CN107456931B - Device and method for generating unstable calcium carbonate mineral phase - Google Patents
Device and method for generating unstable calcium carbonate mineral phase Download PDFInfo
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- CN107456931B CN107456931B CN201710671410.2A CN201710671410A CN107456931B CN 107456931 B CN107456931 B CN 107456931B CN 201710671410 A CN201710671410 A CN 201710671410A CN 107456931 B CN107456931 B CN 107456931B
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- B01J14/00—Chemical processes in general for reacting liquids with liquids; Apparatus specially adapted therefor
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- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2455—Stationary reactors without moving elements inside provoking a loop type movement of the reactants
- B01J19/2465—Stationary reactors without moving elements inside provoking a loop type movement of the reactants externally, i.e. the mixture leaving the vessel and subsequently re-entering it
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- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/181—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by control of the carbonation conditions
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Abstract
The invention provides a method for generating instabilityAn apparatus and method for determining calcium carbonate mineral phases, the apparatus comprising a lower reaction zone, a middle fluidization zone and a top precipitation zone; equimolar Na of the arrangement 2 CO 3 And CaCl 2 The solutions respectively enter from two sides of the lower part of the reactor and are mixed to generate CaCO 3 A crystal; the top reflux is introduced from the bottom at a faster flow rate, has a certain dilution effect on the inlet water solution, and the rising force thereof causes CaCO 3 The crystallization process is in a fluidized state; generated CaCO 3 The crystals are precipitated in a precipitation zone and separated from the solution, and the reacted solution is discharged from a water outlet at the top; the invention aims at CaCO by reflux 3 The influence of crystallization process can inhibit CaCO 3 The formation of stable phase calcite promotes the formation of unstable phases such as aragonite and aragonite, which is beneficial to solving the problem of reactor scaling caused by calcite formation and developing unstable CaCO 3 Research on mineral phase utilization; compared with other methods, the method has the characteristics of simple operation, low cost, easy operation and control and the like.
Description
Technical Field
The invention belongs to the technical field of mineral synthesis processing engineering, and particularly relates to a device and a method for generating an unstable calcium carbonate mineral phase.
Background
In the fields of actual life and engineering, most heat exchange equipment has the problem of dirt with different degrees, and the harm to the equipment is extremely large. Industrial losses due to fouling in industrially developed countries account for about 0.3% of the total national production. The China is a developing country and a country with large energy consumption, and compared with the state that the scale prevention and removal technology is behind, the economic loss caused by scale accounts for higher proportion of GNP.
CaCO 3 Is the main component of the scale and has three distinct mineral phases, calcite, aragonite and aragonite. Calcite is ubiquitous in nature and is the most thermodynamically stable calcium carbonate mineral phase, which is the main component of hard scale and is relatively difficult to clean; aragonite and aragonite CaCO 3 And the non-stable phase is formed into soft scale and is easy to remove. Common scale control techniques include chemical and physical methods. The essence of chemical scale prevention is that chemical reagent is added to prevent calcium carbonate from growing, and the common reagent at present is organic phosphoric acid and polymer, and CaCO is controlled mainly by chelating, lattice distortion, electrostatic repulsion and other actions 3 Crystal growth habit, preventing unstable CaCO 3 Conversion of mineral phases (aragonite and aragonite) to calcite, a stable phaseThe aragonite and aragonite are allowed to exist stably while the formation of calcite in the stable phase is inhibited. Physical scale prevention method, mainly utilizing acoustic, electric, magnetic and other techniques and equipment to purposefully change Ca 2+ 、CO 3 2- And the movement state of water molecules, etc., to maintain unstable CaCO 3 The mineral phase provides kinetic energy, thereby inhibiting the formation of stable phase calcite.
The chemical and physical scale prevention methods are realized by controlling CaCO 3 Crystallization process, caCO is prevented 3 The transition from unstable to stable phase. The former needs to add chemical reagent, which has high cost and is easy to cause secondary pollution to the environment; the latter needs to be equipped with optical, electric and magnetic related devices, has large investment and generally has a treatment effect which is inferior to that of a chemical method. In addition, unstable CaCO 3 The mineral phase has good application prospect, such as aragonite, and is widely applied to the fields of personal care product additives, medical carriers, photoelectric materials, high-grade printing ink, catalyst carriers and the like; the aragonite whisker as a novel inorganic reinforcing material is widely applied to the fields of papermaking, rubber, plastics, medicines and the like. Thus, simple, low cost, environmentally friendly, non-stable CaCO was explored 3 The mineral phase generating device and method have important practical and scientific significance.
Disclosure of Invention
In order to overcome the drawbacks of the prior art described above, the object of the present invention is to provide a device and a method for producing unstable calcium carbonate mineral phases, suppressing CaCO by the operation of the reactor itself 3 Stable phase generation, promotion of unstable phase generation, elimination of influence of dirt on equipment, and CaCO development 3 The comprehensive utilization of the unstable phase provides a simple, low-cost, environmentally friendly apparatus and method.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a device for generating unstable calcium carbonate mineral phase comprises a reaction zone 1, a fluidization zone 2 and a precipitation zone 3, wherein Na is arranged at two sides of the reaction zone 1 2 CO 3 Solution inlet 5 and CaCl 2 A solution inlet 8, a reflux liquid inlet 15 is arranged at the bottom and a middle part is arrangedA water distributor 4 is arranged; the fluidization area 2 is connected with the reaction area 1 and the sedimentation area 3; the sedimentation zone 3 is provided with a reflux liquid outlet 11 and a water outlet 13, and the reflux liquid outlet 11 is connected with a reflux liquid inlet 15 through a pipeline with a reflux pump 12.
The reaction zone 1, the fluidization zone 2 and the sedimentation zone 3 are sequentially arranged from bottom to top, wherein the inner diameter ratio of the reaction zone 1 to the fluidization zone 2 is 1, the height ratio is 0.1-0.2, the inner diameter ratio of the sedimentation zone 3 to the fluidization zone 2 is 2-4, and the height of the sedimentation zone 3 is 18% -25% of the total height of the device.
The inner diameter transition zone at the lower part of the sedimentation zone 3 accounts for 15% -30% of the height of the sedimentation zone 3.
The Na is 2 CO 3 The solution inlet 5 is connected with Na through a pipeline with a water inlet pump I6 2 CO 3 A solution inlet tank 7, caCl 2 The solution inlet 8 is connected with CaCl through a pipeline with a second water inlet pump 9 2 The solution inlet tank 10, the water outlet 13 is connected with the water collecting tank 14 through a pipeline.
The water distributor 4 is arranged at the position of 3/4 of the height in the reaction zone 1 and comprises 8-16 water through holes with the aperture of 1.5mm, and the water distributor 4 is positioned at Na 2 CO 3 Solution inlet 5 and CaCl 2 Below the solution inlet 8.
The invention also provides a method for generating an unstable calcium carbonate mineral phase based on the device, which comprises the following steps:
step one, equimolar high concentration of Na 2 CO 3 And CaCl 2 The solutions were respectively stored in Na 2 CO 3 Solution intake pool 7 and CaCl 2 In the solution water inlet tank 10, na is used as a water source through a first water inlet pump 6 and a second water inlet pump 9 2 CO 3 Solution inlet 5 and CaCl 2 The solution inlet 8 enters the reaction zone 1 and is mixed to generate CaCO 3 A crystal;
step two, the aqueous solution is mixed in the reaction zone 1, and enters a sedimentation zone 3 with gradually larger diameter through a fluidization zone 2, and CaCO is formed due to the weakening of the lifting force and the change of the solution flow direction 3 Slowly depositing the crystallized product in the deposition area 3 to realize solid-liquid two-phase separation, and allowing a part of liquid phase to pass through a reflux liquid outlet11, and the other part of liquid phase is discharged through a water outlet 13 and enters a water collecting tank 14;
step three, reflux liquid enters from a reflux liquid water outlet 11 through a reflux pump 12 from a reflux liquid water inlet 15, and uniform water distribution of reflux is realized through a water distributor 4, and CaCO in the reaction zone 1 is subjected to reflux action force 3 The crystallization process is in a fluidization state, and the dilution of the water inlet solution is accelerated to a certain extent, so that the supersaturation degree of the reaction system is reduced.
Wherein the hydraulic retention time is 40-90min, and the rising flow rate of the reflux liquid in the fluidization area 2 is 1.5-15m/h.
For the generated CaCO 3 The mineral feature analysis of (2) shows that the improvement of the reflux quantity of the device is beneficial to inhibiting CaCO 3 The formation of stable phase calcite, thereby promoting unstable CaCO 3 The generation of crystals; in the unstable phase, mainly aragonite, a small amount of aragonite appears as the reflux increases. Calcite is mostly regular square, aragonite is mainly in the shape of rose, and aragonite is mainly in the shape of needle.
The technical principle of the invention is as follows:
a) By means of solution backflow, the dilution effect of the inflow water in the system is controlled by utilizing the flow rate of the backflow solution, so that the supersaturation degree in the solution is reduced, and CaCO (CaCO) is slowed down 3 The crystallization process of minerals is beneficial to control of the crystallization process;
b) As shown in FIG. 2, in CaCO 3 During crystallization, caCO is first precipitated from supersaturated solution without seed crystals 3 Is amorphous phase, which is converted into CaCO 3 A part of polycrystalline precursor is converted into metastable phase aragonite and aragonite, the other part is converted into stable phase calcite, under the condition of no external force and inhibition of additives, metastable phase is converted into thermodynamically most stable calcite through a dissolution-recrystallization mechanism, and the migration of solute molecules to the surface of metastable crystals can be effectively improved through the action of reflux hydraulic disturbance, and CaCO is prevented from being damaged by the dissolution-recrystallization mechanism 3 The dissolution-recrystallization mechanism of metastable phases plays a role in inhibition, so that the formation of calcite in a stable phase can be inhibited. In addition, studies have shown that the action of external force can change CaCO 3 Is favorable for sub-optimal enthalpy of formationThe stable presence of the stable mineral phase.
Compared with the prior art, the invention inhibits CaCO by continuously running the water inlet and the water outlet of the system and disturbing and fluidizing the crystallization process by the solution backflow 3 Stable phase is generated, and the yield of unstable mineral phase is improved, thus being capable of effectively solving CaCO 3 Scaling problems, promote the stabilization of CaCO 3 And (3) comprehensive utilization of mineral phases. In addition, the invention does not need to add other chemical reagents or be equipped with optical, electric and magnetic related devices, and has the characteristics of simple operation, low investment cost, environmental friendliness and the like.
Drawings
Fig. 1 is a device diagram of an embodiment of the present invention.
FIG. 2 is a diagram of a calcium carbonate mineral crystallization process according to an embodiment of the present invention.
Figure 3 is an XRD analysis of the calcium carbonate mineral phase produced in accordance with an embodiment of the present invention.
FIG. 4 is a graph of electron microscopy analysis of calcium carbonate mineral phase formation in accordance with an embodiment of the present invention.
Detailed Description
Embodiments of the present invention will now be described in detail with reference to the drawings and examples, wherein the specific embodiments described are by way of illustration only and not all examples. All other examples, which are obtained without inventive effort by a person skilled in the art, are within the scope of the present invention.
As shown in FIG. 1, an apparatus for producing an unstable calcium carbonate mineral phase is made of organic glass and has an effective volume of 1L and a height of 727mm and mainly comprises a reaction zone 1, a fluidization zone 2 and a precipitation zone 3 from bottom to top. The inner diameter ratio of the reaction zone 1 and the fluidization zone 2 was 1, the height ratio was 0.1 to 0.2, and in this example, the inner diameter of the reaction zone 1 and the fluidization zone 2 was 31mm, and the height ratio was 0.13. The inner diameter ratio of the sedimentation zone 3 to the fluidization zone 2 is 2-4, the height of the sedimentation zone 3 is 18% -25% of the total height of the device, the inner diameter of the lower part of the sedimentation zone 3 is smaller than the inner diameter of the upper part, the lower inner diameter transition zone accounts for 15% -30% of the height of the sedimentation zone 3, the inner diameter ratio of the sedimentation zone 3 to the fluidization zone 2 is 3 in this embodiment, the height of the sedimentation zone 3 is 22% of the total height of the device, and the lower inner diameter transition zone accounts for 19% of the height of the sedimentation zone 3.
Na of reaction zone 1 2 CO 3 The solution inlet 5 is connected with Na through a pipeline with a water inlet pump I6 2 CO 3 Solution inlet tank 7, caCl in reaction zone 1 2 The solution inlet 8 is connected with CaCl through a pipeline with a second water inlet pump 9 2 Solution enters the tank 10. The water distributor 4 is arranged at the position of 3/4 of the height in the reaction zone 1 and comprises 8-16 water through holes with the aperture of 1.5mm, and in the embodiment, the water distributor 4 comprises 12 water through holes with the aperture of 1.5 mm.
The water outlet 13 of the sedimentation zone 3 is connected with a water collecting tank 14 through a pipeline, and the reflux liquid water outlet 11 of the sedimentation zone 3 is connected with the reflux liquid water inlet 15 at the bottom of the reaction zone 1 through a pipeline with a reflux pump 12. The hydraulic retention time of the device is 40-90min, the rising flow rate of the reflux water in the reflux zone 2 is 1.5-15m/h, the hydraulic retention time is 60min in the embodiment, and the rising flow rate of the reflux water in the fluidization zone 2 is 1.5, 4.2, 8 and 10m/h.
In an embodiment of the invention, a method for producing an unstable calcium carbonate mineral phase comprises the steps of:
step one, equimolar high concentration of Na 2 CO 3 And CaCl 2 The solutions were respectively stored in Na 2 CO 3 Solution intake pool 7 and CaCl 2 In the solution water inlet tank 10, na is used as a water source through a first water inlet pump 6 and a second water inlet pump 9 2 CO 3 Solution inlet 5 and CaCl 2 The solution inlet 8 enters the reactor and is mixed to generate CaCO 3 And (5) a crystal. Na configured in the present embodiment 2 CO 3 And CaCl 2 The solution was 0.05mol/L, i.e., ca ion concentration was 2000mg/L.
Step two, reflux liquid enters from a reflux liquid water outlet 11 through a reflux pump 12 from a reflux liquid water inlet 15, and uniform water distribution of reflux is realized through a water distributor 4, and CaCO in the reaction zone 1 is subjected to reflux action force 3 The crystallization process is in a fluidization state, and the dilution of the water inlet solution is accelerated to a certain extent, so that the supersaturation degree of the reaction system is reduced.
Step three, the aqueous solution is mixed in the reaction zone 1, and the aqueous solution enters the fluidized zone 2 to gradually increase in diameterDue to the weakening of the lifting force and the change of the flow direction of the solution, caCO 3 The crystallization product is slowly deposited in the precipitation zone 3 to realize solid-liquid two-phase separation, one part of liquid phase flows back through the reflux liquid outlet 11, and the other part of liquid phase is discharged from the outlet 13 and enters the water collecting tank 14.
Experimental results show that the improvement of the reflux quantity of the device is beneficial to inhibiting square CaCO 3 The formation of stable phase calcite, thereby promoting unstable CaCO 3 The generation of crystals; in the unstable phase, mainly rose-like spherical aragonite, a small amount of acicular aragonite appears as the reflux amount increases. CaCO under the condition that the rising flow rate of the return water in the return zone 2 is 10m/h 3 The generation of stable phase calcite is obviously inhibited, the content is less than 10 percent, and CaCO is added 3 The proportion of aragonite and aragonite in the unstable phase was up to 90% or more, and the mineralogical characteristics under the experimental conditions are shown in figures 3 and 4.
Claims (3)
1. A method for producing an unstable calcium carbonate mineral phase is realized by a device for producing the unstable calcium carbonate mineral phase, the device for producing the unstable calcium carbonate mineral phase comprises a reaction zone (1), a fluidization zone (2) and a precipitation zone (3), and Na is arranged at two sides of the reaction zone (1) 2 CO 3 Solution inlet (5) and CaCl 2 A solution inlet (8), a reflux liquid inlet (15) is arranged at the bottom, and a water distributor (4) is arranged in the middle; the fluidization zone (2) is connected with the reaction zone (1) and the sedimentation zone (3); the lower inner diameter transition zone of the sedimentation zone (3) accounts for 15% -30% of the height of the sedimentation zone (3), the sedimentation zone (3) is provided with a reflux liquid outlet (11) and a water outlet (13), the reflux liquid outlet (11) and the reflux liquid inlet (15) are connected through a pipeline with a reflux pump (12), wherein the water distributor (4) is arranged at the position of 3/4 of the height in the reaction zone (1) and comprises 8-16 water through holes with the aperture of 1.5mm, and the water distributor (4) is positioned in Na 2 CO 3 Solution inlet (5) and CaCl 2 The lower part of the solution inlet (8);
the method is characterized by comprising the following steps of:
step one, equimolar high concentration of Na 2 CO 3 And CaCl 2 The solutions were respectively stored in Na 2 CO 3 Solution water inlet tank (7) and CaCl 2 In the solution water inlet tank (10), na is used as a water source through a first water inlet pump (6) and a second water inlet pump (9) 2 CO 3 Solution inlet (5) and CaCl 2 A solution water inlet (8) enters the reaction zone (1) and is mixed to generate CaCO 3 A crystal;
step two, the water inlet solution is mixed in the reaction zone (1), enters a sedimentation zone (3) with gradually larger diameter through a fluidization zone (2), and is subjected to CaCO (CaCO) due to the weakening of the lifting force and the change of the solution flow direction 3 Slowly depositing a crystallization product in a precipitation zone (3) to realize solid-liquid two-phase separation, wherein one part of liquid phase flows back through a backflow liquid outlet (11), and the other part of liquid phase is discharged through a water outlet (13) and enters a water collecting tank (14);
step three, reflux liquid enters from a reflux liquid water outlet (11) through a reflux pump (12) from a reflux liquid water inlet (15), and uniform water distribution of reflux is realized through a water distributor (4), and CaCO in the reaction zone (1) is subjected to reflux acting force 3 The crystallization process is in a fluidization state, and the dilution of the water inlet solution is accelerated to a certain extent, so that the supersaturation degree of the reaction system is reduced;
wherein the hydraulic retention time is 40-90min, and the rising flow rate of the reflux liquid in the fluidization area (2) is 1.5-15m/h.
2. The method for producing an unstable calcium carbonate mineral phase according to claim 1, characterized in that the reaction zone (1), the fluidization zone (2) and the sedimentation zone (3) are arranged in this order from bottom to top, wherein the inner diameter ratio of the reaction zone (1) to the fluidization zone (2) is 1, the height ratio is 0.1-0.2, the inner diameter ratio of the sedimentation zone (3) to the fluidization zone (2) is 2-4, and the height of the sedimentation zone (3) is 18% -25% of the total height of the apparatus.
3. The method of forming an unstable calcium carbonate mineral phase according to claim 1, wherein the Na 2 CO 3 The solution inlet (5) is connected with Na through a pipeline with a water inlet pump I (6) 2 CO 3 A solution inlet tank (7), caCl 2 The solution inlet (8) is connected with CaCl through a pipeline with a water inlet pump II (9) 2 The water outlet (13) is connected with the water collecting tank (14) through a pipeline.
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