CN119143160B - Method for preparing high-purity magnesium sulfate - Google Patents
Method for preparing high-purity magnesium sulfate Download PDFInfo
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- CN119143160B CN119143160B CN202411597256.5A CN202411597256A CN119143160B CN 119143160 B CN119143160 B CN 119143160B CN 202411597256 A CN202411597256 A CN 202411597256A CN 119143160 B CN119143160 B CN 119143160B
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- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 title claims abstract description 120
- 229910052943 magnesium sulfate Inorganic materials 0.000 title claims abstract description 59
- 235000019341 magnesium sulphate Nutrition 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 22
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 42
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 35
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 35
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 30
- 239000010459 dolomite Substances 0.000 claims abstract description 28
- 229910000514 dolomite Inorganic materials 0.000 claims abstract description 28
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 21
- 238000001354 calcination Methods 0.000 claims abstract description 16
- 239000004642 Polyimide Substances 0.000 claims abstract description 14
- 229920001721 polyimide Polymers 0.000 claims abstract description 14
- 238000000227 grinding Methods 0.000 claims abstract description 12
- 238000001020 plasma etching Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims description 62
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000001914 filtration Methods 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000006260 foam Substances 0.000 claims description 16
- 238000002791 soaking Methods 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 238000013532 laser treatment Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 230000000630 rising effect Effects 0.000 claims description 2
- 238000005530 etching Methods 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 12
- 239000012535 impurity Substances 0.000 abstract description 11
- 238000001179 sorption measurement Methods 0.000 abstract description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011575 calcium Substances 0.000 abstract description 6
- 229910052791 calcium Inorganic materials 0.000 abstract description 6
- 229910052742 iron Inorganic materials 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 6
- 235000021251 pulses Nutrition 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229910001425 magnesium ion Inorganic materials 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 3
- 239000001095 magnesium carbonate Substances 0.000 description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 206010010774 Constipation Diseases 0.000 description 1
- 201000004624 Dermatitis Diseases 0.000 description 1
- 206010070538 Gestational hypertension Diseases 0.000 description 1
- 201000005624 HELLP Syndrome Diseases 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- 208000005347 Pregnancy-Induced Hypertension Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 206010053262 Skin swelling Diseases 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000013527 bean curd Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910001748 carbonate mineral Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229930002875 chlorophyll Natural products 0.000 description 1
- 235000019804 chlorophyll Nutrition 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 235000013365 dairy product Nutrition 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000013527 degreasing agent Substances 0.000 description 1
- 238000005237 degreasing agent Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 208000002296 eclampsia Diseases 0.000 description 1
- 229910052564 epsomite Inorganic materials 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000000834 fixative Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 150000004688 heptahydrates Chemical class 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000001990 intravenous administration Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000008141 laxative Substances 0.000 description 1
- 230000002475 laxative effect Effects 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-UHFFFAOYSA-L 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 201000011461 pre-eclampsia Diseases 0.000 description 1
- 208000036335 preeclampsia/eclampsia 1 Diseases 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 208000011580 syndromic disease Diseases 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 238000011282 treatment 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
- C01F5/40—Magnesium sulfates
-
- 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)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
本发明属于化工产品制备领域，特别涉及一种制备高纯硫酸镁的方法。本申请通过对白云石进行研磨、煅烧以及氯化镁溶液浸泡处理，利用激光处理和等离子体刻蚀技术制备具有高吸附能力的多孔石墨烯薄膜，对硫酸镁进行提纯。本申请是为了解决现有技术中以白云石为原料制备的硫酸镁中含有钙、铁等杂质，纯度较低，无法满足下游产业的高纯度需求问题，本申请提供一种制备高纯硫酸镁的方法，本申请利用激光处理在聚酰亚胺片材上生成石墨烯，在氧化镁制备硫酸镁的过程中起到吸附作用，既保证了所得硫酸镁产品的纯度，又保证了硫酸镁产品不在吸附中损失。The present invention belongs to the field of chemical product preparation, and particularly relates to a method for preparing high-purity magnesium sulfate. The present application prepares a porous graphene film with high adsorption capacity by grinding, calcining and immersing dolomite in a magnesium chloride solution, and purifies the magnesium sulfate by laser processing and plasma etching technology. The present application is to solve the problem that the magnesium sulfate prepared from dolomite as a raw material in the prior art contains impurities such as calcium and iron, and the purity is low, which cannot meet the high purity requirements of downstream industries. The present application provides a method for preparing high-purity magnesium sulfate. The present application uses laser processing to generate graphene on a polyimide sheet, which plays an adsorption role in the process of preparing magnesium sulfate from magnesium oxide, which not only ensures the purity of the obtained magnesium sulfate product, but also ensures that the magnesium sulfate product is not lost during adsorption.
Description
Technical Field
The invention belongs to the field of chemical product preparation, and particularly relates to a method for preparing high-purity magnesium sulfate.
Background
Magnesium sulfate is an inorganic salt consisting of one magnesium ion and one sulfate ion. It is colorless crystal or white powder at normal temperature and has good water solubility. Magnesium sulfate has a variety of hydrate forms, the most common of which is heptahydrate, also known as epsomite, and is useful in medicine and agriculture. The solubility of magnesium sulfate in water is high, increasing with increasing temperature. It loses crystal water when heated, first becomes monohydrate, and is dehydrated to anhydrous magnesium sulfate when heated further. Anhydrous magnesium sulfate is relatively stable at high temperatures, but under extreme conditions may decompose into magnesium oxide and sulfur trioxide.
Magnesium sulfate is very widely used in the medical field. It can be used as a laxative to help relieve constipation symptoms, and intravenous magnesium sulfate solution is used clinically to treat pregnancy-induced hypertension syndrome, preeclampsia and eclampsia, and when topically applied, magnesium sulfate solution can be used to treat skin inflammation and swelling. In agriculture, magnesium sulfate is also an important trace element fertilizer, magnesium is a component part of chlorophyll and is important for photosynthesis of plants, magnesium sulfate can supplement magnesium element in soil and improve the growth environment of crops, and in addition, magnesium sulfate is also used for adjusting the pH value of the soil, so that plants can absorb other nutrient elements better. Magnesium sulfate has applications in a number of industrial fields. In the textile industry, it serves as a dye fixative to aid in better adhesion of the dye to the fabric, in the paper industry, magnesium sulfate is used to adjust the pH of the pulp and as a filler and coating aid, in leather processing, magnesium sulfate serves as a softener and degreasing agent to improve the quality of the leather. In addition, magnesium sulfate is also used to make other magnesium salts, such as magnesium hydroxide, magnesium carbonate, and the like. In the food industry, magnesium sulfate is sometimes used as a food additive. The modified starch can be used as a coagulant for making bean curd and a stabilizer for processing dairy products. However, due to the side effects which may be caused in the human body, the use of magnesium sulfate in foods is strictly regulated, and the food safety standards of various countries are met, so that the market demand of high-purity magnesium sulfate is very large.
Magnesium sulfate may be extracted from natural sources such as sea water, salt lake water or minerals. The resources are rich in magnesium and other minerals, and pure magnesium sulfate can be obtained through evaporation concentration, precipitation, filtration and other processes. Magnesium sulfate can also be prepared by magnesium oxide, dolomite is a common carbonate mineral, the main components are calcium carbonate and magnesium carbonate, the dolomite is firstly subjected to high-temperature calcination to generate calcium oxide, magnesium oxide and carbon dioxide, the calcium oxide and the magnesium oxide are required to be separated by a physical or chemical method, but calcium in the calcium oxide is difficult to completely remove, besides the main components, the dolomite also contains impurity elements such as iron, silicon, aluminum and the like, and the impurities are partially converted into oxides in the calcination process and enter a final magnesium oxide product, so that the purity of the magnesium sulfate is influenced in the process of preparing the magnesium sulfate from the magnesium oxide.
Disclosure of Invention
In order to solve the problems that in the prior art, the magnesium sulfate prepared by taking dolomite as a raw material contains impurities such as calcium, iron and the like, has low purity and cannot meet the high-purity requirement of downstream industries, the application provides the method for preparing the high-purity magnesium sulfate.
The application provides a method for preparing high-purity magnesium sulfate, which comprises the following steps:
S1, grinding dolomite, calcining, adding a magnesium chloride solution, adding sodium hydroxide, heating, soaking for 30-60min, filtering and drying;
S2, after the reaction furnace is heated to 500 ℃, putting the product obtained in the step S1 into the reaction furnace, heating to 1000 ℃ and obtaining magnesium oxide at a heating rate of 150 ℃ per hour;
s3, respectively cleaning the polyimide sheet by deionized water and alcohol in an ultrasonic manner, performing laser treatment by using a nanosecond laser after drying, wherein the laser power is 3.0-5.5W, the scanning speed is 120-200mm/S, obtaining a laser-induced porous graphene film, and performing oxygen plasma etching on the film;
s4, adding the magnesium oxide obtained in the step S2 into water, adding a porous graphene material, then dripping dilute sulfuric acid into the solution, carrying out severe reaction with foam, stopping adding acid when the foam is reduced, and then filtering by using a filter screen;
S5, adjusting the pH value of the solution obtained by filtering the S4 to 5-6 by sulfuric acid, heating and concentrating, wherein the heating temperature is 160-180 ℃, the heating time is 30-60min, and then drying in an oven at a low temperature, the drying temperature is 40-55 ℃ and the time is 3-4 hours, so that the high-purity magnesium sulfate is obtained.
Further, in step S3, the laser wavelength of the nanosecond laser is 1064nm, the pulse duration is 10ns, and the repetition frequency is 800KHz.
Further, the oxygen plasma etching in the step S3 is performed under the pressure of 0.1Pa-60Pa and the power of 1w-60w for 60-120 seconds.
Further, the mass ratio of the magnesium oxide to the water in the step S4 is 1:1-2.
Further, the polyimide sheet in step S3 has a thickness of 120 to 180. Mu.m.
Further, after grinding the dolomite in the step S1 to 200-250 meshes, the calcining temperature is 500-800 ℃, the heating rate is 150-200 ℃ per hour, the calcining time is kept for 1-3 hours, then the calcining time is heated to 900-1000 ℃ and the calcining time is kept for 0.5-1 hour.
Further, the magnesium chloride solution in the step S1 is 0.5mol/L, the temperature is raised to 50-60 ℃, and the pH value is kept at 11 when sodium hydroxide is added for soaking.
Further, the mass ratio of the dolomite and the magnesium chloride in the step S1 is 1:1-1.5.
Further, the weight ratio of the magnesium oxide to the porous graphene material in the step S4 is 1:0.01-0.1.
The beneficial effects of the application are as follows:
1. According to the method, the carbonate component in the dolomite is decomposed through grinding, calcining and soaking treatment of magnesium chloride solution, so that part of impurities, especially part of calcium and iron elements, are removed. The dolomite is ground into fine particles, so that the surface active sites are increased, and subsequent pyrolysis and chemical reaction are facilitated. High temperature calcination breaks down the carbonates in the dolomite into calcium oxide and magnesium oxide and releases carbon dioxide. At high temperature, the magnesium chloride solution can form more easily separated precipitate with the incompletely decomposed dolomite under alkaline condition, so as to obtain magnesium hydroxide. When the pH value is 10, magnesium ions can be promoted to form magnesium hydroxide precipitates, and other impurity ions are not easy to form precipitates under the pH value condition, so that preliminary purification is realized. The temperature is gradually increased from 500 ℃ to 1000 ℃, so that residual calcium carbonate and magnesium carbonate can be decomposed, impurities are prevented from being left in the final product, the temperature rising rate of 150 ℃ per hour ensures the uniform temperature rise, and the structural change of magnesium oxide caused by local overheating is prevented.
2. The application prepares the porous graphene film with high adsorption capacity by utilizing laser processing and plasma etching technology. The graphene structure can be formed on the surface of the polyimide sheet through processing on the polyimide sheet by a nanosecond laser, and the polyimide sheet has large specific surface area and good adsorption performance. Through oxygen plasma etching, the structure of the graphene film can be further optimized, the impurity adsorption capacity of the graphene film is improved, a large number of adsorption sites are provided for the large specific surface area of the graphene, and impurities such as calcium, iron and the like in the solution can be effectively adsorbed. The inventor finds that when the laser power is 3.0-5.5W, the obtained graphene film has a good adsorption effect on impurities in magnesium sulfate, and when the laser power is more than 5.5W, the graphitization degree of the film is better than that of the laser power of 3.0-5.5W, but the capability of adsorbing calcium and iron impurities in the magnesium sulfate is lower than that of the laser power of 3.0-5.5W. And in the power range, the adsorption capacity of the obtained graphene film on calcium ions is obviously higher than that of magnesium ions, which is probably because the hole sites of the graphene film are stronger in adsorption on the calcium ions.
3. The pH value is adjusted to 5-6 in the last step, so that the magnesium ions can be prevented from forming precipitate again, and the stability of the magnesium sulfate solution is ensured. Heating and concentrating at 160-180deg.C can accelerate water evaporation to promote magnesium sulfate crystal precipitation, and low temperature drying can prevent magnesium sulfate crystal from decomposition or deterioration at high temperature to maintain its purity.
Detailed Description
The technical scheme and effects of the invention are further described by the following specific examples. The following examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. Simple modifications of the invention using the inventive concept are within the scope of the invention as claimed.
The apparatus used in the preparation method of the present invention may employ any apparatus known in the art. The raw materials used in the present invention are commercially available unless otherwise indicated.
Example 1
S1, grinding dolomite to 200 meshes, keeping the calcination temperature at 800 ℃ and the heating rate at 200 ℃ per hour for 1 hour, then heating to 1000 ℃ and keeping for 0.5 hour, cooling, adding 0.5mol/L magnesium chloride solution, wherein the mass ratio of the dolomite to the magnesium chloride is 1:1, then adding sodium hydroxide to adjust the pH value to 11, heating to 50 ℃, soaking for 60 minutes, filtering and drying;
S2, after the reaction furnace is heated to 500 ℃, putting the product obtained in the step S1 into the reaction furnace, heating to 1000 ℃ and obtaining magnesium oxide at a heating rate of 150 ℃ per hour;
S3, respectively ultrasonically cleaning a polyimide sheet with the thickness of 120 mu m by deionized water and alcohol, drying, and then performing laser treatment by using a nanosecond laser with the laser wavelength of 1064nm, the pulse duration of 10ns, the repetition frequency of 800KHz, the laser power of 3.0W and the scanning speed of 120mm/S to obtain a laser-induced porous graphene film, and then performing oxygen plasma etching on the film under the pressure of 0.1Pa and the power of 60W for 60 seconds;
S4, adding 100g of magnesium oxide obtained in the step S2 into water, wherein the weight ratio of the magnesium oxide to the water is 1:1, adding 1g of the porous graphene material obtained in the step S3, dripping dilute sulfuric acid into the solution, carrying out severe reaction with foam, stopping adding acid when the foam is reduced, and filtering;
S5, regulating the pH value of the solution obtained by filtering the S4 to 5 by sulfuric acid, heating and concentrating, wherein the heating temperature is 160 ℃, the heating time is 60min, then drying in an oven at a low temperature, and the drying temperature is 40 ℃ for 4 hours, thus obtaining 258.56g of high-purity magnesium sulfate with the purity of more than or equal to 99.98%.
Example 2
S1, grinding dolomite to 250 meshes, keeping the calcination temperature at 500 ℃ and the heating rate at 150 ℃ per hour for 3 hours, then heating to 900 ℃ and keeping for 1 hour, cooling, adding 0.5mol/L magnesium chloride solution, wherein the mass ratio of the dolomite to the magnesium chloride is 1:1.5, adding sodium hydroxide to adjust the pH value to 11, heating to 60 ℃, soaking for 30 minutes, filtering and drying;
S2, after the reaction furnace is heated to 500 ℃, putting the product obtained in the step S1 into the reaction furnace, heating to 1000 ℃ and obtaining magnesium oxide at a heating rate of 150 ℃ per hour;
S3, respectively ultrasonically cleaning a polyimide sheet with the thickness of 180 mu m by deionized water and alcohol, drying, and then performing laser treatment by using a nanosecond laser with the laser wavelength of 1064nm, the pulse duration of 10ns, the repetition frequency of 800KHz, the laser power of 5.5W and the scanning speed of 200mm/S to obtain a laser-induced porous graphene film, and then performing oxygen plasma etching on the film under the pressure of 60Pa and the power of 1W for 120 seconds;
S4, adding 100g of magnesium oxide obtained in the step S2 into water, wherein the weight ratio of the magnesium oxide to the water is 1:1.5, then adding 10g of the porous graphene material obtained in the step S3, then dripping dilute sulfuric acid into the solution, carrying out severe reaction with foam, stopping adding acid when the foam is reduced, and then filtering;
S5, adjusting the pH value of the solution obtained by filtering the S4 to 6 by sulfuric acid, heating and concentrating, wherein the heating temperature is 180 ℃ and the heating time is 30min, then drying in an oven at low temperature and the drying temperature is 55 ℃ for 3 hours, and obtaining 259.72g of high-purity magnesium sulfate with the purity of more than or equal to 99.98%.
Example 3
S1, grinding dolomite to 220 meshes, keeping the calcination temperature at 700 ℃ and the heating rate at 180 ℃ per hour for 2 hours, then heating to 950 ℃ and keeping for 1 hour, cooling, adding 0.5mol/L magnesium chloride solution, wherein the mass ratio of the dolomite to the magnesium chloride is 1:1.2, then adding sodium hydroxide to adjust the pH value to 11, heating to 55 ℃, soaking for 40 minutes, filtering and drying;
S2, after the reaction furnace is heated to 500 ℃, putting the product obtained in the step S1 into the reaction furnace, heating to 1000 ℃ and obtaining magnesium oxide at a heating rate of 150 ℃ per hour;
S3, respectively ultrasonically cleaning a polyimide sheet with the thickness of 160 mu m by deionized water and alcohol, drying, and then performing laser treatment by using a nanosecond laser with the laser wavelength of 1064nm, the pulse duration of 10ns, the repetition frequency of 800KHz, the laser power of 4.0W and the scanning speed of 160mm/S to obtain a laser-induced porous graphene film, and then performing oxygen plasma etching on the film under the pressure of 40Pa and the power of 30W for 80 seconds;
S4, adding 100g of magnesium oxide obtained in the step S2 into water, wherein the weight ratio of the magnesium oxide to the water is 1:2, then adding 5g of the porous graphene material obtained in the step S3, then dripping dilute sulfuric acid into the solution, carrying out severe reaction with foam, stopping adding acid when the foam is reduced, and then filtering;
S5, adjusting the pH value of the solution obtained by filtering the S4 to 6 by sulfuric acid, heating and concentrating, wherein the heating temperature is 170 ℃, the heating time is 50min, then drying in an oven at a low temperature and the drying temperature is 55 ℃ for 3 hours, and then 256.88g of high-purity magnesium sulfate is obtained, and the purity is more than or equal to 99.98%.
Comparative example 1
S1, grinding dolomite to 250 meshes, keeping the calcination temperature at 500 ℃ and the heating rate at 150 ℃ per hour for 3 hours, then heating to 900 ℃ and keeping for 1 hour, cooling, adding 0.5mol/L magnesium chloride solution, wherein the mass ratio of the dolomite to the magnesium chloride is 1:1.5, adding sodium hydroxide to adjust the pH value to 11, heating to 60 ℃, soaking for 30 minutes, filtering and drying;
S2, after the reaction furnace is heated to 500 ℃, putting the product obtained in the step S1 into the reaction furnace, heating to 1000 ℃ and obtaining magnesium oxide at a heating rate of 150 ℃ per hour;
s3, respectively ultrasonically cleaning a polyimide sheet with the thickness of 180 mu m by deionized water and alcohol, drying, and then performing laser treatment by using a nanosecond laser with the laser wavelength of 1064nm, the pulse duration of 10ns, the repetition frequency of 800KHz, the laser power of 2.5W and the scanning speed of 200mm/S to obtain a laser-induced porous graphene film, and then performing oxygen plasma etching on the film under the pressure of 60Pa and the power of 1W for 120 seconds;
S4, adding 100g of magnesium oxide obtained in the step S2 into water, wherein the weight ratio of the magnesium oxide to the water is 1:1.5, then adding 10g of the porous graphene material obtained in the step S3, then dripping dilute sulfuric acid into the solution, carrying out severe reaction with foam, stopping adding acid when the foam is reduced, and then filtering;
S5, adjusting the pH value of the solution obtained by filtering the S4 to 6 by sulfuric acid, heating and concentrating, wherein the heating temperature is 180 ℃, the heating time is 30min, then drying in an oven at low temperature and the drying temperature is 55 ℃ for 3 hours, and obtaining 238.46g of magnesium sulfate with the purity of 97.5%.
Comparative example 2
S1, grinding dolomite to 250 meshes, keeping the calcination temperature at 500 ℃ and the heating rate at 150 ℃ per hour for 3 hours, then heating to 900 ℃ and keeping for 1 hour, cooling, adding 0.5mol/L magnesium chloride solution, wherein the mass ratio of the dolomite to the magnesium chloride is 1:1.5, adding sodium hydroxide to adjust the pH value to 11, heating to 60 ℃, soaking for 30 minutes, filtering and drying;
S2, after the reaction furnace is heated to 500 ℃, putting the product obtained in the step S1 into the reaction furnace, heating to 1000 ℃ and obtaining magnesium oxide at a heating rate of 150 ℃ per hour;
S3, respectively ultrasonically cleaning a polyimide sheet with the thickness of 180 mu m by deionized water and alcohol, drying, and then performing laser treatment by using a nanosecond laser with the laser wavelength of 1064nm, the pulse duration of 10ns, the repetition frequency of 800KHz, the laser power of 7.0W and the scanning speed of 200mm/S to obtain a laser-induced porous graphene film, and then performing oxygen plasma etching on the film under the pressure of 60Pa and the power of 1W for 120 seconds;
S4, adding 100g of magnesium oxide obtained in the step S2 into water, wherein the weight ratio of the magnesium oxide to the water is 1:1.5, then adding 10g of the porous graphene material obtained in the step S3, then dripping dilute sulfuric acid into the solution, carrying out severe reaction with foam, stopping adding acid when the foam is reduced, and then filtering;
S5, adjusting the pH value of the solution obtained by filtering the S4 to 6 by sulfuric acid, heating and concentrating, wherein the heating temperature is 180 ℃ and the heating time is 30min, then drying in an oven at low temperature and the drying temperature is 55 ℃ for 3 hours, and obtaining 239.58g of magnesium sulfate with the purity of 98.0%.
Comparative example 3
S1, grinding dolomite to 200 meshes, keeping the calcination temperature at 800 ℃ and the heating rate at 200 ℃ per hour for 1 hour, then heating to 1000 ℃ and keeping for 0.5 hour, cooling, adding 0.5mol/L magnesium chloride solution, wherein the mass ratio of the dolomite to the magnesium chloride is 1:1, then adding sodium hydroxide to adjust the pH value to 11, heating to 50 ℃, soaking for 60 minutes, filtering and drying;
S2, after the reaction furnace is heated to 500 ℃, putting the product obtained in the step S1 into the reaction furnace, heating to 1000 ℃ and obtaining magnesium oxide at a heating rate of 150 ℃ per hour;
S3, adding 100g of magnesium oxide obtained in the step S2 into water, wherein the weight ratio of the magnesium oxide to the water is 1:1, adding 1g of graphene produced by Suzhou carbon Feng graphene technology Co., ltd, dripping dilute sulfuric acid into the solution, carrying out severe reaction with foam, stopping adding acid when the foam is reduced, and filtering;
S5, adjusting the pH value of the solution obtained by filtering the S4 to 5 by sulfuric acid, heating and concentrating, wherein the heating temperature is 160 ℃, the heating time is 60min, then drying in an oven at a low temperature, and the drying temperature is 40 ℃ for 4 hours, thus obtaining 258.72g of magnesium sulfate with the purity of 96.4%.
The above comparative example 1 reduced the laser power of step S3 compared to example 2, comparative example 2 increased the laser power of step S3 compared to example 2, and comparative example 3 did not use the graphene film obtained by laser treatment of the polyimide sheet compared to example 1, and it can be seen that the purity of magnesium sulfate obtained in comparative example 1 and comparative example 2 was slightly lower, but the yield reduction was relatively large, and the purity of magnesium sulfate obtained in comparative example 3 was lower, and the graphene used in comparative example 3 was difficult to separate by filtration, so that graphene could adsorb but rather reduced the purity of magnesium sulfate.
Claims (9)
1. A method for preparing high purity magnesium sulfate, comprising the steps of:
S1, grinding dolomite, calcining, adding a magnesium chloride solution, adding sodium hydroxide, heating, soaking for 30-60min, filtering and drying;
S2, after the reaction furnace is heated to 500 ℃, putting the product obtained in the step S1 into the reaction furnace, heating to 1000 ℃ and obtaining magnesium oxide at a heating rate of 150 ℃ per hour;
s3, respectively cleaning the polyimide sheet by deionized water and alcohol in an ultrasonic manner, performing laser treatment by using a nanosecond laser after drying, wherein the laser power is 3.0-5.5W, the scanning speed is 120-200mm/S, obtaining a laser-induced porous graphene film, and performing oxygen plasma etching on the film;
s4, adding the magnesium oxide obtained in the step S2 into water, adding a porous graphene material, then dripping dilute sulfuric acid into the solution, carrying out severe reaction with foam, stopping adding acid when the foam is reduced, and then filtering by using a filter screen;
S5, adjusting the pH value of the solution obtained by filtering the S4 to 5-6 by sulfuric acid, heating and concentrating, wherein the heating temperature is 160-180 ℃, the heating time is 30-60min, and then drying in an oven at a low temperature, the drying temperature is 40-55 ℃ and the time is 3-4 hours, so that the high-purity magnesium sulfate is obtained.
2. The method for preparing high purity magnesium sulfate according to claim 1, wherein:
and step S3, the laser wavelength of the nanosecond laser is 1064nm, the pulse duration is 10ns, and the repetition frequency is 800KHz.
3. The method for preparing high purity magnesium sulfate according to claim 1, wherein:
And step S3, etching by oxygen plasma under the pressure of 0.1Pa-60Pa and the power of 1w-60w for 60-120 seconds.
4. The method for preparing high purity magnesium sulfate according to claim 1, wherein:
and the mass ratio of the magnesium oxide to the water in the step S4 is 1:1-2.
5. The method for preparing high purity magnesium sulfate according to claim 1, wherein:
the thickness of the polyimide sheet in the step S3 is 120-180 mu m.
6. The method for preparing high purity magnesium sulfate according to claim 1, wherein:
Grinding the dolomite in the step S1 to 200-250 meshes, wherein the calcination temperature is 500-800 ℃, the temperature rising rate is 150-200 ℃ per hour, the temperature is kept for 1-3 hours, then the temperature is raised to 900-1000 ℃ and the temperature is kept for 0.5-1 hour.
7. The method for preparing high purity magnesium sulfate according to claim 1, wherein:
and (2) the magnesium chloride solution in the step (S1) is 0.5mol/L, the temperature is raised to 50-60 ℃, and the pH value is kept at 11 when sodium hydroxide is added for soaking.
8. The method for preparing high purity magnesium sulfate according to claim 1, wherein:
The mass ratio of the dolomite and the magnesium chloride in the step S1 is 1:1-1.5.
9. The method for preparing high purity magnesium sulfate according to claim 1, wherein:
and (2) the weight ratio of the magnesium oxide to the porous graphene material in the step (S4) is 1:0.01-0.1.
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| CN101885498A (en) * | 2010-07-17 | 2010-11-17 | 天津市化学试剂研究所 | Method for preparing high-purity magnesium sulfate |
| CN102502724A (en) * | 2011-11-02 | 2012-06-20 | 中国科学院青海盐湖研究所 | Method for preparing magnesia for magnesium cement by using bischofite and dolomite |
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| CN102502724A (en) * | 2011-11-02 | 2012-06-20 | 中国科学院青海盐湖研究所 | Method for preparing magnesia for magnesium cement by using bischofite and dolomite |
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