CN106006745A - Method for continuously preparing soft agglomerated nano manganese carbonate - Google Patents
Method for continuously preparing soft agglomerated nano manganese carbonate Download PDFInfo
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- CN106006745A CN106006745A CN201610334299.3A CN201610334299A CN106006745A CN 106006745 A CN106006745 A CN 106006745A CN 201610334299 A CN201610334299 A CN 201610334299A CN 106006745 A CN106006745 A CN 106006745A
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- manganese
- carbonate
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- manganese sulfate
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
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- 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
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to the technical field of nano materials and particularly relates to a method for continuously preparing soft agglomerated nano magnesium carbonate. Reagent-grade manganese sulfate and a precipitant are used as materials, preventing the reduction in the quality of finished manganese carbonate due to the introduction of impurities to the materials. A continuous feeding mode is used in the synthetic process, so that reaction is continuously carried out and production efficiency is improved. The manganese carbonate prepared herein is less than 30 nm in particle size and is strictly a nano material, the prepared manganese carbonate is spherical and is softly agglomerated, and soft agglomeration is advantageous in that agglomeration easily turns to disagglomeration in use to obtain nanoparticles of primary particle size.
Description
Technical field
The invention belongs to technical field of nano material, particularly relate to one and prepare soft-agglomerated nano-calcium carbonate continuously
The method of manganese.
Background technology
Manganese carbonate is the raw material producing electrolytic manganese metal, can be used for manufacturing permeability magnetic material, is soft magnetic ferrite
One of main component, it may also be used for desulphurization catalyst, enamel pigment, varnish drier and chemical fertilizer add
Agent etc..
Along with the development of new energy technology, the manganese carbonate application in battery material field is more and more extensive, special
It not lithium manganate battery and good development trend that nickel-cobalt-manganese ternary battery presents, more improve carbonic acid
The using value of manganese.It is while manganese carbonate using value improves, the strictest to the prescription of product,
Its purity, crystal formation, granularity largely have influence on the chemical property of electrode material.
At present, the preparation method of nano-calcium carbonate manganese mainly has following several, but all there is various shortcoming:
(1) see that the preparation method of the manganese carbonate that document reports mainly has liquid-phase precipitation method and hydro-thermal brilliant at present
Change method.Wherein, hydrothermal crystallization method needs energy consumption high in preparation process, causes certain energy waste；
Liquid-phase precipitation method is long for reaction time, and granular size is uneven and uses exhibiting high surface activating agent, can be to water body
And environment.
(2) Chinese patent 201010158824.3 discloses the preparation method of a kind of manganese carbonate nanorod,
The method adds surfactant, hydrogen peroxide and lithium carbonate in the solution of manganese chloride and potassium permanganate,
180 DEG C of Water Under thermal responses 16～prepare manganese carbonate nanorod in 24 hours.201410191556.3 it is open
The preparation method of a kind of manganese carbonate nanofiber ball, this invention is to be mixed mutually with sodium potassium tartrate tetrahydrate by manganese chloride
Conjunction is reacted, and forms manganese tartrate precipitation, more this manganese tartrate precipitation is mixed mutually with solution of potassium carbonate
Attaching together in reactor, at 50～200 DEG C, insulation carries out hydrothermal treatment consists in 3～10 hours, and washing obtains
Manganese carbonate fibrous nodules.Morphology control in Preparation Process of Spherical Manganese Carbonate Particles (process engineering journal, 2008
The 2nd phase of volume 8 year, foxtail millet seapeak) disclose one with MnSO4And NH4HCO3For raw material, use low
Temperature chemical precipitation method has been prepared granularity and has been mainly the single dispersing MnCO of 5-6 μm3Spheroidal particle.Hydro-thermal is brilliant
Change method prepares ultra-fine MnCO3Research (electronic component and equipment, the 3rd phase in 2006, Du Zewei) public
Open a kind of with Na2CO3And MnCI2·4H2O is raw material, uses hydrothermal crystallization method to synthesize superfine high-purity
MnCO3, MnCO3Granule is square, and mean diameter is 180nm.Liquid-phase precipitation method prepares single dispersing sub-micro
Meter level spheric manganese carbonate (inorganic chemicals industry, the 8th phase of volume 41 in 2009, foxtail millet seapeak) discloses one
Kind with manganese sulfate for manganese source, ammonium hydrogen carbonate as precipitant, sodium lauryl sulphate is size controlling agent, adopts
The mode being quickly simultaneously introduced with manganese sulfate and two kinds of solution of ammonium hydrogen carbonate, suitably reacts knot by control
Crystal bar part, prepares submicron order monodisperse spherical manganese carbonate granule, and mean diameter is about 540nm, this
The shortcoming of method is that batch (-type) feeds, and is unfavorable for large-scale production, and particle size is at 540nm,
Belong to sub-micrometer range, be not the nano material of stricti jurise.
(2) nano-calcium carbonate manganese prepared by the several method described in is bar-shaped, fibrous or spherical,
Reuniting is hard aggregation, but hard aggregation is in use difficult to dispersion and obtains primary particle size, spherical carbon
Acid manganese particle diameter is the most only submicron order, and particle diameter, more than 500 nanometers, does not reaches nano-calcium carbonate manganese particle diameter and exists
The requirement of 1-100nm.
Summary of the invention
The present invention is directed to the deficiency that above-mentioned prior art exists, it is provided that a kind of particle diameter company within 30nm
The continuous method preparing soft-agglomerated nano-calcium carbonate manganese.
The technical scheme is that one prepares soft-agglomerated nano-sized carbon continuously
The method of acid manganese, step is as follows:
(1) compound concentration is the manganese sulfate solution of 1-2mol/L, adds chemical additives, is contained
The manganese sulfate solution of 0.1-0.3wt% chemical additives；Compound concentration is the precipitant solution of 1-2mol/L；
(2) by the manganese sulfate solution containing chemical additives of step (1) and precipitant solution with continuously
Adding the feeding manner added in reactor, the charging rate of the manganese sulfate solution containing chemical additives is
100-200L/h, the charging rate of precipitant solution is 200-400L/h, with the speed of 200-300r/min
Degree stirs, and control pH is 7-8；
(3) step (2) reaction temperature be 25 DEG C, pressure be 101kPa under the conditions of carry out, to instead
Answer discharging through membrane filtration, use pure water 3 times, carry out solid-liquid separation；
(4) step (3) isolated solid matter is dried under the conditions of 50-90 DEG C 8-12h,
To white or pink colour nano-calcium carbonate manganese, primary particle size is 10-30nm.
Wherein, described chemical additives is hexadecyltrimethylammonium chloride, ammonium citrate or formic acid
One or more mixing.
Described precipitant is one or both mixing of ammonium carbonate or ammonium hydrogen carbonate.
The invention has the beneficial effects as follows:
1, the present invention uses reagent grade sulfuric acid manganese and precipitant to be raw material, it is to avoid because raw material introduces impurity
And make product manganese carbonate quality reduce.Synthesis technique uses continuously the feeding manner added, makes reaction even
Continue and carry out, improve production efficiency.
2, the manganese carbonate minimum grain size that existing manganese carbonate preparation method prepares is 180nm, and the present invention prepares
Manganese carbonate particle diameter less than 30nm, (nano material particle diameter is to belong to proper nano material
1-100nm)。
3, the manganese carbonate that the present invention prepares is shaped as spherical, reunites for soft-agglomerated, and soft-agglomerated advantage exists
Reunite with being easily dispersed during using and open the nano-particle obtaining primary particle size.
Detailed description of the invention
Being described principle and the feature of the present invention below in conjunction with example, example is served only for explaining this
Invention, is not intended to limit the scope of the present invention.
Embodiment 1
A kind of continuous method preparing soft-agglomerated nano-calcium carbonate manganese, step is as follows:
(1) compound concentration is the manganese sulfate solution 1L of 1mol/L, adds 1g cetyl trimethyl bromine
Change ammonium, obtain the manganese sulfate solution containing 0.1wt% chemical additives；Compound concentration is the carbon of 1mol/L
Acid hydrogen ammonium salt solution 2L；
(2) by the manganese sulfate solution containing chemical additives of step (1) and ammonium bicarbonate soln with right
The mode added adds in reactor, and the charging rate of the manganese sulfate solution containing chemical additives is
100L/h, the charging rate of ammonium bicarbonate soln is 200L/h, stirs with the speed of 200r/min,
Controlling pH is 7.0；
(3) step (2) reaction temperature be 25 DEG C, pressure be 101kPa under the conditions of carry out, to instead
Answer discharging through membrane filtration, use pure water 3 times, carry out solid-liquid separation；
(4) step (3) isolated solid matter is dried under the conditions of 50 DEG C 12h, obtains white
Or pink colour nano-calcium carbonate manganese, primary particle size is 10nm.
Embodiment 2
A kind of continuous method preparing soft-agglomerated nano-calcium carbonate manganese, step is as follows:
(1) compound concentration is the manganese sulfate solution 1L of 1.5mol/L, adds 2g ammonium citrate, obtains
Manganese sulfate solution containing 0.2wt% chemical additives；Compound concentration is that the ammonium hydrogen carbonate of 1.5mol/L is molten
Liquid 2L；
(2) by the manganese sulfate solution containing chemical additives of step (1) and ammonium bicarbonate soln with right
The mode added adds in reactor, and the charging rate of the manganese sulfate solution containing chemical additives is
200L/h, the charging rate of ammonium bicarbonate soln is 400L/h, stirs with the speed of 250r/min,
Controlling pH is 7.5；
(3) step (2) reaction temperature be 25 DEG C, pressure be 101kPa under the conditions of carry out, to instead
Answer discharging through membrane filtration, use pure water 3 times, carry out solid-liquid separation；
(4) step (3) isolated solid matter is dried under the conditions of 60 DEG C 10h, obtains white
Or pink colour nano-calcium carbonate manganese, primary particle size is 20nm.
Embodiment 3
A kind of continuous method preparing soft-agglomerated nano-calcium carbonate manganese, step is as follows:
(1) compound concentration is the manganese sulfate solution 1L of 2mol/L, adds 3g formic acid, obtains containing 0.3wt%
The manganese sulfate solution of chemical additives；Compound concentration is the sal volatile 1L of 2mol/L；
(2) by the manganese sulfate solution containing chemical additives of step (1) and sal volatile with to adding
Mode add in reactor, the charging rate of the manganese sulfate solution containing chemical additives is 150L/h,
The charging rate of sal volatile is 150L/h, stirs with the speed of 300r/min, controls pH
It is 8.0；
(3) step (2) reaction temperature be 25 DEG C, pressure be 101kPa under the conditions of carry out, to instead
Answer discharging through membrane filtration, use pure water 3 times, carry out solid-liquid separation；
(4) step (3) isolated solid matter is dried under the conditions of 90 DEG C 8h, obtains white
Or pink colour nano-calcium carbonate manganese, primary particle size is 30nm.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all in the present invention
Spirit and principle within, any modification, equivalent substitution and improvement etc. made, should be included in this
Within bright protection domain.
Claims (3)
1. the continuous method preparing soft-agglomerated nano-calcium carbonate manganese, it is characterised in that step is as follows:
(1) compound concentration is the manganese sulfate solution of 1-2mol/L, adds chemical additives, is contained
The manganese sulfate solution of 0.1-0.3wt% chemical additives；Compound concentration is the precipitant solution of 1-2mol/L；
(2) by the manganese sulfate solution containing chemical additives of step (1) and precipitant solution with continuously
Adding the feeding manner added in reactor, the charging rate of the manganese sulfate solution containing chemical additives is
100-200L/h, the charging rate of precipitant solution is 200-400L/h, with the speed of 200-300r/min
Degree stirs, and control pH is 7-8；
(3) step (2) reaction temperature be 25 DEG C, pressure be 101kPa under the conditions of carry out, to instead
Answer discharging through membrane filtration, use pure water 3 times, carry out solid-liquid separation；
(4) step (3) isolated solid matter is dried under the conditions of 50-90 DEG C 8-12h,
To white or pink colour nano-calcium carbonate manganese, primary particle size is 10-30nm.
Method the most according to claim 1, it is characterised in that described chemical additives is ten
One or more mixing of six alkyl trimethyl ammonium chlorides, ammonium citrate or formic acid.
Method the most according to claim 1, it is characterised in that described precipitant is ammonium carbonate
Or one or both mixing of ammonium hydrogen carbonate.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107331853A (en) * | 2017-08-18 | 2017-11-07 | 郑州大学 | A kind of graphene composite multi-layer spherical manganic acid lithium electrode material with holes and its lithium ion battery of preparation |
| CN110038557A (en) * | 2019-05-20 | 2019-07-23 | 中国科学院海洋研究所 | A kind of electro-catalysis GOx/MnCO3Composite material and its preparation and application |
Citations (2)
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| CN101269840A (en) * | 2008-03-05 | 2008-09-24 | 广州融捷材料科技有限公司 | Spherical manganese carbonate and preparing method thereof |
| CN102120618A (en) * | 2011-01-26 | 2011-07-13 | 江苏方舟新能源股份有限公司 | Preparation method of high-tap density manganese carbonate |
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2016
- 2016-05-19 CN CN201610334299.3A patent/CN106006745B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101269840A (en) * | 2008-03-05 | 2008-09-24 | 广州融捷材料科技有限公司 | Spherical manganese carbonate and preparing method thereof |
| CN102120618A (en) * | 2011-01-26 | 2011-07-13 | 江苏方舟新能源股份有限公司 | Preparation method of high-tap density manganese carbonate |
Non-Patent Citations (1)
| Title |
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| 王俊红: "亚微米级碳酸锰和磷酸锰的制备研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107331853A (en) * | 2017-08-18 | 2017-11-07 | 郑州大学 | A kind of graphene composite multi-layer spherical manganic acid lithium electrode material with holes and its lithium ion battery of preparation |
| CN107331853B (en) * | 2017-08-18 | 2020-09-04 | 郑州大学 | Graphene composite multilayer porous spherical lithium manganate electrode material and lithium ion battery prepared from same |
| CN110038557A (en) * | 2019-05-20 | 2019-07-23 | 中国科学院海洋研究所 | A kind of electro-catalysis GOx/MnCO3Composite material and its preparation and application |
| CN110038557B (en) * | 2019-05-20 | 2022-02-11 | 中国科学院海洋研究所 | Electrocatalysis GOx/MnCO3Composite material, preparation and application thereof |
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Denomination of invention: A method for continuous preparation of soft agglomerated nano manganese carbonate Effective date of registration: 20221111 Granted publication date: 20170818 Pledgee: Yantai Fushan huiran Private Capital Management Co.,Ltd. Pledgor: YANTAI JIALONG NANO INDUSTRY CO.,LTD. Registration number: Y2022980021675 |