CN112919482B - Preparation method of porous silica with high specific surface area - Google Patents
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Abstract
The invention provides a preparation method of porous silica with high specific surface area, which comprises the steps of adding a proper amount of slaked lime into water glass solution for reaction, selectively leaching obtained precipitate by an acid solution to obtain suspension, carrying out solid-liquid separation on the suspension, and washing and drying the obtained solid product to obtain the porous silica with high specific surface area. The porous silica with high specific surface area prepared by the invention has good dispersibility, uniform granularity and S BET 704-870m 2 And/g, can be applied to the fields of separation adsorption, catalysis, photoelectricity, biology, carriers and the like.
Description
Technical Field
The invention relates to the field of inorganic material preparation, in particular to a preparation method of porous silica with high specific surface area.
Background
Porous silica, also known as precipitated hydrated silica, white carbon black, is an amorphous SiO 2 The material is mainly used in the fields of rubber, paint, papermaking, catalysis, carrier, adsorption and the like.
The current preparation methods of silicon dioxide mainly comprise a precipitation method, a sol-gel method and an aerosol method. The silicon dioxide produced by the precipitation method is also called precipitated hydrated silicon dioxide, inorganic silicon is used as a silicon source, sulfuric acid, hydrochloric acid and carbonic acid are used as acidulants, and the silicon dioxide is prepared by precipitation, filter pressing and drying. The precipitation method for producing silicon dioxide has simple process and low requirement on equipment, and inorganic silicon is often used as raw material, and the specific surface area of the obtained silicon dioxide is generally 50-200m 2 And/g. The silica produced by sol-gel method is also called silica gel, mainly uses organic silicon as silicon source, and is made up by using the procedures of gelatinizing, ageing, drying and activating, and its specific surface area is generally 100-500m 2 And/g. The silicon dioxide produced by the gas phase method is nano silicon dioxide and SiCl 4 Organic halosilanes as raw materials and O 2 、H 2 Reacting at 1200-1800 deg.C, cooling, separating, deacidifying to obtain product with particle size of 10-40nm and specific surface area of 200-400m 2 /g。
Chinese patent CN103754885B discloses a method for preparing porous silica by acid leaching, which comprises leaching asbestos tailing powder with hydrochloric acid solution, filtering and washing the slurry after reaction to separate solid-liquid components, filtering to obtain solid residue and caustic sodaReacting under heating to obtain slurry containing sodium silicate, filtering the slurry containing sodium silicate, removing solid residue, adding sodium salt, adding water to proper concentration, adding dispersant, precipitating with acid to obtain hydrated silicon dioxide precipitate, aging the precipitate, filtering, washing, and drying to obtain porous silicon dioxide with specific surface area of 300-370m 2 /g。
Chinese patent CN103303929B discloses a process for preparing high transparency and high dispersibility white carbon black, sodium gluconate is used as slow release agent, added into sodium silicate solution for aging and filtering, the obtained filter cake is beaten in a high speed dispersing machine, fatty acid amide is added into slurry for reaction, the slurry after reaction is spray dried to obtain white carbon black with specific surface area of 251-257m 2 /g。
Chinese patent CN106564924B discloses a method for preparing white carbon black and co-producing calcium chloride by using a one-step method of calcium silicate, fully stirring and mixing the calcium silicate and water, standing, taking suspension or supernatant after sedimentation and separation, adding polyethylene glycol serving as a surfactant, then rapidly dripping hydrochloric acid to enable the pH of the system to be less than 1 to obtain sol, dripping a certain amount of concentrated ammonia water into the sol to enable the pH to be 6-7 to obtain gel, rapidly dripping hydrochloric acid to enable the pH to be less than 1, filtering, washing a filter cake, drying and burning to obtain white carbon black with the specific surface area of 493.17m 2 /g。
Chinese patent CN106430223B discloses a method for preparing white carbon black with high specific surface area by using fluorosilicate, adding alcoholic hydroxyl group to aqueous solution to obtain additive, adding fluorosilicate to aqueous solution, stirring uniformly, then adding ammonia water dropwise, and continuing reaction; after the reaction is completed, the white carbon black is obtained through ageing, filtering, washing and drying, and the specific surface area is 220m 2 /g。
Chinese patent CN105060307B discloses a high specific surface area white carbon black and a production method thereof, solid sodium silicate and water are added into a static pressure kettle, steam is introduced to dissolve to obtain hydrated thin liquid sodium silicate, water and thin liquid sodium silicate are added into a reaction kettle to mix, then inorganic acid aqueous solution is added into the mixed solution in a dropwise manner at a constant rate, steam is introduced to heat and pressurize, sulfuric acid is used for acidification to obtain silica slurry, filter pressing is carried out to wash filter cakes,slurrying the filter cake in a slurrying tank, and spray drying to obtain white carbon black with specific surface area of 200-450m 2 /g。
Chinese patent CN107285350a discloses a method for extracting alumina and co-producing white carbon black by leaching fly ash with hydrochloric acid, preparing white carbon black by sol-gel method, i.e. adding surfactant polyethylene glycol into calcium silicate aqueous solution, heating and stirring; after reaching the specified temperature, quick dripping the fly ash leaching residual liquid, adjusting the pH value of the system to be less than 1, dripping quantitative concentrated ammonia water, and adjusting the pH value to be increased to 6-7; and then adding a certain amount of fly ash leaching residual liquid rapidly, adjusting the pH value to be less than 1, filtering, and cleaning with distilled water until the pH value is neutral to obtain a white carbon black product.
However, when the porous silica is prepared, gel agglomeration is avoided by adding an organic dispersing agent, repeatedly adjusting the pH value of the solution and the like, so that the specific surface area of the product is reduced; and the organic dispersing agent is removed in the subsequent steps by methods such as high-temperature roasting, solvent extraction and the like; the reaction condition is harsh and the production process is complex. In addition, organic wastewater is easily generated in the preparation process, and environmental pollution is caused. Therefore, a preparation method of porous silica with simple process, no pollution and low cost is a future development direction.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of porous silica with high specific surface area, which is characterized in that water glass solution and slaked lime are mixed to generate calcium silicate particles with uniform particle size, calcium ions in a calcium silicate framework and unreacted slaked lime are dissolved into the solution through acid leaching, the specific surface area of the particles is increased, and meanwhile, the product maintains the framework structure of the calcium silicate, so that the porous silica with uniform particle size and high specific surface area is obtained.
The technical scheme adopted by the invention is as follows:
a process for preparing porous silicon dioxide with high specific surface area includes such steps as adding lime hydrate to water glass solution for deposition reaction, selective leaching to obtain suspension, solid-liquid separation, washing and dryingSilicon dioxide; the conditions of the precipitation reaction are as follows: the modulus of the water glass solution is 0.6-3.3, and SiO in the water glass solution 2 The mass fraction of the catalyst is 8-10wt%, the reaction temperature is 15-70 ℃, and the reaction time is 30-180min; the conditions for the selective leaching of the acid solution are as follows: h in acid solution + The concentration of the water is 1-12mol/L, the leaching temperature is 15-90 ℃, and the leaching time is 0.5-168h.
Preferably, the mass ratio of the slaked lime to the water glass solution to the acid solution is 1:8-10:20-50.
Preferably, the acid solution is hydrochloric acid or nitric acid.
Specifically, the preparation method of the porous silica with high specific surface area comprises the following steps:
s1, adding a proper amount of slaked lime into a water glass solution to perform a precipitation reaction to obtain mixed slurry, wherein the conditions of the precipitation reaction are as follows: the modulus of the water glass solution is 0.6-3.3, and SiO in the water glass solution 2 The mass fraction of the catalyst is 8-10wt%, the reaction temperature is 15-70 ℃, the reaction time is 30-180min, and the stirring speed is 50-800r/min;
s2, filtering, washing and drying the slurry obtained in the step S1 to obtain solid powder, wherein the drying conditions are as follows: the drying temperature is 30-200 ℃ and the drying time is 0-48h;
s3, selectively leaching the solid powder obtained in the step S2 by using an acid solution to obtain a suspension, wherein the condition of the acid solution selective leaching is as follows: h in acid solution + The concentration of the water is 1-12mol/L, the leaching temperature is 15-90 ℃, the leaching time is 0.5-168h, and the stirring speed is 50-1500r/min;
s4, carrying out solid-liquid separation on the suspension obtained in the step S3, and washing and drying the obtained solid product to obtain the porous silica with the high specific surface area; the drying conditions are as follows: the drying temperature is 60-200deg.C, and the drying time is 6-48h.
The principle of the invention is as follows:
the preparation principle of the porous silica with high specific surface area is that calcium silicate is converted into silica through acidification, calcium silicate sediment with uniform granularity is generated by taking slaked lime and water glass solution as raw materials, and unreacted slaked lime in a calcium silicate framework is dissolved into the solution through acid leaching; meanwhile, the concentration of protons in the solution is high, the proton competitiveness is strong, and the protons can exchange a large amount of calcium ions on the calcium silicate framework without changing the original calcium silicate framework structure, so that the specific surface area of the particles is increased.
Because the alkalinity of the water glass solution is large, the slaked lime can only be slowly released into the solution, the precipitation reaction between the slaked lime and the water glass is slowly carried out, and calcium silicate particles with rich pores and uniform granularity are generated, and the reaction equation is as follows:
Ca(OH) 2 (s)+Na 2 SiO 3 →CaSiO 3 (s)+2NaOH
in the process of acid leaching of calcium silicate, the mixed unreacted calcium hydroxide reacts with acid, and the product is soluble salt, so that calcium ions are dissolved into the solution; meanwhile, the concentration of protons in the solution is high, the proton competitiveness is strong, the protons can exchange a large amount of calcium ions in the calcium silicate framework, and the original calcium silicate framework structure is not changed, so that the specific surface area of the particles is increased, and the reaction equation is as follows:
Ca(OH) 2 (s)+2H + →2H 2 O+Ca 2+
CaSiO 3 (s)+2H + →H 2 SiO 3 (s)+Ca 2+
compared with the prior art, the invention has the following beneficial effects:
(1) The invention relates to a preparation method of porous silica with high specific surface area, which comprises the steps of adding a proper amount of slaked lime into water glass solution for reaction, selectively leaching obtained precipitate by acid solution to obtain suspension, carrying out solid-liquid separation on the suspension, washing and drying the obtained solid product to obtain the porous silica with high specific surface area, wherein the obtained product has good dispersibility, uniform granularity and S BET 704-870m 2 /g。
(2) The method of the invention does not pass through a sol-gel process, has no gel generation, short process flow, simple operation and low cost, and is expected to realize the further resource utilization of water glass and slaked lime.
(3) The method of the invention does not need organic dispersing agent, secondary impurity removal and no environmental pollution.
(4) The porous silica prepared by the invention has uniform granularity and high specific surface area, and can be applied to the fields of separation adsorption, catalysis, photoelectricity, biology, carrier and the like.
Drawings
Fig. 1 is a process flow diagram of a method for preparing high specific surface area porous silica according to the present invention.
Detailed Description
The particle size distribution of the high specific surface area porous silica prepared in the following examples was analyzed using a wet laser particle sizer; the specific surface area was analyzed by BET method.
Example 1:
(1) Adding a proper amount of slaked lime into the water glass solution to perform precipitation reaction to obtain mixed slurry, wherein the conditions of the precipitation reaction are as follows: the modulus of the water glass solution is 1.0, and SiO in the water glass solution 2 The mass fraction of the lime hydrate is 8.6wt%, the reaction temperature is 15 ℃, the reaction time is 120min, the stirring speed is 150r/min, and the mass ratio of the lime hydrate to the water glass solution is 1:9.5;
(2) Filtering, washing and drying the slurry obtained in the step (1) to obtain solid powder, wherein the drying temperature is 120 ℃, and the drying time is 18 hours;
(3) Leaching the solid powder obtained in the step (2) by hydrochloric acid to obtain a suspension, wherein the leaching conditions are as follows: the concentration of hydrochloric acid is 1mol/L, the leaching temperature is 50 ℃, the leaching time is 12h, the stirring speed is 150r/min, and the mass ratio of slaked lime to hydrochloric acid is 1:30;
(4) And (3) carrying out solid-liquid separation on the suspension obtained in the step (3), and washing and drying the obtained solid product to obtain the porous silica with high specific surface area, wherein the drying temperature is 105 ℃ and the drying time is 6 hours.
Sample analysis and detection results obtained in this example: the silicon dioxide content is 99.2 percent, the specific surface area S BET 762.27m 2 Per gram, pore volume of 0.53cm 3 Per g, average pore diameter of 5.86nm, median particle diameter of 6.43 μm, D 10 4.42 μm, D 90 9.76 μm.
Example 2:
(1) Adding a proper amount of slaked lime into the water glass solution to perform precipitation reaction to obtain mixed slurry, wherein the conditions of the precipitation reaction are as follows: the modulus of the water glass solution is 0.6, and SiO in the water glass solution 2 The mass fraction of the lime hydrate is 10wt%, the reaction temperature is 45 ℃, the reaction time is 30min, the stirring speed is 350r/min, and the mass ratio of the lime hydrate to the water glass solution is 1:8.0;
(2) Filtering, washing and drying the slurry obtained in the step (1) to obtain solid powder, wherein the drying temperature is 60 ℃ and the drying time is 48 hours;
(3) Leaching the solid powder obtained in the step (2) by hydrochloric acid to obtain a suspension, wherein the leaching conditions are as follows: the concentration of hydrochloric acid is 12mol/L, the leaching temperature is 90 ℃, the leaching time is 4 hours, the stirring speed is 425r/min, and the mass ratio of slaked lime to hydrochloric acid is 1:20;
(4) And (3) carrying out solid-liquid separation on the suspension obtained in the step (3), and washing and drying the obtained solid product to obtain the porous silica with high specific surface area, wherein the drying temperature is 60 ℃ and the drying time is 12 hours.
Sample analysis and detection results obtained in this example: the silicon dioxide content is 99.0 percent, the specific surface area S BET 744.47m 2 Per gram, pore volume of 0.98m 3 Per g, average pore diameter of 8.78nm, median particle diameter of 21.89 μm, D 10 11.69 μm, D 90 44.85 μm.
Example 3:
(1) Adding a proper amount of slaked lime into the water glass solution to perform precipitation reaction to obtain mixed slurry, wherein the conditions of the precipitation reaction are as follows: the modulus of the water glass solution is 3.3, and SiO in the water glass solution 2 The mass fraction of the lime hydrate is 8.0wt%, the reaction temperature is 70 ℃, the reaction time is 180min, the stirring speed is 400r/min, and the mass ratio of the lime hydrate to the water glass solution is 1:9.0;
(2) Filtering, washing and drying the slurry obtained in the step (1) to obtain solid powder, wherein the drying time is 0h;
(3) Leaching the solid powder obtained in the step (2) by hydrochloric acid to obtain a suspension, wherein the leaching conditions are as follows: the concentration of hydrochloric acid is 4mol/L, the leaching temperature is 20 ℃, the leaching time is 80h, the stirring speed is 550r/min, and the mass ratio of slaked lime to hydrochloric acid is 1:40;
(4) And (3) carrying out solid-liquid separation on the suspension obtained in the step (3), and washing and drying the obtained solid product to obtain the porous silica with high specific surface area, wherein the drying temperature is 200 ℃ and the drying time is 8 hours.
Sample analysis and detection results obtained in this example: the silicon dioxide content is 99.8 percent, the specific surface area S BET 771.27m 2 Per gram, pore volume of 0.75cm 3 Per g, average pore diameter of 5.89nm, median particle diameter of 7.09 μm, D 10 4.79 μm, D 90 10.79 μm.
Example 4:
(1) Adding a proper amount of slaked lime into the water glass solution to perform precipitation reaction to obtain mixed slurry, wherein the conditions of the precipitation reaction are as follows: the modulus of the water glass solution is 3.3, and SiO in the water glass solution 2 The mass fraction of the lime hydrate is 10.0wt%, the reaction temperature is 30 ℃, the reaction time is 60min, the stirring speed is 800r/min, and the mass ratio of the lime hydrate to the water glass solution is 1:8.6;
(2) Filtering, washing and drying the slurry obtained in the step (1) to obtain solid powder, wherein the drying temperature is 115 ℃ and the drying time is 30 hours;
(3) Leaching the solid powder obtained in the step (2) by nitric acid to obtain a suspension, wherein the leaching conditions are as follows: the concentration of the nitric acid is 12mol/L, the leaching temperature is 60 ℃, the leaching time is 48 hours, the stirring speed is 50r/min, and the mass ratio of the slaked lime to the nitric acid is 1:50;
(4) And (3) carrying out solid-liquid separation on the suspension obtained in the step (3), and washing and drying the obtained solid product to obtain the porous silica with high specific surface area, wherein the drying temperature is 145 ℃ and the drying time is 28 hours.
Sample analysis and detection results obtained in this example: the silicon dioxide content is 99.4 percent, the specific surface area S BET 742.94m 2 Per gram, pore volume of 0.52cm 3 Per g, average pore diameter of 4.21nm, median particle diameter of 5.89 μm, D 10 4.07 μm, D 90 8.74 μm.
Example 5:
(1) Adding a proper amount of slaked lime into the water glass solution to perform precipitation reaction to obtain mixed slurry, wherein the conditions of the precipitation reaction are as follows: the modulus of the water glass solution is 1.6, and SiO in the water glass solution 2 The mass fraction of the lime hydrate is 9.0wt%, the reaction temperature is 65 ℃, the reaction time is 90min, the stirring speed is 550r/min, and the mass ratio of the lime hydrate to the water glass solution is 1:8.3;
(2) Filtering, washing and drying the slurry obtained in the step (1) to obtain solid powder, wherein the drying temperature is 70 ℃ and the drying time is 12 hours;
(3) Leaching the solid powder obtained in the step (2) by hydrochloric acid to obtain a suspension, wherein the leaching conditions are as follows: the concentration of hydrochloric acid is 8mol/L, the leaching temperature is 80 ℃, the leaching time is 12h, the stirring speed is 800r/min, and the mass ratio of slaked lime to hydrochloric acid is 1:20;
(4) And (3) carrying out solid-liquid separation on the suspension obtained in the step (3), and washing and drying the obtained solid product to obtain the porous silica with high specific surface area, wherein the drying temperature is 70 ℃ and the drying time is 24 hours.
Sample analysis and detection results obtained in this example: the silicon dioxide content is 98.7 percent, the specific surface area S BET 773.61m 2 Per gram, pore volume of 0.71cm 3 Per g, average pore diameter of 5.37nm, median particle diameter of 7.75 μm, D 10 5.32 μm, D 90 11.49 μm.
Example 6:
(1) Adding a proper amount of slaked lime into the water glass solution to perform precipitation reaction to obtain mixed slurry, wherein the conditions of the precipitation reaction are as follows: the modulus of the water glass solution is 0.8, and SiO in the water glass solution 2 The mass fraction of the lime hydrate is 9.3wt%, the reaction temperature is 20 ℃, the reaction time is 30min, the stirring speed is 200r/min, and the mass ratio of the lime hydrate to the water glass solution is 1:8.5;
(2) Filtering, washing and drying the slurry obtained in the step (1) to obtain solid powder, wherein the drying time is 0h;
(3) Leaching the solid powder obtained in the step (2) by hydrochloric acid to obtain a suspension, wherein the leaching conditions are as follows: the concentration of hydrochloric acid is 1mol/L, the leaching temperature is 25 ℃, the leaching time is 0.5h, the stirring speed is 550r/min, and the mass ratio of slaked lime to hydrochloric acid is 1:30;
(4) And (3) carrying out solid-liquid separation on the suspension obtained in the step (3), and washing and drying the obtained solid product to obtain the porous silica with high specific surface area, wherein the drying temperature is 150 ℃ and the drying time is 6 hours.
Sample analysis and detection results obtained in this example: the silicon dioxide content is 99.0 percent, the specific surface area S BET 870.16m 2 Per gram, pore volume of 0.80cm 3 Per g, average pore diameter of 6.90nm, median particle diameter of 4.37 μm, D 10 2.99 μm, D 90 6.60 μm.
Example 7:
(1) Adding a proper amount of slaked lime into the water glass solution to perform precipitation reaction to obtain mixed slurry, wherein the conditions of the precipitation reaction are as follows: the modulus of the water glass solution is 2.0, and SiO in the water glass solution 2 The mass fraction of the lime hydrate is 9.2wt%, the reaction temperature is 50 ℃, the reaction time is 150min, the stirring speed is 700r/min, and the mass ratio of the lime hydrate to the water glass solution is 1:10;
(2) Filtering, washing and drying the slurry obtained in the step (1) to obtain solid powder, wherein the drying temperature is 30 ℃, and the drying time is 3 hours;
(3) Leaching the solid powder obtained in the step (2) by nitric acid to obtain a suspension, wherein the leaching conditions are as follows: the concentration of the nitric acid is 2mol/L, the leaching temperature is 15 ℃, the leaching time is 168 hours, the stirring speed is 70r/min, and the mass ratio of the slaked lime to the nitric acid is 1:45;
(4) And (3) carrying out solid-liquid separation on the suspension obtained in the step (3), and washing and drying the obtained solid product to obtain the porous silica with high specific surface area, wherein the drying temperature is 130 ℃ and the drying time is 16 hours.
Sample analysis and detection results obtained in this example: the silicon dioxide content is 99.9 percent, the specific surface area S BET 704.99m 2 Per gram, pore volume of 0.47cm 3 Per g, average pore diameter of 4.03nm, median particle diameter of 7.91 μm, D 10 5.55 μm, D 90 11.30 μm.
Example 8:
(1) Adding a proper amount of slaked lime into the water glass solution to perform precipitation reaction to obtain mixed slurry, wherein the conditions of the precipitation reaction are as follows: the modulus of the water glass solution is 1.2, and SiO in the water glass solution 2 The mass fraction of the lime hydrate is 9.8wt%, the reaction temperature is 35 ℃, the reaction time is 70min, the stirring speed is 300r/min, and the mass ratio of the lime hydrate to the water glass solution is 1:8.1;
(2) Filtering, washing and drying the slurry obtained in the step (1) to obtain solid powder, wherein the drying temperature is 145 ℃, and the drying time is 24 hours;
(3) Leaching the solid powder obtained in the step (2) by hydrochloric acid to obtain a suspension, wherein the leaching conditions are as follows: the concentration of hydrochloric acid is 10mol/L, the leaching temperature is 40 ℃, the leaching time is 4 hours, the stirring speed is 700r/min, and the mass ratio of slaked lime to hydrochloric acid is 1:35;
(4) And (3) carrying out solid-liquid separation on the suspension obtained in the step (3), and washing and drying the obtained solid product to obtain the porous silica with high specific surface area, wherein the drying temperature is 200 ℃ and the drying time is 48 hours.
Sample analysis and detection results obtained in this example: the silicon dioxide content is 99.0 percent, the specific surface area S BET 739.00m 2 Per gram, pore volume of 0.72cm 3 Per g, average pore diameter of 6.13nm, median particle diameter of 3.87 μm, D 10 2.49 μm, D 90 5.89 μm.
Example 9:
(1) Adding a proper amount of slaked lime into the water glass solution to perform precipitation reaction to obtain mixed slurry, wherein the conditions of the precipitation reaction are as follows: the modulus of the water glass solution is 0.6, and SiO in the water glass solution 2 The mass fraction of the lime hydrate is 8.0wt%, the reaction temperature is 15 ℃, the reaction time is 120min, the stirring speed is 50r/min, and the mass ratio of the lime hydrate to the water glass solution is 1:9.3;
(2) Filtering, washing and drying the slurry obtained in the step (1) to obtain solid powder, wherein the drying temperature is 200 ℃, and the drying time is 6 hours;
(3) Leaching the solid powder obtained in the step (2) by hydrochloric acid to obtain a suspension, wherein the leaching conditions are as follows: the concentration of hydrochloric acid is 1mol/L, the leaching temperature is 15 ℃, the leaching time is 2h, the stirring speed is 1500r/min, and the mass ratio of slaked lime to hydrochloric acid is 1:50;
(4) And (3) carrying out solid-liquid separation on the suspension obtained in the step (3), and washing and drying the obtained solid product to obtain the porous silica with high specific surface area, wherein the drying temperature is 80 ℃ and the drying time is 36h.
Sample analysis and detection results obtained in this example: the silicon dioxide content is 99.0 percent, the specific surface area S BET 728.59m 2 Per gram, pore volume of 0.75cm 3 Per g, average pore diameter of 8.44nm, median particle diameter of 10.36 μm, D 10 6.98 μm, D 90 14.97 μm.
Example 10:
(1) Adding a proper amount of slaked lime into the water glass solution to perform precipitation reaction to obtain mixed slurry, wherein the conditions of the precipitation reaction are as follows: the modulus of the water glass solution is 2.8, and SiO in the water glass solution 2 The mass fraction of the lime hydrate is 9.3wt%, the reaction temperature is 25 ℃, the reaction time is 45min, the stirring speed is 600r/min, and the mass ratio of the lime hydrate to the water glass solution is 1:8.7;
(2) Filtering, washing and drying the slurry obtained in the step (1) to obtain solid powder, wherein the drying temperature is 180 ℃, and the drying time is 24 hours;
(3) Leaching the solid powder obtained in the step (2) by hydrochloric acid to obtain a suspension, wherein the leaching conditions are as follows: the concentration of hydrochloric acid is 6mol/L, the leaching temperature is 25 ℃, the leaching time is 24 hours, the stirring speed is 600r/min, and the mass ratio of slaked lime to hydrochloric acid is 1:25;
(4) And (3) carrying out solid-liquid separation on the suspension obtained in the step (3), and washing and drying the obtained solid product to obtain the porous silica with high specific surface area, wherein the drying temperature is 60 ℃ and the drying time is 18 hours.
Sample analysis and detection results obtained in this example: the silicon dioxide content is 99.9 percent, the specific surface area S BET 709.47m 2 Per gram, pore volume of 0.65cm 3 Per g, average pore diameter of 6.89nm, median particle diameter of 4.43 μm, D 10 3.51 μm, D 90 6.97 μm.
Comparative example 1:
the mass ratio of slaked lime to water glass solution in the step (1) is 1:95, and the other steps are the same as in the example 1.
The slaked lime in comparative example 1 reacted with the water glass solution to produce calcium silicate colloid, and calcium silicate solid powder could not be obtained.
Comparative example 2:
the water glass solution described in example 1 was reacted with 1mol/L hydrochloric acid, the mass ratio of water glass solution to hydrochloric acid being 1:30.
Comparative example 2 did not have any precipitate or colloid formation.
Comparative example 3:
the water glass solution described in example 1 was reacted with 1mol/L hydrochloric acid, the mass ratio of water glass solution to hydrochloric acid being 1:10.
Comparative example 3 did not have any precipitate or colloid formation.
Comparative example 4:
the water glass solution described in example 1 was reacted with 12mol/L hydrochloric acid, the mass ratio of water glass solution to hydrochloric acid being 10:1.
Comparative example 4 a large amount of silicic acid colloid was rapidly produced after hydrochloric acid was added, and filtration was impossible with stirring, and a porous silica having a uniform particle size and a high specific surface area was not obtained.
Comparative example 5:
the solid calcium silicate powder obtained in step (2) of example 1 was examined.
Analysis and detection results of the samples obtained in the comparative example: the content of silicon dioxide is 51.30%, the content of calcium oxide is 47.90%, and the specific surface area S of calcium silicate BET 34.31m 2 Per gram, pore volume 0.23cm 3 Per g, average pore diameter of 31.88nm, median particle diameter of 5.67 μm, D 10 3.99 μm, D 90 8.29 μm.
As is clear from comparative example 1, calcium silicate obtained with too little slaked lime produced colloid instead of precipitate at this time, and as is clear from comparative examples 2, 3 and 4, water glass solution was directly reacted with hydrochloric acid to obtain silica precipitate having uniform particle size. As is evident from comparative example 5, the calcium silicate produced was uniform in particle size but too small in specific surface area, consistent with the principles of the present invention.
Claims (1)
1. The preparation method of the porous silica with high specific surface area is characterized by comprising the following steps:
(1) Adding a proper amount of slaked lime into the water glass solution to perform precipitation reaction to obtain mixed slurry, wherein the conditions of the precipitation reaction are as follows: the modulus of the water glass solution is 0.8, and SiO in the water glass solution 2 The mass fraction of the lime hydrate is 9.3wt%, the reaction temperature is 20 ℃, the reaction time is 30min, the stirring speed is 200r/min, and the mass ratio of the lime hydrate to the water glass solution is 1:8.5;
(2) Filtering, washing and drying the slurry obtained in the step (1) to obtain solid powder, wherein the drying time is 0h;
(3) Leaching the solid powder obtained in the step (2) by hydrochloric acid to obtain a suspension, wherein the leaching conditions are as follows: the concentration of hydrochloric acid is 1mol/L, the leaching temperature is 25 ℃, the leaching time is 0.5h, the stirring speed is 550r/min, and the mass ratio of slaked lime to hydrochloric acid is 1:30;
(4) And (3) carrying out solid-liquid separation on the suspension obtained in the step (3), and washing and drying the obtained solid product to obtain the porous silica with high specific surface area, wherein the drying temperature is 150 ℃ and the drying time is 6 hours.
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