CN105271322A - Preparation method of fascicular magnesium carbonate trihydrate crystals - Google Patents
Preparation method of fascicular magnesium carbonate trihydrate crystals Download PDFInfo
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- CN105271322A CN105271322A CN201510625312.6A CN201510625312A CN105271322A CN 105271322 A CN105271322 A CN 105271322A CN 201510625312 A CN201510625312 A CN 201510625312A CN 105271322 A CN105271322 A CN 105271322A
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- magnesium carbonate
- carbonate trihydrate
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Abstract
The invention belongs to the field of mineral processing, and concretely relates to a preparation method of fascicular magnesium carbonate trihydrate crystals. The method comprises the following steps: adding a magnesium chloride hexahydrate solution to an ammonium bicarbonate solution at room temperature while stirring, adding a surfactant SDBS to obtain a reaction slurry, transferring the slurry to an autoclave, heating the slurry to 30-50DEG C, collecting a gas generated in the reaction process to obtain a CO2 gas product, filtering a slurry obtained after the reaction to obtain a filtrate and a filter cake, heating the filtrate at 100-150DEG C for 30-60min, carrying out low temperature condensation on the generated gas to obtain an ammonium chloride product, washing the filter cake with clear water multiple times until no Cl<-> of a washing solution can be detected, sending a solid product to a constant temperature drying box, and drying to obtain the fascicular magnesium carbonate trihydrate crystals. The preparation method of the fascicular magnesium carbonate trihydrate crystals has high efficiency, makes the target product have stable performances, and is a preparation technology with huge latent advantages.
Description
Technical field
The invention belongs to mineral manufacture field, be specifically related to a kind of preparation method of pencil magnesium carbonate trihydrate crystal.
Background technology
The regulation and control synthesis of micron particle is the important component part of micro-nano development in science and technology, is the basis exploring micro-nano structure performance and application thereof.But the composition, structure, pattern etc. of the micron particle obtained due to different synthetic methods and preparation process all have a great difference, and its corresponding uses also changes thereupon.Although in the controlledly synthesis process of micro materials, investigators wish all can realize controlling it in the either phase of its growth, and stop in the stage expected, finally synthesize the micro materials of different-shape.But due to technical reason, the micrometer structure material with special appearance that can synthesize at present only has a few, and the research of most micrometer structure material is still under test.Therefore, synthesis has the inorganic micro materials of property, and the low cost large-scale industrial production technology of research micron functional materials, has important practical value.
Magnesium carbonate trihydrate crystal (MgCO
33H
2o) cost performance is high, receives much attention in field of new.Due to very high purity, heat decomposition temperature is low, and magnesium carbonate trihydrate crystal not only for the preparation of meticulous magnesium salts products such as magnesium nitrate, magnesium sulfate, magnesium hydroxide, magnesium basic carbonates, and becomes the precursor preparing high-purity magnesium oxide.Splendid physico-chemical property and the mechanical property of excellence make it for industries such as medicine, makeup, plastics, coating, rubber, glass, pottery and printings.Production cost is low, preparation condition is gentle, of many uses, determine magnesium carbonate trihydrate crystal and there is great potential using value, the meticulous magnesium salts Chemicals with great potential will be become.
But, magnesium carbonate trihydrate crystal is very responsive to growth conditions, the magnesium carbonate trihydrate crystalline mi pattern with same structure has diversity, preparation at present for magnesium carbonate trihydrate crystal lays particular emphasis on bar-shaped, radial and fan-shaped preparation, has a strong impact on the suitability for industrialized production of magnesium salts fine chemical product.So special appearance regulation and control are grown to serve as the main path of magnesium carbonate trihydrate material functional.Only obtain the magnesiumcarbonate crystalline material with fixture phase composite that size is controlled, pattern is single-minded, magnesium carbonate trihydrate crystalchecked performance can be improved, widen its range of application.
Summary of the invention
For prior art Problems existing, the invention provides a kind of preparation method of pencil magnesium carbonate trihydrate crystal, object increases magnesium salts fine product kind, prolongation products production chain, reduce the production cost of high-purity magnesium salts, obtain high-quality magnesium carbonate trihydrate crystal product simultaneously, for magnesium salts product become more meticulous, High Purity produce technical scheme is provided.
The technical scheme realizing the object of the invention is carried out according to following steps:
(1) take water as solvent, magnesium chloride hexahydrate is mixed with the solution of 0.05 ~ 0.2mol/L, bicarbonate of ammonia is mixed with the solution of 0.1 ~ 0.2mol/L;
(2) at room temperature add in ammonium bicarbonate soln by magnesium chloride hexahydrate solution, stir while adding, stirring velocity is 60r/min, 5 ~ 10min adds complete, and then adds tensio-active agent SDBS, adds complete after 2min, regulate and control pH=9.0 ~ 9.5 with ammoniacal liquor again, obtain reaction paste;
(3) move in autoclave by slurry, be heated to 30 DEG C ~ 50 DEG C to slurry and stir simultaneously, stirring velocity is 60r/min ~ 240r/min, stopped reaction after 30 ~ 60min, collects the gas produced in reaction process and collects, obtain CO
2gas products;
(4) slurries filtration will obtained after reaction, obtain filtrate and filter cake, at 100 ~ 150 DEG C, 30 ~ 60min is heated to filtrate, the gas low temperature condensation produced, obtain ammonium chloride product, remaining liquid after heating to be delivered in step (1) and to add water, with magnesium chloride hexahydrate obtain solution, repeating above-mentioned reaction process; Clear water washing is carried out repeatedly to filter cake, until inspection does not measure Cl in washings
-till, solid product is delivered in thermostatic drying chamber, after dry, obtain pencil magnesium carbonate trihydrate crystal product.
Wherein, the add-on of described tensio-active agent accounts for 0.01% ~ 1% of magnesium chloride hexahydrate solution, ammonium bicarbonate soln and total mass.
Described slurry add-on accounts for 80% of reactor volume.
Described drying conditions is dry 2 ~ 3h at 40 DEG C ~ 50 DEG C.
Compared with prior art, feature of the present invention and beneficial effect are:
The present invention adopts magnesium chloride hexahydrate and bicarbonate of ammonia to synthesize pencil magnesium carbonate trihydrate crystal product as reaction raw materials, and the reaction of generation is:
The features such as the present invention is a kind of low temperature liquid phase reaction process, and this process has makes reaction mass be heated evenly, and is convenient to observe, and generation product property is stable, are very suitable for crystal morphology regulation and control.
Reactant fully dissolves and interacts in reaction system, part Mg in solution
2+with the NH in reaction process
4 +coordination generates Mg (NH
3)
y 2+complex compound, due to Mg (NH
3)
y 2+complex compound is unstable, CO
3 2-the structure adding destruction complex compound of ion, along with CO in reaction system
3 2-increasing of ion, Mg (NH
3)
y 2+in NH
3will by CO
3 2-ion substitution and generate magnesium carbonate trihydrate crystal embryo, forms atom or molecular growth primitive, i.e. crystallization nucleation.When nucleation crystal grain is very little, its crystal high miller index surface is exposed, and grain surface can increase, thus impels between crystal grain and mutually reunite, thus defines the core of radial crystal.Once formation nucleus of crystal, each monocrystal particle in coacervate grows according to respective crystal habit, and the mode that the oriented growth of crystal grain connects mutually with the crystal face that growth velocity is fast usually grows.So on vertical crystal core direction, crystalline growth forms rod-like crystal whisker, defines the branch of pencil crystal.SDBS is added in reaction system, it will be adsorbed in crystal particular crystal plane, and regulation and control magnesium carbonate trihydrate crystal, in the speed of growth of [100] and [001] crystal face, impels crystal to grow fast at [010] crystal face, and finally grow into pencil pattern, as shown in Figure of description Fig. 2.
Technical scheme production technique of the present invention and equipment simple, product yield is high, with low cost, non-environmental-pollution, for green production process, be easy to realize suitability for industrialized production, not only increase the productive rate of pencil magnesium carbonate trihydrate crystal, and improve magnesium salts quality product, improving product self-value, adds magnesium salts fine product kind, extends products production chain, add the productivity of derived product, and the competitive power of the meticulous magnesium salts of China in world market can be strengthened, promote magnesium salts business productivity.
The present invention is by national young Projects: magnesium carbonate whisker Microstructure Development rule and the young Projects of stable crystal formization research (51004064) and country: magnesium carbonate trihydrate crystalline mi Morphological control and formation mechanism study (51204091) thereof are subsidized.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention;
Fig. 2 is that the present invention prepares pencil magnesium carbonate trihydrate crystal growth schematic diagram in pencil magnesium carbonate trihydrate crystallization process;
Fig. 3 is the SEM photo of pencil magnesium carbonate trihydrate crystal prepared by the embodiment of the present invention 1;
Fig. 4 is the SEM photo of pencil magnesium carbonate trihydrate crystal prepared by the embodiment of the present invention 2;
Fig. 5 is the SEM photo of pencil magnesium carbonate trihydrate crystal prepared by the embodiment of the present invention 3;
Fig. 6 is the XRD figure spectrum of pencil magnesium carbonate trihydrate crystal prepared by the embodiment of the present invention 3.
Embodiment
The chemical reagent used in the embodiment of the present invention is commercial analytical pure grade reagents, wherein magnesium chloride hexahydrate is that East China, Shenyang City chemical reagent work produces, bicarbonate of ammonia is that East China, Shenyang City chemical reagent work produces, ammoniacal liquor is that East China, Shenyang City chemical reagent work produces, and Sodium dodecylbenzene sulfonate (SDBS) is the production of Shanghai Chemical Reagent Co., Ltd., Sinopharm Group
The INSTRUMENT MODEL that in the embodiment of the present invention, SEM scanning adopts is Japanese Shimadzu SEM-SS550, and the INSTRUMENT MODEL that XRD figure spectrum adopts is the DX-2000 of Japan.
Embodiment 1
The preparation method of the pencil magnesium carbonate trihydrate crystal of the present embodiment, as shown in Figure 1, carries out according to following steps:
(1) take water as solvent, magnesium chloride hexahydrate is mixed with the solution of 0.05mol/L, bicarbonate of ammonia is mixed with the solution of 0.2mol/L;
(2) at room temperature magnesium chloride hexahydrate solution is added in ammonium bicarbonate soln, stir while adding, stirring velocity is 60r/min, 10min adds complete, and then add tensio-active agent SDBS, add complete after the add-on of tensio-active agent SDBS accounts for 0.01%, 2min of magnesium chloride hexahydrate solution, ammonium bicarbonate soln and total mass, regulate and control pH=9.5 with ammoniacal liquor again, obtain reaction paste;
(3) move in autoclave by slurry, slurry add-on accounts for 80% of reactor volume, is heated to 50 DEG C stirs simultaneously slurry, stirring velocity is 240r/min, stopped reaction after 30min, collects the gas produced in reaction process and collects, obtain CO
2gas products;
(4) slurries filtration will obtained after reaction, obtain filtrate and filter cake, at 100 DEG C, 60min is heated to filtrate, the gas low temperature condensation produced, obtain ammonium chloride product, remaining liquid after heating to be delivered in step (1) and to add water, with magnesium chloride hexahydrate obtain solution, repeating above-mentioned reaction process; 5 clear water washings are carried out, until inspection does not measure Cl in washings to filter cake
-till, solid product is delivered in thermostatic drying chamber, dry 2h at 50 DEG C, obtain pencil magnesium carbonate trihydrate crystal product.
As shown in Figure 3, in picture, crystal is mainly in pencil pattern, is wherein mingled with a small amount of rhabdolith, wherein has no symmetrical pencil pattern crystal for the SEM of pencil magnesium carbonate trihydrate crystal prepared by the present embodiment, crystal structure growth phase to complete, average crystal length 170 μm.
Embodiment 2
The preparation method of the pencil magnesium carbonate trihydrate crystal of the present embodiment, as shown in Figure 1, carries out according to following steps:
(1) take water as solvent, magnesium chloride hexahydrate is mixed with the solution of 0.1mol/L, bicarbonate of ammonia is mixed with the solution of 0.1mol/L;
(2) at room temperature magnesium chloride hexahydrate solution is added in ammonium bicarbonate soln, stir while adding, stirring velocity is 60r/min, 8min adds complete, and then add tensio-active agent SDBS, add complete after the add-on of tensio-active agent SDBS accounts for 0.5%, 2min of magnesium chloride hexahydrate solution, ammonium bicarbonate soln and total mass, regulate and control pH=9.3 with ammoniacal liquor again, obtain reaction paste;
(3) move in autoclave by slurry, slurry add-on accounts for 80% of reactor volume, is heated to 40 DEG C stirs simultaneously slurry, stirring velocity is 240r/min, stopped reaction after 50min, collects the gas produced in reaction process and collects, obtain CO
2gas products;
(4) slurries filtration will obtained after reaction, obtain filtrate and filter cake, at 110 DEG C, 45min is heated to filtrate, the gas low temperature condensation produced, obtain ammonium chloride product, remaining liquid after heating to be delivered in step (1) and to add water, with magnesium chloride hexahydrate obtain solution, repeating above-mentioned reaction process; 5 clear water washings are carried out, until inspection does not measure Cl in washings to filter cake
-till, solid product is delivered in thermostatic drying chamber, dry 2.5h at 45 DEG C, obtain pencil magnesium carbonate trihydrate crystal product.
The SEM photo of pencil magnesium carbonate trihydrate crystal prepared by the present embodiment as shown in Figure 4, in picture, crystal is mainly in pencil pattern, and crystal structure is relatively complete, and fasciculation pattern crystal is relatively many, symmetrical pencil pattern amount of crystals is relatively less, and mean length is at 180 μm.
Embodiment 3
The preparation method of the pencil magnesium carbonate trihydrate crystal of the present embodiment, as shown in Figure 1, carries out according to following steps:
(1) take water as solvent, magnesium chloride hexahydrate is mixed with the solution of 0.2mol/L, bicarbonate of ammonia is mixed with the solution of 0.05mol/L;
(2) at room temperature magnesium chloride hexahydrate solution is added in ammonium bicarbonate soln, stir while adding, stirring velocity is 60r/min, 5min adds complete, and then add tensio-active agent SDBS, add complete after the add-on of tensio-active agent SDBS accounts for 1%, 2min of magnesium chloride hexahydrate solution, ammonium bicarbonate soln and total mass, regulate and control pH=9.0 with ammoniacal liquor again, obtain reaction paste;
(3) move in autoclave by slurry, slurry add-on accounts for 80% of reactor volume, is heated to 40 DEG C stirs simultaneously slurry, stirring velocity is 120r/min, stopped reaction after 60min, collects the gas produced in reaction process and collects, obtain CO
2gas products;
(4) slurries filtration will obtained after reaction, obtain filtrate and filter cake, at 150 DEG C, 30min is heated to filtrate, the gas low temperature condensation produced, obtain ammonium chloride product, remaining liquid after heating to be delivered in step (1) and to add water, with magnesium chloride hexahydrate obtain solution, repeating above-mentioned reaction process; 5 clear water washings are carried out, until inspection does not measure Cl in washings to filter cake
-till, solid product is delivered in thermostatic drying chamber, dry 3h at 40 DEG C, obtain pencil magnesium carbonate trihydrate crystal product;
As shown in Figure 5, in picture, crystal is mainly in pencil pattern for the SEM photo of pencil magnesium carbonate trihydrate crystal prepared by the present embodiment, and crystal grain difference in size is comparatively large, is wherein mingled with a small amount of rhabdolith, grows perfect crystal mean length 150 μm; As shown in Figure 6, there is not other assorted peaks in its XRD figure, the out-degree of magnesiumcarbonate crystal is very high.
Claims (4)
1. a preparation method for pencil magnesium carbonate trihydrate crystal, is characterized in that carrying out according to following steps:
(1) take water as solvent, magnesium chloride hexahydrate is mixed with the solution of 0.05 ~ 0.2mol/L, bicarbonate of ammonia is mixed with the solution of 0.1 ~ 0.2mol/L;
(2) at room temperature add in ammonium bicarbonate soln by magnesium chloride hexahydrate solution, stir while adding, stirring velocity is 60r/min, 5 ~ 10min adds complete, and then adds tensio-active agent SDBS, adds complete after 2min, regulate and control pH=9.0 ~ 9.5 with ammoniacal liquor again, obtain reaction paste;
(3) move in autoclave by slurry, be heated to 30 ~ 50 DEG C to slurry and stir simultaneously, stirring velocity is 60 ~ 240r/min, stopped reaction after 30 ~ 60min, collects the gas produced in reaction process and collects, obtain CO
2gas products;
(4) slurries filtration will obtained after reaction, obtain filtrate and filter cake, at 100 ~ 150 DEG C, 30 ~ 60min is heated to filtrate, the gas low temperature condensation produced, obtain ammonium chloride product, remaining liquid after heating to be delivered in step (1) and to add water, with magnesium chloride hexahydrate obtain solution, repeating above-mentioned reaction process; Clear water washing is carried out repeatedly to filter cake, until inspection does not measure Cl in washings
-till, solid product is delivered in thermostatic drying chamber, after dry, obtain pencil magnesium carbonate trihydrate crystal product.
2. the preparation method of a kind of pencil magnesium carbonate trihydrate crystal according to claim 1, is characterized in that the add-on of described tensio-active agent accounts for 0.01% ~ 1% of magnesium chloride hexahydrate solution, ammonium bicarbonate soln and total mass.
3. the preparation method of a kind of pencil magnesium carbonate trihydrate crystal according to claim 1, is characterized in that described slurry add-on accounts for 80% of reactor volume.
4. the preparation method of a kind of pencil magnesium carbonate trihydrate crystal according to claim 1, is characterized in that described drying conditions is dry 2 ~ 3h at 40 ~ 50 DEG C.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106335912A (en) * | 2016-08-23 | 2017-01-18 | 华东理工大学 | Method for preparing nesquehonite and hydrogen chloride from magnesium chloride and carbon dioxide |
| WO2018139975A1 (en) * | 2017-01-25 | 2018-08-02 | Nanyang Technological University | Enhanced reactive magnesia cement-based concrete mixes |
| CN109019654A (en) * | 2018-10-22 | 2018-12-18 | 南昌航空大学 | A kind of preparation method and device of pencil carbonic acid strontium crystal |
| CN113353960A (en) * | 2021-07-27 | 2021-09-07 | 沈阳理工大学 | Morphology-adjustable magnesium carbonate trihydrate crystal and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106335912A (en) * | 2016-08-23 | 2017-01-18 | 华东理工大学 | Method for preparing nesquehonite and hydrogen chloride from magnesium chloride and carbon dioxide |
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| CN109019654A (en) * | 2018-10-22 | 2018-12-18 | 南昌航空大学 | A kind of preparation method and device of pencil carbonic acid strontium crystal |
| CN109019654B (en) * | 2018-10-22 | 2020-04-28 | 南昌航空大学 | Preparation method of beam-shaped strontium carbonate crystal |
| CN113353960A (en) * | 2021-07-27 | 2021-09-07 | 沈阳理工大学 | Morphology-adjustable magnesium carbonate trihydrate crystal and preparation method thereof |
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