined brine, wherein the concentration of magnesium ions is 0.6mol/L.
Wherein, the raw brine is taken from a fixed-edge salt lake. Detecting raw brine: the magnesium content is 52g/L.
S3, adding 1L of refined brine of the S2 into the reactor for the first batch, and sealing and stirring. Adding the refined carbide slag emulsion of S1 into the refined brine of S2 under stirring, controlling the feeding process to be completed within 20min, and reacting for 20min at 35 ℃. At this time, the pH at the end of the reaction was 10.2; then carrying out an aging reaction for 20 hours;
s4, taking the first batch of reaction slurry as seed slurry, and circularly operating the precipitation reaction of S3 for 20 batches again; and combining the reaction slurry, filtering to obtain a circulating mother solution and a filter cake, washing the filter cake, and calcining at 700 ℃ for 2 hours to obtain magnesium oxide.
Detecting analysis results: magnesium oxide: 99.21%; calcium oxide: 0.28%; iron: 0.003%; hydrochloric acid insoluble matter: 0.02%; whiteness: 95; bulk density 0.22.
Example 2
A method for producing high purity magnesium oxide by brine-carbide slag method, which is the same as the method of example 1, except for comprising the steps of:
s5, purifying the magnesia obtained in the example 1 by hydration reaction; the specific operation is as follows:
s5.1, preparing a hydrating agent solution with the magnesium content of 0.06 mol/L; the hydrating agent solution is obtained by dissolving magnesium chloride and calcium chloride in circulating mother liquor or circulating washing water; wherein the concentration of magnesium ions is 0.06mol/L, and the concentration of calcium ions is 1mol/L.
S5.2, adding 20g of magnesium oxide into 1L of the hydrating agent solution, and carrying out hydration reaction for 30min at 50 ℃; cyclone separation and purification are carried out, and then aging reaction is carried out for 24 hours, so as to obtain seed crystal slurry;
s5.3, circularly operating the hydration reaction of S5.2 for 20 batches; mixing the reaction slurry and filtering to obtain circulating mother liquor and filter cake; the filter cake is washed and filtered, and then calcined at 700 ℃ for 2 hours to obtain purified magnesium oxide.
Detection and analysis: magnesium oxide: 99.4%; calcium oxide: 0.06%; iron: 0.008%; hydrochloric acid insoluble matter: 0.05%; whiteness: 95; bulk density 0.17.
Example 3
A method for producing high-purity magnesium oxide by adopting a brine-carbide slag method comprises the following steps:
s1, pulping and diluting carbide slag with circulating mother liquor or circulating washing water, and performing cyclone separation to obtain refined carbide slag emulsion;
when beating, the feed liquid ratio of carbide slag to circulating mother liquor or circulating washing water is as follows: 1 g/5-10 mL; during cyclone purification, the concentration of the carbide slag slurry is 3-5 wt%.
And detecting the refined carbide slag emulsion after refining, wherein the concentration of calcium hydroxide is 0.32mol/L.
Wherein, the carbide slag is taken from Henan Jiyuan alliance chemical industry and is in powder form. Test results (typical values): drying weight loss: 19%; calcium oxide: 51%.
S2, sequentially adding the circulating mother liquor and carbide slag into brine containing soluble magnesium salt for refining to obtain refined brine; adjusting the mixing ratio of the brine and the circulating mother liquor according to the magnesium sulfate content in the original brine and the calcium chloride content in the circulating mother liquor, wherein the molar ratio of the calcium chloride to the magnesium sulfate is 1.2-1.5:1; the adding amount of carbide slag is controlled by an acidometer to adjust the pH value of refined brine, wherein the pH value of the refined brine is controlled to be about 7.5-8.
Detecting refined brine, wherein the concentration of magnesium ions is 1.3mol/L; the concentration of SO 4-is 2.1g/L; the concentration of iron + manganese tends to be 0.
Wherein, the raw brine is taken from a fixed-edge salt lake. Detecting raw brine: the magnesium content is 61g/L; density 1.31; the magnesium sulfate content was 0.48mol/L.
S3, adding 2L of refined brine of S2 into the reactor, and sealing and stirring. Adding the refined carbide slag emulsion of S1 into the refined brine of S2 under stirring, controlling the feeding process to be completed within 30min, and reacting for 15min at 30 ℃. At this time, the pH at the end of the reaction was 10.5; then carrying out an aging reaction for 2 hours;
s4, taking the first batch of reaction slurry as seed slurry, and circularly operating the precipitation reaction of S3 for 10 batches again; and (3) mixing the reaction slurry, filtering to obtain a circulating mother solution and a filter cake, washing and filtering the filter cake, and calcining at 750 ℃ for reaction for 1 hour to obtain magnesium oxide.
Detection and analysis: magnesium oxide: 98.0%; calcium oxide: 0.9%; iron: 0.18%; hydrochloric acid insoluble matter: 0.5%; whiteness: 94; bulk density 0.19.
Example 4
A method for producing high-purity magnesium oxide by brine-carbide slag method, which is the same as the method of example 3, except that:
further comprises: s5, purifying the magnesia obtained in the example 3 by hydration reaction; the specific operation is as follows:
s5.1, preparing a hydrating agent solution with the magnesium content of 0.2 mol/L;
s5.2, adding 20g of magnesium oxide into 1L of the hydrating agent solution, and carrying out hydration reaction for 40min at 40 ℃; cyclone separation and purification are carried out, and then aging reaction is carried out for 24 hours, so as to obtain seed crystal slurry;
s5.3, circularly operating the hydration reaction of S5.2 for 10 batches; mixing the reaction slurry and filtering to obtain circulating mother liquor and filter cake; the filter cake is washed and filtered, and then calcined at 750 ℃ for reaction for 1 hour, thus obtaining purified magnesium oxide.
Detection and analysis: magnesium oxide: 99.2%; calcium oxide: 0.08%; iron: 0.07%; hydrochloric acid insoluble matter: 0.05%; whiteness: 95; bulk density 0.18.
Example 5
A method for producing high-purity magnesium oxide by brine-carbide slag method, which is the same as in example 1, except that:
s3, adding 1L of refined brine of the S2 into the reactor for the first batch, and sealing and stirring. (refined brine detection: magnesium: 1.01mol/L; SO) 4 - :1.5g/L; iron + manganese: tend to be 0)
Adding the refined carbide slag emulsion of S1 into the refined brine of S2 under stirring, controlling the feeding process to be completed within 20min, and reacting for 20min at 15 ℃. At this time, the pH at the end of the reaction was 10.1; then carrying out an aging reaction for 24 hours;
s4, taking the first batch of reaction slurry as seed slurry, and circularly operating the precipitation reaction of S3 for 5 batches again; and (3) mixing the reaction slurry, filtering to obtain a circulating mother solution and a filter cake, washing and filtering the filter cake, and calcining at 750 ℃ for 2 hours to obtain magnesium oxide.
Example 6
A method for producing high-purity magnesium oxide by brine-carbide slag method, which is the same as the method of example 5, except that:
further comprises: s5, purifying the magnesium oxide obtained in the example 5 through hydration reaction; the specific operation is as follows:
s5.1, preparing a hydrating agent solution with the magnesium content of 0.05 mol/L;
s5.2, adding 50g of magnesium oxide into 1L of the hydrating agent solution, and carrying out hydration reaction for 30min at 60 ℃; cyclone separation and purification are carried out, and then aging reaction is carried out for 24 hours, so as to obtain seed crystal slurry;
s5.3, circularly operating the hydration reaction of S5.2 for 5 batches; mixing the reaction slurry and filtering to obtain circulating mother liquor and filter cake; the filter cake is washed and filtered, and then calcined at 850 ℃ for 2 hours to obtain purified magnesium oxide.
Detection and analysis: magnesium oxide: 99.1%; calcium oxide: 0.11%; iron: 0.007%; hydrochloric acid insoluble matter: 0.05%; whiteness: 96; and (3) performing laser granularity detection: d50 =1.1 micrometers, d98=5 micrometers.
Example 7
A method for producing high-purity magnesium oxide by brine-carbide slag method, which is the same as in example 3, except that:
wherein, the raw brine is taken from a fixed-edge salt lake. Detecting raw brine: magnesium content 45g/L, density: 1.25, magnesium sulfate content: 0.36mol/L.
S3, adding 2L of refined brine of S2 into the reactor, and sealing and stirring. (refined brine detection: magnesium: 0.82 mol; SO) 4 - :1.6g/L; iron + manganese: tend to be 0)
Adding the refined carbide slag emulsion of S1 into the refined brine of S2 under stirring, wherein the (the detection of the refined carbide slag emulsion comprises 0.12mol/L of calcium hydroxide) controlling the feeding process to be completed within 25min, and reacting for 30min at 20 ℃. At this time, the pH at the end of the reaction was 10.1; then carrying out an aging reaction for 24 hours;
s4, taking the first batch of reaction slurry as seed slurry, and circularly operating the precipitation reaction of S3 for 5 batches again; and (3) mixing the reaction slurry, filtering to obtain a circulating mother solution and a filter cake, washing and filtering the filter cake, and calcining at 900 ℃ for 2 hours to obtain magnesium oxide.
Example 8
A method for producing high-purity magnesium oxide by brine-carbide slag method, which is the same as in example 7, except that:
further comprises: s5, purifying the magnesium oxide obtained in the example 7 serving as a raw material through hydration reaction; the specific operation is as follows:
s5.1, preparing a hydrating agent solution with the magnesium content of 0.15 mol/L;
s5.2, adding 100g of magnesium oxide into 1L of the hydrating agent solution, and carrying out hydration reaction for 30min at 60 ℃; performing cyclone separation and purification, and then performing an aging reaction for 12 hours to obtain seed crystal slurry;
s5.3, circularly operating the hydration reaction of S5.2 for 5 batches; mixing the reaction slurry and filtering to obtain circulating mother liquor and filter cake; the filter cake is washed and filtered, and then calcined at 850 ℃ for 2 hours until the weight is constant, thus obtaining the purified magnesium oxide.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (9)
1. The method for producing the high-purity magnesium oxide by adopting the brine-carbide slag method is characterized by comprising the following steps of:
s1, pulping and diluting carbide slag with circulating mother liquor or circulating washing water, and then performing cyclone separation and purification to obtain refined carbide slag emulsion;
s2, sequentially adding the circulating mother liquor and carbide slag into brine containing soluble magnesium salt for refining to obtain refined brine;
s3, adding the refined carbide slag emulsion of S1 into the refined brine of S2, controlling the feeding process to be completed within 20-30 min, reacting for 10-30min at 15-35 ℃, and monitoring the pH value at the end point of the reaction to be 10-11; then carrying out an aging reaction for 2-24 hours;
s4, carrying out cyclic operation on the precipitation reaction of the S3 for 5-20 batches, combining reaction slurry, filtering to obtain cyclic mother liquor and a filter cake, and washing and calcining the filter cake to obtain high-purity magnesium oxide;
in S4, the calcination temperature is 700-900 ℃ and the calcination time is 1-2 h.
2. The method for producing high purity magnesia by brine-carbide slag process according to claim 1, further comprising: s5, purifying the high-purity magnesium oxide of the S4 by a hydration reaction method; the specific operation of the purification treatment is as follows:
s5.1, preparing a hydrating agent solution with the magnesium content of 0.05-0.2 mol/L;
s5.2, adding high-purity magnesium oxide of S4 into the hydrating agent solution of S5.1, and carrying out hydration reaction for 30-60 min at 30-60 ℃; then carrying out an aging reaction for 12-24 hours to obtain seed crystal slurry;
s5.3, circularly operating the hydration reaction of the S5.2 for 5-20 batches; mixing the reaction slurry and filtering to obtain circulating mother liquor and filter cake; and washing and calcining the filter cake to obtain the purified high-purity magnesium oxide.
3. The method for producing high purity magnesia by brine-carbide slag process according to claim 2, wherein in step S5.1, the hydrating agent solution is obtained by dissolving magnesium chloride and calcium chloride in recycled mother liquor or recycled wash water; wherein the concentration of magnesium ions is 0.05-0.2 mol/L, and the concentration of calcium ions is 1mol/L.
4. The method for producing high-purity magnesium oxide by brine-carbide slag according to claim 2, wherein the ratio of the magnesium oxide to the hydrating agent solution in S5.2 is 20-100 g/L.
5. The method for producing high purity magnesia by brine-carbide slag process according to claim 2, wherein in S5.3, the calcination temperature is 700-900 ℃ and the calcination time is 1-2 hours.
6. The method for producing high purity magnesia by brine-carbide slag process according to claim 2, wherein in S3, seed slurry of S5.2 is added to the refined brine before the refined carbide slag emulsion is added dropwise.
7. The method for producing high-purity magnesium oxide by brine-carbide slag method according to claim 1, wherein in step S1, the feed liquid ratio of carbide slag to circulating mother liquor or circulating washing water during pulping is: 1 g/5-10 mL; the concentration of the carbide slag slurry is 3-5 wt% during cyclone separation and purification.
8. The method for producing high-purity magnesium oxide by brine-carbide slag method according to claim 1, wherein in step S2, the molar ratio of calcium chloride in the circulating mother liquor to magnesium sulfate in the brine is 1.2-1.5: 1.
9. the method for producing high purity magnesia by brine-carbide slag process according to claim 1, wherein in step S2, the pH of the refined brine is 7.5-8.0.
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| CN1962446A (en) * | 2006-12-07 | 2007-05-16 | 上海交通大学 | Method for extracting magnesium hydroxide from thick salt water using calcium carbide dreg |
| WO2007088407A1 (en) * | 2006-01-31 | 2007-08-09 | Council Of Scientific And Industrial Research | An improved process for preparation of magnesium oxide |
| CN101759207A (en) * | 2009-01-19 | 2010-06-30 | 陕西嘉裕化工有限公司 | Process for producing high-purity magnesium hydroxide through brine-lime method |
| CN107021655A (en) * | 2017-05-25 | 2017-08-08 | 中国科学院青海盐湖研究所 | The method of comprehensive utilization of industrial residue |
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| WO2007088407A1 (en) * | 2006-01-31 | 2007-08-09 | Council Of Scientific And Industrial Research | An improved process for preparation of magnesium oxide |
| CN1962446A (en) * | 2006-12-07 | 2007-05-16 | 上海交通大学 | Method for extracting magnesium hydroxide from thick salt water using calcium carbide dreg |
| CN101759207A (en) * | 2009-01-19 | 2010-06-30 | 陕西嘉裕化工有限公司 | Process for producing high-purity magnesium hydroxide through brine-lime method |
| CN107021655A (en) * | 2017-05-25 | 2017-08-08 | 中国科学院青海盐湖研究所 | The method of comprehensive utilization of industrial residue |
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