CN111591978A - Preparation method for preparing graphene air filter element on large scale - Google Patents
Preparation method for preparing graphene air filter element on large scale Download PDFInfo
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- CN111591978A CN111591978A CN202010474585.6A CN202010474585A CN111591978A CN 111591978 A CN111591978 A CN 111591978A CN 202010474585 A CN202010474585 A CN 202010474585A CN 111591978 A CN111591978 A CN 111591978A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 6
- 239000010439 graphite Substances 0.000 claims abstract description 6
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 5
- 238000004821 distillation Methods 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000007787 solid Substances 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000011550 stock solution Substances 0.000 description 8
- 239000004964 aerogel Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000002135 nanosheet Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000011007 phosphoric acid Nutrition 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 208000025721 COVID-19 Diseases 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 206010035664 Pneumonia Diseases 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Classifications
-
- 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
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/0001—Making filtering elements
-
- 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
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
Abstract
The invention provides a preparation method for preparing graphene air filter elements in large batch, which comprises the following steps: step 1: mixing graphite and potassium permanganate, adding concentrated sulfuric acid and concentrated phosphoric acid, and reacting for 5-8 hours under the heating condition of 60-90 ℃; step 2: adding ice blocks into the mixed solution obtained in the step 1; and step 3: then adding hydrogen peroxide solution; and 4, step 4: repeatedly centrifuging and rinsing the obtained product with water and ethanol for 3-5 times; and 5: forcibly cooling the solution by using liquid nitrogen or solid carbon dioxide; step 6: and treating by a reduced pressure heating distillation mode to obtain the porous graphene air gel filter element. According to the preparation method for preparing the graphene air filter element on a large scale, the problem of single source of related filter element products is solved by using the preparation process of the filter element taking graphene as a raw material, and the preparation method has the advantages of simple process flow, low production cost, environment-friendly preparation process and the like while ensuring the air filtering quality.
Description
Technical Field
The invention relates to the technical field of air filtration, in particular to a preparation method for preparing graphene air filter elements in a large scale.
Background
Because the hidden trouble of the novel coronary pneumonia (COVID-19) is still in existence, and safe and orderly reworking production is carried out in most areas in China at present, the filtration and purification of air through air filtering equipment such as a mask or an air filter is an effective way for preventing the spread of the new coronary viruses. The raw material of the filter element based on the non-woven fabric as the raw material is single, so that the supply of related products generates unstable influence.
The liquid-phase reduction self-assembly technology is utilized to self-assemble the graphene into the graphene aerogel with the three-dimensional network structure, so that the aims of relieving the stacking trend among graphene sheets, enhancing the integral mechanical compression strength of the material, improving the specific surface area of the material and the like can be achieved.
Disclosure of Invention
In view of the above-mentioned problems of difficulty in large-scale production of aerogel and large material consumption, the present invention provides an improved process for preparing graphene oxide and an in-situ aerogel filter element, wherein the material consumption is reduced to 5%, and the related aerogel filter element has the capability of filtering PM2.5 and PM10 in air at high speed.
The specific technical scheme is as follows:
a preparation method for preparing graphene air filter elements in a large scale comprises the following steps:
step 1: mixing graphite and potassium permanganate, adding concentrated sulfuric acid and concentrated phosphoric acid, and reacting for 5-8 hours under the heating condition of 60-90 ℃;
step 2: adding ice blocks into the mixed solution obtained in the step 1;
and step 3: then adding hydrogen peroxide solution;
and 4, step 4: repeatedly centrifuging and rinsing the obtained product with water and ethanol for 3-5 times;
and 5: forcibly cooling the solution by using liquid nitrogen or solid carbon dioxide;
step 6: and treating by a reduced pressure heating distillation mode to obtain the porous graphene air gel filter element.
Further, in the step 1, the mass ratio of the graphite to the potassium permanganate mixture is 1: 3; the volume ratio of concentrated sulfuric acid to concentrated phosphoric acid is 5-15: 1.
In the step 2, the ice blocks and the mixed solution are added according to the volume ratio of 2: 1.
In the step 5, the forced cooling is freezing for 12-18 h at the temperature of-60 to-70 ℃, and the forced cooling medium is liquid nitrogen or dry ice.
In the step 6, the reduced pressure heating distillation mode conditions are that drying is carried out in a freeze dryer, the temperature of a cold trap is not higher than-68 ℃, the air pressure of a vacuum environment is not higher than 20Pa, and the drying is continuously carried out for 8-12 hours.
According to the preparation method for preparing the graphene air filter element on a large scale, the problem of single source of related filter element products is solved by using the preparation process of the filter element taking graphene as a raw material, and the preparation method has the advantages of simple process flow, low production cost, environment-friendly preparation process and the like while ensuring the air filtering quality.
Due to the ultrahigh surface area of the graphene oxide nano sheet and the wide chemical property, the graphene oxide nano sheet has a wide application prospect in the aspects of water treatment and air treatment. However, the two-dimensional film corresponding to the graphene oxide has a barrier property, air and water cannot be filtered quickly and effectively, the effective specific surface area is reduced due to the superposition of the nano sheets, and the effective area for air and water treatment is reduced. The invention discloses that two-dimensional graphene oxide nanosheets are quickly self-assembled into a three-dimensional porous structure to serve as an air filter element, so that the effective specific surface area is increased to 5000m2Has excellent air permeability and excellent PM2,5 and PM10 filtering effects.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the method provided by the invention, the three-dimensional gel material taking the graphene oxide as the framework has the advantages of high strength, low quality and the like, particularly, the air permeability is improved, and the air resistance in unit area is lower than 20Pa and is far lower than the limit of related products in China.
(2) The method provided by the invention has the advantages that the surface charges and a large number of three-dimensional pore canals greatly improve the filtering effect of PM2.5 and PM10 in the air, and the related synthesis process is green and environment-friendly.
(3) Compared with the prior art, the method provided by the invention greatly shortens the process flow and reduces the production cost.
Drawings
Fig. 1 is one of electron micrographs of a graphene air filter obtained in the example;
fig. 2 is a second electron microscope photograph of the graphene air filter obtained in the example;
fig. 3 shows the test results of the graphene air filter element obtained in the example for filtering high-concentration flue gas continuously and repeatedly.
Detailed Description
The following examples are described in detail.
Firstly, graphene synthesis:
1. raw materials: to a mixture of flake graphite (5g) and potassium permanganate (30g) was slowly added a 9:1 mixture of H2SO4/H3PO4(600:66.7mL) with thorough stirring with a glass rod during the addition.
2. Pretreatment: and (3) putting the stirred solution into a water bath kettle, wherein the water bath temperature is 60 ℃, and adding magnetons to stir the solution in a vortex shape for 10 hours.
If the colloid is viscous in the treatment process and the stirring is not dynamic, the next operation can be directly carried out; the water quantity of the water bath kettle is noticed during the stirring process, and a warning sign is pasted.
3. Diluting: and putting the treated stock solution into the central position of an ice block for ice bath, and adding the ice block for dilution until the volume of the stock solution is about twice that of the stock solution. When the stock solution is more, the stock solution needs to be divided into two parts for treatment.
4. And (3) oxidation: after the ice bath cooling is finished, slowly adding a 30% hydrogen peroxide solution drop by drop, oxidizing, dropping until the solution changes from purple red to orange yellow, ending the titration after slight excess, and stirring the whole process.
5. Washing:
(1) and respectively filling the oxidized solution into centrifuge tubes, wherein the solution in each centrifuge tube is about 60ml, weighing the centrifuge tubes in a tray balance with the same weight, putting the centrifuge tubes into a centrifuge for centrifugation at the rotation speed of 5000rpm/min for 5min, pouring the supernatant into a waste liquid tank after centrifugation, and rinsing the supernatant with deionized water.
(2) Then add concentrated hydrochloric acid and water in a volume ratio of 1:2 into the centrifuge tube to make the solution 30ml, shake to dissolve the solution completely, and pour into another clean beaker.
(3) The liquid after washing the hydrochloric acid solution is respectively added into a centrifuge tube, about 30ml of the liquid is added, 40ml of ethanol is added, the volume of the solution is about 70ml, the solution is placed into a tray balance with a cover, and the solution is weighed, so that the mass is basically consistent. The precipitate was rinsed with deionized water in the same centrifuge.
(4) Adding deionized water to make the volume of the solution be 30ml, fully shaking to completely dissolve the solution, pouring the solution into a new beaker, measuring the pH of the solution to make the pH of the solution be about 4, and stopping the operation, otherwise, repeating the last step, rinsing with water, adding water for centrifugation, wherein the pH is close to neutral and optimal, and the lowest limit of the pH can be controlled to be 4 so as to reduce loss.
6. And placing the processed GO stock solution into a sample bottle, shaking uniformly for about 4 hours, measuring the concentration, and storing for later use.
Secondly, preparing the graphene aerogel:
1. and (3) diluting the GO stock solution obtained in the step (a) to the required concentration, and then putting the diluted GO stock solution into a glass container.
2. And (3) freezing the glass container filled with the GO solution at the temperature of-60 to-70 ℃ for 12 to 18 hours.
3. And transferring the frozen glass container filled with the GO solution to a freeze dryer for drying, wherein the temperature of a cold trap is not higher than-68 ℃, the air pressure of a vacuum environment is not higher than 20Pa, and the heating temperature is not higher than 60 ℃.
4. And continuously drying for 8-12 h, and taking out to obtain the graphene aerogel with the corresponding density.
The obtained graphene aerogel is used as a graphene air filter element, electron microscope photos are shown in fig. 1 and fig. 2, and the comparison result of simulating the high-concentration PM concentration filtering effect by using smoke is shown in fig. 3.
Claims (5)
1. A preparation method for preparing graphene air filter elements in a large scale is characterized by comprising the following steps:
step 1: mixing graphite and potassium permanganate, adding concentrated sulfuric acid and concentrated phosphoric acid, and reacting for 5-8 hours under the heating condition of 60-90 ℃;
step 2: adding ice blocks into the mixed solution obtained in the step 1;
and step 3: then adding hydrogen peroxide solution;
and 4, step 4: repeatedly centrifuging and rinsing the obtained product with water and ethanol for 3-5 times;
and 5: forcibly cooling the solution by using liquid nitrogen or solid carbon dioxide;
step 6: and treating by a reduced pressure heating distillation mode to obtain the porous graphene air gel filter element.
2. The method for preparing the graphene air filter element in large batch according to claim 1, wherein in the step 1, the mass ratio of the mixture of the graphite and the potassium permanganate is 1: 3; the volume ratio of concentrated sulfuric acid to concentrated phosphoric acid is 5-15: 1.
3. The method for preparing the graphene air filter element in large scale according to claim 1, wherein in the step 2, the ice blocks and the mixed solution are added according to a volume ratio of 2: 1.
4. The method for preparing the graphene air filter element in large batch according to claim 1, wherein in the step 5, the forced cooling is performed at a temperature of-60 to-70 ℃ for 12 to 18 hours.
5. The method for preparing a large number of graphene air filter elements according to claim 1, wherein in the step 6, the reduced pressure heating distillation is performed in a freeze dryer under conditions that the temperature of a cold trap is not higher than-68 ℃, the pressure of a vacuum environment is not higher than 20Pa, and the drying is continued for 8-12 hours.
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| CN202010474585.6A CN111591978A (en) | 2020-05-29 | 2020-05-29 | Preparation method for preparing graphene air filter element on large scale |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104401977A (en) * | 2014-10-28 | 2015-03-11 | 同济大学 | Preparation method of graphene aerogel and graphene-carbon nanotube aerogel |
| CN106044752A (en) * | 2016-05-27 | 2016-10-26 | 江苏省特种设备安全监督检验研究院 | Method for preparing high orientation graphene aerogel |
| CN106629681A (en) * | 2016-12-27 | 2017-05-10 | 东南大学 | Preparation method of graphene foam |
| CN108147401A (en) * | 2018-01-12 | 2018-06-12 | 昂星新型碳材料常州有限公司 | The preparation method of graphene aerogel powder and graphene aerogel powder |
| CN108394897A (en) * | 2018-05-25 | 2018-08-14 | 清华-伯克利深圳学院筹备办公室 | A kind of magnanimity preparation method of porous oxidation graphene |
-
2020
- 2020-05-29 CN CN202010474585.6A patent/CN111591978A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104401977A (en) * | 2014-10-28 | 2015-03-11 | 同济大学 | Preparation method of graphene aerogel and graphene-carbon nanotube aerogel |
| CN106044752A (en) * | 2016-05-27 | 2016-10-26 | 江苏省特种设备安全监督检验研究院 | Method for preparing high orientation graphene aerogel |
| CN106629681A (en) * | 2016-12-27 | 2017-05-10 | 东南大学 | Preparation method of graphene foam |
| CN108147401A (en) * | 2018-01-12 | 2018-06-12 | 昂星新型碳材料常州有限公司 | The preparation method of graphene aerogel powder and graphene aerogel powder |
| CN108394897A (en) * | 2018-05-25 | 2018-08-14 | 清华-伯克利深圳学院筹备办公室 | A kind of magnanimity preparation method of porous oxidation graphene |
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Application publication date: 20200828 |