CN110627074B - Preparation method and application of low-heat-conductivity low-bulk-density white carbon black - Google Patents
Preparation method and application of low-heat-conductivity low-bulk-density white carbon black Download PDFInfo
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- CN110627074B CN110627074B CN201911011219.0A CN201911011219A CN110627074B CN 110627074 B CN110627074 B CN 110627074B CN 201911011219 A CN201911011219 A CN 201911011219A CN 110627074 B CN110627074 B CN 110627074B
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- carbon black
- white carbon
- low
- bulk density
- sulfuric acid
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000006229 carbon black Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000002002 slurry Substances 0.000 claims abstract description 29
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 22
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000002270 dispersing agent Substances 0.000 claims abstract description 13
- 238000009413 insulation Methods 0.000 claims abstract description 13
- 239000007785 strong electrolyte Substances 0.000 claims abstract description 13
- 238000000227 grinding Methods 0.000 claims abstract description 11
- 238000009835 boiling Methods 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000004821 distillation Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000004537 pulping Methods 0.000 claims abstract description 3
- 241000872198 Serjania polyphylla Species 0.000 claims abstract 4
- 238000000034 method Methods 0.000 claims description 32
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 16
- 239000011162 core material Substances 0.000 claims description 11
- 150000002191 fatty alcohols Chemical class 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 239000012467 final product Substances 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 229910002056 binary alloy Inorganic materials 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 4
- 239000004576 sand Substances 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 3
- 235000019982 sodium hexametaphosphate 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
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 28
- 239000011148 porous material Substances 0.000 abstract description 13
- 238000009826 distribution Methods 0.000 abstract description 9
- 238000001035 drying Methods 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000499 gel Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- KTUQUZJOVNIKNZ-UHFFFAOYSA-N butan-1-ol;hydrate Chemical compound O.CCCCO KTUQUZJOVNIKNZ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000011049 filling Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000010533 azeotropic distillation Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229960004029 silicic acid Drugs 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004965 Silica aerogel Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- LRCFXGAMWKDGLA-UHFFFAOYSA-N dioxosilane;hydrate Chemical compound O.O=[Si]=O LRCFXGAMWKDGLA-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012536 packaging technology Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/141—Preparation of hydrosols or aqueous dispersions
- C01B33/142—Preparation of hydrosols or aqueous dispersions by acidic treatment of silicates
- C01B33/143—Preparation of hydrosols or aqueous dispersions by acidic treatment of silicates of aqueous solutions of silicates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/146—After-treatment of sols
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
- E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
- E04B1/62—Insulation or other protection; Elements or use of specified material therefor
- E04B1/74—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls
- E04B1/76—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls specifically with respect to heat only
- E04B1/78—Heat insulating elements
- E04B1/80—Heat insulating elements slab-shaped
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
- E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
- E04B1/62—Insulation or other protection; Elements or use of specified material therefor
- E04B1/74—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls
- E04B1/76—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls specifically with respect to heat only
- E04B1/78—Heat insulating elements
- E04B1/80—Heat insulating elements slab-shaped
- E04B1/803—Heat insulating elements slab-shaped with vacuum spaces included in the slab
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A30/00—Adapting or protecting infrastructure or their operation
- Y02A30/24—Structural elements or technologies for improving thermal insulation
- Y02A30/242—Slab shaped vacuum insulation
-
- 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
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B80/00—Architectural or constructional elements improving the thermal performance of buildings
- Y02B80/10—Insulation, e.g. vacuum or aerogel insulation
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Architecture (AREA)
- Inorganic Chemistry (AREA)
- Acoustics & Sound (AREA)
- Dispersion Chemistry (AREA)
- Electromagnetism (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Silicon Compounds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
The invention belongs to the technical field of white carbon black, and discloses a preparation method and application of white carbon black with low heat conduction and low bulk density. The preparation method of the invention comprises the following steps: preparing a sodium silicate solution and a dilute sulfuric acid solution; adding water and sodium silicate solution into a reaction kettle, heating, adding dilute sulfuric acid solution under stirring until the pH value is 8.5-9, and generating gel; raising stirring speed, raising temperature, adding sodium silicate solution and dilute sulfuric acid solution, controlling pH of the reaction system, adding strong electrolyte at a specific time point to control particle size, obtaining white carbon black thin slurry, filtering, washing, pulping and obtaining white carbon black thick slurry; adding dispersant for grinding, and then washing with alcohol, distilling and drying at constant boiling. The preparation process improves the pore volume value of the product by continuing to react on the gel structure and adopting an alcohol washing constant boiling distillation drying method to reduce the heat conductivity coefficient of the heat insulation board; the particle size of the product is reduced by adding strong electrolyte and dispersing agent and superfine grinding, the particle size distribution is narrowed, and the bulk density of the product is reduced.
Description
Technical Field
The invention relates to the technical field of white carbon black, in particular to a preparation method and application of low-heat-conduction low-bulk density white carbon black.
Background
White carbon black is a general term for white powdery X-ray amorphous silicic acid and silicate, and comprises precipitated hydrated silica, fumed silica and silica aerogel, and related products are widely applied to industries such as tire rubber, silicon rubber, sole rubber, paint, animal feed, food additives and the like.
In recent years, white carbon black products are gradually applied and popularized in the building exterior wall heat insulation material industry. The STP ultrathin vacuum insulation board is prepared by compounding a core material prepared from ultrafine silicon dioxide, an additive and an auxiliary agent with a high-strength composite gas barrier film through a vacuumizing packaging technology, and has the remarkable advantages of high fire resistance level (A level) and low thermal conductivity (less than or equal to 0.01W/(m.K)). The realization of low thermal conductivity requires that the white carbon black used as the core material has very low thermal conductivity coefficient; meanwhile, in order to reduce the filling quality of the white carbon black and reduce the production cost, the white carbon black is required to have lower bulk density. At present, most manufacturers of heat-insulating plates use white carbon black prepared by a gas phase method for filling, the stacking density of products by the gas phase method is about 50g/L, and the heat conductivity coefficient of STP ultrathin vacuum heat-insulating plates prepared by taking the products as the main component of the core material is generally 0.007-0.008W/(m.K), so that the use requirement is met. However, the white carbon black prepared by the gas phase method is high in price, and the price of the heat insulation plate is increased, so that the subsequent popularization of the product is affected; the white carbon black product prepared by the common precipitation method has the common problems of larger heat conduction coefficient (more than or equal to 0.012W/(m.K)) and higher bulk density (more than or equal to 60 g/L) of the heat insulation board.
Disclosure of Invention
The invention provides a preparation method of low-heat-conductivity low-bulk density white carbon black, which aims to overcome the defects that the white carbon black prepared by the existing gas phase method is high in price and the white carbon black prepared by the common precipitation method is insufficient in performance. The method starts from the following three aspects, and solves the problems of high heat conductivity coefficient and large bulk density of the white carbon black by a common precipitation method:
(1) Increasing the pore volume of the white carbon black to reduce the thermal conductivity: the core material of the STP ultrathin vacuum insulation board needs to be vacuumized after being filled with white carbon black, kong Rongyue of the white carbon black is large, the larger the volume occupied by a void part is after vacuumization, the higher the vacuum degree of the void part is, the heat conductivity is close to zero, and the lower the heat conductivity of the insulation board prepared by the method is;
(2) Narrowing the white carbon particle size distribution to reduce its bulk density: as shown in FIG. 1, if white carbon black particles are regarded as solid spheres, the bulk density is minimum when the white carbon black particles have only one diameter, namely, in the extreme case shown in FIG. 1- (1), and when the white carbon black particles have multiple diameters, the more particle size types are, namely, the broader particle size distribution is, the higher the bulk density is, and the situation is shown in FIGS. 1- (1) to 1- (3), in the preparation of white carbon black powder, the particle size distribution can be narrowed through process control, so that the purpose of reducing the bulk density is achieved;
(3) The white carbon black has the characteristics of finer powder and lower bulk density: the surface of the white carbon black powder is provided with a large number of silicon hydroxyl groups, the mutual adsorption effect is strong, large-volume and loose aggregates are formed, and the more the aggregates are, the lower the powder bulk density is; the finer the white carbon black powder is, the more active sites of silicon hydroxyl exist on the surface of the unit area particles, the stronger the adsorption effect is, the more and larger the formed agglomerates are, and the lower the bulk density is naturally, so that the proper reduction of the particle size of the white carbon black is helpful for reducing the bulk density.
In order to achieve the purpose of the invention, the preparation method of the low-heat-conduction low-bulk density white carbon black comprises the following steps:
(1) Preparing a sodium silicate solution and a dilute sulfuric acid solution;
(2) Adding water and sodium silicate solution into a reaction kettle, heating, adding dilute sulfuric acid solution under stirring until the pH of the system is reduced to 8.5-9, and generating gel;
(3) Raising the stirring speed to break up gel, heating to 80-90 ℃, adding sodium silicate solution and dilute sulfuric acid solution, controlling the pH of the reaction to be 10.5-11, adding strong electrolyte after 30-40 min, and continuing the reaction for 15-25 min;
(4) Stopping adding the sodium silicate solution, continuously adding the dilute sulfuric acid until the pH value is reduced to 6.0-6.5 to obtain white carbon black dilute slurry, filtering and washing the dilute slurry to obtain a filter cake, and pulping the filter cake to obtain white carbon black thick slurry;
(5) Adding a dispersing agent into the white carbon black thick slurry, and carrying out wet superfine grinding to obtain superfine white carbon black thick slurry;
(6) Adding fatty alcohol into superfine white carbon black thick slurry to form a fatty alcohol-water binary system, firstly heating to constant boiling point of the binary system, removing water by constant boiling distillation, and then continuously heating to remove fatty alcohol to obtain a final product.
Further, the concentration of the sodium silicate solution in the step (1) is 1-1.3 mol/L, and the modulus is 3-3.5; the mass fraction of the dilute sulfuric acid solution is 10-15%.
Further, in the step (2), the temperature is heated to 50-60 ℃, and the dilute sulfuric acid solution is added under the stirring speed of 30-50 r/min.
Further, in the step (3), the stirring speed is increased to 70-90 r/min so as to break up the gel.
Further, the strong electrolyte in the step (3) is one or more of sodium sulfate, sodium chloride or sodium phosphate; preferably, the addition amount of the strong electrolyte in the step (3) is 0.5-3% of the final yield of the white carbon black.
Further, the dispersing agent in the step (5) is one or more of sodium hexametaphosphate, sodium dodecyl sulfate or sodium lignin sulfonate.
Preferably, the addition amount of the dispersing agent in the step (5) is 1-3% of the mass of the white carbon black thick slurry.
Further, the wet superfine grinding in the step (5) is performed by adopting a rod pin type sand mill.
Preferably; the sand mill is a rod pin type sand mill, a 95 zirconia ceramic ball with the diameter of 0.6mm is used as a grinding medium, the rotating speed of a main shaft is 2100-2300 r/min, and the cyclic grinding duration is 12-18 min.
Further, the fatty alcohol in the step (6) is one or more of ethanol, isopropanol or n-butanol.
On the other hand, the invention also provides an application of the white carbon black prepared by the method, namely, the white carbon black is used as a main component of a core material to prepare the STP ultrathin vacuum insulation board.
According to the preparation method, firstly, the silica gel with rich pore structures is prepared, and then the multistage particles with larger pore volume are prepared by continuing the reaction. The addition of the strong electrolyte can prevent the white carbon black particles from further agglomerating, so that the particle size of the white carbon black particles is effectively reduced; the particle size is further reduced in the grinding process and the addition of the dispersing agent, and meanwhile, agglomeration is avoided; when the fatty alcohol is added for constant boiling distillation and drying, the lower surface tension of the fatty alcohol system can avoid the damage of pore structures when the solvent evaporates, and the higher pore volume is kept.
In addition, the method of the invention has the advantages of strong electrolyte, less dispersing agent dosage and low price, and the fatty alcohol is also subjected to closed condensation recovery treatment, so the method has great cost advantage compared with the product prepared by a gas phase method. In addition, the white carbon black product prepared by the method is only used as a filling material when the heat-insulating plate is prepared, so that a small amount of electrolyte, dispersing agent and the like remained in the product have no influence on the application of the product. The pore volume of the white carbon black prepared by the method reaches 2.2-2.6 ml/g, the bulk density is 50-60 g/L, and after the white carbon black is used as a main component of a core material to prepare the STP ultrathin vacuum insulation board, the heat conductivity coefficient of the white carbon black is less than or equal to 0.01W/(m.K) through detection, and the use requirement is basically met.
Drawings
FIG. 1 is a schematic diagram showing the effect of different particle size distributions on bulk density of powder;
FIG. 2 is a graph showing the comparison of the particle size distribution of the products of examples 1-2 of the present invention and comparative examples 1-2.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. It is to be understood that the following description is intended to be illustrative of the invention and not restrictive.
The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
The indefinite articles "a" and "an" preceding an element or component of the invention are not limited to the requirement (i.e. the number of occurrences) of the element or component. Thus, the use of "a" or "an" should be interpreted as including one or at least one, and the singular reference of an element or component includes the plural reference unless the amount clearly dictates otherwise. The technical features of the respective embodiments of the present invention may be combined with each other as long as they do not collide with each other.
Example 1
Firstly, preparing 1.2mol/L sodium silicate solution with the modulus of 3.4 and 15% of diluted sulfuric acid solution, adding water and the sodium silicate solution into a reaction kettle, heating to 55 ℃, controlling the stirring rate to be 50r/min, and then adding the diluted sulfuric acid solution until the pH value of the system is reduced to 8.5, wherein a small amount of gel is formed in the system. And (3) raising the stirring speed to 80r/min, breaking up gel, raising the temperature to 85 ℃, adding the sodium silicate solution and the dilute sulfuric acid, starting timing, controlling the pH of the reaction to be 10.8+/-0.1, adding sodium sulfate with the mass of 1% of the final product when the reaction is carried out for 30min, stopping adding the sodium silicate solution, and stopping adding the dilute sulfuric acid when the pH is reduced to 6.5, thus obtaining the white carbon black dilute slurry. The thin slurry is filtered, washed and pulped to obtain white carbon black thick slurry, and then sodium hexametaphosphate with the mass of 1.5% of the thick slurry is added as a dispersing agent to carry out wet superfine grinding to obtain superfine white carbon black thick slurry. Adding a certain amount of n-butanol into the superfine white carbon black thick slurry, controlling the water content to be below 37.5% (the proportion of water in n-butanol-water azeotropic mixture), heating to the azeotropic point of 92.2 ℃, removing water by azeotropic distillation, continuously heating to the boiling point of n-butanol of 117.7 ℃, removing the residual n-butanol, and obtaining a final product, wherein the n-butanol-water azeotrope is condensed and recovered.
The pore volume of the product is 2.6ml/g according to GB/T21650 by mercury intrusion method, and the median diameter D is measured by BT-9300H laser particle sizer 50 ＝1.13μm，D 98 =10.23 μm; detecting the bulk density of a 100ml cylindrical open stainless steel container by adopting a conventional pouring method, and taking the average value of three detection to be 55.6g/L; after the product is used as the main component of the core material to prepare the STP ultrathin vacuum insulation board, the thermal conductivity coefficient of the product is detected to be 0.007W/(m.K), so that the use requirement is met.
Example 2
Firstly, preparing 1.2mol/L sodium silicate solution with the modulus of 3.4 and 15% of diluted sulfuric acid solution, adding water and the sodium silicate solution into a reaction kettle, heating to 55 ℃, controlling the stirring speed to be 40r/min, and then adding the diluted sulfuric acid solution until the pH value of the system is reduced to 8.8, wherein a small amount of gel is formed in the system. And (3) raising the stirring speed to 85r/min, breaking up gel, raising the temperature to 85 ℃, adding the sodium silicate solution and the dilute sulfuric acid, starting timing, controlling the pH of the reaction to be 10.8+/-0.1, adding sodium chloride with the mass of 1.5% of the final product when the reaction is carried out for 40min, stopping adding the sodium silicate solution, and stopping adding the dilute sulfuric acid when the pH is reduced to 6.5, thus obtaining the white carbon black dilute slurry. The thin slurry is filtered, washed and pulped to obtain white carbon black thick slurry, and then sodium dodecyl sulfate with the mass of 1% of the thick slurry is added as a dispersing agent to carry out wet superfine grinding to obtain superfine white carbon black thick slurry. Adding a certain amount of n-butanol into the superfine white carbon black thick slurry, controlling the water content to be below 37.5% (the proportion of water in n-butanol-water azeotropic mixture), heating to the azeotropic point of 92.2 ℃, removing water by azeotropic distillation, continuously heating to the boiling point of n-butanol of 117.7 ℃, removing the residual n-butanol, and obtaining a final product, wherein the n-butanol-water azeotrope is condensed and recovered.
The pore volume of the product is 2.2ml/g according to GB/T21650 by mercury intrusion method, and the median thereof is measured by BT-9300H laser particle sizerDiameter D 50 ＝1.08μm，D 98 =6.19 μm; detecting the bulk density of a 100ml cylindrical open stainless steel container by adopting a conventional pouring method, and taking the average value of three detection to be 52.5g/L; after the product is used as the main component of the core material to prepare the STP ultrathin vacuum insulation board, the thermal conductivity coefficient of the product is detected to be 0.009W/(m.K), so that the use requirement is met.
Comparative example 1
The white carbon black preparation process of comparative example 1 is different from that of example 1 in that a strong electrolyte is not added to control the growth of white carbon black particles in the reaction stage in which a sodium silicate solution and a dilute sulfuric acid solution are simultaneously added.
The pore volume of the product is 2.4ml/g according to GB/T21650 by mercury intrusion method, and the median diameter D is measured by BT-9300H laser particle sizer 50 ＝1.32μm，D 98 = 84.90 μm; detecting the bulk density of a 100ml cylindrical open stainless steel container by adopting a conventional pouring method, and taking the average value of three detection to be 63.5g/L; after the product is used as a main component of a core material to prepare an STP ultrathin vacuum insulation board, the heat conductivity coefficient of the product is detected to be 0.01W/(m.K), so that the use requirement is met, but the use amount of the white carbon black is increased by about 14.2% compared with that of the embodiment 1 due to the increase of the bulk density.
Comparative example 2
The process for preparing the white carbon black of comparative example 2 is different from that of example 1 in that the superfine white carbon black slurry is subjected to conventional centrifugal spray drying at a drying temperature of 450 ℃ and an air outlet temperature of 95 ℃.
The pore volume of the product is 1.5ml/g according to GB/T21650 by mercury intrusion method, and the median diameter D is measured by BT-9300H laser particle sizer 50 ＝22.14μm，D 98 = 120.10 μm; detecting the bulk density of a 100ml cylindrical open stainless steel container by adopting a conventional pouring method, and taking the average value of three detection to be 67.5g/L; after the product is used as a main component of a core material to prepare an STP ultrathin vacuum insulation board, the heat conductivity coefficient of the product is detected to be 0.013W/(m.K), the use requirement is not met, and the use amount of the white carbon black is increased by about 21.4% compared with that of the embodiment 1 due to the increase of the bulk density.
The particle size distribution of the white carbon black final products of examples 1-2 and comparative examples 1-2 is shown in FIG. 2, and the comparison of other relevant indexes is shown in Table 1.
Table 1 comparison of the respective indices of examples 1-2 and comparative examples 1-2
As can be seen from fig. 2 and table 1:
(1) As can be seen from comparison of comparative example 2 with comparative example 1 and examples 1-2, as pore volume increases, thermal conductivity decreases, demonstrating that constant boiling distillation drying can protect the pore structure of the product and effectively prevent agglomeration compared with conventional high temperature centrifugal spray drying;
(2) Comparing examples 1-2 with comparative example 1, it was found that the three had a close median diameter, but the broader the particle size distribution, the greater the bulk density, indicating that narrowing the particle size distribution of the product helps to reduce its bulk density;
(3) As compared with examples 1-2, comparative example 1 was not added with strong electrolyte in the reaction, D 98 Significantly greater than the other two, indicating that the addition of strong electrolytes has a significant effect on the control of the particle size of the product.
It will be readily appreciated by those skilled in the art that the foregoing is merely illustrative of the present invention and that no limitations are intended to the scope of the invention, except insofar as modifications, equivalents, improvements or changes may be made within the spirit and principles of the invention.
Claims (8)
1. The preparation method of the low-heat-conduction low-bulk density white carbon black is characterized by comprising the following steps of:
(1) Preparing a sodium silicate solution and a dilute sulfuric acid solution;
(2) Adding water and sodium silicate solution into a reaction kettle, heating, adding dilute sulfuric acid solution under stirring until the pH of the system is reduced to 8.5-9, and generating gel;
(3) Raising the stirring speed to break up gel, heating to 80-90 ℃, adding sodium silicate solution and dilute sulfuric acid solution, controlling the pH of the reaction to be 10.5-11, adding strong electrolyte after 30-40 min, and continuing the reaction for 15-25 min;
(4) Stopping adding the sodium silicate solution, continuously adding the dilute sulfuric acid until the pH value is reduced to 6.0-6.5 to obtain white carbon black dilute slurry, filtering and washing the dilute slurry to obtain a filter cake, and pulping the filter cake to obtain white carbon black thick slurry;
(5) Adding a dispersing agent into the white carbon black thick slurry, and carrying out wet superfine grinding to obtain superfine white carbon black thick slurry;
(6) Adding fatty alcohol into superfine white carbon black thick slurry to form a fatty alcohol-water binary system, firstly heating to constant boiling point of the binary system, removing water by constant boiling distillation, and then continuously heating to remove fatty alcohol to obtain a final product;
the concentration of the sodium silicate solution in the step (1) is 1-1.3 mol/L, and the modulus is 3-3.5; the mass fraction of the dilute sulfuric acid solution is 10-15%;
the strong electrolyte in the step (3) is one or more of sodium sulfate, sodium chloride or sodium phosphate; the addition amount of the strong electrolyte in the step (3) is 0.5-3% of the final yield of the white carbon black;
the fatty alcohol is subjected to closed condensation recovery treatment.
2. The method for preparing the white carbon black with low heat conduction and low bulk density according to claim 1, wherein in the step (2), the white carbon black is heated to 50-60 ℃ and the dilute sulfuric acid solution is added under the stirring rate of 30-50 r/min.
3. The method for preparing the low-heat-conductivity low-bulk density white carbon black according to claim 1, wherein the stirring speed is increased to 70-90 r/min in the step (3) so as to break up gel.
4. The method for preparing the low-heat-conductivity low-bulk-density white carbon black according to claim 1, wherein the dispersing agent in the step (5) is one or more of sodium hexametaphosphate, sodium dodecyl sulfate or sodium lignin sulfonate.
5. The method for preparing the white carbon black with low heat conduction and low bulk density according to claim 1, wherein the adding amount of the dispersing agent in the step (5) is 1-3% of the mass of the white carbon black thick slurry.
6. The method for preparing the white carbon black with low heat conduction and low bulk density according to claim 1, wherein the wet superfine grinding in the step (5) is performed by a bar pin type sand mill.
7. The method for preparing the low-heat-conductivity low-bulk-density white carbon black according to claim 1, wherein the fatty alcohol in the step (6) is one or more of ethanol, isopropanol or n-butanol.
8. The application of the low-heat-conductivity low-bulk density white carbon black prepared by the preparation method of any one of claims 1 to 7, which is characterized in that the low-heat-conductivity low-bulk density white carbon black is used as a main component of a core material to prepare an STP ultrathin vacuum insulation board.
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