CN112479237A - Method for preparing anhydrous magnesium carbonate by directly utilizing salt lake brine - Google Patents
Method for preparing anhydrous magnesium carbonate by directly utilizing salt lake brine Download PDFInfo
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- magnesium carbonate
- anhydrous magnesium
- salt lake
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- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 title claims abstract description 86
- 239000012267 brine Substances 0.000 title claims abstract description 36
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- 239000000243 solution Substances 0.000 claims abstract description 28
- 239000011259 mixed solution Substances 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004202 carbamide Substances 0.000 claims abstract description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 13
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000000967 suction filtration Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000003337 fertilizer Substances 0.000 claims abstract description 5
- 229940072033 potash Drugs 0.000 claims abstract description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 5
- 235000015320 potassium carbonate Nutrition 0.000 claims abstract description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 4
- 229910052796 boron Inorganic materials 0.000 claims abstract description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims abstract description 4
- 235000019341 magnesium sulphate Nutrition 0.000 claims abstract description 4
- 239000001103 potassium chloride Substances 0.000 claims abstract description 4
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000011777 magnesium Substances 0.000 claims description 22
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 230000001276 controlling effect Effects 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 9
- 238000002360 preparation method Methods 0.000 abstract description 8
- 239000012796 inorganic flame retardant Substances 0.000 abstract description 3
- 239000004033 plastic Substances 0.000 abstract description 2
- 229920003023 plastic Polymers 0.000 abstract description 2
- 239000005060 rubber Substances 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000001095 magnesium carbonate Substances 0.000 description 17
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 17
- 229910052749 magnesium Inorganic materials 0.000 description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 11
- 235000014380 magnesium carbonate Nutrition 0.000 description 10
- 239000002245 particle Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 241001131796 Botaurus stellaris Species 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- 159000000003 magnesium salts Chemical class 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- ULELVMREKQKXGU-UHFFFAOYSA-M O.O.O.O.C([O-])([O-])=O.[NH4+].[Mg+] Chemical compound O.O.O.O.C([O-])([O-])=O.[NH4+].[Mg+] ULELVMREKQKXGU-UHFFFAOYSA-M 0.000 description 1
- 241000219977 Vigna Species 0.000 description 1
- 235000010726 Vigna sinensis Nutrition 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- YXIZUXGMHQUZQH-UHFFFAOYSA-N diazanium hydrogen carbonate Chemical compound [NH4+].[NH4+].OC([O-])=O.OC([O-])=O YXIZUXGMHQUZQH-UHFFFAOYSA-N 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229930013686 lignan Natural products 0.000 description 1
- 150000005692 lignans Chemical class 0.000 description 1
- 235000009408 lignans Nutrition 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Images
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
- C01F5/24—Magnesium carbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
Abstract
The invention relates to a method for preparing anhydrous magnesium carbonate by directly utilizing salt lake brine, which comprises the following steps: firstly extracting potash magnesium sulphate fertilizer, then extracting potassium chloride and then extracting boron from salt lake brine to finally obtain sulfate type brine; adding urea into brine, adjusting the pH value of the mixed solution to 7.0-14.0, uniformly stirring, placing in a reaction kettle, controlling the reaction temperature to 120-250 ℃, reacting for 1-12 h, and naturally cooling to room temperature to obtain a reaction solution; and (3) carrying out suction filtration and washing on the reaction liquid until the pH value is 7.0, and drying at the temperature of 40-200 ℃ for 4-48 h to obtain the anhydrous magnesium carbonate. The preparation method provided by the invention is simple to operate, efficient and energy-saving, the used raw materials are low in price, the large-scale industrial production of the anhydrous magnesium carbonate powder can be realized, and the prepared anhydrous magnesium carbonate can be used as a novel inorganic flame retardant and can be used as an inorganic flame retardant additive for products such as plastics, rubber and the like.
Description
Technical Field
The invention belongs to the technical field of preparation of anhydrous magnesium carbonate micro-nano materials, and particularly relates to a method for preparing anhydrous magnesium carbonate by directly utilizing salt lake brine.
Background
The Qinghai firewood wood basin is a lake region with the most abundant salt lake resources in China, and the proven magnesium salt reserves for mining are about 65 hundred million tons, which account for about 96.8 percent of the reserves in China. The magnesium salt in the salt lake is characterized in that magnesium and salts such as potassium, sodium, calcium, lithium and the like are closely symbiotic. However, due to the lack of applicable technologies and corresponding basic research, the development and utilization of magnesium resources lags behind the development of potassium and lithium resources in salt lakes. During the production of potassium salt, 10 times of magnesium salt as potassium salt is discharged. The old brine is the part which is left in the production of the potash fertilizer and is difficult to recycle, and most enterprises treat the old brine as waste materials at present. After the potassium element is extracted, a large amount of high-magnesium brine is discharged back to a salt pan, so that not only is the magnesium resource wasted greatly, but also the depletion of the potassium resource and the serious pollution to the environment are caused. In recent years, many researches on the preparation of magnesium-based functional materials with high added value, such as magnesium hydroxide, basic magnesium carbonate, magnesium oxide and the like, by taking salt lake old brine as a raw material are carried out, so that waste materials are changed into valuable materials, and an important way for utilizing salt lake magnesium resources and solving the problem of environmental protection is provided.
With the rapid development of the aviation industry, the aerospace industry, the electronics industry, the information industry and the like, magnesium and magnesium alloy become green engineering materials with the best development and application potential due to good metal characteristics. The anhydrous magnesium carbonate as a novel magnesium-based functional material is widely concerned by researchers due to the unique physicochemical property of the anhydrous magnesium carbonate, and the preparation and the application of the anhydrous magnesium carbonate become scientific research hotspots. Anhydrous magnesium carbonate, i.e. containing no crystal water in the crystal structure, of formula MgCO3. The anhydrous magnesium carbonate powder is nontoxic and tasteless, can stably exist in air environment, and is insoluble in water. In nature, anhydrous magnesium carbonate is mainly found in magnesite and dolomite, and thus anhydrous magnesium carbonate prepared by direct grinding processing of minerals usually contains Fe2+，Mn2+And the like, and the quality and the purity are not high. The anhydrous magnesium carbonate can replace basic magnesium carbonate and hydrated magnesium carbonate to be added into plastics, rubber, ceramics and daily necessities, has the functions of flame retardance, reinforcement, abrasion resistance and the like, and most importantly, the anhydrous magnesium carbonate can be decomposed to generate MgO and release a large amount of CO when being heated or calcined to the temperature of 500 ℃ at 300 DEG C2The endothermic amount per unit in the reaction process was 864J/g. Anhydrous magnesium carbonate, because of the ability to absorb a large amount of heat during the decomposition process, the product is notContaining toxic substances and generating a large amount of CO2The flame retardant can effectively dilute combustible gas and block oxygen sources, so that the flame retardant is regarded as a novel inorganic flame retardant by scientific researchers and can be used for preparing fireproof coatings and fireproof flame retardance of various electrical appliance materials.
Before 2007, anhydrous magnesium carbonate, a chemical product, is not successfully synthesized at home and abroad, and the anhydrous magnesium carbonate only exists in the basic magnesium carbonate synthesis process all the time, namely a metastable product, and is never used independently as an independent chemical product. Until the Shenxing team of Beijing university of science and technology prepared anhydrous magnesium carbonate by a two-step process for the first time, they utilized MgCl2•6H2O is a magnesium source and reacts with CO in an aqueous solution system at normal pressure2And NH3Firstly, preparing intermediate product magnesium ammonium carbonate tetrahydrate double salt crystal Mg (NH)4)2(CO3)2•4H2O, and then thermally decomposing the crystal at 200 ℃ to prepare the crystal of the whisker-shaped anhydrous magnesium carbonate, but the production process still has the problems of single product, high cost, intermittent process and the like. The anhydrous magnesium carbonate is still in the initial stage of research as a new chemical product, and is more and more concerned by broad scholars, and researchers also research some methods for preparing anhydrous magnesium carbonate in laboratories in recent years and obtain a series of achievements. In foreign countries, Swanson et al first use magnesite as raw material, and introduce CO into a high-temperature high-pressure reaction vessel at 200 deg.C and 30 atm2To prepare anhydrous MgCO with the average grain diameter of 2-4 um3. Sandengen et al, adding 3MgCO at normal pressure3•Mg(OH)2•3H2O is dissolved in 95 wt.% aqueous diethylene glycol solution, and CO is continuously introduced from the outside2Stirring and refluxing for reaction for 3 days at 150 ℃ to generate anhydrous MgCO3. Cheung et al prepare anhydrous MgCO by sol-gel method3The content of the mesoporous powder is 82-86 wt.%, and the application of the powder as a drug carrier is researched. Lorenzo and the like respectively heat the basic magnesium carbonate for 2-240 hours at 120 ℃, 150 ℃ and 180 ℃, and the preparation of anhydrous MgCO from the basic magnesium carbonate is analyzed3The kinetic process of (a). In China, the Chinese character 'Liangwen' is fixed through high temperature and high pressureBy using MgCO3•3H2O is used as a raw material, and the anhydrous MgCO can be prepared by reacting for 1 hour at the high temperature and the high pressure of 800 ℃ and 3GPa3. The three-dimensional flower-like anhydrous MgCO with the average grain diameter of about 15 um can be prepared under the conditions of 180 ℃ and 24 hours of hydrothermal treatment by using urea as a precipitator, magnesium chloride as a magnesium source and sodium citrate for assisting the hydrothermal reaction in high vibration and the like3And three-dimensional spherical anhydrous MgCO having an average particle diameter of about 20 um3. Lignan and the like can prepare rhombohedral anhydrous MgCO with the thickness of about 10 um by taking magnesium chloride as a magnesium source and an ammonium carbonate-ammonium bicarbonate system as a precipitator under the conditions of hydrothermal reaction at 140 ℃ for 9 hours3. The anhydrous MgCO with rhombohedral structure is prepared by the cowpea and the like through a two-step method3And (3) powder. Self-made MgCO by Tianpeng, etc3•3H2O is taken as a raw material, and is mixed with NH4Cl, researching the influence of hydrothermal temperature, time, system polarity, precursor size and the like on the structure and appearance of the product, carrying out hydrothermal reaction for 24 hours at 160 ℃, and preparing the anhydrous MgCO3. Ni and the like are used for preparing rhombohedral anhydrous MgCO with the average grain diameter of 30 um by taking hexamethylenetetramine and magnesium acetate as raw materials and reacting for 24 hours at the temperature of 160 DEG C3. Lou et al prepared single crystal anhydrous MgCO by mixing metallic sodium, carbon tetrachloride and magnesium carbonate, and reacting at 500 deg.C for 20 hr3. The invention discloses a method for preparing anhydrous magnesium carbonate by using magnesium-containing mother liquor, which mainly comprises the steps of introducing ammonia gas into the mother liquor, adjusting the pH value to 10.0-12.0 to obtain Mg (OH)2Adding CO to the slurry2Preparing carbonization mother liquor until the pH value is 7.5-8.0, and heating the carbonization mother liquor at the temperature of 30-80 ℃ to prepare MgCO3•3H2O, then MgCO3•3H2Calcining O at the temperature of 200-300 ℃ to prepare the anhydrous magnesium carbonate.
In general, Mg is present at room temperature and normal pressure2+Is very easy to react with water molecules or OH-The hydrous magnesium carbonate is generated by combination, so the preparation condition of the anhydrous magnesium carbonate is generally carried out at high temperature and high pressure at present, the reaction condition is harsh, the reaction time is long, the requirement on equipment is high, and CO is required to be continuously introduced from the outside2And the preparation process is complicated. And the anhydrous magnesium carbonate prepared at present has the problems of poor dispersity, uneven size and the like. Industrial powder materials widely used in various fields need to have the characteristics of uniform size, good dispersibility and the like. Therefore, for anhydrous MgCO3One of the research directions is to improve the reaction efficiency, simplify the reaction process, shorten the reaction time and prepare the anhydrous MgCO with uniform size and good dispersibility3And (3) powder materials.
Disclosure of Invention
The technical problem to be solved is as follows: aiming at the problems of harsh reaction conditions, long reaction time, high requirement on equipment, complicated preparation process and the like existing in the process of extracting anhydrous magnesium carbonate in the prior art, the invention provides the method for preparing the anhydrous magnesium carbonate by directly utilizing the salt lake brine, and the method has the advantages of simple process, mild conditions, low raw material price, good dispersibility and uniform size of the prepared anhydrous magnesium carbonate.
The technical scheme is as follows: a method for preparing anhydrous magnesium carbonate by directly utilizing salt lake brine comprises the following steps:
the method comprises the following steps: firstly extracting potash magnesium sulphate fertilizer, then extracting potassium chloride and then extracting boron from salt lake brine to finally obtain sulfate type brine;
step two: adding urea into the brine obtained in the first step, adjusting the pH value of the mixed solution to 7.0-14.0, uniformly stirring, placing the mixed solution into a reaction kettle, controlling the reaction temperature to be 120-250 ℃, reacting for 1-12 hours, and naturally cooling to room temperature to obtain a reaction solution;
step three: and (4) carrying out suction filtration and washing on the reaction liquid obtained in the step two until the pH value is 7.0, and drying at the temperature of 40-200 ℃ for 4-48 h to obtain the anhydrous magnesium carbonate.
In the step one, the urea and the Mg in the brine2+The molar ratio of (0.5-4.0): 1.
And in the second step, the stirring time is 10-60 min, and the stirring speed is 100-600 r/min.
NaOH and Na are used in the second step2CO3、NaHCO3Or KOH adjusts the pH value of the mixed solution.
The above NaOH and Na2CO3、NaHCO3Or the concentration of KOH is from 0.1mol/L to its corresponding saturation concentration.
Has the advantages that: the method for preparing anhydrous magnesium carbonate by directly utilizing salt lake brine provided by the invention has the following beneficial effects:
1. the method has the advantages of simple process flow, mild conditions, simple required equipment and easy operation;
2. the invention has lower production cost and low price of the used raw materials, and the waste old brine of the salt lake is used as the raw material, thereby not only increasing the additional utilization value of the salt lake, but also being beneficial to solving the environmental protection problem;
3. the method is energy-saving and efficient, and the anhydrous magnesium carbonate with good dispersity and uniform particle size can be prepared in a short time.
Drawings
FIG. 1 is an SEM photograph of anhydrous magnesium carbonate prepared in example 1;
FIG. 2 is an SEM photograph of anhydrous magnesium carbonate prepared in example 2;
FIG. 3 is an SEM photograph of anhydrous magnesium carbonate prepared in example 3;
FIG. 4 is an SEM photograph of anhydrous magnesium carbonate prepared in example 4;
FIG. 5 is an SEM photograph of anhydrous magnesium carbonate prepared in example 5;
FIG. 6 shows XRD results of anhydrous magnesium carbonate prepared in examples 1-5.
Detailed Description
In order to facilitate an understanding of the present invention, the present invention will be described more fully and in detail with reference to the preferred embodiments, but the scope of the present invention is not limited to the specific embodiments described below.
The chemical reagents used in the examples of the present invention, unless otherwise specified, are commercially available in a conventional manner.
The salt lake brines used in the examples below were all taken from the west Ginell lake. The salt lake brine is firstly extracted with potash magnesium sulphate fertilizer, and then potassium chloride and boron are extracted to obtain sulfate type brine. The salt lake brine is pretreated to remove particle impurities such as silt and the like.
Example 1
A method for preparing anhydrous magnesium carbonate by directly utilizing salt lake brine comprises the following steps: adding urea into bittern to control the content of urea and Mg in bittern2+Adjusting the initial pH of the mixed solution to 8.5 by using a 5 mol/L NaOH solution with a molar ratio of 2.5:1, magnetically stirring the mixed solution for 20 min at a stirring speed of 200 r/min, placing the mixed solution into a 100 mL reaction kettle, placing the reaction kettle into an oven, setting the temperature of the oven to be 180 ℃, and naturally cooling the reaction kettle to room temperature after reacting for 6 h to obtain a reaction solution; and (3) carrying out suction filtration on the reaction solution, washing the reaction solution for three times by using deionized water until the pH value is 7.0, and drying the reaction solution for 12 hours in a drying oven at the temperature of 80 ℃ to obtain anhydrous magnesium carbonate powder. As can be seen from FIG. 1, the particle size of the obtained anhydrous magnesium carbonate was about 5 um, and the yield of the anhydrous magnesium carbonate was 71.3% in the reaction system.
Example 2
A method for preparing anhydrous magnesium carbonate by directly utilizing salt lake brine comprises the following steps: adding urea into bittern to control the content of urea and Mg in bittern2+Adjusting the initial pH of the mixed solution to 8.0 by using a 5 mol/L NaOH solution according to a molar ratio of 2.0:1, magnetically stirring the mixed solution for 20 min at a stirring speed of 300 r/min, placing the mixed solution into a 100 mL reaction kettle, placing the reaction kettle into an oven, setting the temperature of the oven to be 180 ℃, and naturally cooling the reaction kettle to room temperature after reacting for 3 h to obtain a reaction solution; and (3) carrying out suction filtration on the reaction solution, washing the reaction solution for three times by using deionized water until the pH value is 7.0, and drying the reaction solution for 12 hours in a drying oven at the temperature of 80 ℃ to obtain anhydrous magnesium carbonate powder. As can be seen from FIG. 2, the particle size of the obtained anhydrous magnesium carbonate is about 3-6 um, and the yield of the anhydrous magnesium carbonate in the reaction system is 61.9%.
Example 3
A method for preparing anhydrous magnesium carbonate by directly utilizing salt lake brine comprises the following steps: adding urea into bittern to control the content of urea and Mg in bittern2+Adjusting the initial pH of the mixed solution to 9.0 with 5 mol/L NaOH solution at a molar ratio of 2.5:1, magnetically stirring the mixed solution for 20 min at a stirring speed of 400 r/min, placing the mixed solution in a 100 mL reaction kettle, and reactingPlacing the reaction kettle into an oven, setting the temperature of the oven to be 180 ℃, and naturally cooling the reaction kettle to room temperature after reacting for 2 hours to obtain reaction liquid; and (3) carrying out suction filtration on the reaction solution, washing the reaction solution for three times by using deionized water until the pH value is 7.0, and drying the reaction solution for 12 hours in a drying oven at the temperature of 80 ℃ to obtain anhydrous magnesium carbonate powder. As can be seen from FIG. 3, the particle size of the obtained anhydrous magnesium carbonate is about 3-6 um, and the yield of the anhydrous magnesium carbonate in the reaction system is 70.1%.
Example 4
A method for preparing anhydrous magnesium carbonate by directly utilizing salt lake brine comprises the following steps: adding urea into bittern to control the content of urea and Mg in bittern2+Adjusting the initial pH of the mixed solution to 9.7 by using a 5 mol/L NaOH solution according to a molar ratio of 3.5:1, magnetically stirring the mixed solution for 20 min at a stirring speed of 500 r/min, placing the mixed solution into a 100 mL reaction kettle, placing the reaction kettle into an oven, setting the temperature of the oven to be 180 ℃, and naturally cooling the reaction kettle to room temperature after reacting for 6 h to obtain a reaction solution; and (3) carrying out suction filtration on the reaction solution, washing the reaction solution for three times by using deionized water until the pH value is 7.0, and drying the reaction solution for 12 hours in a drying oven at the temperature of 80 ℃ to obtain anhydrous magnesium carbonate powder. As can be seen from FIG. 4, the particle size of the obtained anhydrous magnesium carbonate is about 7-10 um, and the yield of the anhydrous magnesium carbonate in the reaction system is 74.3%.
Example 5
A method for preparing anhydrous magnesium carbonate by directly utilizing salt lake brine comprises the following steps: adding urea into bittern to control the content of urea and Mg in bittern2+Adjusting the initial pH of the mixed solution to 9.7 by using a 5 mol/L NaOH solution according to a molar ratio of 3.5:1, magnetically stirring the mixed solution for 20 min at a stirring speed of 500 r/min, placing the mixed solution into a 100 mL reaction kettle, placing the reaction kettle into an oven, setting the temperature of the oven to be 180 ℃, and naturally cooling the reaction kettle to room temperature after reacting for 3 h to obtain a reaction solution; and (3) carrying out suction filtration on the reaction solution, washing the reaction solution for three times by using deionized water until the pH value is 7.0, and drying the reaction solution for 12 hours in a drying oven at the temperature of 80 ℃ to obtain anhydrous magnesium carbonate powder. As can be seen from FIG. 5, the particle size of the obtained anhydrous magnesium carbonate is about 3-6 um, and the yield of the anhydrous magnesium carbonate in the reaction system is 67.7%.
XRD results of the anhydrous magnesium carbonate prepared in the above examples are shown in FIG. 6, and the results show that the anhydrous magnesium carbonate prepared is anhydrous magnesium carbonate, which corresponds to JCPDS 08-0479.
The embodiments of the present invention have been described in detail with reference to the above examples, but the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (5)
1. A method for preparing anhydrous magnesium carbonate by directly utilizing salt lake brine is characterized by comprising the following steps:
the method comprises the following steps: firstly extracting potash magnesium sulphate fertilizer, then extracting potassium chloride and then extracting boron from salt lake brine to finally obtain sulfate type brine;
step two: adding urea into the brine obtained in the first step, adjusting the pH value of the mixed solution to 7.0-14.0, uniformly stirring, placing the mixed solution into a reaction kettle, controlling the reaction temperature to be 120-250 ℃, reacting for 1-12 hours, and naturally cooling to room temperature to obtain a reaction solution;
step three: and (4) carrying out suction filtration and washing on the reaction liquid obtained in the step two until the pH value is 7.0, and drying at the temperature of 40-200 ℃ for 4-48 h to obtain the anhydrous magnesium carbonate.
2. The method for preparing anhydrous magnesium carbonate by directly utilizing salt lake brine according to claim 1, which is characterized in that: in the second step, the urea and Mg in the brine2+The molar ratio of (0.5-4.0): 1.
3. The method for preparing anhydrous magnesium carbonate by directly utilizing salt lake brine according to claim 1, which is characterized in that: and in the second step, the stirring time is 10-60 min, and the stirring speed is 100-600 r/min.
4. The method for preparing anhydrous magnesium carbonate by directly utilizing salt lake brine according to claim 1, which is characterized in that: NaOH and Na are used in the second step2CO3、NaHCO3Or regulating the pH value of the mixed solution by KOH。
5. The method for preparing anhydrous magnesium carbonate by directly utilizing salt lake brine according to claim 4, which is characterized in that: the NaOH and the Na2CO3、NaHCO3Or the concentration of KOH is from 0.1mol/L to its corresponding saturation concentration.
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