CN110745873A - Mo6+Preparation method of basic nickel carbonate doped microspheres - Google Patents
Mo6+Preparation method of basic nickel carbonate doped microspheres Download PDFInfo
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- CN110745873A CN110745873A CN201810812285.7A CN201810812285A CN110745873A CN 110745873 A CN110745873 A CN 110745873A CN 201810812285 A CN201810812285 A CN 201810812285A CN 110745873 A CN110745873 A CN 110745873A
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- basic nickel
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- nickel carbonate
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- 229910000008 nickel(II) carbonate Inorganic materials 0.000 title claims abstract description 103
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 title claims abstract description 103
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000004005 microsphere Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 92
- 239000002002 slurry Substances 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 238000003756 stirring Methods 0.000 claims abstract description 48
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 39
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 27
- 150000002815 nickel Chemical class 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 18
- 239000012266 salt solution Substances 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 14
- 239000012452 mother liquor Substances 0.000 claims abstract description 13
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 13
- 238000003825 pressing Methods 0.000 claims abstract description 13
- 230000008719 thickening Effects 0.000 claims abstract description 9
- 150000002751 molybdenum Chemical class 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 64
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 56
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 28
- 235000017550 sodium carbonate Nutrition 0.000 claims description 28
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 24
- 239000001099 ammonium carbonate Substances 0.000 claims description 24
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 23
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 23
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 150000002500 ions Chemical class 0.000 claims description 12
- 229910001453 nickel ion Inorganic materials 0.000 claims description 12
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 11
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 11
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 8
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- 238000004537 pulping Methods 0.000 abstract description 11
- 238000000926 separation method Methods 0.000 abstract description 10
- 230000001699 photocatalysis Effects 0.000 abstract description 8
- 230000007547 defect Effects 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 abstract 1
- 239000002562 thickening agent Substances 0.000 description 19
- 229910015667 MoO4 Inorganic materials 0.000 description 18
- 239000012295 chemical reaction liquid Substances 0.000 description 15
- 230000002572 peristaltic effect Effects 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 5
- 229910003562 H2MoO4 Inorganic materials 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/06—Carbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
- B01J27/236—Hydroxy carbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
- C01P2002/54—Solid solutions containing elements as dopants one element only
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
The invention discloses Mo6+The preparation method of the basic nickel carbonate doped microspheres is realized by the following steps: 1) respectively preparing a carbonate solution and a nickel salt solution; 2) adding the two solutions into a reactor at the same time, controlling the pH value of the system to be 7.9-8.3, reacting for 1-2 h, and then carrying out thickening treatment on the reaction solution to obtain basic nickel carbonate slurry; 3) carrying out filter pressing on the basic nickel carbonate slurry to remove mother liquor, pulping, transferring to a reaction kettle, adding ethanol water solution of molybdenum salt, and stirring for reaction to obtain Mo6+Doping basic nickel carbonate slurry; 4) and washing and drying the slurry at high temperature to obtain the target object. The preparation process of the invention is simple and easy, and Mo is6+Lattice defects are formed after doping, and the electron separation efficiency is promoted, so that the prepared Mo6+The doped basic nickel carbonate microsphere has the photocatalysis effect which is more than 3 times higher than that of the common basic nickel carbonateAnd (4) performance is improved.
Description
Technical Field
The invention belongs to the technical field of preparation of basic nickel carbonate microspheres, and particularly relates to Mo6+A preparation method of basic nickel carbonate doped microspheres.
Background
At present, there are two methods for synthesizing basic nickel carbonate in domestic enterprises, one synthesis process is that ammonium carbonate or ammonium bicarbonate and nickel salt are adopted to carry out precipitation reaction; and the other method is to adopt soda ash and a nickel salt solution for precipitation reaction, the pH value is required to be adjusted to be more than 8.5 during synthesis by the method, nickel can be basically and completely precipitated, the amount of the needed soda ash is more than 35% more than the theoretical amount, the excessive base cannot be recycled, the Na content in a product obtained by washing and drying materials is more than 300ppm, the operation steps are complicated, and the structures of the basic nickel carbonate prepared by the two methods are free of other doping elements, so that the obtained basic nickel carbonate has few uses.
Disclosure of Invention
In view of the above, the main objective of the present invention is to provide a Mo6+The preparation method of the doped basic nickel carbonate microspheres solves the problem of low catalytic performance of the basic nickel carbonate obtained in the prior art in the catalytic process.
In order to achieve the purpose, the technical scheme of the invention is realized as follows: mo6+The preparation method of the basic nickel carbonate doped microspheres is realized by the following steps:
step 2, adding a carbonate solution and a nickel salt solution into a reactor simultaneously, keeping the flow rate of the nickel salt solution unchanged in the feeding process, adjusting the pH value of a flow control system of the carbonate solution to be 7.9-8.3, reacting for 1-2 h, then carrying out thickening treatment on the reaction solution, and continuing to react for 8-18 h to obtain basic nickel carbonate slurry;
and 3, performing filter pressing on the basic nickel carbonate slurry obtained in the step 2 to remove the mother liquor, slurrying the basic nickel carbonate slurry, transferring the slurry into a reaction kettle, adding an ethanol aqueous solution of molybdic acid into the reaction kettle, and stirring for reaction to obtain Mo6+Doping basic nickel carbonate slurry;
Preferably, in the step 1, the carbonate is at least one of sodium carbonate, ammonium carbonate and ammonium bicarbonate; the nickel salt is at least one of nickel sulfate, nickel chloride and nickel nitrate.
Preferably, in the step 2, the flow rate of the sodium carbonate solution is 5-500L/h; the flow rate of the nickel salt solution is 50-500L/h.
Preferably, in the step 3, Mo is contained in the ethanol aqueous solution of molybdic acid6+The ion concentration is 0.05-0.2 mol/L, and the volume ratio of ethanol to water in the ethanol aqueous solution of the molybdenum salt is 1: 1.
Preferably, in the step 3, the flow rate of the ethanol aqueous solution of molybdenum salt is 10-15% of the flow rate of the nickel salt solution.
Preferably, in the step 3, the Mo is6+The molar weight of the molybdenum element in the doped basic nickel carbonate slurry accounts for 0.01-1% of the sum of the molar weight of the molybdenum element and the molar weight of the nickel element.
Preferably, in the step 3, the temperature of the stirring reaction is 50-60 ℃, and the time of the stirring reaction is 20-25 h.
Preferably, in the step 4, the temperature during drying is 120-150 ℃.
Preferably, in the step 4, the drying time is 2-5 h.
Compared with the prior art, the method has simple and easy operation and simple and easy preparation process, and Mo is used6+After doping, the conductivity and the thermal conductivity of the basic nickel carbonate are effectively improved, the electronic service life is prolonged, the photocatalytic performance is improved, and the prepared Mo6+The doped basic nickel carbonate microsphere has the photocatalytic performance more than 3 times higher than that of common basic nickel carbonate, improves the apparent density and the fluidity of the basic nickel carbonate, and is convenient for packaging and batch transportation.
Drawings
FIG. 1 shows Mo obtained in example 1 of the present invention6+SEM picture of doping basic nickel carbonate microsphere;
FIG. 2 shows Mo in an embodiment of the present invention6+The device structure of the doping basic nickel carbonate microsphere is shown schematically.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides Mo6+The preparation method of the basic nickel carbonate doped microspheres is realized by the following steps:
step 2, feeding by using a peristaltic pump, adding a carbonate solution and a nickel salt solution into a reactor at the same time, keeping the flow rate of the nickel salt solution to be 50-500L/h unchanged in the feeding process, controlling the pH value of the system to be 7.9-8.3 by adjusting the flow rate of the carbonate solution (the flow rate of the sodium carbonate solution is 5-500L/h), reacting for 1-2 h, starting a concentrator (the stirring rate of the concentrator is 5-10r/min), and continuing to react for 8-18 h to obtain basic nickel carbonate slurry;
and 3, performing filter pressing on the basic nickel carbonate slurry obtained in the step 2 to remove the mother liquor, pulping, transferring to a reaction kettle, and adding Mo into the reaction kettle6+Molybdic acid (H) having an ion concentration of 0.05 to 0.2mol/L2MoO4) The aqueous solution of ethanol is stirred and reacted for 20 to 25 hours at the temperature of 50 to 60 ℃, and Mo is obtained, wherein the molar weight of the Mo element accounts for 0.01 to 1 percent of the sum of the molar weights of the Mo element and the Ni element6+Doping basic nickel carbonate slurry; wherein molybdic acid (H)2MoO4) The volume ratio of ethanol to water in the ethanol aqueous solution is 1: 1; addition of molybdic acid (H)2MoO4) The flow of the ethanol aqueous solution is 10-15% of the flow of the nickel salt solution;
The embodiment of the invention also provides a method for preparing the Mo6+The device for doping the basic nickel carbonate microspheres comprises a reaction body 1, a dense body 2 and a cyclone separation body 3, wherein the reaction body 1, the dense body 2 and the cyclone separation body 3 are sequentially connected through a pipeline 4 to form a loop.
Further, a reaction liquid outlet 11 is arranged on the side wall of the lower end of the reaction body 1, a reaction liquid inlet 21 is arranged at the bottom of the thickening body 2, the reaction liquid outlet 11 and the reaction liquid inlet 21 are connected through a pipeline, and the distance from the reaction liquid inlet 21 to the horizontal plane is higher than that from the reaction liquid outlet 11 to the horizontal plane.
Further, a first control valve 41 is provided on the pipe 4 connecting the reaction liquid flow outlet 11 and the reaction liquid flow inlet 21.
Further, a second stirring component 22 is arranged in the thickening body 2, the second stirring component 22 is positioned in the central position in the thickening body 2, and a reaction liquid overflow outlet 23 is arranged on the side wall of the upper end of the thickening body 2.
Further, the second stirring assembly 22 includes a second stirring motor 221, a second stirring shaft 222, and a stirring unit 223, the stirring unit 223 is fixedly connected to the lower end of the second stirring shaft 222, the second stirring motor (221) is disposed at the upper end of the second stirring shaft 222 and drives the second stirring shaft 222 and the stirring unit 223 to rotate around the axis. Further, the stirring unit 223 includes at least two right-trapezoid stirring blades 2231, the two right-trapezoid stirring blades 2231 are vertically and symmetrically fixed to the lower end of the second stirring shaft 222, and the short sides of the two right-trapezoid stirring blades 2231 are disposed near the reactant liquid inlet 21.
Further, the shape of the inclined sides of the two right-angled trapezoidal stirring blades 2231 is adapted to the shape of the lower end of the thickening body 2.
Furthermore, the upper end of the cyclone separation body 3 is provided with a supernatant overflow port 31, the side wall of the cyclone separation body 3 is provided with a reaction liquid overflow port 32, and the reaction liquid overflow port 32 is connected with a reaction liquid overflow port 23 arranged on the side wall of the upper end of the thickening body 2 through a pipeline 4; the bottom of the cyclone separation body 3 is provided with a solid-containing liquid outlet 33, the upper end of the reaction body 1 is provided with a solid-containing liquid inlet, and the solid-containing liquid outlet 33 is connected to the solid-containing liquid inlet through a pipe 4.
Further, a pneumatic diaphragm pump 42 is provided on the pipe 4 connecting the reaction liquid overflow inlet 32 and the reaction liquid overflow outlet 23.
Further, a second control valve 43 is provided in a pipe connecting the solid-containing liquid outflow port 33 and the solid-containing liquid inflow port.
Further, a carbonate feeding pipe 12, a nickel salt pipe 13, a first stirring assembly 14 and a pH measuring assembly 15 are arranged in the reaction body 1, the first stirring assembly 14 is located at the central position in the reaction body 1, and the carbonate feeding pipe 12 and the nickel salt pipe 13 are symmetrically arranged on two sides in the reaction body 1; the pH measuring unit 15 is disposed at the lower end of the reaction body 1.
Further, the first stirring assembly 14 includes a first stirring motor 141, a first stirring shaft 142, and a first stirring blade 143, the first stirring blade 143 is fixed at the lower end of the first stirring shaft 142, the first stirring motor 141 is disposed at the upper end of the first stirring shaft 142, and drives the first stirring shaft 142 and the first stirring blade 143 to rotate around the axis.
Further, the pH measuring unit 15 includes a pH measuring pipe 151 and a pH measuring instrument 152, and the pH measuring instrument 152 is connected to the reaction body 1 through the pH measuring pipe 151.
Further, the outer layer of the reaction body 1 is provided with a vacuum heat-preserving jacket 16, the bottom of the vacuum heat-preserving jacket 16 is provided with a condensed water inlet 161, and the side of the vacuum heat-preserving jacket 16 is provided with a steam outlet 162.
Further, the bottom of the reaction body 1 is provided with a discharge port 17 and a sewage outlet 18.
Further, two fixing brackets 19 are symmetrically arranged below the reaction body 1.
The working principle of the device is as follows: the basic nickel carbonate particles can settle down to the bottom of the thickener under the action of gravity, the materials adhered to the bottom are returned to the kettle through low-speed stirring, meanwhile, the tiny particles cannot settle and are discharged from the reaction liquid overflow port 23 to the cyclone separation body 3, the cyclone separation body 3 carries out cyclone separation on the liquid containing the tiny solid particles, the supernatant is discharged from the supernatant overflow port 31, and the solid-containing liquid returns to the reaction body 1, so that the concentration in the kettle is continuously improved, and the uniformity of the particle size of the particles in the kettle and the microspherical shape are ensured.
Example 1
step 2, feeding by using a peristaltic pump, adding a sodium carbonate solution and a nickel sulfate solution into a reactor at the same time, keeping the flow rate of the nickel sulfate solution at 200L/h in the feeding process, controlling the pH value of the system to be 8.1 +/-2 by adjusting the flow rate of the sodium carbonate solution (the flow rate of the sodium carbonate solution is 5-500L/h), reacting for 1.5h, starting a thickener (the stirring rate of the thickener is 5-10r/min), and continuing to react for 15h to obtain basic nickel carbonate slurry;
and 3, carrying out filter pressing on the basic nickel carbonate slurry obtained in the step 2 to remove the mother liquor, pulping, transferring to a reaction kettle, and adding Mo into the reaction kettle6+Molybdic acid (H) having an ion concentration of 0.1mol/L2MoO4) Wherein the volume ratio of ethanol to water is 1:1, adding molybdic acid H2MoO4The flow of the ethanol aqueous solution is 12 percent of the flow of the nickel sulfate solution added), and the mixture is stirred and reacted for 22 hours at the temperature of 55 ℃, so as to obtain Mo of which the molar weight of the molybdenum element accounts for 0.1 percent of the sum of the molar weights of the molybdenum element and the nickel element6+Doping basic nickel carbonate slurry;
Example 2
step 2, feeding by using a peristaltic pump, adding a sodium carbonate solution and a nickel sulfate solution into a reactor at the same time, keeping the flow rate of the nickel sulfate solution at 500L/h in the feeding process, controlling the pH value of the system to be 8.1 +/-2 by adjusting the flow rate of the sodium carbonate solution (the flow rate of the sodium carbonate solution is 5-500L/h), reacting for 1h, starting a thickener (the stirring rate of the thickener is 5-10r/min), and continuing to react for 8h to obtain basic nickel carbonate slurry;
and 3, carrying out filter pressing on the basic nickel carbonate slurry obtained in the step 2 to remove the mother liquor, pulping, transferring to a reaction kettle, and adding Mo into the reaction kettle6+Molybdic acid (H) having an ion concentration of 0.05mol/L2MoO4) Wherein the volume ratio of ethanol to water is 1:1, and molybdic acid (H) is added2MoO4) The flow of the ethanol aqueous solution is 10 percent of the flow of the nickel sulfate solution added), and the mixture is stirred and reacted for 25 hours at 50 ℃ to obtain Mo of which the molar weight of the molybdenum element accounts for 0.01 percent of the sum of the molar weights of the molybdenum element and the nickel element6+Doping basic nickel carbonate slurry;
Example 3
step 2, feeding by using a peristaltic pump, adding a sodium carbonate solution and a nickel sulfate solution into a reactor at the same time, keeping the flow rate of the nickel sulfate solution unchanged in the feeding process, controlling the pH value of the system to be 8.1 +/-2 by adjusting the flow rate of the sodium carbonate solution (the flow rate of the sodium carbonate solution is 5-500L/h), reacting for 2 hours, starting a thickener (the stirring rate of the thickener is 5-10r/min), and continuing to react for 18 hours to obtain basic nickel carbonate slurry;
and 3, carrying out filter pressing on the basic nickel carbonate slurry obtained in the step 2 to remove the mother liquor, pulping, transferring to a reaction kettle, and adding Mo into the reaction kettle6+Molybdic acid (H) having an ion concentration of 0.2mol/L2MoO4) Wherein the volume ratio of ethanol to water is 1:1, and molybdic acid (H) is added2MoO4) The flow of the ethanol aqueous solution is 15 percent of the flow of the nickel sulfate solution added), and the mixture is stirred and reacted for 20 hours at the temperature of 60 ℃ to obtain Mo of which the molar weight of the molybdenum element accounts for 1 percent of the sum of the molar weights of the molybdenum element and the nickel element6+Doping basic nickel carbonate slurry;
Example 4
step 2, feeding by using a peristaltic pump, adding an ammonium carbonate solution and a nickel sulfate solution into a reactor at the same time, keeping the flow rate of the nickel sulfate solution unchanged in the feeding process, controlling the pH value of the system to be 8.1 +/-2 by adjusting the flow rate of the ammonium carbonate solution (the flow rate of the ammonium carbonate solution is 5-500L/h), reacting for 1.5h, starting a thickener (the stirring rate of the thickener is 5-10r/min), and continuously reacting for 15h to obtain basic nickel carbonate slurry;
and 3, carrying out filter pressing on the basic nickel carbonate slurry obtained in the step 2 to remove the mother liquor, pulping, transferring to a reaction kettle, and adding Mo into the reaction kettle6+Molybdic acid (H) having an ion concentration of 0.05mol/L2MoO4) Wherein the volume ratio of ethanol to water is 1:1, and molybdic acid (H) is added2MoO4) The flow of the ethanol aqueous solution is 10 percent of the flow of the nickel sulfate solution added), and the mixture is stirred and reacted for 25 hours at 50 ℃ to obtain Mo of which the molar weight of the molybdenum element accounts for 0.01 percent of the sum of the molar weights of the molybdenum element and the nickel element6+Doping basic nickel carbonate slurry;
Example 5
step 2, feeding by using a peristaltic pump, adding a sodium carbonate solution and a nickel chloride solution into a reactor at the same time, keeping the flow rate of the nickel chloride solution unchanged in the feeding process, controlling the pH value of the system to be 8.1 +/-2 by adjusting the flow rate of the sodium carbonate solution (the flow rate of the sodium carbonate solution is 5-500L/h), reacting for 1.5h, starting a thickener (the stirring rate of the thickener is 5-10r/min), and continuing to react for 15h to obtain basic nickel carbonate slurry;
and 3, carrying out filter pressing on the basic nickel carbonate slurry obtained in the step 2 to remove the mother liquor, pulping, transferring to a reaction kettle, and adding Mo into the reaction kettle6+Molybdic acid (H) having an ion concentration of 0.2mol/L2MoO4) Wherein the volume ratio of ethanol to water is 1:1, and molybdic acid (H) is added2MoO4) The flow of the ethanol aqueous solution is 15 percent of the flow of the nickel chloride solution added), and the mixture is stirred and reacted for 20 hours at the temperature of 60 ℃ to obtain Mo of which the molar weight of the molybdenum element accounts for 1 percent of the sum of the molar weights of the molybdenum element and the nickel element6+Doping basic nickel carbonate slurry;
Example 6
step 2, feeding by using a peristaltic pump, adding an ammonium carbonate solution and a nickel chloride solution into a reactor at the same time, keeping the flow rate of the nickel chloride solution at 500L/h unchanged in the feeding process, controlling the pH value of the system to be 8.1 +/-2 by adjusting the flow rate of the ammonium carbonate solution (the flow rate of the ammonium carbonate solution is 5-500L/h), reacting for 1h, starting a thickener (the stirring rate of the thickener is 5-10r/min), and continuing to react for 8h to obtain basic nickel carbonate slurry;
and 3, carrying out filter pressing on the basic nickel carbonate slurry obtained in the step 2 to remove the mother liquor, pulping, transferring to a reaction kettle, and adding Mo into the reaction kettle6+Molybdic acid (H) having an ion concentration of 0.1mol/L2MoO4) Wherein the volume ratio of ethanol to water is 1:1, adding molybdic acid H2MoO4The flow of the ethanol aqueous solution is 12 percent of the flow of the nickel chloride solution added), and the mixture is stirred and reacted for 22 hours at the temperature of 55 ℃, so as to obtain Mo of which the molar weight of the molybdenum element accounts for 0.1 percent of the sum of the molar weights of the molybdenum element and the nickel element6+Doping basic nickel carbonate slurry;
Example 7
step 2, feeding by using a peristaltic pump, adding a sodium carbonate solution and a nickel nitrate solution into a reactor at the same time, keeping the flow rate of the nickel nitrate solution at 500L/h in the feeding process, controlling the pH value of the system to be 8.1 +/-2 by adjusting the flow rate of the sodium carbonate solution (the flow rate of the sodium carbonate solution is 5-500L/h), reacting for 1h, starting a thickener (the stirring rate of the thickener is 5-10r/min), and continuing to react for 8h to obtain basic nickel carbonate slurry;
and 3, carrying out filter pressing on the basic nickel carbonate slurry obtained in the step 2 to remove the mother liquor, pulping, transferring to a reaction kettle, and adding Mo into the reaction kettle6+Molybdic acid (H) having an ion concentration of 0.2mol/L2MoO4) Wherein the volume ratio of ethanol to water is 1:1, and molybdic acid (H) is added2MoO4) The flow of the ethanol aqueous solution is 15 percent of the flow of the nickel nitrate solution added), and the mixture is stirred and reacted for 20 hours at the temperature of 60 ℃ to obtain Mo of which the molar weight of the molybdenum element accounts for 1 percent of the sum of the molar weights of the molybdenum element and the nickel element6+Doping basic nickel carbonate slurry;
Example 8
step 2, feeding by using a peristaltic pump, adding an ammonium carbonate solution and a nickel nitrate solution into a reactor at the same time, keeping the flow rate of the nickel nitrate solution unchanged at 5L/h in the feeding process, controlling the pH value of the system to be 8.1 +/-2 by adjusting the flow rate of the ammonium carbonate solution (the flow rate of the ammonium carbonate solution is 5-500L/h), reacting for 2h, starting a thickener (the stirring rate of the thickener is 5-10r/min), and continuing to react for 18h to obtain basic nickel carbonate slurry;
and 3, carrying out filter pressing on the basic nickel carbonate slurry obtained in the step 2 to remove the mother liquor, pulping, transferring to a reaction kettle, and adding Mo into the reaction kettle6+Molybdic acid (H) having an ion concentration of 0.1mol/L2MoO4) Wherein the volume ratio of ethanol to water is 1:1, adding molybdic acid H2MoO4The flow rate of the ethanol aqueous solution is 12 percent of the flow rate of the nickel nitrate solution added, and the mixture is stirred at the temperature of 55 DEG CStirring for 22h to obtain Mo, wherein the molar weight of the molybdenum element accounts for 0.1 percent of the sum of the molar weights of the molybdenum element and the nickel element6+Doping basic nickel carbonate slurry;
Example 9
step 2, feeding by using a peristaltic pump, adding an ammonium bicarbonate solution and a nickel sulfate solution into a reactor at the same time, keeping the flow rate of the nickel sulfate solution unchanged in the feeding process, controlling the pH value of the system to be 8.1 +/-2 by adjusting the flow rate of the ammonium bicarbonate solution (the flow rate of the ammonium bicarbonate solution is 5-500L/h), reacting for 2 hours, starting a thickener (the stirring rate of the thickener is 5-10r/min), and continuously reacting for 18 hours to obtain basic nickel carbonate slurry;
and 3, carrying out filter pressing on the basic nickel carbonate slurry obtained in the step 2 to remove the mother liquor, pulping, transferring to a reaction kettle, and adding Mo into the reaction kettle6+Molybdic acid (H) having an ion concentration of 0.05mol/L2MoO4) Wherein the volume ratio of ethanol to water is 1:1, and molybdic acid (H) is added2MoO4) The flow of the ethanol aqueous solution is 10 percent of the flow of the nickel sulfate solution added), and the mixture is stirred and reacted for 25 hours at 50 ℃ to obtain Mo of which the molar weight of the molybdenum element accounts for 0.01 percent of the sum of the molar weights of the molybdenum element and the nickel element6+Doping basic nickel carbonate slurry;
Performance testing experiments:
mo obtained in examples 1 to 96+The basic nickel carbonate doped microspheres are subjected to performance detection, and the detection results are as follows:
table 1Mo obtained in examples 1 to 96+Data for comparing decomposition rate of basic nickel carbonate doped microspheres to methylene blue solution
From table 1, it can be derived: the basic nickel carbonate microsphere obtained by the invention has better photocatalytic performance than that of common basic nickel carbonate, and the photocatalytic efficiency is improved by more than 3 times;
the invention has simple operation and simple and easy preparation process, and Mo is6+After doping, lattice defects are formed to promote electron separation efficiency, and the apparent density is up to 1.2g/cm3Above, at the same time, the Mo obtained by the preparation is enabled6+The doped basic nickel carbonate microsphere has the photocatalytic performance which is more than 3 times higher than that of the common basic nickel carbonate, increases the loose packing density and the fluidity of the basic nickel carbonate, is convenient for packaging and batch transportation, and also extends the strong light absorption capability in the field of photocatalysis, excites photo-generated carrier pairs and improves the photocatalytic performance.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention.
Claims (9)
1. Mo6+The preparation method of the doped basic nickel carbonate microspheres is characterized by comprising the following steps:
step 1, respectively preparing a carbonate solution with carbonate ion concentration of 1.0-2.0 mol/L and a nickel salt solution with nickel ion concentration of 0.5-2.0 mol/L;
step 2, adding a carbonate solution and a nickel salt solution into a reactor simultaneously, keeping the flow rate of the nickel salt solution unchanged in the feeding process, adjusting the pH value of a flow control system of the carbonate solution to be 7.9-8.3, reacting for 1-2 h, then carrying out thickening treatment on the reaction solution, and continuing to react for 8-18 h to obtain basic nickel carbonate slurry;
and 3, carrying out filter pressing on the basic nickel carbonate slurry obtained in the step 2 to remove the mother liquor, and pulpingTransferring the mixture into a reaction kettle, adding an ethanol aqueous solution of molybdic acid into the reaction kettle, and stirring for reaction to obtain Mo6+Doping basic nickel carbonate slurry;
step 4, for the Mo obtained in the step 36+Washing the basic nickel carbonate doped slurry, and drying at high temperature to obtain Mo6+Doping basic nickel carbonate microspheres.
2. Mo according to claim 16+The preparation method of the basic nickel carbonate doped microspheres is characterized in that in the step 1, the carbonate is at least one of sodium carbonate, ammonium carbonate and ammonium bicarbonate; the nickel salt is at least one of nickel sulfate, nickel chloride and nickel nitrate.
3. Mo according to claim 26+The preparation method of the doped basic nickel carbonate microspheres is characterized in that in the step 2, the flow of the sodium carbonate solution is 5-500L/h; the flow rate of the nickel salt solution is 50-500L/h.
4. Mo according to claim 36+The preparation method of the basic nickel carbonate doped microspheres is characterized in that in the step 3, Mo is contained in the ethanol aqueous solution of molybdic acid6+The ion concentration is 0.05-0.2 mol/L, and the volume ratio of ethanol to water in the ethanol aqueous solution of the molybdenum salt is 1: 1.
5. Mo according to claim 46+The preparation method of the basic nickel carbonate doped microspheres is characterized in that in the step 3, the flow rate of the ethanol aqueous solution of molybdenum salt is 10-15% of the flow rate of the nickel salt solution.
6. Mo according to claim 56+The preparation method of the basic nickel carbonate doped microspheres is characterized in that in the step 3, Mo is added6+The molar weight of the molybdenum element in the doped basic nickel carbonate slurry accounts for 0.01-1% of the sum of the molar weight of the molybdenum element and the molar weight of the nickel element.
7. Mo according to claim 66+The preparation method of the doped basic nickel carbonate microspheres is characterized in that in the step 3, the stirring reaction temperature is 50-60 ℃, and the stirring reaction time is 20-25 h.
8. Mo according to claim 76+The preparation method of the basic nickel carbonate doped microspheres is characterized in that in the step 4, the drying temperature is 120-150 ℃.
9. A Mo according to any one of claims 1 to 86+The preparation method of the doped basic nickel carbonate microspheres is characterized in that in the step 4, the drying time is 2-5 hours.
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| CN111807426A (en) * | 2020-06-22 | 2020-10-23 | 荆门市格林美新材料有限公司 | Mass production method of large-particle-size basic nickel carbonate |
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