CN112358586B - Low-cost preparation method of carbon aerogel precursor - Google Patents
Low-cost preparation method of carbon aerogel precursor Download PDFInfo
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- 239000002243 precursor Substances 0.000 title claims abstract description 68
- 239000004966 Carbon aerogel Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000011259 mixed solution Substances 0.000 claims abstract description 56
- 239000007864 aqueous solution Substances 0.000 claims abstract description 44
- 239000000203 mixture Substances 0.000 claims abstract description 42
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000001816 cooling Methods 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000002002 slurry Substances 0.000 claims abstract description 20
- 239000000725 suspension Substances 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 238000010992 reflux Methods 0.000 claims abstract description 17
- 238000004945 emulsification Methods 0.000 claims abstract description 16
- 239000004094 surface-active agent Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000004132 cross linking Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 230000001804 emulsifying effect Effects 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000005457 ice water Substances 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 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 9
- 239000002904 solvent Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 150000007530 organic bases Chemical group 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 27
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000004090 dissolution Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 22
- 230000001276 controlling effect Effects 0.000 description 12
- 239000000839 emulsion Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 230000001105 regulatory effect Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 238000003763 carbonization Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004964 aerogel Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011240 wet gel Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention discloses a low-cost preparation method of a carbon aerogel precursor, which comprises the following steps: adding phenol into formaldehyde aqueous solution, adding a catalyst, and stirring for dissolution to obtain a mixture aqueous solution; refluxing the mixture water solution to a critical state to be solidified at 55-85 ℃, then rapidly cooling, and stopping the reaction process to obtain a precursor water solution with a certain crosslinking degree; adding the surfactant into the white oil, and uniformly stirring at room temperature to prepare a white oil mixed solution; taking a small part of white oil mixed liquor for standby, and heating the rest of white oil mixed liquor to a certain temperature; controlling the flow ratio of the precursor aqueous solution and the cold white oil mixed solution, and fully mixing the precursor aqueous solution and the cold white oil mixed solution into suspension in an emulsifying pump; the suspension liquid is discharged out of the emulsification pump and directly enters hot white oil for full reaction to obtain precursor white oil slurry; and finally, filtering and washing the slurry to obtain the carbon aerogel precursor. The method has the advantages of low raw material price, low production cost, high product performance, safety and environmental protection.
Description
Technical Field
The invention belongs to the technical field of carbon aerogel synthesis, and particularly relates to a preparation method of a carbon aerogel precursor, in particular to a method for preparing the carbon aerogel precursor by taking phenol as a raw material.
Background
The carbon aerogel material has excellent performance and has good application potential in novel batteries, environmental protection, biomedical and other national strategic emerging industries. However, due to the reasons of expensive raw materials, complex preparation process, long production period, large-scale production difficulty and the like, the carbon aerogel product has high cost, is unacceptable in market and is difficult to industrialize.
In recent years, domestic research on carbon aerogel production processes is increasing, and mass production has been achieved. In the current mature production process, resorcinol and formaldehyde are mixed in a certain proportion into an oil phase for dispersion, and then polymerized at a certain temperature.
A method for preparing carbon aerogel disclosed in chinese patent application 201611110955.8, the method comprising the steps of: step one, resorcinol and formaldehyde are used as raw materials, organic amine is used as a catalyst, water is used as a solvent, and the mixture is stirred uniformly to carry out gel reaction to obtain an intermediate product; aging the obtained intermediate product to obtain organic wet gel; step three, vacuumizing and drying the organic wet gel to obtain organic aerogel; and fourthly, placing the organic aerogel in a carbonization furnace, heating and carbonizing under the protection of nitrogen, and naturally cooling to room temperature to obtain the carbon aerogel. However, as the price of chemical raw materials increases, the price of resorcinol is so high (10-12 ten thousand yuan/ton in 2020) that the cost price of carbon aerogel prepared by adopting resorcinol is higher than that of super-active carbon of competing products, and the market competitiveness is lost.
Phenol is inexpensive (1 ten thousand yuan/ton in 2020), and can be used as a substitute for resorcinol or polymerized with formaldehyde to obtain a precursor. However, since phenol contains only one hydroxyl group, ortho-para-reactivity is far less than resorcinol, resulting in a slow polymerization rate. Moreover, the precursor prepared from phenol has the problems of shrinkage, collapse of internal structure and low specific surface area after carbonization, and the quality of subsequent products is affected. In addition, phenol is soluble in white oil, which causes insufficient reaction, low yield, difficult separation from white oil and the like, and is not beneficial to environmental protection. The above problems limit the cost-effective production of carbon aerogel precursors from phenol instead of expensive resorcinol.
Disclosure of Invention
The invention aims at solving the problems existing in the prior art, and provides a low-cost preparation method of a carbon aerogel precursor, which has the advantages of low raw material price, low production cost, high product performance, safety and environmental protection.
In order to solve the problems, the technical scheme of the invention is as follows: the mixed solution of phenol and formaldehyde is refluxed to a critical state to be solidified at high temperature, at this time, the phenol and formaldehyde are polymerized into chain shape, the reaction rate reaches the fastest, and ice water is used for cooling to stop the reaction. The critical reaction solution was cut with an emulsion pump, and the droplets were separated with a white oil containing a surfactant to prevent re-adhesion. And (3) adding the cut granular critical reaction liquid into high-temperature white oil, restarting the reaction, and instantly solidifying the reaction liquid.
The invention discloses a low-cost preparation method of a carbon aerogel precursor, which specifically comprises the following steps:
(1) Adding phenol into formaldehyde aqueous solution, adding a catalyst, stirring and dissolving to obtain a mixture aqueous solution; the catalyst is one of potassium hydroxide, sodium hydroxide and calcium hydroxide, the molar ratio of the phenol to formaldehyde is generally controlled within the range of 1 (1.3-3.3), and the preferable range is 1 (1.5-3); the stirring and dissolving temperature is controlled to be in the range of 30-60 ℃,
the catalyst can also be organic base triethylamine.
(2) Refluxing the mixture aqueous solution obtained in the step (1) to a critical state to be solidified at the temperature of 55-85 ℃, then rapidly placing the mixture aqueous solution in ice water for cooling, and stopping the reaction process to obtain a precursor aqueous solution with a certain crosslinking degree;
the preferable reflux temperature is controlled in the range of 60-80 ℃ and the reflux time is controlled in the range of 1-8 hours.
(3) Mixing a surfactant and white oil, and uniformly stirring and mixing at room temperature to prepare a white oil mixed solution; the surfactant is span 80 or other surfactants with similar properties.
(4) And (3) naturally cooling 1.8-10.0% of the total amount of the white oil mixed solution for standby, and heating the rest of the white oil mixed solution to 75-105 ℃.
(5) And (3) respectively feeding the precursor aqueous solution obtained in the step (2) and the white oil mixed solution which is naturally cooled for standby in the step (4) into an emulsifying pump to be fully mixed into suspension, wherein the flow ratio of the precursor aqueous solution to the white oil mixed solution is generally controlled within the range of (8-50): 1, and preferably within the range of (9-15): 1.
(6) The suspension liquid is discharged out of the emulsification pump and directly enters the heated white oil mixed liquid to fully react with the heated white oil mixed liquid, so as to obtain precursor white oil slurry; the reaction temperature is controlled to be 80-95 ℃ and the reaction time is 10-30 hours.
(7) The precursor white oil slurry is subjected to solid-liquid separation and washing to obtain a carbon aerogel precursor; the washing uses any one solvent of methanol, ethanol and dichloromethane, and a mixed solvent of two or three solvents.
Compared with the prior art, the low-cost preparation method of the carbon aerogel precursor has the following beneficial effects:
(1) And the low-cost phenol is adopted to replace the expensive resorcinol, so that the cost is saved.
(2) Phenol and formaldehyde are pre-reacted for a period of time, so that the phenol is polymerized to a certain extent, the reactivity of the phenol is improved, the subsequent reaction can be rapidly carried out, the shrinkage and collapse of a precursor are reduced, the specific surface area of a subsequent carbonized sample is improved, and the product quality is improved.
(3) The pre-reaction causes the polymerization of phenol formaldehyde, the molecular weight is increased, the reaction is more complete, the reaction yield is improved, and the cost is saved.
(4) Almost no phenol enters the white oil after the pre-reaction, and the white oil is easier to recycle and more environment-friendly.
Description of the embodiments
In order to describe the present invention, a method for preparing a carbon aerogel precursor according to the present invention at low cost will be described in further detail with reference to examples. The invention is not limited to the examples.
Examples
(1) Adding 94.11g of phenol into 121.74g of formaldehyde aqueous solution with the mass concentration of 37%, wherein the molar ratio of the phenol to the formaldehyde is 1:1.5, adding 0.9g of sodium hydroxide, stirring and dissolving, and controlling the stirring and dissolving temperature within the range of 30-60 ℃ to obtain a mixture aqueous solution;
(2) Refluxing the mixture water solution at 80 ℃ for 7 hours and 15 minutes until the mixture water solution reaches a critical state to be solidified, then rapidly placing the mixture water solution into ice water for cooling, and stopping the reaction process to obtain a precursor water solution with a certain crosslinking degree;
(3) Adding 5ml of surfactant span 80 into 500ml of white oil, and uniformly stirring at room temperature to prepare a white oil mixed solution;
(4) Naturally cooling 30ml of white oil mixed solution for standby, and heating the rest white oil mixed solution to 95 ℃;
(5) Starting an emulsion pump, regulating the rotating speed to 1000r/min, and controlling the flow ratio of the precursor aqueous solution to the white oil mixed solution for natural cooling to be 10:1, fully mixing the two materials into suspension in an emulsification pump;
(6) The suspension is discharged out of an emulsification pump and directly enters the heated white oil mixed solution to fully react with the heated white oil mixed solution, and the mixture is continuously kept at 95 ℃ to fully react for 10 hours to obtain precursor white oil slurry;
(7) Finally, the slurry is subjected to solid-liquid separation and washing to obtain a carbon aerogel precursor.
Examples
(1) Adding 94.11g of phenol into 121.74g of formaldehyde aqueous solution with the mass concentration of 37%, wherein the molar ratio of the phenol to the formaldehyde is 1:1.5, adding 0.9g of sodium hydroxide, stirring and dissolving, and controlling the stirring and dissolving temperature within the range of 30-60 ℃ to obtain a mixture aqueous solution;
(2) Refluxing the mixture water solution at 60 ℃ for 12 hours and 20 minutes until the mixture water solution reaches a critical state to be solidified, then rapidly placing the mixture water solution into ice water for cooling, and stopping the reaction process to obtain a precursor water solution with a certain crosslinking degree;
(3) Adding 300ml of white oil into 5ml of surfactant span 80, and uniformly stirring at room temperature to prepare a white oil mixed solution;
(4) Naturally cooling 10ml of white oil mixed solution for standby, and heating the rest white oil mixed solution to 95 ℃;
(5) Starting an emulsion pump, regulating the rotating speed to 1000r/min, and controlling the flow ratio of the precursor aqueous solution to the white oil mixed solution for natural cooling to be 10:1, fully mixing the two materials into suspension in an emulsification pump;
(6) The suspension is discharged out of an emulsification pump and directly enters the heated white oil mixed solution to fully react with the heated white oil mixed solution, and the mixture is continuously kept at 95 ℃ to fully react for 12 hours to obtain precursor white oil slurry;
(7) Finally, the slurry is subjected to solid-liquid separation and washing to obtain a carbon aerogel precursor.
Examples
(1) Adding 47.06g of phenol into 60.87g of formaldehyde aqueous solution with the mass concentration of 37%, wherein the molar ratio of the phenol to the formaldehyde is 1:1.5, adding 0.5g of sodium hydroxide, stirring and dissolving, and controlling the stirring and dissolving temperature within the range of 30-60 ℃ to obtain a mixture aqueous solution;
(2) Refluxing the mixture water solution at 70 ℃ for 8 hours and 55 minutes until the mixture water solution reaches a critical state to be solidified, then rapidly placing the mixture water solution into ice water for cooling, and stopping the reaction process to obtain a precursor water solution with a certain crosslinking degree;
(3) Adding 500ml of white oil into 5ml of surfactant span 80, and uniformly stirring at room temperature to prepare a white oil mixed solution;
(4) Naturally cooling 10ml of white oil mixed solution for standby, and heating the rest white oil mixed solution to 90 ℃;
(5) Starting an emulsion pump, regulating the rotating speed to 1000r/min, and controlling the flow ratio of the precursor aqueous solution to the white oil mixed solution for natural cooling to be 10:1, fully mixing the two materials into suspension in an emulsification pump;
(6) The suspension is discharged out of an emulsification pump and directly enters the heated white oil mixed solution to fully react with the heated white oil mixed solution, and the mixture is continuously kept at 90 ℃ to fully react for 15 hours to obtain precursor white oil slurry;
(7) Finally, the slurry is subjected to solid-liquid separation and washing to obtain a carbon aerogel precursor.
Examples
(1) Adding 47.06g of phenol into 121.74g of formaldehyde aqueous solution with the mass concentration of 37%, wherein the molar ratio of the phenol to the formaldehyde is 1:3, adding 0.5g of sodium hydroxide, stirring and dissolving, and controlling the stirring and dissolving temperature within the range of 30-60 ℃ to obtain a mixture aqueous solution;
(2) Refluxing the mixture water solution at 80 ℃ for 8 hours and 30 minutes until the mixture water solution reaches a critical state to be solidified, then rapidly placing the mixture water solution into ice water for cooling, and stopping the reaction process to obtain a precursor water solution with a certain crosslinking degree;
(3) Adding 3ml of surfactant span 80 into 300ml of white oil, and uniformly stirring at room temperature to prepare a white oil mixed solution;
(4) Naturally cooling 30ml of white oil mixed solution for standby, and heating the rest white oil mixed solution to 80 ℃;
(5) Starting an emulsion pump, regulating the rotating speed to 1000r/min, and controlling the flow ratio of the precursor aqueous solution to the white oil mixed solution for natural cooling to be 10:1, fully mixing the two materials into suspension in an emulsification pump;
(6) The suspension is discharged out of an emulsification pump and directly enters the heated white oil mixed solution to fully react with the heated white oil mixed solution, and the mixture is continuously kept at 80 ℃ to fully react for 24 hours to obtain precursor white oil slurry;
(7) Finally, the slurry is subjected to solid-liquid separation and washing to obtain a carbon aerogel precursor.
Examples
(1) Adding 47.06g of phenol into 121.74g of formaldehyde aqueous solution with the mass concentration of 37%, wherein the molar ratio of the phenol to the formaldehyde is 1:3, adding 1g of sodium hydroxide, stirring and dissolving, and controlling the stirring and dissolving temperature within the range of 30-60 ℃ to obtain a mixture aqueous solution;
(2) Refluxing the mixture water solution at 90 ℃ for 6 hours and 25 minutes until the mixture water solution reaches a critical state to be solidified, then rapidly placing the mixture water solution into ice water for cooling, and stopping the reaction process to obtain a precursor water solution with a certain crosslinking degree;
(3) Adding 600ml of white oil into 6ml of surfactant span 80, and uniformly stirring at room temperature to prepare a white oil mixed solution;
(4) Naturally cooling 30ml of white oil mixed solution for standby, and heating the rest white oil mixed solution to 90 ℃;
(5) Starting an emulsion pump, regulating the rotating speed to 1000r/min, and controlling the flow ratio of the precursor aqueous solution to the white oil mixed solution for natural cooling to be 10:1, fully mixing the two materials into suspension in an emulsification pump;
(6) The suspension is discharged out of an emulsification pump and directly enters the heated white oil mixed solution to fully react with the heated white oil mixed solution, and the mixture is continuously kept at 90 ℃ to fully react for 12 hours to obtain precursor white oil slurry;
(7) Finally, the slurry is subjected to solid-liquid separation and washing to obtain a carbon aerogel precursor.
Examples
(1) Adding 47.06g of phenol into 81.16g of formaldehyde aqueous solution with the mass concentration of 37%, wherein the molar ratio of the phenol to the formaldehyde is 1:2, adding 0.5g of sodium hydroxide, stirring and dissolving, and controlling the stirring and dissolving temperature within the range of 30-60 ℃ to obtain a mixture aqueous solution;
(2) Refluxing the mixture water solution at 60 ℃ for 8 hours and 30 minutes until the mixture water solution reaches a critical state to be solidified, then rapidly placing the mixture water solution into ice water for cooling, and stopping the reaction process to obtain a precursor water solution with a certain crosslinking degree;
(3) Adding 500ml of white oil into 5ml of surfactant span 80, and uniformly stirring at room temperature to prepare a white oil mixed solution;
(4) Taking 50ml of white oil mixed solution, naturally cooling for standby, and heating the rest white oil mixed solution to 80 ℃;
(5) Starting an emulsion pump, regulating the rotating speed to 1000r/min, and controlling the flow ratio of the precursor aqueous solution to the white oil mixed solution for natural cooling to be 10:1, fully mixing the two materials into suspension in an emulsification pump;
(6) The suspension is discharged out of an emulsification pump and directly enters the heated white oil mixed solution to fully react with the heated white oil mixed solution, and the mixture is continuously kept at 80 ℃ to fully react for 15 hours to obtain precursor white oil slurry;
(7) Finally, the slurry is subjected to solid-liquid separation and washing to obtain a carbon aerogel precursor.
The tap density and specific surface area of the dried and carbonized precursor prepared in examples 1-6 were measured as follows:
table 1 comparison of examples with phenol without reflux, yield of resorcinol, tap density of carbonization, specific surface area
| Phenol (non-reflux) | Resorcinol | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | |
| Yield/% | 75.2 | 99.9 | 99.8 | 98.2 | 99.5 | 99.5 | 99.6 | 99.2 |
| Tap density g/cm 3 | 0.7273 | 0.8385 | 0.8281 | 0.8366 | 0.8577 | 0.7923 | 0.7852 | 0.8088 |
| Specific surface area m 2 /g | 2.5 | 536 | 520 | 533 | 505 | 678 | 623 | 578 |
From the table, the carbon aerogel precursor prepared by the method has high tap density and greatly improved specific surface area after being dried and carbonized. Can replace resorcinol to prepare the precursor.
Claims (4)
1. A low cost method for preparing a carbon aerogel precursor, comprising the steps of:
(1) Adding phenol into formaldehyde aqueous solution, adding a catalyst, stirring and dissolving to obtain a mixture aqueous solution, and controlling the stirring and dissolving temperature to be 30-60 ℃; the catalyst is one of potassium hydroxide, sodium hydroxide and calcium hydroxide, and the molar ratio of the phenol to the formaldehyde is controlled within the range of 1 (1.3-3.3);
(2) Refluxing the mixture aqueous solution obtained in the step (1) to a critical state to be solidified at the temperature of 55-85 ℃, controlling the refluxing time to be 1-8 hours, then rapidly placing the mixture aqueous solution in ice water for cooling, and stopping the reaction process to obtain a precursor aqueous solution with a certain crosslinking degree;
(3) Mixing a surfactant and white oil, and uniformly stirring and mixing at room temperature to prepare a white oil mixed solution; the surfactant is span 80;
(4) Naturally cooling 1.8-10.0% of the total amount of the white oil mixed solution for standby, and heating the rest white oil mixed solution to 75-105 ℃;
(5) Respectively feeding the precursor aqueous solution obtained in the step (2) and the white oil mixed solution for natural cooling in the step (4) into an emulsifying pump to be fully mixed into suspension, and controlling the flow ratio of the precursor aqueous solution to the white oil mixed solution for natural cooling to be (8-50): 1;
(6) The suspension liquid is discharged out of an emulsification pump and directly enters the heated white oil mixed liquid to fully react with the heated white oil mixed liquid, the reaction temperature is 80-95 ℃, and the reaction time is 10-30 hours, so that precursor white oil slurry is obtained;
(7) The precursor white oil slurry is subjected to solid-liquid separation and washing to obtain a carbon aerogel precursor; the washing uses any one solvent of methanol, ethanol and dichloromethane, and a mixed solvent of two or three solvents.
2. A low cost method for preparing a carbon aerogel precursor, comprising the steps of:
(1) Adding phenol into formaldehyde aqueous solution, adding a catalyst, stirring and dissolving to obtain a mixture aqueous solution, and controlling the stirring and dissolving temperature to be 30-60 ℃; the catalyst is organic base triethylamine, and the molar ratio of phenol to formaldehyde is controlled within the range of 1 (1.3-3.3);
(2) Refluxing the mixture aqueous solution obtained in the step (1) to a critical state to be solidified at the temperature of 55-85 ℃, controlling the refluxing time to be 1-8 hours, then rapidly placing the mixture aqueous solution in ice water for cooling, and stopping the reaction process to obtain a precursor aqueous solution with a certain crosslinking degree;
(3) Mixing a surfactant and white oil, and uniformly stirring and mixing at room temperature to prepare a white oil mixed solution; the surfactant is span 80;
(4) Naturally cooling 1.8-10.0% of the total amount of the white oil mixed solution for standby, and heating the rest white oil mixed solution to 75-105 ℃;
(5) Respectively feeding the precursor aqueous solution obtained in the step (2) and the white oil mixed solution for natural cooling in the step (4) into an emulsifying pump to be fully mixed into suspension, and controlling the flow ratio of the precursor aqueous solution to the white oil mixed solution to be (8-50): 1;
(6) The suspension liquid is discharged out of an emulsification pump and directly enters the heated white oil mixed liquid to fully react with the heated white oil mixed liquid, the reaction temperature is 80-95 ℃, and the reaction time is 10-30 hours, so that precursor white oil slurry is obtained;
(7) The precursor white oil slurry is subjected to solid-liquid separation and washing to obtain a carbon aerogel precursor; the washing uses any one solvent of methanol, ethanol and dichloromethane, and a mixed solvent of two or three solvents.
3. A low cost method of preparing a carbon aerogel precursor as claimed in claim 1 or claim 2, wherein: in the step (1), the molar ratio of phenol to formaldehyde is controlled to be 1 (1.5-3), and the flow ratio of the precursor aqueous solution to the white oil mixed solution in the step (5) is controlled to be (9-15): 1.
4. A method of low cost preparation of a carbon aerogel precursor as claimed in claim 3 wherein: the reflux temperature in the step (2) is controlled to be 60-80 ℃.
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