CN114433018B - Chlorine-containing volatile organic compound adsorbent and preparation method thereof - Google Patents
Chlorine-containing volatile organic compound adsorbent and preparation method thereof Download PDFInfo
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- CN114433018B CN114433018B CN202011197031.2A CN202011197031A CN114433018B CN 114433018 B CN114433018 B CN 114433018B CN 202011197031 A CN202011197031 A CN 202011197031A CN 114433018 B CN114433018 B CN 114433018B
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 57
- 239000000460 chlorine Substances 0.000 title claims abstract description 37
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 34
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 44
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 33
- 238000001035 drying Methods 0.000 claims abstract description 22
- 239000002006 petroleum coke Substances 0.000 claims abstract description 19
- 230000004048 modification Effects 0.000 claims abstract description 18
- 238000012986 modification Methods 0.000 claims abstract description 18
- 238000010926 purge Methods 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 229910052709 silver Inorganic materials 0.000 claims abstract description 13
- 239000004332 silver Substances 0.000 claims abstract description 13
- 230000003647 oxidation Effects 0.000 claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 239000013067 intermediate product Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000000047 product Substances 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- 238000001179 sorption measurement Methods 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 32
- 239000007789 gas Substances 0.000 claims description 23
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 229910001923 silver oxide Inorganic materials 0.000 claims description 11
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000012159 carrier gas Substances 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000001307 helium Substances 0.000 claims description 7
- 229910052734 helium Inorganic materials 0.000 claims description 7
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 4
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 claims description 3
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 claims description 3
- PNLQPWWBHXMFCA-UHFFFAOYSA-N 2-chloroprop-1-ene Chemical compound CC(Cl)=C PNLQPWWBHXMFCA-UHFFFAOYSA-N 0.000 claims description 3
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 claims description 3
- 239000002608 ionic liquid Substances 0.000 claims description 3
- QTBFPMKWQKYFLR-UHFFFAOYSA-N isobutyl chloride Chemical compound CC(C)CCl QTBFPMKWQKYFLR-UHFFFAOYSA-N 0.000 claims description 3
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 claims description 3
- 229910001958 silver carbonate Inorganic materials 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- -1 trichloroethylene, tetrachloroethylene, 1,2, 3-trichloropropene Chemical class 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000003929 acidic solution Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims 1
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000003575 carbonaceous material Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 description 30
- 238000011068 loading method Methods 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229960001701 chloroform Drugs 0.000 description 3
- 230000000382 dechlorinating effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000005539 carbonized material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 231100000584 environmental toxicity Toxicity 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 231100001244 hazardous air pollutant Toxicity 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000329 molecular dynamics simulation Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 231100001239 persistent pollutant Toxicity 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification 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
- 150000003839 salts Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
-
- 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
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/25—Coated, impregnated or composite adsorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/206—Organic halogen compounds
-
- 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
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention relates to a chlorine-containing volatile organic compound adsorbent and a preparation method thereof, comprising the following steps: (1) After drying petroleum coke, adding a silver-containing compound and potassium hydroxide, uniformly mixing, and carrying out high-temperature treatment under an inert atmosphere; (2) Cooling, washing and drying the high-temperature treated product to obtain the Ag-carrying Ag + An activated carbon intermediate; (3) And (3) performing oxidation modification on the intermediate product, and then adopting inert gas to purge to prepare the adsorbent. The invention takes petroleum coke as raw material, and the prepared adsorbent is used for adsorbing chlorine-containing volatile organic compounds by in-situ synthesis of active carbon materials and surface modification, and has higher selectivity and chlorine capacity.
Description
Technical Field
The invention belongs to the technical field of adsorbents, and particularly relates to a chlorine-containing volatile organic compound adsorbent and a preparation method thereof.
Background
Chlorine-containing volatile organics (Chlorinated Volatile Organic Compounds, CVOCs) are a class of contaminants commonly found in environmental media, including chlorinated alkanes, chlorinated alkenes, chlorinated aromatic hydrocarbons, and the like. Generally, these CVOCs are mainly derived from petrochemical, printing, pharmaceutical and other industries. Global chloromethane production capacity in 2017 was 280 ten thousand tons/year, with methylene chloride used as a solvent, and the U.S. consumption was stable. The newly established 188 kinds of toxic gases (Hazardous Air Pollutants) in the U.S. national environmental protection agency list has 32 kinds of halogenated VOCs. CVOCs are considered persistent pollutants, difficult to degrade in the environment, and have greater environmental toxicity than other volatile organic compounds. Most CVOCs are insoluble in water, and CVOCs released into the atmosphere destroy the ozone layer, form photochemical smog and global warming, and have a three-effect on the human body, so that the release of CVOCs is limited by strict laws and regulations, and the national legislation prescribes that the CVOCs can be released after being treated. Currently, CVOCs are listed in a highly toxic chemical list by a plurality of countries, and are one of target pollutants for emission reduction and treatment.
Currently, CVOCs treatment technologies mainly comprise adsorption, absorption, membrane separation, combustion, condensation and other technologies. Compared with other treatment technologies, the adsorption method has the advantages of good purification effect, low energy consumption, simple operation and low running cost, and is an ideal CVOCs treatment technology. Common adsorbents include activated carbon, biomass materials, silica, and the like. Activated carbon adsorption is a typical adsorption method, but only activated carbon is used for adsorbing CVOCs, mainly physical adsorption is used, the adsorption capacity is small, and the adsorption effect is to be improved. Most of the existing adsorbents have poor selectivity to organic chloride in gas phase and low adsorption chlorine capacity, so that the conventional adsorbents are difficult to adsorb and remove CVOCs to meet the emission limit specified in GB31571-2015, a multi-stage activated carbon adsorption tower is required to be arranged, and investment and operation cost are exponentially increased.
CN103357242a discloses a pressure swing adsorption and/or temperature swing adsorption method, which comprises two or more adsorption towers filled with one or more adsorbents of silica gel, activated carbon, activated alumina or carbon molecular sieves and a series of program-controlled valves to form an adsorption separation system, wherein the adsorption separation system is used for carrying out adsorption and fine desorption on chlorine-containing industrial mixed gas, and the total content of chloride is controlled to be less than 5ppm at the outlet at the upper end of the adsorption tower. The process requires the grading of multiple adsorbents, the use of temperature and/or pressure swing adsorption processes, and these materials have poor selectivity for chlorine-containing compounds.
CN103611495a discloses an adsorbent for removing organic chloride from hydrocarbon-containing stream and its preparation method, which contains modified zeolite molecular sieve, inorganic macroporous material and clay component. The zinc ion modified zeolite molecular sieve contained in the adsorbent shows very high reactivity to organic chloride, compared with the prior art, the adsorbent has higher selective adsorption capacity to organic chloride, has wide use temperature range and low reactivity, and is suitable for removing at least one organic chloride from hydrocarbon-containing streams containing hydrogen, hydrocarbon and chloride. The method mainly uses transition metal zinc ion exchange modified faujasite catalyst, and the preparation process is complex by kneading macropores and binders.
CN106554802a discloses a liquid-phase dechlorinating agent, which is prepared by adding active carbon into a strong oxidizing medium to perform oxidation modification to obtain modified active carbon, then carrying out loading treatment by using a mixed solution of soluble metal salt and other auxiliary agents, and finally drying and activating the loaded modified active carbon in protective atmosphere or vacuum to obtain a dechlorinating agent finished product. The dechlorinating agent is mainly used in a liquid phase, and the removal effect of organic chloride in the gas phase is to be improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a chlorine-containing volatile organic compound adsorbent and a preparation method thereof. The invention takes petroleum coke as raw material, and the prepared adsorbent is used for adsorbing chlorine-containing volatile organic compounds by in-situ synthesis of active carbon materials and surface modification, and has higher selectivity and chlorine capacity.
The invention provides a preparation method of a chlorine-containing volatile organic compound adsorbent, which comprises the following steps:
(1) After drying petroleum coke, adding a silver-containing compound and potassium hydroxide, uniformly mixing, and carrying out high-temperature treatment under an inert atmosphere;
(2) Cooling, washing and drying the high-temperature treated product to obtain the Ag-carrying Ag + An activated carbon intermediate;
(3) And (3) performing oxidation modification on the intermediate product, and then adopting inert gas to purge to prepare the adsorbent.
In the step (1), the drying temperature of the petroleum coke is 60-150 ℃, preferably 80-120 ℃, and the drying time is 2-8 h, preferably 3-5 h.
In the step (1), the silver-containing compound is at least one of silver carbonate, silver nitrate, silver oxide and the like, preferably silver oxide.
In the step (1), the mass ratio of the petroleum coke to the silver-containing compound is 8:1-40:1, preferably 10:1-20:1.
In the step (1), the mass ratio of the potassium hydroxide to the petroleum coke is 0.1:1-10:1, preferably 1:1-6:1.
In the step (1), the inert atmosphere is in the presence of at least one of nitrogen, helium, argon and the like.
In the step (1), the high temperature treatment temperature is 600-1000 ℃, preferably 700-900 ℃, and the treatment time is 30-180 min, preferably 60-120 min. Further, it is preferable that the high temperature treatment is performed under a microwave condition, and the microwave frequency is 2400-2500MHz and the power is 3-5kw.
In the step (2), the cooling is performed in the presence of nitrogen, and the sample is ground into powder after cooling and washed.
In the step (2), the washing adopts an acidic solution with the pH value not more than 7, and the washing is carried out until the pH value of the filtrate is neutral. The acid is at least one of hydrochloric acid, sulfuric acid, nitric acid, acetic acid and the like, preferably acetic acid.
In the step (2), the drying temperature is 60-150 ℃, preferably 80-120 ℃, and the drying time is 2-10 h, preferably 4-8 h.
In the step (3), the oxidation modification adopts gas oxidation, and the gas mainly comprises oxygen and carrier gas, wherein the volume content of the oxygen is 0.1-15%, and preferably 3-10%. The carrier gas is at least one of nitrogen, helium, argon, and the like, preferably nitrogen.
In the step (3), the time of the oxidative modification is 0.5-48 h, preferably 4-24 h; volume airspeed of 6-600 h -1 Preferably 50 to 300. 300h -1 。
In the step (3), the inert gas is at least one of nitrogen, helium, argon and the like, preferably nitrogen.
Further, the activated carbon intermediate is immersed in the [ EMIM ] [ Cl ] ionic liquid for a period of time of 1-2 hours before oxidative modification.
In the step (3), the purging airspeed is 60-300 h -1 Preferably 100 to 200 hours -1 The method comprises the steps of carrying out a first treatment on the surface of the The purging time is 0.1 to 24 hours, preferably 0.5 to 8 hours.
The chlorine-containing volatile organic compound adsorbent is prepared by the method. The specific surface area of the prepared adsorbent is 800-3900 m 2 Per gram, the pore volume is 0.4-1.20 cm 3 Per g, the most probable pore size is 0.3-0.7 nm, and the Ag loading is 1.37-2.33 wt.%.
The adsorbent provided by the invention is mainly used for adsorbing chlorine-containing volatile organic compounds in gas. The chlorine-containing volatile organic compounds are mainly as follows: at least one of chloroform, carbon tetrachloride, 1, 2-dichloroethane, 1, 2-tetrachloroethane, 1, 3-tetrachloropropane, hexachloroethane, methylene chloride, chloroisobutane, trichloroethylene, tetrachloroethylene, 1,2, 3-trichloropropene, 2-chloropropene, and the like.
The adsorbent is used for adsorbing the chlorine-containing volatile organic compounds in the gas, and adopts fixed bed adsorption, and the adsorption conditions are as follows: adsorption is carried out at normal temperature and normal pressure, and the volume airspeed is 1000-1200 h -1 . The concentration of the chlorine-containing volatile organic compounds in the gas is lower than 7 multiplied by 10 5 mg/m 3 When the concentration of the chlorine-containing volatile organic compounds at the outlet of the adsorption tower is more than 5 multiplied by 10 3 mg/m 3 At this time, the penetration is 255 to 430mg/g of penetration chlorine capacity.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention is a modified activated carbon adsorbent which is directionally designed based on the shape selection theory of the adsorbent and the morphological identification of the chlorine-containing volatile organic compounds. Common organic chlorides are mainly: trichloromethane, carbon tetrachloride, 1, 2-dichloroethane, 1, 2-tetrachloroethane, 1, 3-tetrachloropropane, hexachloroethane, methylene chloride, chloroisobutane, trichloroethylene, tetrachloroethylene, 1,2, 3-trichloropropene, 2-chloropropene, and the like; the molecular dynamics diameters of the modified activated carbon adsorbents are 0.2940nm, 0.2914nm, 0.3450nm, 0.4323nm, 0.5152nm, 0.4368nm, 0.2980nm, 0.4495nm, 0.4311nm, 0.4318nm, 0.5206nm and 0.2394nm, and the kinetic diameters of the modified activated carbon adsorbents are smaller than 0.6nm, so that the inventor researches out the modified activated carbon adsorbents with the most probable pore diameters of 0.3-0.7 nm, and the modified activated carbon adsorbents have higher selectivity and chlorine capacity for chlorine-containing volatile organic matters.
(2) Mixing petroleum coke with silver-containing compound and potassium hydroxide, and high-temperature treatment to synthesize Ag-bearing Ag with high dispersivity in situ + Activated carbon, ag + Is easy to form sigma bond with pi electron of organic chloride, ag + The d orbit of (2) can feed back electron cloud to pi orbit of gas organic chloride to generate complexation, thereby improving adsorption selectivity of CVOCs.
(3) The modified adsorbent prepared by the invention belongs to pi complex adsorbents, is a typical adsorbent with weak chemical bonds, and also solves the problem of difficult regeneration of traditional chemical adsorption on the premise of improving the selectivity to organic chloride in gas phase.
Detailed Description
The method and effect of the present invention will be described in detail with reference to examples. The embodiments and specific operation procedures are given on the premise of the technical scheme of the invention, but the protection scope of the invention is not limited to the following embodiments. In the present invention, wt.% is mass fraction.
The experimental methods in the following examples, unless otherwise specified, are all conventional in the art. The experimental materials used in the examples described below, unless otherwise specified, were purchased from conventional biochemical reagent stores.
The specific surface area, pore size distribution and the most probable pore size of the sample in the following examples and comparative examples were N at low temperature 2 The content of the organic chloride in the gas phase was measured by a microcoulomb meter and the silver loading was detected by an ICP instrument.
Example 1
(1) 100g of petroleum coke is taken, dried for 5 hours at 120 ℃, uniformly mixed with 300g of potassium hydroxide and 10g of silver oxide, and treated for 30 minutes at 900 ℃ under nitrogen atmosphere.
(2) And (3) cooling the sample under the protection of nitrogen, grinding the cooled sample into powder, adding the powder into an acetic acid solution with the concentration of 10wt percent for washing, washing with deionized water until the pH value of the filtrate is neutral, and then drying at 120 ℃ for 6 hours to obtain an activated carbon intermediate product.
(3) The prepared activated carbon intermediate is subjected to oxidation modification by using gas (carrier gas is nitrogen) with the volume content of 5% of oxygen at room temperature, wherein the modification time is 6h, and the volume space velocity is 100h -1 Then purged with nitrogen at a space velocity of 100h -1 The purging time is 6h, and the adsorbent is prepared.
The specific surface area of the prepared adsorbent is 2900m 2 Per g, pore volume of 1.09cm 3 Per g, the most probable pore size is 0.6-0.7 nm, and the Ag loading is 2.3wt.%.
Example 2
(1) 100g of petroleum coke is taken, dried for 8 hours at 80 ℃, uniformly mixed with 100g of potassium hydroxide and 10g of silver oxide, and treated for 120 minutes at 700 ℃ under nitrogen atmosphere.
(2) And (3) cooling the sample under the protection of nitrogen, grinding the cooled sample into powder, adding the powder into hydrochloric acid solution with the concentration of 10wt percent for washing, washing with deionized water until the pH value of the filtrate is neutral, and then drying at 120 ℃ for 4 hours to obtain an activated carbon intermediate product.
(3) The prepared activated carbon intermediate is subjected to oxidation modification by using gas with 3% of oxygen volume content (carrier gas is nitrogen) at room temperature, and the airspeed is 50h -1 The treatment time was 4 hours, followed by purging with nitrogen gas at a space velocity of 100 hours -1 The purging time is 6h, and the adsorbent is prepared.
The specific surface area of the prepared adsorbent is 933m 2 Per g, pore volume of 0.49cm 3 Per g, the most probable pore size is 0.3-0.5 nm, and the Ag loading is 2.12wt.%.
Example 3
(1) 100g of petroleum coke is taken, dried for 3 hours at 150 ℃, uniformly mixed with 600g of potassium hydroxide and 5g of silver oxide, and treated for 90 minutes at 800 ℃ under nitrogen atmosphere.
(2) And (3) cooling the sample under the protection of nitrogen, grinding the cooled sample into powder, adding the powder into sulfuric acid solution with the concentration of 10wt percent for washing, washing with deionized water until the pH value of the filtrate is neutral, and then drying at 100 ℃ for 5 hours to obtain an activated carbon intermediate product.
(3) The prepared activated carbon intermediate is subjected to oxidation modification by using gas with the oxygen volume content of 10% (carrier gas is nitrogen) at room temperature, and the airspeed is 200h -1 The treatment time was 4 hours, followed by purging with nitrogen gas at a space velocity of 200 hours -1 The purging time is 5h, and the adsorbent is prepared.
The specific surface area of the prepared adsorbent is 2505m 2 Per g, pore volume of 0.91cm 3 Per g, the most probable pore size is 0.5-0.6 nm, and the Ag loading is 1.37wt.%.
Example 4
The difference from example 1 is that: the silver-containing compound employs silver carbonate instead of silver oxide. The specific surface area of the prepared adsorbent is 3079m 2 Per g, pore volume of 1.15cm 3 Per g, the most probable pore size is 0.6-0.7 nm, and the Ag loading is 1.89wt.%.
Example 5
The difference from example 1 is that: the silver-containing compound employs silver nitrate instead of silver oxide. The specific surface area of the prepared adsorbent is 2810m 2 Per g, pore volume of 0.99cm 3 Per g, the most probable pore size is 0.6-0.7 nm, and the Ag loading is 1.61wt.%.
Example 6
The difference from example 1 is that: helium is used for all inert gases instead of nitrogen. The specific surface area of the prepared adsorbent is 2905m 2 Per g, pore volume of 1.09cm 3 Per g, the most probable pore size is 0.6-0.7 nm, and the Ag loading is 2.28wt.%.
Example 7
The difference from example 1 is that: the high temperature treatment in the step (2) is carried out under the microwave condition, the microwave frequency is 2450 MHz, and the power is 4 kw. The specific surface area of the prepared adsorbent is 2950m 2 Per g, pore volume of 1.11cm 3 Per g, the most probable pore size is 0.6-0.7 nm, and the Ag loading is 2.34wt.%.
Example 8
The difference from example 1 is that: step (3) the activated carbon intermediate is subjected to [ EMIM ] before oxidative modification][Cl]Immersing in ionic liquid for 1h. The specific surface area of the prepared adsorbent is 2950m 2 Per g, pore volume of 1.11cm 3 Per g, the most probable pore size is 0.6-0.7 nm, and the Ag loading is 2.38wt.%.
Comparative example 1
The difference from example 1 is that: step (1) does not add potassium hydroxide. The specific surface area of the prepared adsorbent is 51m 2 Per g, pore volume of 0.03cm 3 Load of Ag was 0.06 wt.%/g.
Comparative example 2
The difference from example 1 is that: and (3) adopting copper oxide to replace silver oxide in the step (1). The specific surface area of the prepared adsorbent is 2766m 2 Per g, pore volume of 1.17cm 3 Per g, the most probable pore size is 0.7-0.8 nm, and the Cu loading is 4.25wt.%.
Comparative example 3
The difference from example 1 is that: and (3) adopting ferric sulfate to replace silver oxide in the step (1). The specific surface area of the prepared adsorbent is 2866m 2 Per g, pore volume of 1.0cm 3 Per g, the most probable pore size is 0.6-0.7 nm, and the loading of Fe is 0.93wt.%.
Comparative example 4
The difference from example 1 is that: and (3) replacing petroleum coke with coconut shell carbonized materials in the step (1). The specific surface area of the prepared adsorbent is 1842m 2 Per g, pore volume of 10.87cm 3 Per g, the most probable pore size is 0.8-1.0 nm, and the Ag loading is 1.97wt.%.
Comparative example 5
The difference from example 1 is that: the high temperature treatment temperature in the step (1) is 400 ℃. The specific surface area of the prepared adsorbent is 61m 2 Per g, pore volume of 0.31cm 3 Per g, the most probable pore size is 0.01-0.03 nm, and the Ag loading is 0.41wt.%.
Test example 1
The adsorbents prepared in examples 1 to 8 and comparative examples 1 to 6 were used for adsorption of chlorine-containing volatile organic compounds in gases. The chlorine-containing organic matter in the exhaust gas is mainly: trichloromethane, carbon tetrachloride, 1, 2-dichloroethane, tetrachloroethane, wherein the concentration of the organic chloride is 6.89×10 5 mg/L. Adopting fixed bed adsorption, wherein the adsorption conditions are as follows: normal temperature, normal pressure and volume space velocity of 1200h -1 Test ofThe results are shown in Table 1.
TABLE 1
Test example 2
The adsorbents prepared in example 1 and comparative examples 1 to 5 were used for adsorbing chlorine-containing volatile organic compounds in a gas, and the total amount of organic compounds in the exhaust gas was 17500 mg/m 3 Wherein the chlorine-containing organic compound is mainly carbon tetrachloride and tetrachloroethylene, and the concentration of the organic chloride is 9710mg/m 3 . Adopting fixed bed adsorption, wherein the adsorption conditions are as follows: normal temperature, normal pressure and volume space velocity of 1200h -1 The test results are shown in Table 2, and the units are mg/m 3 。
TABLE 2
Claims (25)
1. The preparation method of the adsorbent containing the chlorine volatile organic compounds is characterized by comprising the following steps: (1) After drying petroleum coke, adding a silver-containing compound and potassium hydroxide, uniformly mixing, and carrying out high-temperature treatment under an inert atmosphere; the silver-containing compound is at least one of silver carbonate, silver nitrate and silver oxide; the mass ratio of the petroleum coke to the silver-containing compound is 8:1-40:1; the mass ratio of the potassium hydroxide to the petroleum coke is 0.1:1-10:1; the high temperature treatment temperature is 600-1000 ℃ and the treatment time is 30-180 min; (2) Cooling, washing and drying the high-temperature treated product to obtain the Ag-carrying Ag + An activated carbon intermediate; (3) And (3) performing oxidation modification on the intermediate product, and then adopting inert gas to purge to prepare the adsorbent.
2. The method according to claim 1, characterized in that: in the step (1), the drying temperature of the petroleum coke is 60-150 ℃ and the drying time is 2-8 h.
3. The method according to claim 2, characterized in that: in the step (1), the drying temperature of the petroleum coke is 80-120 ℃ and the drying time is 3-5 h.
4. The method according to claim 1, characterized in that: in the step (1), the silver-containing compound is silver oxide.
5. The method according to claim 1 or 4, characterized in that: the mass ratio of the petroleum coke to the silver-containing compound is 10:1-20:1.
6. The method according to claim 1, characterized in that: the mass ratio of the potassium hydroxide to the petroleum coke is 1:1-6:1.
7. The method according to claim 1, characterized in that: in the step (1), the inert atmosphere is in the presence of at least one of nitrogen, helium and argon.
8. The method according to claim 1, characterized in that: in the step (1), the high-temperature treatment temperature is 700-900 ℃ and the treatment time is 60-120 min.
9. The method according to claim 1 or 8, characterized in that: the high temperature treatment is carried out under the microwave condition, the microwave frequency is 2400-2500MHz, and the power is 3-5kw.
10. The method according to claim 1, characterized in that: the cooling is carried out in the presence of nitrogen, and after cooling, the sample is ground into powder for washing.
11. The method according to claim 1, characterized in that: in the step (2), the washing adopts an acidic solution with the pH value not more than 7, and the washing is carried out until the pH value of the filtrate is neutral; the acid is at least one of hydrochloric acid, sulfuric acid, nitric acid and acetic acid.
12. The method according to claim 1, characterized in that: in the step (2), the drying temperature is 60-150 ℃ and the drying time is 2-10 h.
13. The method according to claim 12, wherein: in the step (2), the drying temperature is 80-120 ℃ and the drying time is 4-8 h.
14. The method according to claim 1, characterized in that: in the step (3), the oxidation modification adopts gas oxidation, wherein the gas mainly comprises oxygen and carrier gas, and the volume content of the oxygen is 0.1-15%; the carrier gas is at least one of nitrogen, helium and argon.
15. The method according to claim 14, wherein: wherein the volume content of oxygen is 3-10%; the carrier gas is nitrogen.
16. The method according to claim 1, characterized in that: in the step (3), the time of the oxidative modification is 0.5 to 48 hours, and the volume space velocity is 6 to 600 h -1 。
17. The method according to claim 16, wherein: in the step (3), the time of the oxidative modification is 4-24 hours; volume airspeed of 50-300 h -1 。
18. The method according to claim 1, characterized in that: in the step (3), the inert gas is at least one of nitrogen, helium and argon.
19. The method according to claim 1, characterized in that: in the step (3), the activated carbon intermediate is immersed in the [ EMIM ] [ Cl ] ionic liquid for a period of time, and the immersion time is 1-2h before oxidation modification.
20. The method according to claim 1, characterized in that: in the step (3), the purging airspeed is 60-300 h -1 The purging time is 0.1-24 h.
21. The method according to claim 20, wherein: in the step (3), the purging airspeed is 100-200 h -1 The method comprises the steps of carrying out a first treatment on the surface of the The purging time is 0.5-8 h.
22. A chlorine-containing volatile organic compound adsorbent prepared by the method of any one of claims 1 to 21.
23. The use of the adsorbent of claim 22 for the adsorption of chlorine-containing volatile organic compounds in gases, said chlorine-containing volatile organic compounds being essentially: at least one of chloroform, carbon tetrachloride, 1, 2-dichloroethane, 1, 2-tetrachloroethane, 1, 3-tetrachloropropane, hexachloroethane, dichloromethane, chloroisobutane, trichloroethylene, tetrachloroethylene, 1,2, 3-trichloropropene, and 2-chloropropene.
24. Use of an adsorbent according to claim 23, wherein: the adsorbent is used for adsorbing the chlorine-containing volatile organic compounds in the gas, and adopts fixed bed adsorption, wherein the adsorption conditions are as follows: adsorption is carried out at normal temperature and normal pressure, and the volume airspeed is 1000-1200 h -1 。
25. Use of an adsorbent according to claim 23 or 24, characterized in that: the concentration of the chlorine-containing volatile organic compounds in the gas is lower than 7 multiplied by 10 5 mg/m 3 。
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Effective date of registration: 20231227 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |