CN117185300A - Method for preparing fluorosilicate crystals based on black talc - Google Patents
Method for preparing fluorosilicate crystals based on black talc Download PDFInfo
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- CN117185300A CN117185300A CN202311247712.9A CN202311247712A CN117185300A CN 117185300 A CN117185300 A CN 117185300A CN 202311247712 A CN202311247712 A CN 202311247712A CN 117185300 A CN117185300 A CN 117185300A
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- 239000013078 crystal Substances 0.000 title claims abstract description 48
- 229940104869 fluorosilicate Drugs 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000000454 talc Substances 0.000 title claims abstract description 31
- 229910052623 talc Inorganic materials 0.000 title claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 98
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 78
- 238000002386 leaching Methods 0.000 claims abstract description 48
- 238000001556 precipitation Methods 0.000 claims abstract description 45
- 239000010703 silicon Substances 0.000 claims abstract description 45
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 45
- 239000007788 liquid Substances 0.000 claims abstract description 43
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 235000012222 talc Nutrition 0.000 claims abstract description 30
- 238000005554 pickling Methods 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 21
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 235000021110 pickles Nutrition 0.000 claims abstract description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000003158 alcohol group Chemical group 0.000 claims abstract description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 121
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 66
- 239000011780 sodium chloride Substances 0.000 claims description 33
- 235000002639 sodium chloride Nutrition 0.000 claims description 33
- -1 silicon ions Chemical class 0.000 claims description 27
- 238000002347 injection Methods 0.000 claims description 20
- 239000007924 injection Substances 0.000 claims description 20
- 230000001376 precipitating effect Effects 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 239000011775 sodium fluoride Substances 0.000 claims description 3
- 235000013024 sodium fluoride Nutrition 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000011734 sodium Substances 0.000 abstract description 28
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 23
- 229910052708 sodium Inorganic materials 0.000 abstract description 23
- 238000010828 elution Methods 0.000 abstract description 4
- 235000019441 ethanol Nutrition 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 239000008367 deionised water Substances 0.000 description 21
- 229910021641 deionized water Inorganic materials 0.000 description 21
- 239000002253 acid Substances 0.000 description 13
- 239000007787 solid Substances 0.000 description 12
- 238000001878 scanning electron micrograph Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000002596 correlated effect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000026267 regulation of growth Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 239000011573 trace mineral Substances 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Silicon Compounds (AREA)
Abstract
The application provides a method for preparing fluorosilicate crystals based on black talc. The method comprises the following steps: mixing and reacting black talcum with pickle liquor to obtain the pickle liquor; the pickling solution comprises hydrofluoric acid and pickling aid, wherein the pickling aid is one or more selected from hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid; respectively introducing the leaching solution and the precipitation solution into a micro-channel interface for mixing, forming fluorosilicate precipitation in a reaction micro-channel, and then carrying out solid-liquid separation to obtain fluorosilicate precipitation; the precipitation solution comprises a precipitant and a solvent, wherein the precipitant comprises sodium ions, and the solvent is an alcohol substance. The method can well reduce the concentration of silicon in the solution after silicon precipitation through ethanol elution in the precipitation process; meanwhile, ethanol can be used as a surface regulator to regulate and control the formed sodium fluosilicate crystal form to form a hexagonal star-shaped crystal, and the crystal is regular and fixed in morphology and uniform in size.
Description
Technical Field
The present application relates to the field of black talc, and in particular to a method for preparing fluorosilicate crystals based on black talc.
Background
Black talcum is a kind of silicate mineral, which is rich in silicon resource and has reserve of over 10 hundred million tons in Guangfeng area of the Shao city in Jiangxi province. The method comprises the steps of leaching silicon in the black talc by a wet leaching method to obtain a silicon-rich leaching solution, and separating the silicon in the leaching solution by a sodium salt precipitation method to obtain fluorosilicate, wherein the concentration of the silicon in the solution is always 2-3 g/L due to certain solubility of the fluorosilicate, so that the silicon is always the most main impurity when other elements are separated subsequently. Meanwhile, fluorosilicate crystals obtained by a conventional precipitation method are disordered and different in size, and have great limitations on subsequent synthesis of silicon dioxide, synthesis and research of downstream products such as fluoride fluorescent powder and the like.
Disclosure of Invention
The application mainly aims to provide a method for preparing fluorosilicate crystals based on black talcum, which aims to solve the technical problems of mess and different sizes of fluorosilicate crystals prepared by a conventional method.
To achieve the above object, the present application provides a method for preparing fluorosilicate crystals based on black talc, comprising the steps of:
mixing and reacting black talcum with pickle liquor to obtain the pickle liquor; the pickling solution comprises hydrofluoric acid and pickling aid, wherein the pickling aid is one or more selected from hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid;
respectively introducing the leaching solution and the precipitation solution into a micro-channel interface for mixing, forming fluorosilicate precipitation in a reaction micro-channel, and then carrying out solid-liquid separation to obtain fluorosilicate precipitation;
the precipitation solution comprises a precipitant, the precipitant comprises sodium ions, and a solvent is added into at least one of the precipitation solution and the leaching solution, wherein the solvent is an alcohol substance.
According to the embodiment of the application, in the pickling solution, the mass concentration of hydrofluoric acid is 1% -10%, and the mass concentration of auxiliary pickling is 1% -10%. The pickling aid is hydrochloric acid.
According to an embodiment of the present application, the step of mixing and reacting black talc with pickle liquor comprises:
adding the black talcum into the pickle liquor, wherein the solid-liquid ratio is 0.01-0.1 g/mL, and reacting for 3-8 h under the conditions of stirring speed of 100-600 rpm and 60-100 ℃.
According to an embodiment of the application, the alcohol is ethanol.
According to the embodiment of the application, the raw materials of the precipitant comprise one or more of sodium hydroxide, sodium chloride, sodium sulfate and sodium fluoride, and the ratio of sodium ions in the precipitant to the mass of silicon in the leaching solution is 1-1.5.
According to the embodiment of the application, only the precipitating solution is added with the solvent, and the raw materials of the precipitating solution comprise the solvent and the precipitating agent solution, wherein the volume ratio of the precipitating agent solution to the solvent is 1:10-1:1.
According to an embodiment of the application, the leachate and the precipitant are mixed in a vortex manner.
According to an embodiment of the application, the type dimensions of the reaction micro-pipe include:
the inner diameter of the reaction micro-pipeline is 0.8-mm-1.2-mm, and the length of the reaction micro-pipeline is 2.5-7.5-m.
According to an embodiment of the application, the step of forming fluorosilicate precipitates in the reaction microchannels with the leachate and the precipitant comprises:
the leaching solution and the precipitant are respectively introduced into a micro-channel interface for mixing so as to satisfy the following conditions: in unit time, the ratio of the quantity of sodium ions in the precipitant entering the micro-channel interface to the quantity of silicon ions in the leaching solution entering the micro-channel interface is as follows: :2:1-3:1.
According to an embodiment of the application, the concentration of silicon ions in the leachate is 5-9 g/L and the concentration of sodium ions in the precipitant is 9-20 g/L.
The injection flow rates of the leaching solution and the precipitant are 1-5 mL/min, the injection time is 5-20 min, and the reaction temperature is 15-45 ℃.
In the method for preparing fluorosilicate by using black talc, silicon in the black talc is leached by acid leaching liquid, so that a leaching liquid rich in silicon is obtained. Ethanol is used as a solvent and a crystal regulator, and then the precipitation process enhancement of the fluorosilicate and the crystal form regulation of the fluorosilicate are realized in a micro-channel by a micro-fluidic technology. The method can well reduce the concentration of silicon in the solution after silicon precipitation by ethanol elution in the precipitation process, and greatly reduce the doping of silicon impurities for recycling other elements in the solution after the subsequent silicon precipitation; meanwhile, ethanol can be used as a surface regulator to regulate and control the formed sodium fluosilicate crystal form to form a hexagonal star-shaped crystal, and the crystal is regular and fixed in morphology and uniform in size.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present application, and other drawings may be obtained according to the structures shown in these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a microfluidic technique for enhancing fluorosilicate precipitation and crystal growth regulation thereof in accordance with one embodiment of the present application;
FIG. 2 is a comparison of silicon concentration in the solutions after the reactions of examples 2, 3, 4, 5 of the present application;
FIG. 3 is an XRD pattern for sodium fluorosilicate in example 5 of the present application;
FIG. 4 is an SEM image of sodium fluorosilicate of example 5 of the present application;
FIG. 5 is an SEM image of sodium fluorosilicate of example 6 of the present application;
FIG. 6 is an SEM image of sodium fluorosilicate of example 7 of the present application;
FIG. 7 is an SEM image of sodium fluorosilicate of example 8 of the present application;
FIG. 8 is an SEM image of sodium fluorosilicate of comparative example 1 of the present application.
11. A first syringe; 12. a second syringe; 20. a syringe pump; 30. a microchannel interface; 40. a reaction microchannel;
31. a first liquid inlet; 32. a second liquid inlet; 33. and a liquid outlet.
The achievement of the object, functional features and advantages of the present application will be further described with reference to the drawings in connection with the embodiments.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present application without making any inventive effort, are intended to fall within the scope of the present application.
It should be noted that all directional indicators (such as upper and lower … …) in the embodiments of the present application are merely used to explain the relative positional relationship, movement conditions, etc. between the components in a specific posture (as shown in the drawings), and if the specific posture is changed, the directional indicator is changed accordingly.
Furthermore, descriptions such as those referred to as "first," "second," and the like, are provided for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implying an order of magnitude of the indicated technical features in the present disclosure. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature.
Moreover, the technical solutions of the embodiments of the present application may be combined with each other, but it is necessary to be based on the fact that those skilled in the art can implement the embodiments, and when the technical solutions are contradictory or cannot be implemented, it should be considered that the combination of the technical solutions does not exist, and is not within the scope of protection claimed by the present application.
The applicant has found through research that the formation of conventional fluorosilicates is generally carried out in a substantial amount of a vessel (e.g., beaker, reactor). In the forming process, as the sodium fluosilicate has certain solubility, the silicon element in the solution after precipitation still has higher concentration. Meanwhile, the generated fluorosilicate forms large-particle-size agglomeration due to concentration non-uniformity factors, and the subsequent utilization is adversely affected. The fluorosilicate crystals thus formed are disordered and of varying sizes.
Based on this, the embodiment of the present application provides a method for preparing fluorosilicate crystals based on black talc, see fig. 1, comprising the steps of:
s100, mixing and reacting the black talcum with the pickle liquor to obtain the pickle liquor. Wherein the pickling solution comprises hydrofluoric acid and pickling aid, and the pickling aid is one or more selected from hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid.
In this step, the contact of the black talc with the pickling solution reacts, which may also be referred to as leaching the black talc. Specifically, standing the leached supernatant until the upper layer is clear and transparent, and then carrying out solid-liquid separation; the separated liquid is a leaching solution.
The pickle liquor is mixed acid and at least comprises hydrofluoric acid. The pickling solution further comprises an acid or acids selected from hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, which acid or acids may be referred to as pickling aid.
Hydrofluoric acid can be combined with Si in the black talc to break Si-O, si-Mg bond in the black talc to form SiF 6 2- And then dissolves into the solution. After other acids (pickle liquor) are added, the acidity of the solution can be further enhanced, and the leaching effect of Si is improved.
In some embodiments, the hydrofluoric acid is present in the pickling solution at a concentration of 1% to 10% by mass and the co-pickling solution is present at a concentration of 1% to 10% by mass.
In some embodiments, the hydrofluoric acid is present in the pickling solution at a concentration of 5% to 10% by mass and the co-pickling solution is present at a concentration of 7% to 10% by mass.
In some embodiments, the co-pickling is hydrochloric acid.
And 200, respectively introducing the leaching solution and the precipitation solution into the micro-channel interface 30 for mixing, forming fluorosilicate precipitation in the reaction micro-channel 40, and then carrying out solid-liquid separation to obtain the fluorosilicate precipitation. The precipitation solution comprises a precipitant, the precipitant comprises sodium ions, and a solvent is added into at least one of the precipitation solution and the leaching solution, wherein the solvent is an alcohol substance.
The elution agent includes various addition modes. The eluent may be added to the precipitation solution, the leachate, or both the precipitation solution and the leachate, respectively. The solvent is alcohol such as ethanol, methanol, etc.
Taking the example of a solvent that is added only to the precipitation solution, in some embodiments the precipitation agent includes sodium ions and is an aqueous solution that includes sodium ions. Adding an ethanol solvent in the process of precipitating the fluorosilicate, so that the solution is a water-ethanol solution system, and the fluorosilicate in the solution is further separated out due to extremely low solubility of the fluorosilicate in alcohol substances, thereby enhancing the precipitation of the fluorosilicate and reducing the concentration of the fluorosilicate in the solution; on the other hand, the ethanol can also be used as a surfactant to be adsorbed on the surface of the fluorosilicate, so that the crystal growth process of the fluorosilicate is regulated and controlled, and the crystal form of the sodium fluorosilicate is controlled. Furthermore, by further combining with a micro-fluidic technology, the reaction can be precisely controlled, and the crystal form and the particle uniformity of the fluorosilicate crystal can be regulated and controlled while strengthening precipitation is realized.
Referring to fig. 1, the leachate and precipitant may be separately passed into the microchannel interface 30 for mixing. The leaching and precipitating agents may be introduced into the microchannel interface 30 at the same injection flow rate or at different injection flow rates. Illustratively, the precipitant and the leaching solution are respectively loaded in the first syringe 11 and the second syringe 12, and the respective injection flow rates are controlled by controlling the advancing speeds of the respective syringes through the syringe pump 20.
Illustratively, the microchannel interface 30 includes a first liquid inlet 31, a second liquid inlet 32, and a liquid outlet 33, i.e., the microchannel interface 30 may be a three-way interface. Wherein, the leaching solution and the precipitating agent respectively enter the cavity of the micro-channel interface 30 through the first liquid inlet 31 and the second liquid inlet 32 for mixing. The mixed solution enters the reaction micro-pipeline 40 through the liquid outlet 33, and reacts in the reaction micro-pipeline 40. Of course, the leaching solution and precipitant may also continue to mix in the reaction microchannel 40 and react.
The types of the micro-channel interface 30 (the shapes of the first liquid inlet 31, the second liquid inlet 32 and the liquid outlet 33) comprise tee interfaces such as T-shaped interfaces, Y-shaped interfaces and the like.
The three-way interface of the Y-shaped and the like means that the first liquid inlet 31 and the second liquid inlet 32 are symmetrically arranged about the liquid outlet 33, and the first liquid inlet 31 and the second liquid inlet 32 are obliquely arranged towards the liquid outlet 33.
The tee joint of the T-shaped structure indicates that the first liquid inlet 31 and the second liquid inlet 32 are symmetrically arranged about the liquid outlet 33, and the first liquid inlet 31 and the second liquid inlet 32 are perpendicular to the liquid outlet 33.
The micro-channel interface 30 may be made of PEEK (polyetheretherketone), PTFE (polytetrafluoroethylene), or the like. The micro-channel interface 30 is a phi 1/8, phi 1/16 type interface. The diameter of the mixing chamber inside the microchannel may be 0.4-mm-1.2 mm.
In the leaching solution, si mainly adopts SiF 6 2- In the form of (a) Na after adding a precipitant (sodium ion) + Can be combined with SiF 6 2- Combine to form Na 2 SiF 6 Precipitation and further separation from the solution.
2Na + +SiF 6 2- =Na 2 SiF 6
The system after the reaction in the reaction micro-pipe 40 includes Na 2 SiF 6 Precipitation and solution. The solid of the solid-liquid separation is Na 2 SiF 6 The mixture is precipitated and the mixture is stirred,the liquid may be referred to as a post-silicon precipitation solution, which contains primarily elemental magnesium, and in some embodiments may be up to 16g/L in concentration for recovery. The solution after precipitating silicon also has trace elements of Fe, al and Ca, but only has the concentration of 0.5-0.8 g/L.
In particular, microfluidics have the characteristics of small size, large specific surface area, ordered flow, and the ability to achieve rapid mixing of chemical reactions, rapid reactions, provide uniform reaction times, and the like. The micro-fluidic technology can realize instant and uniform mixing of materials according to the precise proportion, avoid uneven concentration and eliminate side reactions caused by the uneven concentration. The mass transfer process can be enhanced in the microfluid, the mass transfer precipitation process of the fluorosilicate in a water-ethanol system can be accelerated, and simultaneously, the three phases of the water-ethanol-fluorosilicate in each micro-area can be controlled to be consistent in the micro-channel, so that the adsorption of ethanol on the surface of the fluorosilicate can be accurately controlled, and the purpose of accurately regulating and controlling the fluorosilicate crystal form is achieved.
In the method for preparing fluorosilicate by using black talc, silicon in the black talc is leached by acid leaching liquid, so that a leaching liquid rich in silicon is obtained. Ethanol is used as a solvent and a crystal regulator, and then the precipitation process enhancement of the fluorosilicate and the crystal form regulation of the fluorosilicate are realized in a micro-channel by a micro-fluidic technology. The method can well reduce the concentration of silicon in the solution after silicon precipitation by ethanol elution in the precipitation process, and greatly reduce the doping of silicon impurities for recycling other elements in the solution after the subsequent silicon precipitation; meanwhile, ethanol can be used as a surface regulator to regulate and control the formed sodium fluosilicate crystal form to form a hexagonal star-shaped crystal, and the crystal is regular and fixed in morphology and uniform in size.
Because the concentration of silicon in the solution after silicon deposition is reduced, the purity of the recovered metal in the solution after silicon deposition is improved, and the content of silicon impurities is reduced.
In some embodiments, the step of mixing the black talc with the pickle liquor comprises:
adding black talcum into pickle liquor, wherein the solid-liquid ratio is 0.01-0.1 g/mL, and reacting at the stirring speed of 100-600 rpm and the temperature of 60-100 ℃ for 3-8 h.
Under this condition, the leaching reaction in the black talc is promoted by means of heating, stirring, or the like. The reaction temperature of the stirred reaction is 60-100 ℃, and in some embodiments, the reaction temperature of the stirred reaction is 70-100 ℃.
The reaction time for the stirred reaction is 3-8 h, and in some embodiments, the reaction time for the stirred reaction is 3-5 hours.
In some embodiments, the raw materials of the precipitant include one or more of sodium hydroxide, sodium chloride, sodium sulfate, and sodium fluoride, and the ratio of the amount of sodium ions in the precipitant to the amount of silicon in the leachate is 1-1.5.
The amount of silicon in the leachate can be calculated by measuring the silicon content in the leachate through icp. Illustratively, the excess factor of the amount of precipitant added substance to the amount of silicon substance is 1-1.3.
In some embodiments, the leachate and precipitant are mixed in a vortex manner.
Applicant studies have found that the type of microchannel interface 30 can affect the manner in which the leachate and precipitant are mixed. By adopting a Y-shaped three-way interface, the leaching liquid fluid and the precipitant fluid are mixed in a parallel flow mode. By adopting a T-shaped three-way interface, the leaching liquid fluid and the precipitating agent fluid are mixed in a vortex mode. Compared with the prior art, the method has the advantages of mixing in a vortex mode, better subsequent reaction effect, uniform morphology of the fluorosilicate crystal, smaller particle size and higher purity. Thus, the leachate and the precipitant are mixed in a vortex manner. Such as a T-tee interface.
In some embodiments, the type dimensions of the reaction microchannels 40 include:
the inner diameter of the reaction micro-pipe 40 is 0.8-mm-1.2-mm, and the length of the reaction micro-pipe 40 is 2.5-7.5-m.
The length of the reaction microchannels 40 will to some extent determine the length of time for which both the leachate and the precipitant react. Too long a length of the reaction micro-pipe 40 may cause a phenomenon of pipe blockage, resulting in failure to obtain fluorosilicate crystals from the reaction micro-pipe 40.
The length and internal diameter of the reaction microchannels 40 will, to some extent, determine the duration of the reaction of both the leachate and the precipitant. The reaction microchannel 40 is a reaction vessel in which the two react. Taking the length of the reaction microchannels 40 as an example, the length of the reaction microchannels 40 is required to ensure that the precipitation reaction to form sodium fluorosilicate is complete at least within the reaction microchannels 40, i.e., the reaction is complete when exiting the length of the reaction microchannels 40. Meanwhile, the length of the reaction micro-pipeline 40 cannot be too long, if the reaction micro-pipeline 40 is too long, the formed sodium fluosilicate solid is easily accumulated in the micro-pipeline, and the sodium fluosilicate cannot be collected due to pipe blockage.
Because the solubility of sodium fluosilicate in ethanol is obviously smaller than that of sodium fluosilicate in water, after ethanol is added in a reaction system, sodium fluosilicate is easier to separate out in water, which is equivalent to the increase of the generation speed of sodium fluosilicate in practice, so that the long tube length can block the tube instead. Thus, the inner diameter of the reaction microchannels 40 is 0.8mm to 1.2mm, and the length of the reaction microchannels 40 is 2.5 to 7.5m. Such as reaction microchannels 40 having a length of 2.5m to 5m.
Illustratively, the inner diameter of the reaction microchannels 40 is 0.5mm, 0.8mm, 1.0mm or 1.2mm.
Illustratively, the reaction microchannels 40 are 2.5m, 3m, 6m or 7.5m in length.
In some embodiments, the reaction microchannels 40 are helically arranged in the same direction and the diameter of each helical segment is the same. For example, the reaction micro-pipe 40 is wound using a cylindrical mold, ensuring that the winding diameter is the same, so that the reaction micro-pipe 40 as a whole assumes a spiral structure. The winding diameter of the reaction micro-pipeline 40 can be the same by winding the cylindrical die, the flowing state of the solution in the reaction micro-pipeline 40 and the stress state of the particles can be further ensured to be the same, and the consistency of the reaction is further ensured. In some embodiments, the spiral segments of the reaction micro-pipe 40 are distributed at equal intervals, so that the solution flowing state and the particle stress state in the reaction micro-pipe 40 are further ensured to be the same, and the consistency of the reaction is further improved.
In some embodiments, the step of forming a fluorosilicate precipitate in the microchannel with the leachate and the precipitating agent comprises:
the leaching solution and the precipitating agent are respectively introduced into the micro-channel interface 30 to be mixed so as to meet the following conditions: the ratio of the amount of sodium ions in the precipitant entering the microchannel interface 30 to the amount of silicon ions in the leachate entering the microchannel interface 30 per unit time is: 2:1-3:1.
In this embodiment, the amount of sodium ions in the precipitant entering the microchannel interface 30 is primarily determined by two factors. 1. Sodium ion concentration of the precipitant. 2. Flow rate of the precipitant. The two are multiplied to obtain the quantity of sodium ions in the precipitant entering the micro-channel interface 30 in unit time.
In some embodiments, the concentration of the leaching agent and the flow rate of the leaching agent are positively correlated, and the concentration of the precipitant and the flow rate of the precipitant are positively correlated.
In some embodiments, the concentration of silicon ions in the leachate is 5-9 g/L and the concentration of sodium ions in the precipitant is 9-20 g/L.
The injection flow rates of the leaching solution and the precipitant are 1-5 mL/min, the injection time is 5-20 min, and the reaction temperature is 15-45 ℃.
Example 1
Taking HF (with the concentration of 49%) of 36.73 mL and HCl (with the concentration of 37%) of 64.86 mL into a polytetrafluoroethylene reaction kettle, adding 198.41 mL deionized water, and preparing 300 mL of mixed acid of 6% HF and 8% HCl; adding 30 g black talcum into the mixed acid, placing the mixed acid in an oil bath, fully and uniformly mixing and stirring the mixed acid at a rotation speed of 500 rpm, and heating the mixed acid to 80 ℃ to react for 4 h; after the reaction, standing for 10 minutes, and filtering to obtain leaching liquid.
The Si concentration in the obtained leachate was measured by means of icp and found to be 13.75. 13.75 g/L.
Example 2
20ml of the leachate obtained in example 1 was diluted with 20ml of deionized water to 40ml, and 40ml of diluted leachate having Si concentration of 6.88. 6.88 g/L was obtained. 1.38g of NaCl was added to 40mL deionized water and dissolved well to prepare a NaCl solution. The prepared NaCl solution is extracted 40 and ml by a first injector 11, the leaching solution diluted 40 and ml is extracted by a second injector 12, the first injector 11 and the second injector 12 are arranged in an injection pump 20, and simultaneously, the two solutions are injected into a reaction pipeline with the inner diameter of 1 mm and the length of 7.5 and m at the flow rate of 2 ml/min for 20 min, and a suction filter bottle is placed at an outlet to directly collect solids generated from the reaction micro-pipeline 40, so that sodium fluosilicate crystals are obtained.
Example 3
20ml of the leachate obtained in example 1 was diluted with 20ml of deionized water to 40ml, and 40ml of diluted leachate having Si concentration of 6.88. 6.88 g/L was obtained. 1.38g of NaCl was added to 35 mL deionized water, and the mixture was dissolved sufficiently, and 5ml of absolute ethanol was added to prepare a NaCl solution. The prepared NaCl solution is extracted 40 and ml by a first injector 11, the leaching solution diluted 40 and ml is extracted by a second injector 12, the first injector 11 and the second injector 12 are arranged in an injection pump 20, and simultaneously, the two solutions are injected into a reaction pipeline with the inner diameter of 1 mm and the length of 7.5 and m at the flow rate of 2 ml/min for 20 min, and a suction filter bottle is placed at an outlet to directly collect solids generated from the reaction micro-pipeline 40, so that sodium fluosilicate crystals are obtained.
Example 4
20ml of the leachate obtained in example 1 was diluted with 20ml of deionized water to 40ml, and 40ml of diluted leachate having Si concentration of 6.88. 6.88 g/L was obtained. 1.38g of NaCl was added to 30 mL deionized water, and the mixture was dissolved sufficiently, and 10ml of absolute ethanol was added to prepare a NaCl solution. The prepared NaCl solution is extracted 40 and ml by a first injector 11, the leaching solution diluted 40 and ml is extracted by a second injector 12, the first injector 11 and the second injector 12 are arranged in an injection pump 20, and simultaneously, the two solutions are injected into a reaction pipeline with the inner diameter of 1 mm and the length of 7.5 and m at the flow rate of 2 ml/min for 20 min, and a suction filter bottle is placed at an outlet to directly collect solids generated from the reaction micro-pipeline 40, so that sodium fluosilicate crystals are obtained.
Example 5
20ml of the leachate obtained in example 1 was diluted with 20ml of deionized water to 40ml, and 40ml of diluted leachate having Si concentration of 6.88. 6.88 g/L was obtained. 1.38g of NaCl was added to 25 mL deionized water, and the mixture was dissolved sufficiently, and 15ml of absolute ethanol was added to prepare a NaCl solution. The prepared NaCl solution is extracted 40 and ml by a first injector 11, the leaching solution diluted 40 and ml is extracted by a second injector 12, the first injector 11 and the second injector 12 are arranged in an injection pump 20, and simultaneously, the two solutions are injected into a reaction pipeline with the inner diameter of 1 mm and the length of 7.5 and m at the flow rate of 2 ml/min for 20 min, and a suction filter bottle is placed at an outlet to directly collect solids generated from the reaction micro-pipeline 40, so that sodium fluosilicate crystals are obtained.
FIG. 2 shows the comparison of the silicon concentration in the solutions after the reactions of examples 2, 3, 4, 5. It can be seen from the graph that after the reaction of the system without adding ethanol, the silicon concentration in the solution reaches 2.65g/L, and when the ethanol is added into the system and reacted, the silicon concentration in the solution is obviously reduced, and the higher the ethanol adding proportion is, the lower the concentration of the residual silicon is, and when the ethanol adding amount is 15ml, the concentration of the residual silicon is only 0.97g/L. It has been demonstrated that ethanol has a significant strengthening effect on fluorosilicate precipitation.
Fig. 3 and 4 are XRD patterns and SEM patterns, respectively, of sodium fluorosilicate obtained in example 5. As can be seen from fig. 3, the obtained solid XRD diffraction peak was only one species of sodium fluorosilicate, and no other impurity peak. As can be seen from FIG. 4, the sodium fluosilicate obtained after the ethanol is added is in a shape of a hexagon, the grain size is about 20-30 mu m, the grains are uniform and regular, and the crystal is greatly different from the traditional rod-shaped and hexagonal prism-shaped sodium fluosilicate crystals, which proves that the ethanol has a regulating effect on the crystal growth process of the sodium fluosilicate crystals.
Example 6
The difference from example 5 is that the length of the reaction micro-pipe 40 is 2.5. 2.5m, and the other is the same as example 5.
FIG. 5 is an SEM image of sodium fluorosilicate obtained in example 6, from which it was found that the sodium fluorosilicate obtained after the reaction in a 2.5m length microchannel had a "hexagram" shape with a particle size of about 20-30. Mu.m.
Example 7
The difference from example 5 is that the length of the reaction micro-pipe 40 is 5m, and the other is the same as example 5.
FIG. 6 is an SEM image of sodium fluorosilicate obtained in example 7, from which it was found that the sodium fluorosilicate obtained after the reaction in a microchannel having a length of 5m was "hexagram" shaped and had a particle size of about 20-30. Mu.m.
Example 8
The leachate from example 1 of 20ml was diluted to 40ml by adding 30 ml deionized water, and 40ml of diluted leachate having a Si concentration of 10.31 g/L was obtained. Adding 2.08 and g NaCl into 25 and mL deionized water, dissolving thoroughly, and adding 15ml of absolute ethanol to prepare NaCl solution. The prepared NaCl solution is extracted 40 and ml by a first injector 11, the leaching solution diluted 40 and ml is extracted by a second injector 12, the first injector 11 and the second injector 12 are arranged in an injection pump 20, and simultaneously, the two solutions are injected into a reaction pipeline with the inner diameter of 1 mm and the length of 7.5 and m at the flow rate of 2 ml/min for 20 min, and a suction filter bottle is placed at an outlet to directly collect solids generated from the reaction micro-pipeline 40, so that sodium fluosilicate crystals are obtained.
FIG. 7 is an SEM image of sodium fluorosilicate obtained in example 8, from which it was found that the sodium fluorosilicate obtained after reaction in the microchannel was "hexagram" shaped, with a particle size of about 40-50 μm.
Example 9
20ml of the leachate obtained in example 1 was diluted with 20ml of deionized water to 40ml, and 40ml of diluted leachate having Si concentration of 6.88. 6.88 g/L was obtained. 1.38g of NaCl is added into 25 mL deionized water, and then 15ml of absolute ethyl alcohol is added to prepare NaCl solution which is fully dissolved. The NaCl solution prepared by 40ml is extracted through a first injector 11, the leaching solution diluted by 40ml is extracted through a second injector 12, the first injector 11 and the second injector 12 are arranged in an injection pump 20, and simultaneously, the two solutions are injected into a reaction pipeline with the inner diameter of 1 mm and the length of 5m at the flow rate of 1 ml/min for 40 min, and a suction filtration bottle is placed at an outlet to directly collect solids generated from the reaction micro-pipeline 40, so that sodium fluosilicate crystals are obtained.
Example 10
20ml of the leachate obtained in example 1 was diluted with 20ml of deionized water to 40ml, and 40ml of diluted leachate having Si concentration of 6.88. 6.88 g/L was obtained. 1.38g of NaCl is added into 25 mL deionized water, and then 15ml of absolute ethyl alcohol is added to prepare NaCl solution which is fully dissolved. The prepared NaCl solution is extracted 40 and ml by a first injector 11, the leaching solution diluted 40 and ml is extracted by a second injector 12, the first injector 11 and the second injector 12 are arranged in an injection pump 20, and simultaneously, the two solutions are injected into a reaction pipeline with the inner diameter of 1 mm and the length of 7.5 and m at the flow rate of 4 ml/min for 10 min, and a suction filter bottle is placed at an outlet to directly collect solids generated from the reaction micro-pipeline 40, so that sodium fluosilicate crystals are obtained.
Comparative example 1
20ml of the leachate obtained in example 1 was diluted with 20ml of deionized water to 40ml, and 40ml of diluted leachate having Si concentration of 6.88. 6.88 g/L was obtained. 1.38g of NaCl was added to 25 mL deionized water, and the mixture was dissolved sufficiently, and 15ml of absolute ethanol was added to prepare a NaCl solution. And stirring and mixing the diluted leaching solution and the prepared NaCl solution in a beaker, reacting for 30min, and carrying out solid-liquid separation after the reaction is finished to obtain sodium fluosilicate crystals.
Fig. 8 is an SEM image of sodium fluorosilicate obtained in comparative example 1. From fig. 5, it can be found that the sodium fluorosilicate crystals synthesized in the beaker are disordered and have no fixed morphology features, which also proves that the microfluidics technology has a regulating effect on the growth process of the sodium fluorosilicate crystals.
Comparative example 2
20ml of the leachate obtained in example 1 was diluted with 20ml of deionized water to 40ml, and 40ml of diluted leachate having Si concentration of 6.88. 6.88 g/L was obtained. 1.38g of NaCl was added to 25 mL deionized water, and the mixture was dissolved sufficiently, and 15ml of absolute ethanol was added to prepare a NaCl solution. The prepared NaCl solution was withdrawn 40ml by the first syringe 11, the diluted leaching solution was withdrawn 40ml by the second syringe 12, the first syringe 11 and the second syringe 12 were placed in the syringe pump 20, and simultaneously, the two solutions were injected into a reaction tube having an inner diameter of 1 mm and a length of 10m at a flow rate of 2 ml/min for a predetermined injection time of 20 min, and a suction filter flask was placed at the outlet to directly collect solids generated from the reaction micro-tube 40, thereby obtaining sodium fluosilicate crystals.
At an injection time of about 2 minutes, a tube blockage occurred. The results show that the length of the reaction pipeline in the reaction process is not too long, and the length of the reaction pipeline should be controlled to be relatively suitable.
Comparative example 3
20ml of the leachate obtained in example 1 was diluted with 20ml of deionized water to 40ml, and 40ml of diluted leachate having Si concentration of 6.88. 6.88 g/L was obtained. 1.38g of NaCl was added to 25 mL deionized water, and the mixture was dissolved sufficiently, and 15ml of absolute ethanol was added to prepare a NaCl solution. The prepared NaCl solution was withdrawn 40. 40ml by the first syringe 11, the diluted leaching solution was withdrawn 40. 40ml by the second syringe 12, the first syringe 11 and the second syringe 12 were placed in the syringe pump 20, and simultaneously, the two solutions were injected into a reaction tube having an inner diameter of 1 mm and a length of 7.5m at a flow rate of 0.5 ml/min for a predicted injection time of 80 min, and a suction filter flask was placed at the outlet to directly collect solids generated from the reaction micro-tube 40, thereby obtaining sodium fluosilicate crystals.
At an injection time of about 4 minutes, a tube blockage occurred. The results indicate that the flow rate of the fluid during the reaction should not be too low and should be controlled within a relatively suitable range.
In the above technical solution of the present application, the above is only a preferred embodiment of the present application, and therefore, the patent scope of the present application is not limited thereto, and all the equivalent structural changes made by the description of the present application and the content of the accompanying drawings or the direct/indirect application in other related technical fields are included in the patent protection scope of the present application.
Claims (10)
1. A process for preparing fluorosilicate crystals based on black talc, comprising the steps of:
mixing and reacting black talcum with pickle liquor to obtain the pickle liquor; the pickling solution comprises hydrofluoric acid and pickling aid, wherein the pickling aid is one or more selected from hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid;
respectively introducing the leaching solution and the precipitation solution into a micro-channel interface for mixing, forming fluorosilicate precipitation in a reaction micro-channel, and then carrying out solid-liquid separation to obtain fluorosilicate precipitation;
the precipitation solution comprises a precipitant, the precipitant comprises sodium ions, and a solvent is added into at least one of the precipitation solution and the leaching solution, wherein the solvent is an alcohol substance.
2. The method according to claim 1, characterized in that in the pickling solution the mass concentration of hydrofluoric acid is 1-10% and the mass concentration of pickling aid is 1-10%; the pickling aid is hydrochloric acid.
3. The method of claim 1, wherein the step of mixing and reacting the black talc with the pickle liquor comprises:
adding the black talcum into the pickle liquor, wherein the solid-liquid ratio is 0.01-0.1 g/mL, and reacting for 3-8 h under the conditions of stirring speed of 100-600 rpm and 60-100 ℃.
4. The method of claim 1, wherein the alcohol is ethanol.
5. The method according to claim 1, wherein the raw materials of the precipitant include one or more of sodium hydroxide, sodium chloride, sodium sulfate and sodium fluoride, and the ratio of the amount of sodium ions in the precipitant to the amount of silicon in the leachate is 1 to 1.5.
6. The method according to any one of claims 1 to 5, wherein only the precipitating solution is added with a solvent, and the raw materials of the precipitating solution include a solvent and a precipitating agent solution, and the volume ratio of the precipitating agent solution to the solvent is 1:10-1:1.
7. The method of claim 1, wherein the leachate and the precipitant are mixed in a vortex manner.
8. The method of claim 1, wherein the type size of the reaction microchannels comprises:
the inner diameter of the reaction micro-pipeline is 0.8-mm-1.2-mm, and the length of the reaction micro-pipeline is 2.5-7.5-m.
9. The method of claim 1, wherein the step of forming fluorosilicate precipitates in the reaction microchannels with the leachate and the precipitant comprises:
the leaching solution and the precipitant are respectively introduced into a micro-channel interface for mixing so as to satisfy the following conditions: in unit time, the ratio of the quantity of sodium ions in the precipitant entering the micro-channel interface to the quantity of silicon ions in the leaching solution entering the micro-channel interface is as follows: 2:1-3:1.
10. The method of claim 9, wherein the concentration of silicon ions in the leachate is 5-9 g/L and the concentration of sodium ions in the precipitant is 9-20 g/L;
the injection flow rates of the leaching solution and the precipitant are 1-5 mL/min, the injection time is 5-20 min, and the reaction temperature is 15-45 ℃.
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| GB727770A (en) * | 1953-04-20 | 1955-04-06 | Paul Caldwell | Improvements in digestion of phosphate rock |
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| CN103333240A (en) * | 2013-07-22 | 2013-10-02 | 北海开元生物科技有限公司 | Method for reclaiming human albumin from component IV precipitate |
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