CN106006745B - A kind of method for continuously preparing soft-agglomerated nano-calcium carbonate manganese - Google Patents
A kind of method for continuously preparing soft-agglomerated nano-calcium carbonate manganese Download PDFInfo
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- CN106006745B CN106006745B CN201610334299.3A CN201610334299A CN106006745B CN 106006745 B CN106006745 B CN 106006745B CN 201610334299 A CN201610334299 A CN 201610334299A CN 106006745 B CN106006745 B CN 106006745B
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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
Abstract
The invention belongs to technical field of nano material, more particularly to a kind of method for continuously preparing soft-agglomerated nano-calcium carbonate manganese.The present invention use reagent grade sulfuric acid manganese and precipitating reagent for raw material, it is to avoid reduce product manganese carbonate quality because of raw material introducing impurity.Using the continuous pair of feeding manner added in synthesis technique, reaction is carried out continuously, production efficiency is improved.Manganese carbonate particle diameter produced by the present invention is less than 30nm, belongs to proper nano material, and obtained manganese carbonate is shaped as spherical, reunites and is to reunite with being easily dispersed during use for soft-agglomerated, soft-agglomerated advantage to open the nano particle for obtaining primary particle size.
Description
Technical field
The invention belongs to technical field of nano material, more particularly to a kind of side for continuously preparing soft-agglomerated nano-calcium carbonate manganese
Method.
Background technology
Manganese carbonate be produce electrolytic manganese metal raw material, available for manufacture permeability magnetic material, be soft magnetic ferrite it is main into
/ mono-, it may also be used for desulphurization catalyst, enamel pigment, varnish drier and fertilizer additive etc..
With the development of new energy technology, application of the manganese carbonate in battery material field is more and more extensive, particularly mangaic acid
The good development trend that lithium battery and nickel-cobalt-manganese ternary battery show, more improves the application value of manganese carbonate.Manganese carbonate
Also more strict to the quality requirement of product while application value is improved, its purity, crystal formation, granularity largely influence
To the chemical property of electrode material.
At present, the preparation method of nano-calcium carbonate manganese mainly has following several, but there are various shortcomings：
(1) seeing the preparation method of the manganese carbonate of document report at present mainly has liquid-phase precipitation method and hydrothermal crystallization method.Wherein,
Hydrothermal crystallization method needs high energy consumption in preparation process, causes certain energy waste；Liquid-phase precipitation method is long reaction time, particle
Size is uneven and uses exhibiting high surface activating agent, and water body and environment can be polluted.
(2) Chinese patent 201010158824.3 discloses a kind of preparation method of manganese carbonate nanorod, and this method is in chlorine
Change and surfactant, hydrogen peroxide and lithium carbonate added in the solution of manganese and potassium permanganate, under the conditions of 180 DEG C hydro-thermal reaction 16~
Prepare manganese carbonate nanorod within 24 hours.201410191556.3 a kind of preparation method of manganese carbonate nanofiber ball is disclosed, should
Invention is to mix manganese chloride and sodium potassium tartrate tetrahydrate to be reacted, and forms manganese tartrate precipitation, then this manganese tartrate is sunk
Form sediment to mix with solution of potassium carbonate and be fitted into reactor, be incubated 3~10 hours at 50~200 DEG C and carry out hydro-thermal process, washing
Obtain manganese carbonate fibrous nodules.In Preparation Process of Spherical Manganese Carbonate Particles pattern control (process engineering journal, 2008 volume 8
2nd phase, grain seapeak) one kind is disclosed with MnSO4And NH4HCO3For raw material, granularity master has been prepared using the cryochemistry precipitation method
To be 5-6 μm of single dispersing MnCO3Spheric granules.Hydrothermal crystallization method prepares ultra-fine MnCO3Research (electronic component and equipment,
3rd phase in 2006, Du Zewei) one kind is disclosed with Na2CO3And MnCI2·4H2O is raw material, is synthesized using hydrothermal crystallization method
Superfine high-purity MnCO3, MnCO3Particle is square, and average grain diameter is 180nm.It is spherical that liquid-phase precipitation method prepares monodispersed submicron level
Manganese carbonate (inorganic chemicals industry, the 8th phase of volume 41 in 2009, grain seapeak) disclose one kind by manganese source of manganese sulfate, ammonium hydrogen carbonate
It is particle size controling agent for precipitating reagent, lauryl sodium sulfate, is quickly added simultaneously using two kinds of solution of manganese sulfate and ammonium hydrogen carbonate
Mode, by controlling suitable reactive crystallization condition, prepare submicron order monodisperse spherical manganese carbonate particle, average grain diameter
About 540nm, the shortcoming of the method is that batch (-type) is fed, and is unfavorable for large-scale production, and particle size is in 540nm, category
It is not the nano material of stricti jurise in sub-micrometer range.
(2) nano-calcium carbonate manganese prepared by the several method described in is bar-shaped, fibrous or spherical, is reunited for hard group
It is poly-, but hard aggregation is difficult to disperse to obtain primary particle size in use, spherical manganese carbonate particle diameter is also only submicron order,
Particle diameter does not reach requirement of the nano-calcium carbonate manganese particle diameter in 1-100nm more than 500 nanometers.
The content of the invention
The present invention continuously prepares soft group there is provided a kind of particle diameter for the deficiency that above-mentioned prior art is present within 30nm
The method of poly- nano-calcium carbonate manganese.
The technical scheme that the present invention solves above-mentioned technical problem is as follows：A kind of side for continuously preparing soft-agglomerated nano-calcium carbonate manganese
Method, step is as follows：
(1) compound concentration is 1-2mol/L manganese sulfate solution, adds chemical additives, obtains containing 0.1-0.3wt%
The manganese sulfate solution of chemical additives；Compound concentration is 1-2mol/L precipitant solution；
(2) by the manganese sulfate solution containing chemical additives and precipitant solution of step (1) with the continuous pair of charging added
Mode is added in reactor, and the charging rate of the manganese sulfate solution containing chemical additives is 100-200L/h, precipitant solution
Charging rate be 200-400L/h, stirred with 200-300r/min speed, control pH for 7-8；
(3) step (2) reaction temperature be 25 DEG C, pressure be progress under the conditions of 101kPa, film mistake is passed through to reaction discharging
Filter, with pure water 3 times, carry out separation of solid and liquid；
(4) solid matter for isolating step (3) dries 8-12h under the conditions of 50-90 DEG C, obtains white or pink colour is received
Rice manganese carbonate, primary particle size is 10-30nm.
Wherein, described chemical additives are hexadecyltrimethylammonium chloride, one kind of ammonium citrate or formic acid or two
Plant mixed above.
Described precipitating reagent is one or two kinds of mixing of ammonium carbonate or ammonium hydrogen carbonate.
The beneficial effects of the invention are as follows：
1st, the present invention use reagent grade sulfuric acid manganese and precipitating reagent for raw material, it is to avoid make product carbon because of raw material introducing impurity
Sour manganese quality reduction.Using the continuous pair of feeding manner added in synthesis technique, reaction is carried out continuously, production efficiency is improved.
2nd, manganese carbonate minimum grain size made from existing manganese carbonate preparation method is 180nm, manganese carbonate produced by the present invention
Particle diameter is less than 30nm, belongs to proper nano material (nano material particle diameter is 1-100nm).
3rd, manganese carbonate produced by the present invention is shaped as spherical, reunites and is to use process for soft-agglomerated, soft-agglomerated advantage
Middle reunion, which is easily dispersed, opens the nano particle for obtaining primary particle size.
Embodiment
The principle and feature of the present invention are described below in conjunction with example, the given examples are served only to explain the present invention, and
It is non-to be used to limit the scope of the present invention.
Embodiment 1
A kind of method for continuously preparing soft-agglomerated nano-calcium carbonate manganese, step is as follows：
(1) compound concentration is 1mol/L manganese sulfate solution 1L, adds 1g cetyl trimethylammonium bromides, is contained
The manganese sulfate solution of 0.1wt% chemical additives；Compound concentration is 1mol/L ammonium bicarbonate soln 2L；
(2) by the manganese sulfate solution containing chemical additives and ammonium bicarbonate soln of step (1) by pair plus in the way of add
Enter in reactor, the charging rate of the manganese sulfate solution containing chemical additives is 100L/h, the charging speed of ammonium bicarbonate soln
Spend for 200L/h, stirred with 200r/min speed, it is 7.0 to control pH；
(3) step (2) reaction temperature be 25 DEG C, pressure be progress under the conditions of 101kPa, film mistake is passed through to reaction discharging
Filter, with pure water 3 times, carry out separation of solid and liquid；
(4) solid matter for isolating step (3) dries 12h under the conditions of 50 DEG C, obtains white or pink colour nano-sized carbon
Sour manganese, primary particle size is 10nm.
Embodiment 2
A kind of method for continuously preparing soft-agglomerated nano-calcium carbonate manganese, step is as follows：
(1) compound concentration is 1.5mol/L manganese sulfate solution 1L, adds 2g ammonium citrates, obtains brilliant containing 0.2wt%
The manganese sulfate solution of type controlling agent；Compound concentration is 1.5mol/L ammonium bicarbonate soln 2L；
(2) by the manganese sulfate solution containing chemical additives and ammonium bicarbonate soln of step (1) by pair plus in the way of add
Enter in reactor, the charging rate of the manganese sulfate solution containing chemical additives is 200L/h, the charging speed of ammonium bicarbonate soln
Spend for 400L/h, stirred with 250r/min speed, it is 7.5 to control pH；
(3) step (2) reaction temperature be 25 DEG C, pressure be progress under the conditions of 101kPa, film mistake is passed through to reaction discharging
Filter, with pure water 3 times, carry out separation of solid and liquid；
(4) solid matter for isolating step (3) dries 10h under the conditions of 60 DEG C, obtains white or pink colour nano-sized carbon
Sour manganese, primary particle size is 20nm.
Embodiment 3
A kind of method for continuously preparing soft-agglomerated nano-calcium carbonate manganese, step is as follows：
(1) compound concentration is 2mol/L manganese sulfate solution 1L, adds 3g formic acid, obtains controlling containing 0.3wt% crystal formations
The manganese sulfate solution of agent；Compound concentration is 2mol/L sal volatile 1L；
(2) by the manganese sulfate solution containing chemical additives and sal volatile of step (1) by pair plus in the way of add
In reactor, the charging rate of the manganese sulfate solution containing chemical additives is 150L/h, and the charging rate of sal volatile is
150L/h, is stirred with 300r/min speed, and it is 8.0 to control pH；
(3) step (2) reaction temperature be 25 DEG C, pressure be progress under the conditions of 101kPa, film mistake is passed through to reaction discharging
Filter, with pure water 3 times, carry out separation of solid and liquid；
(4) solid matter for isolating step (3) dries 8h under the conditions of 90 DEG C, 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, be not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent substitution and improvements made etc. should be included in the scope of the protection.
Claims (1)
1. a kind of method for continuously preparing soft-agglomerated nano-calcium carbonate manganese, it is characterised in that step is as follows：
(1) compound concentration is 1-2mol/L manganese sulfate solution, adds chemical additives, obtains containing 0.1-0.3wt% crystal formations
The manganese sulfate solution of controlling agent；Compound concentration is 1-2mol/L precipitant solution；
(2) by the manganese sulfate solution containing chemical additives and precipitant solution of step (1) with the continuous pair of feeding manner added
Add in reactor, the charging rate of the manganese sulfate solution containing chemical additives is 100-200L/h, precipitant solution plus
Material speed is 200-400L/h, is stirred with 200-300r/min speed, and it is 7-8 to control pH；
(3) step (2) reaction temperature be 25 DEG C, pressure be progress under the conditions of 101kPa, to reaction discharging by membrane filtration, use
Pure water 3 times, carries out separation of solid and liquid；
(4) solid matter for isolating step (3) dries 8-12h under the conditions of 50-90 DEG C, obtains white or pink colour nano-sized carbon
Sour manganese, primary particle size is 10-30nm；
Described chemical additives mix for the one or more of hexadecyltrimethylammonium chloride, ammonium citrate or formic acid
Close；
Described precipitating reagent is one or two kinds of mixing of ammonium carbonate or ammonium hydrogen carbonate.
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| 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 |
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| 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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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 |
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