CN115744996A - Preparation method and product of porous micro-nano spherical manganous-manganic oxide material - Google Patents
Preparation method and product of porous micro-nano spherical manganous-manganic oxide material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 55
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 238000005245 sintering Methods 0.000 claims abstract description 69
- 238000000034 method Methods 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 239000011656 manganese carbonate Substances 0.000 claims abstract description 33
- 235000006748 manganese carbonate Nutrition 0.000 claims abstract description 33
- 229940093474 manganese carbonate Drugs 0.000 claims abstract description 33
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims abstract description 33
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000243 solution Substances 0.000 claims abstract description 30
- 239000002002 slurry Substances 0.000 claims abstract description 25
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 23
- 238000001556 precipitation Methods 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 17
- 150000002696 manganese Chemical class 0.000 claims abstract description 16
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000012266 salt solution Substances 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 239000002270 dispersing agent Substances 0.000 claims abstract description 7
- 238000012216 screening Methods 0.000 claims abstract description 6
- 239000012298 atmosphere Substances 0.000 claims description 20
- 239000011572 manganese Substances 0.000 claims description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- 238000001694 spray drying Methods 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000002386 leaching Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 description 15
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- 229910052748 manganese Inorganic materials 0.000 description 10
- 239000004005 microsphere Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 239000002086 nanomaterial Substances 0.000 description 9
- 239000000654 additive Substances 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 5
- 239000001099 ammonium carbonate Substances 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 229940099596 manganese sulfate Drugs 0.000 description 5
- 239000011702 manganese sulphate Substances 0.000 description 5
- 235000007079 manganese sulphate Nutrition 0.000 description 5
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 230000002572 peristaltic effect Effects 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 4
- 235000012501 ammonium carbonate Nutrition 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 239000000696 magnetic material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 206010028980 Neoplasm Diseases 0.000 description 3
- 238000003018 immunoassay Methods 0.000 description 3
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 3
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000004043 responsiveness Effects 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 229910001289 Manganese-zinc ferrite Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- JIYIUPFAJUGHNL-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Zn++].[Zn++] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Zn++].[Zn++] JIYIUPFAJUGHNL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013399 early diagnosis Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000005408 paramagnetism Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000005502 phase rule Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012066 reaction slurry Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- -1 solid phase method Chemical compound 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method and a product of a porous micro-nano spherical manganous-manganic oxide material, relates to the technical field of preparation of manganous-manganic oxide, and aims to solve the problem that the porous micro-nano spherical structure is difficult to obtain by preparing manganous-manganic oxide by the existing method; respectively dissolving manganese salt and carbonate in pure water to obtain a manganese salt solution and a carbonate solution; adding bottom water into a reaction kettle, adding a dispersing agent, gradually adding the two solutions into the reaction kettle for precipitation, and controlling the solid-liquid ratio, the pH value and the temperature of the bottom water during the precipitation reaction to obtain manganese carbonate slurry; filtering, washing and drying to obtain manganese carbonate dry powder; placing the powder in a muffle furnace, and adjusting a sintering curve to be three stages of sintering which are continuously carried out to obtain a sintered material; screening the fired material through a screen to obtain porous micro-nano spherical trimanganese tetroxide; the production process flow is simple, the industrialization is easy, and the porous micro-nano spherical manganous-manganic oxide can be prepared.
Description
Technical Field
The invention relates to the technical field of manganous-manganic oxide preparation, in particular to a preparation method and a product of a porous micro-nano spherical manganous-manganic oxide material.
Background
Cancer is one of the most main reasons threatening the health and happiness of people, the early diagnosis and intervention are very important, and the accurate determination of serum tumor markers is more important. At present, immunoassay is proved to be an ideal method for measuring trace tumor markers, and the magnetic polymer microspheres gradually replace the planar carriers used in the traditional immunoassay. The magnetic micro-nano material is a material with micro-nano characteristics and magnetic responsiveness, has larger specific surface area and stronger magnetic responsiveness, and is expected to be applied to immunoassay and replace magnetic polymer microspheres.
The soft magnetic material is a magnetic material having a low coercive force and a high magnetic permeability, can achieve a maximum magnetization intensity with a minimum external magnetic field, and exhibits excellent paramagnetism. Thus, the micro-nano soft magnetic material is a judicious choice for preparing the immunomagnetic microspheres. The manganous-manganic oxide material is applied to the field of soft magnetic manganese-zinc ferrite for many years in a large scale, and is also applied to the fields of thermistors, pigments, catalysts and the like in a small amount. There are various industrial methods for preparing trimanganese tetroxide, including solid phase method, liquid phase method, etc. The solid phase method is to heat the metal manganese or manganese oxide, hydroxide, sulfate, sulfite, carbonate, nitrate and permanganate in air or oxygen to 1000 deg.c for burning, cooling and crushing to obtain mangano-manganic oxide. The liquid phase method is divided into two process routes of a metal manganese suspension oxidation method and a manganese salt solution precipitation oxidation method, wherein the metal manganese suspension oxidation method is that electrolytic metal manganese pieces are crushed to a certain granularity by a dry method or a wet method, pure water is added to prepare a suspension, then a catalytic agent is added, and air or oxygen is introduced to carry out catalytic oxidation reaction to prepare trimanganese tetroxide; the manganese salt solution precipitation oxidation method is a preparation method which adopts manganese salt as a raw material and uses air to oxidize bivalent manganese in the solution into trimanganese tetroxide under the alkaline condition.
The preparation method of the micro-nano material is classified and can be mainly summarized into two main categories: from top to bottom and from bottom to top. The top-down method is mainly to reduce the size of particles to nano particles by some physical methods, wherein the most typical method is a physical pulverization method, and in addition, the top-down method also comprises a chemical method for preparing micro-nano materials from top to bottom by corrosion and the like. The bottom-up method is mostly to increase the size of the material from small to large by using atoms or molecules as constituent units and mainly by some chemical methods, wherein a chemical vapor method, a chemical coprecipitation method, a thermal decomposition method, a micro-emulsion method, a hydrothermal method, a solvothermal method, a sol-gel method and the like are common methods for preparing the micro-nano material, and in addition, the bottom-up method also comprises a physical method for preparing the micro-nano material by evaporation and condensation and the like. Compared with the physical crushing method and the liquid phase precipitation method, the method has more advantages in the aspects of batch production and the like, and the liquid phase rule is better for controlling the appearance of the material. The magnetic micro-nano material belongs to one branch of the micro-nano material, and the preparation method of the micro-nano material is also suitable for the magnetic micro-nano material.
In patent application with publication number CN112390292A and name of invention of a bulk phase doping type trimanganese tetroxide and a preparation method and application thereof, a method for preparing trimanganese tetroxide by a liquid phase precipitation oxidation method is disclosed, but secondary particles of the trimanganese tetroxide material prepared by the method are more densely agglomerated and have lower specific surface area, and the trimanganese tetroxide material with a porous micro-nano spherical structure is difficult to obtain.
Disclosure of Invention
The invention aims to provide a preparation method and a product of a porous micro-nano spherical manganous-manganic oxide material, and aims to solve the problem that the porous micro-nano spherical structure is difficult to obtain by preparing manganous-manganic oxide by the existing method.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a porous micro-nano spherical manganous-manganic oxide material comprises the following specific steps:
s1, respectively dissolving manganese salt and carbonate in pure water to obtain a manganese salt solution and a carbonate solution, wherein CO is 3 2- The amount of substance is not less than Mn 2+ ；
S2, adding bottom water into a reaction kettle, adding a dispersing agent, gradually adding the two solutions obtained in the step S1 into the reaction kettle at a certain speed respectively for precipitation, and controlling the solid-to-liquid ratio to be 10% -50%, the pH value of the bottom water to be 5-9 and the temperature to be 40-90 ℃ during precipitation reaction to obtain manganese carbonate slurry;
s3, filtering, washing and drying the manganese carbonate slurry to obtain manganese carbonate dry powder;
s4, placing the manganese carbonate dry powder in a muffle furnace, adjusting a sintering curve into three continuous stages, raising the temperature of the first-stage sintering to 200-600 ℃, preserving heat for 1-12h, raising the temperature of the second-stage sintering to 700-900 ℃, preserving heat for 1-10h, raising the temperature of the third-stage sintering to 1000-1200 ℃, preserving heat for 4-20h, and sintering to obtain a sintered material;
s5, screening the material after burning through a screen to obtain the porous micro-nano spherical manganous-manganic oxide.
Preferably, in step S1, the manganese salt solution has a concentration of 0.5 to 2mol/L, the carbonate solution has a concentration of 0.5 to 3mol/L, and Mn is added 2+ With CO 3 2- The mass ratio of (b) is 0.3 to 1:1.
preferably, in the step S2, the feeding speed of the manganese salt solution is 5-30 ml/min, and the feeding speed of the carbonate solution is determined according to Mn in the reaction system 2+ With CO 3 2- The mass ratio of (A) is 0.3 to 0.6:1, determining.
Preferably, in step S2, the amount of the bottom water added is 10 to 200ml.
Preferably, in step S2, the dispersant is one or more of ethanol, polyethylene glycol, sodium dodecyl sulfate, n-octanol, and sodium oleate, and the addition amount is 0.1g to 1g.
Preferably, in the step S3, centrifugation or filter pressing is adopted for filtration, uniform slurry washing or leaching is adopted for washing, spray drying or flash drying is adopted for drying, and the moisture content of the manganese carbonate dry powder is 0.1-0.3%.
Preferably, in step S4, the sintering atmosphere for the first-stage sintering is nitrogen and/or argon, the sintering atmosphere for the second-stage sintering and the third-stage sintering is oxygen and/or air, and the gas amount of the sintering atmosphere is 20-100 m 3 /h。
Preferably, in step S4, the temperature increase rate of sintering is 0.5 to 10 ℃/min.
Preferably, in step S4, the charged thickness of the manganese carbonate dried powder is 1 to 20cm.
Preferably, in step S5, the mesh opening is 300 to 400 mesh.
The invention provides another technical scheme that: a product prepared by any one of the methods is mangano-manganic oxide which has a porous micro-nano spherical structure.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the preparation method of the porous micro-nano spherical manganous-manganic oxide material, the micro-morphology and the particle size distribution of manganese carbonate can be effectively regulated and controlled by controlling the precipitation condition of the manganese carbonate and the additive; in the subsequent process of preparing the manganous-manganic oxide by roasting, the roasting process and the sintering atmosphere are controlled, so that micro-nano spherical crystal grains can be effectively prevented from growing, and the consistency and the stability of the product are improved.
2. According to the preparation method of the porous micro-nano spherical manganous oxide material, the precipitation process and the roasting process of manganese carbonate are controlled, additives are added, the nucleation process of manganous oxide can be effectively controlled, and the porous micro-nano spherical manganous oxide material with regular particle appearance, high porosity, uniform particle size distribution and high specific surface area is obtained.
3. According to the preparation method of the porous micro-nano spherical manganous-manganic oxide material, the porous manganous-manganic oxide is prepared by roasting manganese carbonate, and the porous manganous-manganic oxide can be easily prepared due to the escape of CO2 gas in the roasting process, so that the production process flow is simple and the industrialization is easy to realize.
4. The product prepared by the preparation method of the porous micro-nano spherical manganous-manganic oxide material can provide a stable porous structure for the synthesis of subsequent soft magnetic materials and can also provide a good space for active substances carried by immune magnetic microspheres.
Detailed Description
The preparation method of the porous micro-nano spherical manganous-manganic oxide material comprises the following steps:
s1, respectively dissolving manganese salt and carbonate in pure water to obtain a manganese salt solution and a carbonate solution, wherein CO is 3 2- The amount of substance is not less than Mn 2+ ；
In a preferred embodiment, the manganese salt solution has a concentration of 0.5 to 2mol/L, the carbonate solution has a concentration of 0.5 to 3mol/L, and Mn is added 2+ With CO 3 2- The mass ratio of (A) is 0.3 to 1:1.
s2, adding bottom water into a reaction kettle, adding a dispersing agent, gradually adding the two solutions obtained in the step S1 into the reaction kettle at a certain speed respectively for precipitation, and controlling the solid-to-liquid ratio to be 10% -50%, the pH value of the bottom water to be 5-9 and the temperature to be 40-90 ℃ during precipitation reaction to obtain manganese carbonate slurry;
in a preferred embodiment, the above manganese salt solution is fed at a rate of 5 to 30ml/min, and the carbonate solution is fed at a rate according to the Mn in the reaction system 2+ With CO 3 2- The mass ratio of (b) is 0.3-0.6: 1, determining.
In a preferred embodiment, the amount of the bottom water added is 10 to 200ml.
In a preferred embodiment, the dispersant is one or more of ethanol, polyethylene glycol, sodium dodecyl sulfate, n-octanol and sodium oleate, and the addition amount is 0.1-1 g.
S3, filtering, washing and drying the manganese carbonate slurry to obtain manganese carbonate dry powder;
in a preferred embodiment, the filtration is centrifugal or filter pressing, the washing is even pulp washing or drip washing, the drying is spray drying or flash drying, and the moisture content of the manganese carbonate dry powder is 0.1-0.3%.
S4, placing the manganese carbonate dry powder in a muffle furnace, adjusting a sintering curve to be divided into three continuous stages, namely, raising the temperature to 200-600 ℃ for heat preservation for 1-12h for the first-stage sintering, raising the temperature to 700-900 ℃ for heat preservation for 1-10h for the second-stage sintering, raising the temperature to 1000-1200 ℃ for heat preservation for 4-20h for the third-stage sintering, and sintering to obtain a sintered material;
in a preferred embodiment, the sintering atmosphere of the first-stage sintering is nitrogen and/or argon, the sintering atmosphere of the second-stage sintering and the third-stage sintering is oxygen and/or air, and the gas amount of the sintering atmosphere is 20-100 m 3 /h。
In a preferred embodiment, the temperature increase rate in the sintering is 0.5 to 10 ℃/min.
In a preferred embodiment, the charge thickness of the above-mentioned manganese carbonate dry powder is 1 to 20cm.
S5, screening the material after burning through a screen to obtain the porous micro-nano spherical manganous-manganic oxide.
In a preferred embodiment, the mesh has a mesh size of 300 to 400 mesh.
The present invention will be described in detail below with reference to specific examples in order to facilitate the understanding of the present invention for those skilled in the art, but the scope of the present invention is not limited to the following specific examples.
Example 1: a preparation method of a porous micro-nano spherical mangano-manganic oxide material for immune magnetic microspheres comprises the following steps:
(1) Respectively dissolving manganese sulfate and ammonium carbonate in pure water to obtain 1000ml of 1mol/L manganese sulfate solution and 1000ml of 1.2mol/L ammonium carbonate solution, mn 2+ ：CO 3 2- ＝0.83；
(2) Adding the solution obtained in the step (1) into a reaction kettle through a peristaltic pump for precipitation, wherein 100ml of bottom water is pre-added into the reaction kettle, the feeding speed is controlled to be 10ml/min, the solid-liquid ratio is 30%, the pH value of a reaction system is 6, an additive is polyethylene glycol, the adding amount is 0.3g, the reaction temperature is 80 ℃, and manganese carbonate slurry with a certain particle size distribution is obtained;
(3) Filtering the slurry obtained in the step (2) by using a centrifugal machine, homogenizing, washing and spray drying to obtain manganese carbonate dry powder with the water content of 0.2%;
(4) Placing the dried powder obtained in the step (3) in a muffle furnace, wherein the muffle furnace sintering curve is adjusted to be in a charging thickness of 2 cm: first-stage sintering: keeping the temperature at 400 ℃ for 6h, heating rate of 1 ℃/min, nitrogen atmosphere and gas amount of 60m 3 H; and (3) secondary sintering: keeping the temperature at 700 ℃ for 6h, heating rate of 0.5 ℃/min, air atmosphere of 60m 3 H; three-stage sintering: keeping the temperature at 1000 ℃ for 12h, heating rate of 0.5 ℃/min, oxygen atmosphere of 60m 3 H is the ratio of the total weight of the catalyst to the total weight of the catalyst. The three-stage sintering process is continuously carried out, and a sintered material is obtained after sintering;
(5) And (4) screening the calcined material obtained in the step (4) through a screen with the aperture of 300 meshes to obtain the porous micro-nano spherical manganous-manganic oxide material.
Example 2: a preparation method of a porous micro-nano spherical mangano-manganic oxide material for immune magnetic microspheres comprises the following steps:
(1) Respectively dissolving manganese sulfate and sodium carbonate in pure water to obtain 1000ml of 2mol/L manganese sulfate solution and 1000ml of 2.4mol/L sodium carbonate solution, mn 2+ ：CO 3 2- ＝0.83；
(2) Adding the solution obtained in the step (1) into a reaction kettle through a peristaltic pump for precipitation, wherein 50ml of bottom water is pre-added into the reaction kettle, the feeding speed is controlled to be 5ml/min during the precipitation, the solid-to-liquid ratio is 40%, the pH value of a reaction system is 6.5, an additive is polyethylene glycol + sodium oleate, the adding amount is 0.3g +0.1g, the reaction temperature is 90 ℃, and manganese carbonate slurry with certain particle size distribution is obtained;
(3) Filtering the slurry obtained in the step (2) by using a filter press, homogenizing, washing and spray drying to obtain manganese carbonate dry powder with the water content of 0.2%;
(4) Placing the dried powder obtained in the step (3) in a muffle furnace, wherein the muffle furnace sintering curve is adjusted to be in a charging thickness of 2 cm: first-stage sintering: keeping the temperature at 350 ℃ for 12h, heating up at the rate of 1 ℃/min, and keeping the gas flow at 60m in the nitrogen atmosphere 3 H; and (3) second-stage sintering: keeping the temperature at 750 ℃ for 6h, heating rate of 0.5 ℃/min, oxygen atmosphere of 60m 3 H; three-stage sintering: keeping the temperature at 1050 ℃ for 12h, heating rate of 0.5 ℃/min, oxygen atmosphere of 60m 3 H is the ratio of the total weight of the catalyst to the total weight of the catalyst. The three-stage sintering process is continuously carried out, and a sintered material is obtained after sintering;
(5) And (4) sieving the calcined material obtained in the step (4) through a sieve with 400 meshes of aperture to obtain the porous micro-nano spherical manganous-manganic oxide material.
Example 3: a preparation method of a porous micro-nano spherical manganous-manganic oxide material for immune magnetic microspheres comprises the following steps:
(1) Respectively dissolving manganese sulfate and ammonium bicarbonate in pure water to obtain 300ml of 3mol/L sulfurManganese acid solution and 1000ml of 1.8mol/L sodium carbonate solution, mn 2+ ：CO 3 2- ＝0.5；
(2) Adding the solution obtained in the step (1) into a reaction kettle through a peristaltic pump for precipitation, wherein 100ml of bottom water is pre-added into the reaction kettle, the feeding speed is controlled to be 20ml/min during the precipitation, the solid-to-liquid ratio is 20%, the pH value of a reaction system is 7, the additive is ethanol + octanol + sodium dodecyl sulfate, the adding amount is 0.3g +0.1g, and the reaction temperature is 70 ℃, so as to obtain manganese carbonate slurry with a certain particle size distribution;
(3) Filtering the slurry obtained in the step (2) by using a filter press, homogenizing, washing and spray-drying to obtain manganese carbonate dry powder with the water content of 0.2%;
(4) Placing the dried powder obtained in the step (3) in a muffle furnace, wherein the muffle furnace sintering curve is adjusted to be 1cm of charging thickness: first-stage sintering: keeping the temperature at 450 ℃ for 12h, heating up at a rate of 1 ℃/min, and keeping the gas flow at 80m in a nitrogen atmosphere 3 H; and (3) secondary sintering: keeping the temperature at 700 ℃ for 6h, heating rate of 0.5 ℃/min, oxygen atmosphere of 60m 3 H; three-stage sintering: the temperature is kept at 1100 ℃ for 12h, the heating rate is 0.5 ℃/min, the oxygen atmosphere is 60m 3 H is the ratio of the total weight of the catalyst to the total weight of the catalyst. The three-stage sintering process is continuously carried out, and a sintered material is obtained after sintering;
(5) And (4) sieving the calcined material obtained in the step (4) through a sieve with 400 meshes of aperture to obtain the porous micro-nano spherical manganous-manganic oxide material.
Example 4: a preparation method of a porous micro-nano spherical manganous-manganic oxide material for immune magnetic microspheres comprises the following steps:
(1) Respectively dissolving manganese chloride and ammonium carbonate in pure water to obtain 1000ml of 2mol/L manganese chloride solution and 1000ml of 2.2mol/L ammonium carbonate solution, mn 2+ ：CO 3 2- ＝0.91；
(2) Adding the solution obtained in the step (1) into a reaction kettle through a peristaltic pump for precipitation, wherein 150ml of bottom water is pre-added into the reaction kettle, the feeding speed is controlled to be 15ml/min, the solid-to-liquid ratio is 30%, the pH value of a reaction system is 7.5, the additives are ethanol, n-octanol and sodium dodecyl sulfate, the adding amount is 0.2g +0.1g, the reaction temperature is 80 ℃, and manganese carbonate slurry with a certain particle size distribution is obtained;
(3) Filtering the slurry obtained in the step (2) by using a centrifugal machine, washing, and performing flash evaporation drying to obtain manganese carbonate dry powder with the water content of 0.3%;
(4) And (4) placing the dried powder obtained in the step (3) in a muffle furnace, wherein the muffle furnace sintering curve is adjusted to be 1cm in charging thickness: first-stage sintering: keeping the temperature at 450 ℃ for 10h, heating up at a rate of 1 ℃/min, and keeping the gas flow at 60m in a nitrogen atmosphere 3 H; and (3) second-stage sintering: keeping the temperature at 750 ℃ for 8h, heating rate of 0.5 ℃/min, oxygen atmosphere of 60m 3 H; three-stage sintering: the temperature is kept at 1100 ℃ for 10h, the heating rate is 0.5 ℃/min, the oxygen atmosphere is 60m 3 H is used as the reference value. The three-stage sintering process is continuously carried out, and a sintered material is obtained after sintering;
(5) And (4) screening the calcined material obtained in the step (4) through a screen with the aperture of 300 meshes to obtain the porous micro-nano spherical manganous-manganic oxide material.
Example 5: a preparation method of a porous micro-nano spherical manganous-manganic oxide material for immune magnetic microspheres comprises the following steps:
(1) Respectively dissolving manganese acetate and sodium carbonate in pure water to obtain 1000ml of 1mol/L manganese acetate solution and 1000ml of 1.2mol/L sodium carbonate solution, mn 2+ ：CO 3 2- ＝0.83；
(2) Adding the solution obtained in the step (1) into a reaction kettle through a peristaltic pump for precipitation, wherein 200ml of bottom water is pre-added into the reaction kettle, the feeding speed is controlled to be 20ml/min during the precipitation, the solid-to-liquid ratio is 10%, the pH value of a reaction system is 8, the additives are ethanol, n-octanol and sodium dodecyl sulfate, the adding amount is 0.2g +0.1g, and the reaction temperature is 80 ℃, so as to obtain manganese carbonate slurry with certain particle size distribution;
(3) Filtering the slurry obtained in the step (2) by using a centrifugal machine, washing and spraying to obtain manganese carbonate dry powder with the water content of 0.2%;
(4) Placing the dried powder obtained in the step (3) in a muffle furnace, wherein the charging thickness is 0.5cm, and the sintering curve of the muffle furnace is adjusted to be: first-stage sintering: keeping the temperature at 500 ℃ for 6h, heating up at a rate of 1 ℃/min, and keeping the gas flow at 60m in a nitrogen atmosphere 3 H; and (3) second-stage sintering: keeping the temperature at 800 ℃ for 8h, heating rate of 0.5 ℃/min, oxygen atmosphere of 60m 3 H; three-stage sintering: keeping the temperature at 1000 ℃ for 12h, heating rate of 0.5 ℃/min, oxygen atmosphere of 60m 3 H is the ratio of the total weight of the catalyst to the total weight of the catalyst. The three-stage sintering process is continuously carried out, and a sintered material is obtained after sintering;
(5) And (4) sieving the calcined material obtained in the step (4) through a sieve with 400 meshes of aperture to obtain the porous micro-nano spherical manganous-manganic oxide material.
Comparative example 1:
(1) Adding 1 ton of electrolytic manganese metal sheet into a horizontal ball mill, and performing dry ball milling for 120min to obtain manganese particles with median diameter D 50 Manganese slurry of 10 μm;
(2) 10m in the first direction 3 Adding 1m into a reaction kettle 3 Adding 25Kg of ammonium chloride serving as a catalyst into the reaction kettle respectively, adding the prepared manganese slurry into the reaction kettle, adding deionized water into the reaction kettle to dilute the manganese slurry to obtain reaction slurry with the manganese concentration of 30% by mass, starting a stirring impeller in the reaction kettle, adjusting a frequency converter, and setting the rotating speed of the stirring impeller to be 400r/min; simultaneously introducing air into the reaction kettle, and adjusting the air flow to 150m 3 /h，
(3) Continuously reacting until the pH value of the slurry is reduced to 6.5 to obtain mangano-manganic oxide slurry;
(4) And (3) putting the manganous-manganic oxide slurry into a stirrer, adding deionized water, stirring for 30 minutes, washing and filtering in a vacuum filtration mode, and finally drying to obtain a manganous-manganic oxide product.
The manganous manganic oxide product prepared in the comparative example 1 is not in a porous micro-nano spherical structure, cannot be used for preparing immunomagnetic microspheres, and is low in product value, and the manganous manganic oxide products prepared in the examples 1 to 5 are all in a good porous micro-nano spherical structure, and are simple in production process flow and easy to industrialize.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are also within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope defined by the claims.
The present invention is not described in detail, but is known to those skilled in the art.
Claims (10)
1. A preparation method of a porous micro-nano spherical manganous-manganic oxide material is characterized by comprising the following specific steps:
s1, respectively dissolving manganese salt and carbonate in pure water to obtain a manganese salt solution and a carbonate solution, wherein CO is 3 2- The amount of the substance is not less than Mn 2+ ；
S2, adding bottom water into a reaction kettle, adding a dispersing agent, gradually adding the two solutions obtained in the step S1 into the reaction kettle at a certain speed respectively for precipitation, and controlling the solid-to-liquid ratio to be 10% -50%, the pH value of the bottom water to be 5-9 and the temperature to be 40-90 ℃ during precipitation reaction to obtain manganese carbonate slurry;
s3, filtering, washing and drying the manganese carbonate slurry to obtain manganese carbonate dry powder;
s4, placing the manganese carbonate dry powder in a muffle furnace, adjusting a sintering curve into three continuous stages, raising the temperature of the first-stage sintering to 200-600 ℃, preserving heat for 1-12h, raising the temperature of the second-stage sintering to 700-900 ℃, preserving heat for 1-10h, raising the temperature of the third-stage sintering to 1000-1200 ℃, preserving heat for 4-20h, and sintering to obtain a sintered material;
s5, screening the material after burning through a screen to obtain the porous micro-nano spherical manganous-manganic oxide.
2. The preparation method of the porous micro-nano spherical manganous-manganic oxide material according to claim 1, characterized by comprising the following steps: in the step S1, the concentration of the manganese salt solution is 0.5-2 mol/L, the concentration of the carbonate solution is 0.5-3 mol/L, and Mn 2+ With CO 3 2- The mass ratio of (A) is 0.3 to 1:1.
3. the preparation method of the porous micro-nano spherical mangano-manganic oxide material according to claim 1, which is characterized by comprising the following steps: in the step S2, manganeseThe feeding speed of the salt solution is 5-30 ml/min, and the feeding speed of the carbonate solution is according to Mn in the reaction system 2+ With CO 3 2- The mass ratio of (b) is 0.3-0.6: 1, determining.
4. The preparation method of the porous micro-nano spherical manganous-manganic oxide material according to claim 1, characterized by comprising the following steps: in the step S2, the adding amount of the bottom water is 10-200 ml.
5. The preparation method of the porous micro-nano spherical manganous-manganic oxide material according to claim 1 or 4, which is characterized by comprising the following steps: in the step S2, the dispersant is one or more of ethanol, polyethylene glycol, sodium dodecyl sulfate, n-octanol and sodium oleate, and the addition amount is 0.1g to 1g.
6. The preparation method of the porous micro-nano spherical manganous-manganic oxide material according to claim 1, characterized by comprising the following steps: in the step S3, centrifugation or filter pressing is adopted for filtration, uniform slurry washing or leaching is adopted for washing, spray drying or flash drying is adopted for drying, and the moisture content of the manganese carbonate dry powder is 0.1-0.3%.
7. The preparation method of the porous micro-nano spherical manganous-manganic oxide material according to claim 1, characterized by comprising the following steps: in the step S4, the sintering atmosphere of the first-stage sintering is nitrogen and/or argon, the sintering atmosphere of the second-stage sintering and the third-stage sintering is oxygen and/or air, and the gas amount of the sintering atmosphere is 20-100 m 3 /h。
8. The preparation method of the porous micro-nano spherical manganous-manganic oxide material according to claim 1, characterized by comprising the following steps: in the step S4, the temperature rise rate of sintering is 0.5-10 ℃/min.
9. The preparation method of the porous micro-nano spherical manganous-manganic oxide material according to claim 1, characterized by comprising the following steps: in the step S5, the aperture of the screen mesh is 300-400 meshes.
10. A product prepared by the method of any one of claims 1-9, wherein: the product is manganous-manganic oxide which has a porous micro-nano spherical structure.
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