CN111994906A - Nitrogen-doped porous activated carbon material, preparation method and application - Google Patents
Nitrogen-doped porous activated carbon material, preparation method and application Download PDFInfo
- Publication number
- CN111994906A CN111994906A CN202010832919.2A CN202010832919A CN111994906A CN 111994906 A CN111994906 A CN 111994906A CN 202010832919 A CN202010832919 A CN 202010832919A CN 111994906 A CN111994906 A CN 111994906A
- Authority
- CN
- China
- Prior art keywords
- nitrogen
- activated carbon
- doped porous
- carbon material
- porous activated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 148
- 239000000463 material Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 27
- 239000012855 volatile organic compound Substances 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000004140 cleaning Methods 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000011148 porous material Substances 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 15
- 238000003763 carbonization Methods 0.000 claims abstract description 14
- 230000004913 activation Effects 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 238000009826 distribution Methods 0.000 claims abstract description 8
- 230000003213 activating effect Effects 0.000 claims abstract description 6
- 238000010000 carbonizing Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 238000001994 activation Methods 0.000 claims description 13
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 10
- 239000013543 active substance Substances 0.000 claims description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000012935 ammoniumperoxodisulfate Substances 0.000 claims description 7
- -1 nitrogen sugar alcohol Chemical class 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 4
- 230000007935 neutral effect 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
- 238000003883 substance clean up Methods 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 239000003517 fume Substances 0.000 abstract description 9
- 239000003921 oil Substances 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 238000000746 purification Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 239000007787 solid Substances 0.000 description 13
- 239000000779 smoke Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000001179 sorption measurement Methods 0.000 description 11
- 150000001299 aldehydes Chemical class 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 235000012239 silicon dioxide Nutrition 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010411 cooking Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920001661 Chitosan Polymers 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010058467 Lung neoplasm malignant Diseases 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 208000000453 Skin Neoplasms Diseases 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000008162 cooking oil Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 201000005202 lung cancer Diseases 0.000 description 1
- 208000020816 lung neoplasm Diseases 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000009656 pre-carbonization Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- XJKVPKYVPCWHFO-UHFFFAOYSA-N silicon;hydrate Chemical compound O.[Si] XJKVPKYVPCWHFO-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 201000000849 skin cancer Diseases 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000009777 vacuum freeze-drying Methods 0.000 description 1
Images
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
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/305—Addition of material, later completely removed, e.g. as result of heat treatment, leaching or washing, e.g. for forming pores
- B01J20/3057—Use of a templating or imprinting material ; filling pores of a substrate or matrix followed by the removal of the substrate or matrix
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Carbon And Carbon Compounds (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Catalysts (AREA)
Abstract
The invention provides a preparation method of a nitrogen-doped porous activated carbon material, which comprises the following steps: dissolving a template agent, a mixed carbon source and a catalyst in a solvent, and preparing a nitrogen-doped porous activated carbon material after carbonizing, template removing, cleaning, drying, activating, washing and drying; wherein the mass ratio of the template agent to the mixed carbon source to the catalyst is (9-10): (11-12): (14-15). Compared with the prior art, the preparation method provided by the invention adopts a template method to obtain the nitrogen-doped porous activated carbon material through the procedures of carbonization, template removal and activation, and has the advantages of flexible and controllable material pore diameter, uniform pore diameter distribution, higher specific surface, high nitrogen content which can reach 15-20%, and great suitability for purifying volatile organic compounds in kitchen oil fume.
Description
Technical Field
The invention relates to the field of adsorption material preparation and environmental purification, in particular to a nitrogen-doped porous activated carbon material, a preparation method and application thereof.
Background
With the rapid development of the economy of China and the increasing improvement of the living standard of people, the catering industry is rapidly developed. According to the yearbook of Beijing city statistics, the income of lodging catering industry with the quota higher than the limit is dramatically increased from 612.5 hundred million yuan in 08 years to 925.8 hundred million yuan in 2012 years, and the increase range reaches 51 percent; the number of enterprises above the quota is increased from 800 to about 1600, the rise reaches 100%, and the growth is shown year by year.
The rapid development of the catering industry greatly increases the emission of oil smoke generated in the cooking process of a kitchen. Cooking fumes of a kitchen contain a large amount of toxic and harmful substances, such as particulate matters (PM2.5, PM10), Volatile Organic Compounds (VOCs), Polycyclic Aromatic Hydrocarbons (PAHs) and the like. If these toxic and harmful substances are discharged to the air without treatment, complaints about restaurant discharge will be increased and the burden on the environment will be increased. Volatile Organic Compounds (VOCs) not only have the highest emission concentration, but also have odor which seriously affects the normal life of residents, and the purified VOCs do not react with ozone to generate secondary organic aerosol, and then are converted into PM2.5, so that haze is generated. Meanwhile, long-term exposure to oil smoke increases the risk of lung cancer and skin cancer.
Aiming at the research of the purification technology of the kitchen oil fume, the device mainly focuses on the purification technology of particulate matters and the arrangement of collection and discharge. The Chinese patent application (CN201810876511.8) adopts an electrostatic technology to treat particulate matters, thereby reducing the emission of oil smoke. Chinese patent (CN201820933880.1) adopts the mode of installing the rotatory net dish additional, purifies the oil smoke particulate matter through rotatory separation. However, these techniques do not provide effective treatment of volatile organic compounds. This is mainly because the volatile organic compounds of the cooking fumes have the following characteristics: the composition is complex and comprises a plurality of components such as alkane, alkene, aldehyde ketone and the like; the air quantity is large, and the concentration is low; many factors are affected, including cooking methods, food materials, dishes and the like, and further purification of volatile organic compounds in the cooking oil fume becomes a difficult point.
In view of the above, the chinese patent application (CN109028207A) adopts a synergistic technique of static electricity and photocatalysis to purify volatile organic compounds in oil smoke, but the method has short retention time at high wind speed, incomplete reaction, low purification efficiency, and risk of secondary pollution. Chinese patent application (CN109045740A) adopts an activated carbon filter bed to purify volatile organic compounds, but the activated carbon has low adsorption capacity for aldehyde and ketone and is easy to saturate; meanwhile, the proportion of aldehydes and ketones in the kitchen oil smoke reaches 50-80%, so that the service cycle of the conventional activated carbon is greatly shortened, and the conventional activated carbon is quickly adsorbed and saturated.
Therefore, Chinese patent application (CN102951636) provides a preparation method of nitrogen-doped chitosan-based activated carbon, which adopts chitosan as a raw material to prepare the nitrogen-doped chitosan-based activated carbon through dissolution, freeze drying and high-temperature carbonization. The invention patent application (CN104495792A) adopts a wood biomass liquefaction product as a raw material, and the wood biomass liquefaction product is mixed with mesoporous silicon dioxide, water and sulfuric acid to prepare the nitrogen-doped material after impregnation, pre-carbonization, carbonization and sintering. Compared with pure activated carbon, the nitrogen-doped activated carbon material has improved purification efficiency, but the method provided by the invention has the advantages of less raw material sources and high price, and the prepared material has low nitrogen content, and the purification efficiency is still not satisfactory, so that the method is not suitable for industrial mass production.
In addition, the invention patent application (CN105390672A) takes glucose as a carbon source and urea as a nitrogen source, adds the glucose as the carbon source and the urea as the nitrogen source into sodium chloride and sodium silicate aqueous solution with a certain mass ratio, and then obtains the three-dimensional nitrogen-doped mesoporous carbon ultrathin nanosheet through the steps of vacuum freeze drying, carbonization and the like. The Chinese patent application (CN108262077A) uses sugar as carbon source and pyridine, urea and melamine as nitrogen source to prepare high-strength monolithic catalyst, and the mixture is preferably pyridine and aniline. The two preparation methods adopt saccharides as a carbon source, although the price is low, the nitrogen content of the prepared material is 3.68-4.58%, the nitrogen content is low, the pore diameter of the material is uncontrollable, the preparation process is complicated, and the purification effect on volatile organic compounds is not obvious.
In view of the above, it is necessary to provide a technical solution to the above problems.
Disclosure of Invention
One of the objects of the present invention is: provides a preparation method of a nitrogen-doped porous activated carbon material, and solves the problems of complicated preparation process, uncontrollable material pore diameter and low nitrogen content of the existing nitrogen-doped porous activated carbon material.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a nitrogen-doped porous activated carbon material comprises the following steps: dissolving a template agent, a mixed carbon source and a catalyst in a solvent, and preparing a nitrogen-doped porous activated carbon material after carbonizing, template removing, cleaning, drying, activating, washing and drying; wherein the mass ratio of the template agent to the mixed carbon source to the catalyst is (9-10): (11-12): (14-15).
Compared with the conventional pre-oxidation-post-treatment and in-situ doping methods, the preparation method has the advantages that the preparation process is simple, the material pore diameter is easy to control, the nitrogen content of the prepared nitrogen-doped porous activated carbon material is up to 15-20% which is 3-5 times of that of the two methods, the high nitrogen content provides more adsorption sites for aldehydes in oil smoke, the adsorption capacity for the aldehydes is greatly improved, and the method is more suitable for purifying volatile organic compounds in kitchen oil smoke.
Preferably, the preparation method comprises the following steps:
s1, dissolving the template agent, the mixed carbon source and the catalyst in a solvent, drying, and then raising the temperature to 600-800 ℃ for carbonization to obtain a carbonized sample;
s2, removing a template from the carbonized sample obtained in the step S1 by using a template removing agent, and then cleaning and drying to obtain an unactivated sample;
s3, activating the unactivated sample obtained in the step S2 with an active substance at a rate of 3-5 ℃/min to 600-800 ℃ under an inert gas;
and S4, after the activation is finished, washing the activated sample, and drying to obtain the nitrogen-doped porous activated carbon material.
The inventors have found that the use of a low or medium activation temperature is more favorable for activating hydrogen atoms, which are more prone to form hydrogen bonds with the C ═ O functional groups of aldehydes; the activated carbon is doped with nitrogen atoms, the higher the nitrogen content is, the stronger the electric negativity is, the number of activated hydrogen atoms is increased, the larger the adsorption amount of aldehyde substances is, and the proportion of aldehyde ketone in the kitchen oil smoke reaches 50-80%, so that the material disclosed by the invention has a better purification effect on volatile organic matters in the kitchen oil smoke.
Preferably, the template agent is IBN-9 type silicon dioxide; the mixed carbon source comprises p-phenylenediamine and non-nitrogen sugar alcohol, wherein the mass ratio of the p-phenylenediamine to the non-nitrogen sugar alcohol is (4-5): (5-4); the catalyst is ammonium peroxodisulfate; the solvent is toluene and/or carbon tetrachloride. P-phenylenediamine is used as one of carbon sources, the p-phenylenediamine contains a benzene ring and an amino group, the benzene ring is influenced by the amino group, so that the activity of hydrogen on the ortho-para position of the amino group on the benzene ring is enhanced, the subsequent activation of hydrogen atoms is facilitated, and the reaction rate of the hydrogen atoms and C ═ O is increased; in addition, the mixed use of the two carbon sources also helps to retain nitrogen therein, and increases the nitrogen content of the nitrogen-doped porous activated carbon material.
Preferably, in step S1, the template agent, the mixed carbon source and the catalyst are dissolved in the solvent under the ultrasonic condition for 10-30 min, then dried at 80-100 ℃, then raised to 600-800 ℃ at the rate of 3-5 ℃/min under inert gas, and kept for 3-5 h, and carbonization is completed.
Preferably, in step S2, the concentration of the template removing solution is 10 to 15%, and the sample is dried at 100 to 105 ℃ after being washed, so as to obtain an unactivated sample. The template removing agent can be hydrofluoric acid or sodium hydroxide, the template removing agent is adopted for cleaning, then deionized water and ethanol are used as cleaning agents for secondary cleaning, and then the template removing agent is placed in a vacuum drying oven to be dried at the temperature of 100-105 ℃.
Preferably, in step S3, the active substance is at least one of sodium hydroxide, potassium hydroxide and calcium hydroxide, and the mass ratio of the active substance to the unactivated sample is (2-3): (1-2). Preferably, the active substance is sodium hydroxide.
Preferably, in step S3, the activation time is 1-3 h at 600-800 ℃.
Preferably, in step S4, the activated sample is washed to be neutral, and then dried at 110 to 120 ℃ to obtain the nitrogen-doped porous activated carbon material. And washing the activated sample by using hydrochloric acid, then washing the sample for the second time by using deionized water until the sample is neutral, and then drying the sample in a vacuum drying oven at 110-120 ℃ to obtain the nitrogen-doped porous activated carbon material.
The invention also aims to provide a nitrogen-doped porous activated carbon material, which is prepared by the preparation method of any one of the nitrogen-doped porous activated carbon materials, wherein the pore size distribution range of the nitrogen-doped porous activated carbon material is 1.5-2.3 nm, and the nitrogen content is 15-20%. The material has uniform pore diameter distribution, can uniformly and comprehensively adsorb volatile organic matters, and the uniformly distributed pore diameter can also increase the adsorption capacity of the nitrogen-doped activated carbon material to a greater extent so as to ensure the oil fume purification effect.
Preferably, the specific surface area of the nitrogen-doped porous activated carbon material is 920-2(ii) a pore volume of 0.73 to 0.75cm3(ii) in terms of/g. The nitrogen-doped porous activated carbon material obtained by the method has a high specific surface area which can reach 1200m2The contact area between the oil fume and the oil fume is increased during adsorption, and volatile organic matters are easier to adsorb.
The invention also aims to provide a nitrogen-doped porous activated carbon material applied to volatile organic compound purification, wherein the nitrogen-doped porous activated carbon material is the nitrogen-doped porous activated carbon material.
Preferably, the volatile organic compounds are volatile organic compounds in kitchen oil smoke.
Preferably, the volatile organic compound comprises an aldehyde ketone volatile organic compound.
Compared with the prior art, the invention has the beneficial effects that:
1) according to the preparation method provided by the invention, the nitrogen-doped porous activated carbon material is obtained by adopting a template method through the processes of carbonization, template removal and activation, the material has flexible and controllable pore diameter and uniform pore diameter distribution, has a higher specific surface and high nitrogen content which can reach 15-20%, and is very suitable for purifying volatile organic compounds in kitchen oil fume.
2) The preparation method has the advantages of simple preparation process, low cost of adopted raw materials, rich raw material sources, low activation temperature in the preparation process, strong industrial operability and suitability for industrial mass production.
3) The nitrogen-doped porous activated carbon material provided by the invention increases the active sites of the reaction, and improves the wettability and stability of the surface of the material; and the electronegativity is increased, so that the surrounding hydrogen atoms are activated to react with the volatile organic compounds, for example, the hydrogen atoms are combined with C ═ O functional groups of aldehydes to form hydrogen bonds, the hydrogen bonds are far stronger than those of the aldehyde substances, and the aldehyde substances are directly combined with the active carbon, and the purification rate of the volatile organic compounds is improved.
Drawings
FIG. 1 is N of Nitrogen-doped porous activated carbon in example 12Adsorption characteristic curve chart.
FIG. 2 is a graph showing the breakthrough of hexanal adsorbed by nitrogen-doped porous activated carbon in example 1 and conventional activated carbon in comparative example 1.
Detailed Description
In order to make the technical solutions and advantages of the present invention clearer, the present invention and its advantages will be described in further detail below with reference to the following detailed description and the accompanying drawings, but the embodiments of the present invention are not limited thereto.
Example 1
100mg of IBN-9 type silica, 60mg of p-phenylenediamine, 60mg of nitrogen-free glucitol and 150mg of ammonium peroxodisulfate were weighed respectively and mixed in 200ml of a toluene solution, and the mixed solution was subjected to ultrasonic treatment for 10min and then stirred and dried at 80 ℃. The resulting solid was heated to 600 ℃ at 3 ℃/min under nitrogen and held for 5 hours. Cleaning the carbonized solid by using 10% HF solution to remove the silicon dioxide template agent; and then respectively washing the sample for 3 times by using deionized water and ethanol, and drying the washed sample in a vacuum drying oven at 100 ℃. After cleaning, 87mg of an unactivated sample is obtained, the sample and 175mg of NaOH are mixed and ground, then the sample is heated to 600 ℃ at the speed of 3 ℃/min and is kept for 1h, then the sample is cooled to the room temperature, 1M hydrochloric acid is used for cleaning for 3 times, and deionized water is used for cleaning until the pH value of the solution is 7, so that the nitrogen-doped porous activated carbon material is obtained.
Example 2
90mg of IBN-9 type silica, 55mg of p-phenylenediamine, 60mg of nitrogen-free glucitol and 145mg of ammonium peroxodisulfate were weighed respectively and mixed in 200ml of a carbon tetrachloride solution, and the mixed solution was subjected to ultrasonic treatment for 20min and then stirred and dried at 80 ℃. The resulting solid was heated to 800 ℃ at 5 ℃/min under nitrogen and held for 3 hours. And (3) cleaning the carbonized solid by using 15% HF solution to remove the silicon dioxide template agent. Then, the sample is washed for 3 times by using deionized water and ethanol respectively, and the washed sample is placed in a vacuum drying oven to be dried at the temperature of 105 ℃. And (3) obtaining 80mg of an unactivated sample after cleaning, mixing and grinding the sample and 160mg of NaOH, heating to 800 ℃ at the speed of 5 ℃/min, keeping the temperature for 1h, cooling to room temperature, cleaning for 3 times by using 1M hydrochloric acid, and cleaning by using deionized water until the pH value of the solution is 7 to obtain the nitrogen-doped porous activated carbon material.
Example 3
50mg of IBN-9 type silica, 28mg of p-phenylenediamine, 30mg of nitrogen-free glucitol and 75mg of ammonium peroxodisulfate were weighed out respectively and mixed in 100ml of a toluene solution, and the mixed solution was subjected to ultrasonic treatment for 10min, followed by stirring and drying at 90 ℃. The resulting solid was heated to 600 ℃ at 5 ℃/min under nitrogen and held for 3 hours. And (3) cleaning the carbonized solid by using 15% HF solution to remove the silicon dioxide template agent. And then respectively washing the sample for 3 times by using deionized water and ethanol, and drying the washed sample in a vacuum drying oven at 100 ℃. After cleaning, 35mg of an unactivated sample is obtained, the sample is mixed and ground with 70mg of NaOH, then heated to 700 ℃ at the speed of 5 ℃/min and kept for 1h, then cooled to room temperature, cleaned for 3 times with 1M hydrochloric acid, and cleaned with distilled water until the pH of the solution is 7, and the nitrogen-doped porous activated carbon material is obtained.
Example 4
Different from example 1 is the carbonization process, the obtained solid is heated to 800C at 5 ℃/min under nitrogen atmosphere and kept for 5 hours.
The rest is the same as embodiment 1, and the description is omitted here.
Example 5
In contrast to example 1, the activation process was followed by milling the unactivated sample with 175mg NaOH, followed by heating to 800 ℃ at 5 ℃/min for 3 h.
The rest is the same as embodiment 1, and the description is omitted here.
Example 6
Different from example 1, which is a carbonization process and an activation process, the obtained solid was heated to 800 ℃ at 5 ℃/min under an atmosphere of nitrogen and maintained for 5 hours. Cleaning the carbonized solid by using 10% HF solution to remove the silicon dioxide template agent; and then respectively washing the sample for 3 times by using deionized water and ethanol, and drying the washed sample in a vacuum drying oven at 100 ℃. After washing, 87mg of an unactivated sample was obtained, which was mixed with 175mg of NaOH and ground, and then heated to 800 ℃ at 5 ℃/min for 3 h.
The rest is the same as embodiment 1, and the description is omitted here.
Example 7
Different from example 2 is the content of the templating agent, the mixed carbon source and the catalyst. 90mg of silicon dioxide of the IBN-9 type, 28mg of p-phenylenediamine, 30mg of nitrogen-free glucitol and 75mg of ammonium peroxodisulfate.
The rest is the same as embodiment 2, and the description is omitted here.
Example 8
Different from example 3 is the content of the templating agent, the mixed carbon source and the catalyst. 50mg of silicon dioxide of the IBN-9 type, 55mg of p-phenylenediamine, 60mg of azosugar alcohol and 145mg of ammonium peroxodisulfate.
The rest is the same as embodiment 3, and the description is omitted here.
Example 9
Different from example 2 is a carbonization process and an activation process, and the obtained solid was heated to 600 ℃ at 3 ℃/min under an atmosphere of nitrogen and maintained for 5 hours. Cleaning the carbonized solid by using 10% HF solution to remove the silicon dioxide template agent; and then respectively washing the sample for 3 times by using deionized water and ethanol, and drying the washed sample in a vacuum drying oven at 100 ℃. After washing, 87mg of an unactivated sample was obtained, which was mixed and ground with 160mg of NaOH and then heated to 600 ℃ at 3 ℃/min for 3 h.
The rest is the same as embodiment 2, and the description is omitted here.
Example 10
Different from example 3, which is a carbonization process and an activation process, the obtained solid was heated to 600 ℃ at 3 ℃/min under an atmosphere of nitrogen and maintained for 5 hours. Cleaning the carbonized solid by using 10% HF solution to remove the silicon dioxide template agent; and then respectively washing the sample for 3 times by using deionized water and ethanol, and drying the washed sample in a vacuum drying oven at 100 ℃. After washing, 87mg of an unactivated sample was obtained, which was mixed and ground with 70mg of NaOH, and then heated to 800 ℃ at 5 ℃/min for 3 hours.
The rest is the same as embodiment 3, and the description is omitted here.
Comparative example 1
This comparative example is a conventional activated carbon.
The nitrogen-doped porous activated carbon material prepared in example 1 was subjected to isothermal adsorption curve and pore size distribution test, and the results are shown in fig. 1.
The results in FIG. 1 show that it has a high specific surface area of 1170m2Is/g, and the pore size distribution is uniform.
The nitrogen-doped porous activated carbon material prepared in example 1 and the conventional activated carbon in comparative example 1 were subjected to filtration performance and dirt holding capacity tests of characteristic hexanal in lampblack, and the results are shown in fig. 2.
The results in fig. 2 show that the initial filtration efficiency of the nitrogen-doped porous activated carbon material of the invention on hexanal can reach 82%, which is at least 12% higher than that of the conventional activated carbon; the nitrogen-doped porous activated carbon material provided by the invention has a dirt holding capacity of 60.2mg/g for hexanal, which is 2 times of the dirt holding capacity of the conventional activated carbon.
Similarly, the nitrogen-doped porous activated carbon materials prepared in the embodiments 2 to 10 were subjected to an isothermal adsorption curve and a pore size distribution test, and the nitrogen-doped porous activated carbon materials in the embodiments 2 to 3 were applied to a filter, and the purification rate of the oil smoke VOCs was tested at 30 ppm. The results are shown in Table 1.
Specific surface area (m)2/g) | Content of nitrogen element | Purification rate of VOCs | |
Example 2 | 1035 | 16.3% | 85% |
Example 3 | 980 | 17.2% | 85% |
Example 4 | 1026 | 16.9% | 84% |
Example 5 | 1049 | 16.1% | 83% |
Example 6 | 978 | 15.2 | 83% |
Example 7 | 760 | 9.2% | 62% |
Example 8 | 750 | 10.1% | 69% |
Example 9 | 992 | 15.8% | 84% |
Example 10 | 968 | 16.1% | 83% |
According to the test results, the nitrogen-doped porous activated carbon material prepared by the invention has a good purification effect on volatile organic compounds, and particularly has an adsorption effect on aldehyde and ketone substances. However, in the preparation process of the material, the content ratio of the carbon source to the catalyst and the like should be well regulated and controlled, and the preparation conditions of carbonization and activation should be well controlled, so as to prepare the nitrogen-doped porous activated carbon material with excellent purification effect on volatile organic compounds.
Variations and modifications to the above-described embodiments may become apparent to those skilled in the art from the disclosure and teachings of the above description. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (10)
1. A preparation method of a nitrogen-doped porous activated carbon material is characterized by comprising the following steps: dissolving a template agent, a mixed carbon source and a catalyst in a solvent, and preparing a nitrogen-doped porous activated carbon material after carbonizing, template removing, cleaning, drying, activating, washing and drying; wherein the mass ratio of the template agent to the mixed carbon source to the catalyst is (9-10): (11-12): (14-15).
2. The method of claim 1, comprising the steps of:
s1, dissolving the template agent, the mixed carbon source and the catalyst in a solvent, drying, and then raising the temperature to 600-800 ℃ for carbonization to obtain a carbonized sample;
s2, removing a template from the carbonized sample obtained in the step S1 by using a template removing agent, and then cleaning and drying to obtain an unactivated sample;
s3, activating the unactivated sample obtained in the step S2 with an active substance at a rate of 3-5 ℃/min to 600-800 ℃ under an inert gas;
and S4, after the activation is finished, washing the activated sample, and drying to obtain the nitrogen-doped porous activated carbon material.
3. The method of claim 2, wherein the templating agent is IBN-9 type silica; the mixed carbon source comprises p-phenylenediamine and non-nitrogen sugar alcohol, wherein the mass ratio of the p-phenylenediamine to the non-nitrogen sugar alcohol is (4-5): (5-4); the catalyst is ammonium peroxodisulfate; the solvent is toluene and/or carbon tetrachloride.
4. The preparation method according to claim 2, wherein in step S1, the template, the mixed carbon source and the catalyst are dissolved in the solvent under ultrasonic conditions for 10-30 min, and then dried at 80-100 ℃, and then heated to 600-800 ℃ at a rate of 3-5 ℃/min under inert gas, and kept for 3-5 h, thereby completing carbonization.
5. The preparation method according to claim 2, wherein in step S2, the concentration of the template removing agent solution is 10-15%, and the sample is dried at 100-105 ℃ after being washed to obtain an unactivated sample.
6. The preparation method according to claim 2, wherein in step S3, the active substance is at least one of sodium hydroxide, potassium hydroxide and calcium hydroxide, and the mass ratio of the active substance to the unactivated sample is (2-3): (1-2).
7. The method as claimed in claim 2, wherein the activation time at 600-800 ℃ in step S3 is 1-3 h.
8. The preparation method according to claim 2, wherein in step S4, the activated sample is washed to be neutral and then dried at 110-120 ℃ to obtain the nitrogen-doped porous activated carbon material.
9. The nitrogen-doped porous activated carbon material is characterized by being prepared by the preparation method of the nitrogen-doped porous activated carbon material according to any one of claims 1 to 8, wherein the pore size distribution range of the nitrogen-doped porous activated carbon material is 1.5-2.3 nm, and the nitrogen content is 15-20%.
10. A nitrogen-doped porous activated carbon material applied to volatile organic compound purification, characterized in that the nitrogen-doped porous activated carbon material is the nitrogen-doped porous activated carbon material according to claim 9.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010832919.2A CN111994906A (en) | 2020-08-18 | 2020-08-18 | Nitrogen-doped porous activated carbon material, preparation method and application |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010832919.2A CN111994906A (en) | 2020-08-18 | 2020-08-18 | Nitrogen-doped porous activated carbon material, preparation method and application |
Publications (1)
Publication Number | Publication Date |
---|---|
CN111994906A true CN111994906A (en) | 2020-11-27 |
Family
ID=73472617
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010832919.2A Pending CN111994906A (en) | 2020-08-18 | 2020-08-18 | Nitrogen-doped porous activated carbon material, preparation method and application |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111994906A (en) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107128918A (en) * | 2017-05-26 | 2017-09-05 | 桂林电子科技大学 | A kind of preparation and its application of N doping porous active Carbon Materials |
CN107217482A (en) * | 2017-07-10 | 2017-09-29 | 西安科技大学 | A kind of polyaniline hybridized electrode materials of nitrogen-phosphor codoping porous carbon membrane@with interface covalent linkage and preparation method thereof |
CN110683541A (en) * | 2019-11-27 | 2020-01-14 | 天津合众汇能科技有限公司 | Method for preparing double electric layer capacitor activated carbon by template method |
-
2020
- 2020-08-18 CN CN202010832919.2A patent/CN111994906A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107128918A (en) * | 2017-05-26 | 2017-09-05 | 桂林电子科技大学 | A kind of preparation and its application of N doping porous active Carbon Materials |
CN107217482A (en) * | 2017-07-10 | 2017-09-29 | 西安科技大学 | A kind of polyaniline hybridized electrode materials of nitrogen-phosphor codoping porous carbon membrane@with interface covalent linkage and preparation method thereof |
CN110683541A (en) * | 2019-11-27 | 2020-01-14 | 天津合众汇能科技有限公司 | Method for preparing double electric layer capacitor activated carbon by template method |
Non-Patent Citations (1)
Title |
---|
郭丹丹: "氮掺杂多孔碳材料的制备及其在超级电容器上的应用", 《中国优秀博硕士学位论文全文数据库(硕士)工程科技I辑》 * |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN110813240B (en) | Preparation method and application of ultrahigh-performance biomass-based banana peel oriented activated carbon VOCs adsorbent | |
CN110935280B (en) | Nitrogen-doped mesoporous bamboo-based biochar and application thereof | |
JP2013539411A (en) | Multi-aperture carbon particle air purifier and method for producing the same | |
CN114259978B (en) | Preparation process of efficient coal-fired flue gas mercury removal adsorbent and product thereof | |
CN109174151A (en) | One kind is for three-dimensional porous boron nitride composite of air cleaning and preparation method thereof | |
CN107684916B (en) | Monolithic catalyst using carbonized wood as carrier for removing formaldehyde at low temperature and preparation method thereof | |
CN108816190B (en) | Alumina-activated carbon composite material and preparation method thereof | |
CN110237808A (en) | A kind of silylating reagent method of Y molecular sieve | |
CN113231020A (en) | Activated carbon with improved adsorption efficiency and preparation method thereof | |
CN109967033A (en) | A kind of modified rice husk biomass carbon and preparation method thereof | |
CN112642394A (en) | Preparation method of honeycomb zeolite molecular sieve adsorbent | |
CN109082880B (en) | Functional activated carbon fiber, preparation method and application thereof | |
CN106044744A (en) | Preparation method and application of graphene-lignin-based composite hierarchical pore carbon plate material | |
CN113713768B (en) | High-temperature-resistant active carbon composite adsorbent and preparation method and application thereof | |
CN107486148B (en) | Preparation method of niobium modified activated carbon, product and application thereof | |
CN110538553A (en) | Preparation method of tourmaline-based negative ion air purification functional composite filter material | |
CN116272860B (en) | VOCs treated regenerated activated carbon and preparation method thereof | |
CN111994906A (en) | Nitrogen-doped porous activated carbon material, preparation method and application | |
CN101698483A (en) | Lanthanum-doped mesoporous silica, preparation method and application thereof as additives of filter tip | |
CN111298761B (en) | Modified sepiolite adsorbent and preparation method and application thereof | |
CN114887655B (en) | Nanometer NiO-VO X /TiO 2 Molecular sieve composite catalyst and preparation method and application thereof | |
CN103537259A (en) | Novel organic waste gas adsorption material and preparation method thereof | |
CN109772146B (en) | Air purification material and preparation method and application thereof | |
CN112058228A (en) | Formaldehyde scavenging agent and preparation method thereof | |
CN114146698A (en) | Regeneration method of silica gel particles in solid adsorbent tube |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201127 |