CN109985601B - Activated carbon fiber adsorbent for adsorbing volatile organic compounds and preparation method thereof - Google Patents
Activated carbon fiber adsorbent for adsorbing volatile organic compounds and preparation method thereof Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 239000003463 adsorbent Substances 0.000 title claims abstract description 46
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 59
- 238000001179 sorption measurement Methods 0.000 claims abstract description 44
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 42
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 30
- 239000002243 precursor Substances 0.000 claims description 44
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 41
- 229910052698 phosphorus Inorganic materials 0.000 claims description 41
- 239000011574 phosphorus Substances 0.000 claims description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 28
- 239000011259 mixed solution Substances 0.000 claims description 23
- 239000004094 surface-active agent Substances 0.000 claims description 21
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 15
- -1 phenolic aldehyde Chemical class 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 9
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 229920005610 lignin Polymers 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 5
- 239000010426 asphalt Substances 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 5
- 150000003904 phospholipids Chemical class 0.000 claims description 4
- HAMFTKGWBFNGRM-UHFFFAOYSA-N C1=CC=CC=C1.P(=O)(N)(N)N Chemical compound C1=CC=CC=C1.P(=O)(N)(N)N HAMFTKGWBFNGRM-UHFFFAOYSA-N 0.000 claims description 3
- 239000003876 biosurfactant Substances 0.000 claims description 3
- 239000002563 ionic surfactant Substances 0.000 claims description 3
- 239000002736 nonionic surfactant Substances 0.000 claims description 3
- NBSCHQHZLSJFNQ-GASJEMHNSA-N D-Glucose 6-phosphate Chemical compound OC1O[C@H](COP(O)(O)=O)[C@@H](O)[C@H](O)[C@H]1O NBSCHQHZLSJFNQ-GASJEMHNSA-N 0.000 claims description 2
- VFRROHXSMXFLSN-UHFFFAOYSA-N Glc6P Natural products OP(=O)(O)OCC(O)C(O)C(O)C(O)C=O VFRROHXSMXFLSN-UHFFFAOYSA-N 0.000 claims description 2
- VFRROHXSMXFLSN-SLPGGIOYSA-N aldehydo-D-glucose 6-phosphate Chemical compound OP(=O)(O)OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O VFRROHXSMXFLSN-SLPGGIOYSA-N 0.000 claims description 2
- MCWXGJITAZMZEV-UHFFFAOYSA-N dimethoate Chemical compound CNC(=O)CSP(=S)(OC)OC MCWXGJITAZMZEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 abstract description 27
- 239000011248 coating agent Substances 0.000 abstract description 12
- 238000000576 coating method Methods 0.000 abstract description 12
- 150000002576 ketones Chemical class 0.000 abstract description 7
- 150000001299 aldehydes Chemical class 0.000 abstract description 5
- 125000004122 cyclic group Chemical group 0.000 abstract description 5
- 238000003795 desorption Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 229920006395 saturated elastomer Polymers 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 11
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 10
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 10
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 8
- 229920002239 polyacrylonitrile Polymers 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229920000297 Rayon Polymers 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 3
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 125000005233 alkylalcohol group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 1
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- 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
- B01D53/04—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 with stationary adsorbents
-
- 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
-
- 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
- B01J20/28014—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 form
- B01J20/28023—Fibres or filaments
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention provides an activated carbon fiber adsorbent for adsorbing volatile organic compounds, which comprises the following components in percentage by weight: 1-30% of phosphorus-doped nitrogen carbide and 70-99% of activated carbon fiber. The invention further provides a preparation method of the active carbon fiber adsorbent for volatile organic compound adsorption. The activated carbon fiber adsorbent for adsorbing volatile organic compounds and the preparation method thereof can prepare the phosphorus-doped nitrogen carbide coating with higher activity, improve the adsorption and desorption efficiency of aldehyde and ketone volatile organic compounds, and greatly improve the cyclic adsorption performance of the adsorbent.
Description
Technical Field
The invention belongs to the technical field of environmental pollution treatment, relates to an activated carbon fiber adsorbent for volatile organic compound adsorption and a preparation method thereof, and particularly relates to a phosphorus-doped nitrogen carbide modified activated carbon fiber adsorbent for volatile organic compound adsorption and a preparation method thereof.
Background
Volatile Organic Compounds (VOCs) are organic compounds having a saturated vapor pressure of more than 70Pa at normal temperature and a boiling point of 260 ℃ or less at normal pressure, such as many benzene series, hydrocarbons, alcohols, and the like, and are common pollutants in the atmospheric environment. In modern industries, enterprises such as chemical industry, petrochemical industry, pharmacy, electronics, chemical fiber, rubber, paint and the like, and technical processes such as printing, coating, painting and the like all relate to the generation and emission of VOCs waste gas, wherein benzene series has strong three-cause effects (mutation, carcinogenesis and teratogenesis), has great harm to ecological environment and human health, and needs to be monitored and treated.
Activated Carbon Fiber (ACF) is a novel carbon adsorption material developed by combining carbon fiber technology and activated carbon technology, and compared with the traditional granular activated carbon (Granular activated carbon), the Activated Carbon Fiber (ACF) has the characteristics of large specific surface area, developed micropores, narrow pore size distribution, high adsorption speed, strong adsorption capacity, easy regeneration and the like. In order to improve the adsorption capacity of the activated carbon fiber to atmospheric pollutants to the maximum extent, a series of modification work of the activated carbon fiber is carried out at home and abroad.
Document 1(Zhang et al, Journal of the American Chemical Society, 2010, 132, p. 6294 to 6295) reports a hexafluorophosphoric acid type ionic liquid (Bmim-PF) comprising 1-butyl-3 methyl-imidazole 6 ) As a phosphorus-containing additive, with dicyandiamide to obtain a series of phosphorus-modified nitrogen carbides (g-C) 3 N 4 ) The content of phosphorus element in the material can reach 3.5 percent at most. Document 2 (wangyongfang et al, journal of physics and chemistry, 2016, vol. 32, 2 nd, pages 481-492) reports that different types of phosphorus-containing activated carbon prepared by phosphoric acid activation modification has a maximum content of phosphorus element of only 5.8%. Further improving the content of phosphorus is the key to optimize the adsorption performance of the phosphorus-modified activated carbon, and researches on the application of the phosphorus-doped nitrogen carbide-modified activated carbon fiber in adsorbing volatile organic compounds still have been rarely reported.
Disclosure of Invention
In view of the above disadvantages of the prior art, the present invention aims to provide an activated carbon fiber adsorbent which is economical, energy-saving, green and environment-friendly, and a preparation method thereof, so as to achieve extremely high adsorption and desorption efficiency and excellent cyclic adsorption performance for aldehyde and ketone volatile organic compounds.
In order to achieve the above and other related objects, the present invention provides an activated carbon fiber adsorbent for volatile organic compound adsorption, comprising the following components by weight:
1 to 30 percent of phosphorus-doped nitrogen carbide,
70-99% of activated carbon fiber.
Preferably, the activated carbon fiber adsorbent for adsorbing volatile organic compounds comprises the following components in percentage by weight:
5 to 20 percent of phosphorus-doped nitrogen carbide,
80-95% of activated carbon fiber.
Preferably, in the phosphorus-doped nitrogen carbide, the doping amount of the phosphorus element in the nitrogen carbide is 1-30 wt%. The phosphorus-doped nitrogen carbide is obtained by reacting a phosphorus-containing precursor with a nitrogen-containing precursor.
Preferably, the activated carbon fiber is selected from one of a glue-based activated carbon fiber, a Polyacrylonitrile (PAN) -based activated carbon fiber, a phenol-formaldehyde-based activated carbon fiber, a pitch-based activated carbon fiber, a polyvinyl alcohol (PVA) -based activated carbon fiber, and a lignin activated carbon fiber.
The second aspect of the present invention provides a method for preparing an activated carbon fiber adsorbent for volatile organic compound adsorption, comprising the following steps:
1) dissolving a phosphorus-containing precursor and a nitrogen-containing precursor in water, gradually dropwise adding a surfactant, and stirring until the phosphorus-containing precursor and the nitrogen-containing precursor are completely dissolved to obtain a mixed solution;
2) soaking the activated carbon fiber in the mixed solution obtained in the step 1), uniformly stirring, heating, performing ultrasonic treatment, and drying to obtain the required activated carbon fiber adsorbent.
Preferably, in the step 1), the mass ratio of the phosphorus-containing precursor to the nitrogen-containing precursor to water is (1-20) to (60-98).
Preferably, in step 1), the phosphorus-containing precursor is selected from one of glucose-6-phosphate, benzene phosphoramide or aminotrimethylene phosphonic acid.
Preferably, in step 1), the nitrogen-containing precursor is selected from one of urea, cyanamide or dicyandiamide.
Preferably, in step 1), the surfactant is a phosphorus-containing surfactant, and the phosphorus-containing surfactant is selected from one of phosphate ionic surfactants, polyoxyethylene phosphate nonionic surfactants or phospholipid biosurfactants.
Preferably, in the step 1), the addition amount of the surfactant is 1-5% of the total mass of the mixed solution.
Preferably, in the step 1), the stirring temperature is normal temperature. The normal temperature is 20-30 ℃.
Preferably, in the step 2), the activated carbon fiber is selected from one of a glue-based activated carbon fiber, a Polyacrylonitrile (PAN) -based activated carbon fiber, a phenol-formaldehyde-based activated carbon fiber, a pitch-based activated carbon fiber, a polyvinyl alcohol (PVA) -based activated carbon fiber, and a lignin activated carbon fiber.
Preferably, in the step 2), the ratio of the added mass g of the activated carbon fiber to the added volume mL of the mixed solution is 1: 1-5.
Preferably, in step 2), the heating conditions are as follows: heating temperature: 120-220 ℃; heating time: 1-48 h.
Preferably, in the step 2), the time of the ultrasonic treatment is 0.1-3 h.
Preferably, in step 2), the drying conditions are as follows: drying temperature: 80-110 ℃; heating time: 12-48 h.
The modified activated carbon fiber adsorbents with different phosphorus-doped nitrogen carbide coating amounts can be prepared by adjusting the proportion of the phosphorus-containing precursor to the nitrogen-containing precursor (1-20) to (1-20)) and the proportion of the activated carbon fiber to the mixed solution (1-5)).
The third aspect of the invention provides the use of the activated carbon fiber modified adsorbent in volatile organic compound adsorption.
Preferably, the volatile organic compound is selected from one or two of aldehyde organic compounds or ketone organic compounds.
More preferably, the aldehyde organic compound is a general chemical definition of the aldehyde organic compound.
Further preferably, the aldehyde organic is selected from one or more of formaldehyde, acetaldehyde and propionaldehyde.
More preferably, the ketone organic is a ketone organic in the general chemical definition.
Further preferably, the ketone organic is selected from one or more of acetone, butanone and acetophenone.
Preferably, the adsorbent is filled in a fixed bed reactor, and the volatile organic compound-containing gas is introduced.
More preferably, the reaction temperature is 0-80 ℃.
More preferably, the volatile organic compound-containing gas can be operated under a certain pressure, and the pressure is 0.1-10 MPa.
More preferablyThe airspeed of the volatile organic compound-containing air is 500-20000 h -1 。
More preferably, the volatile organic compound-containing gas has a volatile organic compound concentration of 10 to 9000 ppm.
As described above, according to the activated carbon fiber adsorbent for adsorbing volatile organic compounds and the preparation method thereof provided by the present invention, activated carbon fibers are dispersed in an aqueous solution of a precursor such as phosphorus and nitrogen, sealed and heated to a certain temperature, and reacted for a period of time to obtain a modified activated carbon fiber adsorbent, which has the following beneficial effects:
(1) the phosphorus-doped nitrogen carbide modified activated carbon fiber adsorbent prepared by the invention can be used for preparing a nano phosphorus-doped nitrogen carbide coating layer by reasonably controlling the concentration and hydrothermal time of each precursor solution, so that the nano phosphorus-doped nitrogen carbide coating layer is uniformly distributed on the pore channel surface of the activated carbon fiber on a nano scale, and finally, the phosphorus-doped nitrogen carbide coating layer with uniform, continuous and high bonding strength is generated on the surface of the activated carbon fiber through in-situ reduction.
(2) According to the invention, through the phase-phase crosslinking reaction of precursors such as phosphorus, nitrogen and the like, the content of phosphorus is greatly improved, the stability of the phosphorus on the surface of the activated carbon is enhanced, the phosphorus is not easy to run off or react in the traditional heating desorption process of volatile organic compounds, and the cyclic adsorption performance of the activated carbon fiber is improved.
(3) The invention adopts the phosphorus-containing surfactant to disperse the precursor polymers such as phosphorus, nitrogen and the like, so that the particle size of the polymer is smaller, and the phosphorus element is uniformly distributed in the nitrogen carbide coating, thereby being beneficial to further enhancing the large pi-bond conjugated system of the nitrogen carbide.
(4) Because the phosphorus-doped nitrogen carbide coating with higher activity has an excellent electronic structure, the activated carbon fiber modified adsorbent has higher stability for easily polymerized aldehydes, ketones and the like, and prevents the reaction polymerization of the aldehydes and the ketones, so that the desorption efficiency is extremely high, and the cyclic adsorption performance of the adsorbent can be greatly improved.
Detailed Description
The present invention is further illustrated below with reference to specific examples, which are intended to be illustrative only and not to limit the scope of the invention.
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Example 1:
preparing 100g of mixed solution by taking 6-glucose phosphate as a phosphorus-containing precursor and urea as a nitrogen-containing precursor according to the mass ratio of 1:1:98, adding 1g of alkyl alcohol ether phosphate as a surfactant, and stirring at room temperature until dissolution is completed.
Weighing 200g of viscose-based active carbon fiber, soaking the viscose-based active carbon fiber in the prepared mixed solution, uniformly stirring, keeping the temperature at 120 ℃ for 1 hour, performing ultrasonic treatment for 0.1 hour, and drying at 80 ℃ for 12 hours to obtain the phosphorus-doped nitrogen carbide modified active carbon fiber adsorbent with the coating amount of 1 percent.
Respectively filling the original viscose-based activated carbon fiber and the modified activated carbon fiber adsorbent in a fixed bed reactor, controlling the reaction temperature at 0 ℃, introducing volatile organic gas containing formaldehyde under the pressure of 0.1MPa, controlling the concentration of the formaldehyde at 10ppm, and controlling the airspeed at 500h -1 The benzene adsorption efficiency of the original viscose-based activated carbon fiber is 80%, the saturated adsorption capacity is 200mg/g, the formaldehyde adsorption efficiency of the modified activated carbon fiber is 93%, and the saturated adsorption capacity is 267 mg/g.
Example 2:
benzene phosphoramide is taken as a phosphorus-containing precursor, cyanamide is taken as a nitrogen-containing precursor, 100g of mixed solution is prepared according to the mass ratio of 20:20:60, 5g C16-fatty alcohol polyoxyethylene ether phosphate is added as a surfactant, and the mixture is stirred at room temperature until the dissolution is completed.
Weighing 93g of polyacrylonitrile-based active carbon fiber, soaking the polyacrylonitrile-based active carbon fiber in the prepared mixed solution, uniformly stirring, keeping the temperature at 220 ℃ for 48 hours, carrying out ultrasonic treatment for 3 hours, and drying at 110 ℃ for 48 hours to obtain the phosphorus-doped nitrogen carbide modified active carbon fiber adsorbent with the coating amount of 30%.
Respectively filling original polyacrylonitrile-based active carbon fiber and the modified active carbon fiber adsorbent in a fixed bed reactor, controlling the reaction temperature at 80 ℃, introducing acetone-containing volatile organic gas under the pressure of 10MPa, controlling the concentration of acetone at 9000ppm and the space velocity at 20000h -1 The acetone adsorption efficiency of the original polyacrylonitrile-based active carbon fiber is 75%, the saturated adsorption capacity is 220mg/g, the acetone adsorption efficiency of the modified active carbon fiber is 90%, and the saturated adsorption capacity is 362 mg/g.
Example 3:
taking aminotrimethylene phosphonic acid as a phosphorus-containing precursor and dicyanodiamide as a nitrogen-containing precursor, preparing 100g of mixed solution according to the mass ratio of 10:15:75, adding 2g of polyoxyethylene lauryl ammonium phosphate as a surfactant, and stirring at room temperature until dissolution is completed.
Weighing 100g of phenolic active carbon fiber, soaking the phenolic active carbon fiber in the prepared mixed solution, uniformly stirring, keeping the temperature at 150 ℃ for 12h, carrying out ultrasonic treatment for 1h, and drying at 100 ℃ for 24h to obtain the phosphorus-doped nitrogen carbide modified active carbon fiber adsorbent with the coating amount of 20%.
Respectively filling the original phenolic aldehyde-based active carbon fiber and the modified active carbon fiber adsorbent into a fixed bed reactor, controlling the reaction temperature at 25 ℃, introducing acetaldehyde-containing volatile organic gas under the pressure of 8MPa, controlling the concentration of acetaldehyde to be 200ppm, and controlling the space velocity to be 1000h -1 The acetaldehyde adsorption efficiency of the original phenolic aldehyde-based activated carbon fiber is 83 percent, the saturated adsorption capacity is 312mg/g, the acetaldehyde adsorption efficiency of the modified activated carbon fiber is 97 percent, and the saturated adsorption capacity is 472 mg/g.
Example 4:
preparing 100g of mixed solution by taking 6-phosphoglucose as a phosphorus-containing precursor and dicyanodiamine as a nitrogen-containing precursor according to the mass ratio of 5:10:85, adding 3g of lecithin as a surfactant, and stirring at room temperature until dissolution is completed.
Weighing 100g of asphalt-based active carbon fiber, soaking the asphalt-based active carbon fiber in the prepared mixed solution, uniformly stirring, keeping the temperature constant at 180 ℃ for 16h, carrying out ultrasonic treatment for 1.5h, and drying at 95 ℃ for 36h to obtain the phosphorus-doped nitrogen carbide modified active carbon fiber adsorbent with the coating amount of 15%.
Respectively filling the original asphalt-based active carbon fiber and the modified active carbon fiber adsorbent in a fixed bed reactor, controlling the reaction temperature at 40 ℃, introducing butanone-containing volatile organic gas under the pressure of 1MPa, controlling the concentration of butanone to be 2000ppm, and controlling the space velocity to be 3000h -1 The benzene adsorption efficiency of the original asphalt-based activated carbon fiber is 86 percent, the saturated adsorption capacity is 306mg/g, the butanone adsorption efficiency of the modified activated carbon fiber is 98 percent, and the saturated adsorption capacity is 498 mg/g.
Example 5:
benzene phosphamide is taken as a phosphorus-containing precursor, urea is taken as a nitrogen-containing precursor, 100g of mixed solution is prepared according to the mass ratio of 5:5:90, 1.5g of alkyl alcohol ether phosphate is added as a surfactant, and the mixture is stirred at room temperature until the dissolution is completed.
And weighing 90g of polyvinyl alcohol (PVA) -based active carbon fiber, soaking the 90g of PVA-based active carbon fiber in the prepared mixed solution, uniformly stirring, keeping the temperature at 220 ℃ for 30h, performing ultrasonic treatment for 2h, and drying at 105 ℃ for 20h to obtain the phosphorus-doped nitrogen carbide modified active carbon fiber adsorbent with the coating amount of 10%.
Respectively filling original polyvinyl alcohol-based active carbon fiber and the modified active carbon fiber adsorbent in a fixed bed reactor, controlling the reaction temperature at 55 ℃, introducing volatile organic gas containing propionaldehyde under the pressure of 2MPa, controlling the concentration of the propionaldehyde to be 5000ppm, and controlling the airspeed to 10000h -1 The propionaldehyde adsorption efficiency of the original polyvinyl alcohol-based activated carbon fiber is 76%, the saturated adsorption capacity is 302mg/g, the propionaldehyde adsorption efficiency of the modified activated carbon fiber is 99%, and the saturated adsorption capacity is 510 mg/g.
Example 6:
taking aminotrimethylene phosphonic acid as a phosphorus-containing precursor and cyanamide as a nitrogen-containing precursor, preparing 100g of mixed solution according to the mass ratio of 3:5:92, adding 4g of soft phospholipid as a surfactant, and stirring at room temperature until dissolution is completed.
Weighing 20g of lignin activated carbon fiber, soaking the lignin activated carbon fiber in the prepared mixed solution, uniformly stirring, keeping the temperature at 200 ℃ for 8h, carrying out ultrasonic treatment for 3h, and drying at 110 ℃ for 18h to obtain the phosphorus-doped nitrogen carbide modified activated carbon fiber adsorbent with the coating amount of 28%.
Respectively filling the raw lignin activated carbon fiber and the modified activated carbon fiber adsorbent in a fixed bed reactor, controlling the reaction temperature at 65 ℃, introducing acetophenone-containing volatile organic gas under the pressure of 0.2MPa, controlling the concentration of acetophenone to be 500ppm, and controlling the airspeed to be 15000h -1 The acetophenone adsorption efficiency of the original lignin activated carbon fiber is 73 percent, the saturated adsorption capacity is 289mg/g, the acetophenone adsorption efficiency of the modified activated carbon fiber is 99 percent, and the saturated adsorption capacity is 506 mg/g.
In conclusion, the activated carbon fiber adsorbent for adsorbing volatile organic compounds and the preparation method thereof provided by the invention can be used for preparing the phosphorus-doped nitrogen carbide coating with higher activity, improve the adsorption and desorption efficiency of the volatile organic compounds, and greatly improve the cyclic adsorption performance of the adsorbent. Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (8)
1. An activated carbon fiber adsorbent comprises the following components in percentage by weight:
5 to 20 percent of phosphorus-doped nitrogen carbide,
80-95% of activated carbon fiber;
in the phosphorus-doped nitrogen carbide, the doping amount of the phosphorus element in the nitrogen carbide is 1-30 wt%;
the activated carbon fiber is selected from one of phenolic aldehyde-based activated carbon fiber, asphalt-based activated carbon fiber, polyvinyl alcohol-based activated carbon fiber and lignin activated carbon fiber;
the activated carbon fiber adsorbent is prepared by the following method, and the method comprises the following steps:
1) dissolving a phosphorus-containing precursor and a nitrogen-containing precursor in water, gradually dropwise adding a surfactant, and stirring until the phosphorus-containing precursor and the nitrogen-containing precursor are completely dissolved to obtain a mixed solution;
2) soaking activated carbon fibers in the mixed solution obtained in the step 1), uniformly stirring, heating, performing ultrasonic treatment, and drying to obtain the required activated carbon fiber adsorbent;
in step 1), any one or more of the following conditions are included:
A1) the phosphorus-containing precursor is selected from one of 6-phosphoglucose, benzene phosphamide or amino trimethylene phosphonic acid;
A2) the nitrogen-containing precursor is selected from one of urea, cyanamide or dicyanodiamide;
A3) the surfactant is a phosphorus-containing surfactant, and the phosphorus-containing surfactant is selected from one of phosphate ionic surfactants, polyoxyethylene phosphate nonionic surfactants or phospholipid biosurfactants;
in the step 1), the mass ratio of the phosphorus-containing precursor to the nitrogen-containing precursor to water is (1-20) to (60-98);
in the step 2), the heating conditions are as follows: heating temperature: 120-220 ℃; heating time: 1-48 h.
2. The method for preparing an activated carbon fiber adsorbent according to claim 1, comprising the steps of:
1) dissolving a phosphorus-containing precursor and a nitrogen-containing precursor in water, gradually dropwise adding a surfactant, and stirring until the phosphorus-containing precursor and the nitrogen-containing precursor are completely dissolved to obtain a mixed solution;
2) soaking activated carbon fiber in the mixed solution obtained in the step 1), uniformly stirring, heating, performing ultrasonic treatment, and drying to obtain the required activated carbon fiber adsorbent;
in step 1), any one or more of the following conditions are included:
A1) the phosphorus-containing precursor is selected from one of glucose-6-phosphate, benzene phosphoramide or aminotrimethylene phosphonic acid;
A2) the nitrogen-containing precursor is selected from one of urea, cyanamide or dicyanodiamide;
A3) the surfactant is a phosphorus-containing surfactant, and the phosphorus-containing surfactant is selected from one of phosphate ionic surfactants, polyoxyethylene phosphate nonionic surfactants or phospholipid biosurfactants.
3. The method for preparing the activated carbon fiber adsorbent according to claim 2, wherein in the step 1), the mass ratio of the phosphorus-containing precursor to the nitrogen-containing precursor to the water is (1-20) to (60-98).
4. The preparation method of the activated carbon fiber adsorbent according to claim 2, wherein in the step 1), the addition amount of the surfactant is 1-5% of the total mass of the mixed solution.
5. The method for preparing the activated carbon fiber adsorbent according to claim 2, wherein in the step 2), the ratio of the added mass g of the activated carbon fiber to the added volume mL of the mixed solution is 1: 1-5.
6. The method for preparing the activated carbon fiber adsorbent according to claim 2, wherein the step 2) comprises any one or more of the following conditions:
B1) the heating conditions are as follows: heating temperature: 120-220 ℃; heating time: 1-48 h;
B2) the ultrasonic time is 0.1-3 h;
B3) the drying conditions are as follows: drying temperature: 80-110 ℃; heating time: 12-48 h.
7. Use of the activated carbon fiber adsorbent according to claim 1 for volatile organic compound adsorption.
8. The use according to claim 7, characterized in that the adsorbent is packed in a fixed bed reactor and the volatile organic compound-containing gas is introduced.
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