CN112495317B - Method for continuously preparing carbon aerogel precursor - Google Patents
Method for continuously preparing carbon aerogel precursor Download PDFInfo
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- CN112495317B CN112495317B CN202011245498.XA CN202011245498A CN112495317B CN 112495317 B CN112495317 B CN 112495317B CN 202011245498 A CN202011245498 A CN 202011245498A CN 112495317 B CN112495317 B CN 112495317B
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- white oil
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- carbon aerogel
- aqueous solution
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- 239000002243 precursor Substances 0.000 title claims abstract description 67
- 239000004966 Carbon aerogel Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 18
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000004945 emulsification Methods 0.000 claims abstract description 26
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000007864 aqueous solution Substances 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 239000000725 suspension Substances 0.000 claims abstract description 20
- 239000002002 slurry Substances 0.000 claims abstract description 18
- 239000004094 surface-active agent Substances 0.000 claims abstract description 16
- 239000004964 aerogel Substances 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 230000035484 reaction time Effects 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 239000011259 mixed solution Substances 0.000 claims description 23
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical group CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000004005 microsphere Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000002309 gasification Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000003763 carbonization Methods 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 11
- 238000000967 suction filtration Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
Classifications
-
- 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
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a method for continuously preparing a carbon aerogel precursor, which comprises the following steps: adding resorcinol into a formaldehyde aqueous solution, and stirring and dissolving to obtain an aerogel precursor aqueous solution; adding a surfactant into the white oil, and stirring for dissolving; controlling the flow ratio of the precursor aqueous solution and the white oil to fully mix the precursor aqueous solution and the white oil into suspension in an emulsification pump; the suspension liquid is taken out of the emulsification pump and directly enters the tubular reactor to be heated so as to enable the aqueous solution to fully react, and precursor white oil slurry is obtained; and finally, filtering and washing the slurry to obtain the carbon aerogel precursor. The method has the advantages of accurate temperature control, accurate control of reaction time, simple operation, high production efficiency, safety and environmental protection, and the prepared carbon aerogel precursor has high tap density after drying and carbonization, has a certain specific surface area, can be further activated to obtain carbon aerogel with higher specific surface area, and can be applied to the production of the carbon aerogel.
Description
Technical Field
The invention belongs to the field of carbon aerogel preparation, and particularly relates to a continuous preparation method of a carbon aerogel precursor, which can be applied to carbon aerogel production.
Background
The carbon aerogel has good application potential in national strategic emerging industries of novel batteries, environmental protection, biological medical treatment and the like, and particularly, as a substitute of super activated carbon, the carbon aerogel shows excellent performances of low resistivity, high specific capacitance and strong cycle performance in a super capacitor. But the carbon aerogel product is difficult to industrialize due to the reasons of complex preparation process, long production period, high continuous production difficulty and the like.
In recent years, domestic research on carbon aerogel production processes has increased, and mass production has been achieved. In the preparation process of the carbon aerogel precursor, a special shape and a special pore structure are formed, so that the subsequent drying and carbon activation are facilitated.
In the existing mature production process, the preparation of the carbon aerogel precursor adopts a one-pot method: in a reaction kettle, resorcinol and formaldehyde enter an oil phase according to a certain proportion for dispersion, and then are polymerized at a certain temperature. In the actual production process, the polymerization process of resorcinol and formaldehyde to form polymer (RF) in the reaction kettle generates a lot of heat, and the released heat can accelerate the reaction speed, so that the whole reaction temperature exceeds the preset temperature and even boils. The high temperature causes rapid evaporation of water in the polymer (RF), and the polymer (RF) structure collapses due to the force of hydrogen bonding, and the porous structure decreases, resulting in a decrease in specific surface area. This exotherm is more severe as the amount, concentration of material increases. In addition, the uncontrollable production mode is not beneficial to safety and environmental protection of workshop production.
Therefore, with the increase of the demand of the carbon aerogel, the one-pot method of the traditional reaction kettle cannot meet the requirement of large-scale production, and the batch production of the carbon aerogel is severely restricted.
Disclosure of Invention
The invention aims to solve the problems in the prior art, and provides a method for continuously preparing a carbon aerogel precursor, which can realize accurate temperature control and accurate reaction time control, is simple to operate, has high production efficiency, and is safe and environment-friendly.
In order to achieve the above object, the method for continuously preparing the carbon aerogel precursor comprises the following steps:
(1) preparing a solution: adding resorcinol into a formaldehyde aqueous solution, stirring and dissolving to obtain an aerogel precursor aqueous solution; mixing a surfactant with white oil, stirring and dissolving to prepare a white oil mixed solution; the molar ratio of the resorcinol to the formaldehyde is 1: (1.5-3), wherein the surfactant accounts for 10-60% of the volume of the white oil mixed solution;
in this step, the stirring and dissolving temperature is preferably controlled to be in the range of 0 to 30 ℃, preferably in the range of 20 to 30 ℃; the surfactant is span 80 or other surfactants with properties similar to span 80, and the ratio of the surfactant to the volume of the white oil mixed solution is preferably 10-30%.
(2) Continuous emulsification: respectively feeding the aerogel precursor aqueous solution and the white oil mixed solution into an emulsification pump to fully mix into suspension, and controlling the volume flow ratio of the aerogel precursor aqueous solution to the white oil mixed solution to be (1-5) to (1-2);
in the step, the volume flow ratio of the aerogel precursor aqueous solution to the white oil mixed solution is controlled to be (0.3-1): 1, preferably (0.3-0.8): 1.
(3) Continuous reaction preparation: the suspension liquid is discharged from the emulsification pump and directly enters the tubular reactor to be heated so as to fully react the suspension liquid, and a precursor white oil slurry is obtained;
in this step, the heating temperature of the tubular reactor is generally controlled within the range of 60 to 95 ℃, and the reaction time is controlled within the range of 2 to 24 hours, preferably 7 to 20 hours.
(4) And (3) performing solid-liquid separation and washing on the precursor white oil slurry to obtain the porous microspheric carbon aerogel precursor.
The preferable scheme is as follows: in the step (4), any one solvent or a mixed solvent of two or three of methanol, ethanol and dichloromethane is used for washing.
The further preferred scheme is as follows: in the step (1), the mass concentration of the formaldehyde aqueous solution is 35-39%, and the mass concentration of the formaldehyde aqueous solution sold on the market is generally 37%.
Compared with the prior art, the method for continuously preparing the carbon aerogel precursor has the following beneficial effects:
(1) the method uses the tubular reactor to heat and prepare the carbon aerogel precursor, and the heating mode has better heat transfer capacity than the traditional reaction kettle, can better realize energy exchange, and can realize accurate temperature control.
(2) The invention enables the materials to be heated to the reaction temperature instantly, the materials leave the reactor after the reaction is finished, and the temperature is rapidly reduced.
(3) The method can wait for the subsequent treatment of the discharged material by only preparing the water phase and the oil phase and setting the mass flow meter and the temperature in proportion, can realize the continuous production of the carbon aerogel precursor compared with the traditional reaction kettle, and has simple operation and high production efficiency.
(4) The tubular reactor used in the invention has small volume, and compared with the traditional reaction kettle, the tubular reactor has the advantages of extremely less material quantity which instantaneously participates in the reaction, safety and environmental protection.
Detailed Description
In order to describe the present invention, the method for continuously preparing a carbon aerogel precursor according to the present invention will be described in further detail with reference to the following examples. The invention is not limited to the examples.
(1) Stirring and dissolving resorcinol and formaldehyde at the molar ratio of 1:1.5 at 30 ℃ to obtain an aerogel precursor aqueous solution;
(2) adding a surfactant span 80 into 15# white oil, and uniformly stirring at 30 ℃ to prepare a white oil mixed solution, wherein the span 80 accounts for 10% of the volume of the white oil mixed solution;
(3) controlling the flow rate of the precursor water solution to be 30ml/min, the flow rate of the white oil to be 10ml/min, the flow rate ratio to be 3:1 and the rotation speed of an emulsification pump to be 1000r/min, and fully mixing the precursor water solution and the white oil in the emulsification pump to form suspension;
(4) preheating a tubular reactor to 80 ℃ in advance, directly feeding the suspension out of an emulsification pump into the tubular reactor, and allowing the material to flow in the tubular reactor for 10 hours to obtain precursor white oil slurry;
(5) and finally, carrying out suction filtration and washing by dichloromethane on the slurry, and carrying out suction filtration to obtain the porous microspheric carbon aerogel precursor.
Example 2:
(1) stirring and dissolving resorcinol and formaldehyde according to the molar ratio of 1:2 at 20 ℃ to obtain an aerogel precursor aqueous solution;
(2) adding a surfactant span 80 into 15# white oil, and uniformly stirring at 20 ℃ to prepare a white oil mixed solution, wherein the span 80 accounts for 20% of the volume of the white oil mixed solution;
(3) controlling the flow rate of the precursor water solution to be 50ml/min, the flow rate of the white oil to be 10ml/min, the flow rate ratio to be 5:1, and the rotating speed of an emulsification pump to be 1000r/min, so that the precursor water solution and the white oil are fully mixed into suspension in the emulsification pump;
(4) preheating a tubular reactor to 90 ℃ in advance, directly feeding the suspension out of an emulsification pump into the tubular reactor, and allowing the material to flow in the tubular reactor for 7.5 hours to obtain precursor white oil slurry;
(5) and finally, centrifuging the slurry, washing with ethanol at 60 ℃, and centrifuging to obtain the porous microspheric carbon aerogel precursor.
Example 3:
(1) stirring and dissolving resorcinol and formaldehyde according to the molar ratio of 1:3 at 30 ℃ to obtain an aerogel precursor aqueous solution;
(2) adding a surfactant span 80 into 15# white oil, and uniformly stirring at 30 ℃ to prepare a white oil mixed solution, wherein the span 80 accounts for 10% of the volume of the white oil mixed solution;
(3) controlling the flow rate of the precursor water solution to be 30ml/min, the flow rate of the white oil to be 30ml/min, the flow rate ratio to be 1:1 and the rotation speed of an emulsification pump to be 1000r/min, and fully mixing the precursor water solution and the white oil in the emulsification pump to form suspension;
(4) preheating a tubular reactor to 95 ℃ in advance, directly feeding the suspension out of an emulsification pump into the tubular reactor, and allowing the material to flow in the tubular reactor for 7.5 hours to obtain precursor white oil slurry;
(5) and finally, carrying out suction filtration and washing by dichloromethane on the slurry, and carrying out suction filtration to obtain the porous microspheric carbon aerogel precursor.
Example 4:
(1) stirring and dissolving resorcinol and formaldehyde according to the molar ratio of 1:1 at 30 ℃ to obtain an aerogel precursor aqueous solution;
(2) adding a surfactant span 80 into 15# white oil, and uniformly stirring at 30 ℃ to prepare a white oil mixed solution, wherein the span 80 accounts for 10% of the volume of the white oil mixed solution;
(3) controlling the flow rate of the precursor water solution to be 10ml/min, the flow rate of the white oil to be 10ml/min, the flow rate ratio to be 1:1 and the rotation speed of an emulsification pump to be 1000r/min, and fully mixing the precursor water solution and the white oil in the emulsification pump to form suspension;
(4) preheating a tubular reactor to 60 ℃ in advance, directly feeding the suspension out of an emulsification pump into the tubular reactor, and allowing the material to flow in the tubular reactor for 20 hours to obtain precursor white oil slurry;
(5) and finally, carrying out suction filtration and washing by dichloromethane on the slurry, and carrying out suction filtration to obtain the porous microspheric carbon aerogel precursor.
Example 5:
(1) stirring and dissolving resorcinol and formaldehyde according to the molar ratio of 1:3 at 30 ℃ to obtain an aerogel precursor aqueous solution;
(2) adding a surfactant span 80 into 15# white oil, and uniformly stirring at 30 ℃ to prepare a white oil mixed solution, wherein the span 80 accounts for 10% of the volume of the white oil mixed solution;
(3) controlling the flow rate of the precursor water solution to be 10ml/min, the flow rate of the white oil to be 20ml/min, the flow rate ratio to be 1:2, and the rotating speed of an emulsification pump to be 1000r/min, so that the precursor water solution and the white oil are fully mixed into suspension in the emulsification pump;
(4) preheating a tubular reactor to 70 ℃ in advance, directly feeding the suspension out of an emulsification pump into the tubular reactor, and allowing the material to flow in the tubular reactor for 10 hours to obtain precursor white oil slurry;
(5) and finally, centrifuging the slurry, washing with dichloromethane, and centrifuging to obtain the porous microspheric carbon aerogel precursor.
Example 6:
(1) stirring and dissolving resorcinol and formaldehyde according to the molar ratio of 1:1.5 at 20 ℃ to obtain an aerogel precursor aqueous solution;
(2) adding a surfactant span 80 into 15# white oil, and uniformly stirring at 20 ℃ to prepare a white oil mixed solution, wherein the span 80 accounts for 60% of the volume of the white oil mixed solution;
(3) controlling the flow rate of the precursor water solution to be 30ml/min, the flow rate of the white oil to be 10ml/min, the flow rate ratio to be 3:1 and the rotation speed of an emulsification pump to be 1000r/min, and fully mixing the precursor water solution and the white oil in the emulsification pump to form suspension;
(4) preheating a tubular reactor to 80 ℃ in advance, directly feeding the suspension out of an emulsification pump into the tubular reactor, and allowing the material to flow in the tubular reactor for 15 hours to obtain precursor white oil slurry;
(5) and finally, carrying out suction filtration and dichloromethane washing on the slurry, and carrying out suction filtration to obtain the porous microspheric carbon aerogel precursor.
Through detection, the tap density and specific surface area of the porous microsphere carbon aerogel precursors prepared in examples 1 to 6 after drying and carbonization are as follows:
TABLE 1 tap density and specific surface area of carbonization in each example
As can be seen from the above table, the carbon aerogel precursor prepared by the method disclosed by the invention is high in tap density after being dried and carbonized, has a certain specific surface area, and can be further activated to obtain carbon aerogel with a higher specific surface area.
Claims (4)
1. A method for continuously preparing a carbon aerogel precursor is characterized by comprising the following steps:
(1) preparing a solution: adding resorcinol into a formaldehyde aqueous solution, stirring and dissolving, and controlling the stirring and dissolving temperature to be within the range of 20-30 ℃ to obtain an aerogel precursor aqueous solution; mixing a surfactant with white oil, stirring and dissolving to prepare a white oil mixed solution; the molar ratio of the resorcinol to the formaldehyde is 1: (1.5-3), wherein the surfactant accounts for 10-60% of the volume of the white oil mixed solution;
(2) continuous emulsification: respectively feeding the aerogel precursor aqueous solution and the white oil mixed solution into an emulsification pump to fully mix into suspension, and controlling the volume flow ratio of the aerogel precursor aqueous solution to the white oil mixed solution to be (1-5) to (1-2);
(3) continuous reaction preparation: the suspension liquid is discharged from the emulsification pump and directly enters the tubular reactor to be heated so as to fully react the suspension liquid, and precursor white oil slurry is obtained; the heating temperature of the tubular reactor is controlled within the range of 60-95 ℃, and the reaction time is controlled within the range of 7-20 hours;
(4) and (3) performing solid-liquid separation and washing on the precursor white oil slurry to obtain the porous microspheric carbon aerogel precursor.
2. The method of claim 1, wherein the carbon aerogel precursor is prepared by a continuous gasification process, comprising: in the step (4), any one solvent or a mixed solvent of two or three solvents of methanol, ethanol and dichloromethane is used for washing.
3. The method for continuously producing a carbon aerogel precursor according to claim 2, wherein: in the step (1), the surfactant is span 80.
4. The process for continuously producing a carbon aerogel precursor according to claim 1, 2, or 3, wherein: in the step (1), the surfactant accounts for 10-30% of the volume of the white oil mixed solution.
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| AU5017985A (en) * | 1984-11-05 | 1986-06-03 | Owens-Corning Fiberglas Corporation | Glass fiber size and impregnant compositions |
| CN102091595B (en) * | 2011-01-12 | 2012-11-07 | 华东理工大学 | Method for preparing spherical carbon aerogel with specific absorbability for low density lipoprotein |
| CN104157883B (en) * | 2014-07-14 | 2016-08-24 | 浙江大学 | A kind of preparation method of DMFC anode |
| CN107021889B (en) * | 2017-06-08 | 2019-09-27 | 联化科技（台州）有限公司 | A kind of preparation method and device of aromatic chlorinated object |
| CN107051366B (en) * | 2017-06-09 | 2018-06-29 | 山东诺为制药流体系统有限公司 | A kind of continuous flow tubular reactor system and reaction control system |
| CN109575072A (en) * | 2019-01-14 | 2019-04-05 | 绍兴上虞易瑞化工有限公司 | A kind of novel synthesis of diphenyl phosphine chloride |
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