CN115970642B - Dechlorination agent with high specific surface area and high chlorine capacity and preparation method thereof - Google Patents
Dechlorination agent with high specific surface area and high chlorine capacity and preparation method thereof Download PDFInfo
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- CN115970642B CN115970642B CN202211544842.4A CN202211544842A CN115970642B CN 115970642 B CN115970642 B CN 115970642B CN 202211544842 A CN202211544842 A CN 202211544842A CN 115970642 B CN115970642 B CN 115970642B
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 44
- 239000000460 chlorine Substances 0.000 title claims abstract description 30
- 238000006298 dechlorination reaction Methods 0.000 title claims abstract description 27
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 17
- 239000003463 adsorbent Substances 0.000 claims abstract description 16
- -1 alkali metal salt Chemical class 0.000 claims abstract description 14
- 238000003763 carbonization Methods 0.000 claims abstract description 10
- 239000002131 composite material Substances 0.000 claims abstract description 8
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 56
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 11
- 230000000382 dechlorinating effect Effects 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000004698 Polyethylene Substances 0.000 claims description 9
- 229920000573 polyethylene Polymers 0.000 claims description 9
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910001868 water Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 6
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims description 5
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 5
- MEBONNVPKOBPEA-UHFFFAOYSA-N 1,1,2-trimethylcyclohexane Chemical compound CC1CCCCC1(C)C MEBONNVPKOBPEA-UHFFFAOYSA-N 0.000 claims description 4
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 2
- 229940057838 polyethylene glycol 4000 Drugs 0.000 claims description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 7
- 238000000034 method Methods 0.000 abstract description 15
- 239000002243 precursor Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 2
- 239000002736 nonionic surfactant Substances 0.000 abstract description 2
- 239000005011 phenolic resin Substances 0.000 abstract description 2
- 229920001568 phenolic resin Polymers 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 24
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 24
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 24
- 238000001179 sorption measurement Methods 0.000 description 11
- 230000035515 penetration Effects 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910001038 basic metal oxide Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000012946 outsourcing Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention belongs to the technical field of adsorbent materials, and relates to a dechlorination agent with high specific surface area and high chlorine capacity and a preparation method thereof. The invention adopts nonionic surfactant and soluble phenolic resin to carry out free assembly as a carbon source precursor, then soluble alkali metal salt is added, and the dechlorination agent is prepared by high-temperature carbonization treatment; and a small amount of cross-linking agent is added during the preparation of the carbon source precursor, so that the probability of collapse of a mesoporous carbon skeleton in the high-temperature carbonization process can be greatly reduced, the thermal stability of the composite material is improved, and the dechlorination agent is ensured to have a very high specific surface area.
Description
Technical Field
The invention belongs to the technical field of adsorbent materials, and relates to a dechlorination agent with high specific surface area and high chlorine capacity and a preparation method thereof.
Background
In a continuous chemical production device, in order to keep high-efficiency and stable catalytic activity, noble metal supported catalysts such as palladium, platinum, rhodium and the like need to be regenerated intermittently or continuously. In the catalyst regeneration process, chlorine substances such as chlorine and tetrachloroethylene are often added to promote the uniform distribution of the active components of the catalyst again, reduce the particle size and improve the dispersity of the active components. Inevitably, chlorine substances dispersing active components of the catalyst enter a reactor along with the catalyst, hydrogen chloride and a small amount of chlorine organic matters are generated under the combined action of a high-temperature reaction environment and the catalyst, and the hydrogen chloride, water and hydrogen sulfide in the materials are in the same environment, so that an HCl-H 2S-H2 O system is extremely easy to form, and the catalyst has extremely strong corrosiveness, and along with the entering of effluent materials of the reactor into downstream equipment, metal pipelines and equipment are corroded; the hydrogen chloride reacts with ammonia substances to generate ammonium salt, and the cooling equipment is blocked and destroyed. Thus, the reactor effluent is compressed and then provided with a dechlorination tank to preferentially remove hydrogen chloride from the product.
At present, the dechlorinating agent for industrial application is prepared by kneading and forming basic metal oxides such as CaO, na 2 O, znO and the like as main components with an Al 2O3 carrier or loading the basic metal oxides on the carrier, and the basic metal oxides and hydrogen chloride are subjected to chemical adsorption to achieve the effect of removing the hydrogen chloride. However, the dechlorinating agent in industrial application has poor mass transfer effect at lower material temperature, the penetration chlorine capacity is generally lower than 30%, the service life of the dechlorinating agent is far lower than a design value, and the stable operation of downstream equipment of the device is affected. In addition, the cost of purchasing new dechlorinating agent, high-risk replacement operation, waste agent outsourcing treatment and the like is greatly increased, and the running cost of enterprises is increased in an intangible way.
Disclosure of Invention
The invention aims to provide a preparation method of a dechlorination agent with high specific surface area and high chlorine capacity, and the dechlorination agent prepared by the method
The technical scheme adopted for solving the technical problems is as follows:
A preparation method of a dechlorinating agent with high specific surface area and high chlorine capacity comprises the following steps:
Step one: resorcinol, a template agent, a cross-linking agent and sodium hydroxide solid are dissolved in proper amount of absolute ethyl alcohol, and the mol ratio of resorcinol to the template agent is 1: (0.01-0.1), the mol ratio of resorcinol to cross-linking agent is 1: (0.01-0.1), the mol ratio of resorcinol to sodium hydroxide is: 1: (2-3);
step two: pouring 35-40 wt% formaldehyde aqueous solution into a separating funnel under the conditions of constant temperature and stirring in a water bath at 30-50 ℃, adding the formaldehyde aqueous solution into the liquid in the step one, and continuing stirring for 30min after the dripping is finished, wherein the molar ratio of resorcinol to formaldehyde is as follows: 1: (1-3);
Step three: dissolving M xCly solid in 70-80 wt% ethanol water solution, keeping the temperature in a water bath at 30-50 ℃, adding the solution into the liquid obtained in the second step under stirring, stirring for 2 hours, pouring the solution into a culture dish, putting the culture dish into a 40-70 ℃ oven, evaporating the solution, transferring the solution into a blast oven, and drying the solution at the constant temperature of 120-180 ℃ for 3-6 hours to obtain a solid sample;
The M xCly solid is two of NaCl, KCl, caCl 2、MgCl2、AlCl3、MnCl2, and the molar ratio is 1: (0.3-3);
Step four: crushing and grinding the solid sample to 80-120 meshes, and putting the solid sample into a horizontal tube type heating furnace for carbonization treatment to obtain the mesoporous composite material, namely the dechlorinated adsorbent.
Preferably, the template agent is one or more of P123, F127, F108, polyethylene glycol-2000, polyethylene glycol-4000, 18-crown ether-6, hexadecylamine, hexadecyltrimethyl ammonium bromide, trioctyl methyl ammonium chloride and tetrabutyl ammonium bromide. Preferably, the template agent is one or more of P123, F127, polyethylene glycol-2000 and 18-crown ether-6. Most preferably, the template agent is one or two of F127 and polyethylene glycol-2000.
Preferably, the molar ratio of resorcinol to template agent is 1: (0.03-0.06).
Preferably, the cross-linking agent is one or more of diethylenetriamine, triethylenetetramine, hexamethylenetetramine, N-methylenebisacrylamide, p-benzoyl quinone dioxime, propylenediamine, trimethylol propane, bismaleimide, divinylbenzene and trimethylcyclohexane. Preferably, the cross-linking agent is one or more of p-benzoyl quinone dioxime, hexamethylenetetramine, N-methylene bisacrylamide and bismaleimide. Most preferably, the cross-linking agent is one or two of N, N-methylene bisacrylamide and bismaleimide.
Preferably, the mol ratio of resorcinol to the crosslinking agent is 1: (0.05-0.1).
Preferably, the M xCly solid is two of NaCl, KCl, caCl 2、AlCl3, and the molar ratio is 1: (0.5-2).
Preferably, the M xCly solid is KCl and CaCl 2, and the mol ratio of resorcinol to KCl to CaCl 2 is 1: (1-2): (1-2), the optimal ratio is 1: (1.5-2): (1.5-2).
Preferably, in the third step, the condition of constant temperature drying is that of constant temperature drying at 130 ℃ for 6 hours.
Preferably, the carbonization treatment conditions described in the fourth step: the protective gas is inert gas with the purity of more than or equal to 99.999 percent, the gas flow is 100-500 mL/min, the temperature is raised to 700-1000 ℃ from the room temperature at the heating rate of 1-3 ℃/min for 3-8 hours, and then the temperature is naturally lowered to the room temperature. It is further preferred that the temperature is raised to 700℃at a rate of 2℃per minute.
Preferably, the inert gas is one of nitrogen, helium and argon.
The dechlorination agent with high specific surface area and high chlorine capacity is prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention adopts nonionic surfactant and soluble phenolic resin to carry out free assembly as a carbon source precursor, then soluble alkali metal salt is added, and the dechlorination agent is prepared by high-temperature carbonization treatment. A small amount of cross-linking agent is added during the preparation of the carbon source precursor, so that the probability of collapse of a mesoporous carbon skeleton in the high-temperature carbonization process can be greatly reduced, the thermal stability of the composite material is improved, and the dechlorination agent is ensured to have a very high specific surface area;
(2) The specific surface area of the mesoporous K 2 O-CaO-C composite material prepared by the dechlorinating agent disclosed by the invention is as follows: 858 to 943m 2/g, and has an average pore diameter of: 3.6-6.4 nm, pore volume is: 1.0-1.6 cm 3/g; the penetration chlorine capacity is: 51.1 to 60.4 percent; the dechlorination agent has smaller pore diameter and higher specific surface area, so that the residence time of hydrogen chloride on the surface of the adsorbent is further increased, and the adsorption capacity of the dechlorination agent is improved;
(3) The dechlorination active component K 2 O, caO precursor and the carbon skeleton precursor are calcined together at high temperature, and K 2 O, caO can be firmly inlaid on the surface of mesoporous carbon, so that the dechlorination active component K 2 O, caO precursor has better binding force than the active component loaded by an impregnation method reported in some patents;
(4) The dechlorination agent prepared by the method has the advantages of simple operation, large chlorine capacity and low cost, and is prepared by taking mesoporous carbon as a framework, so that the method is very simple and convenient for treating and replacing waste agents, and has considerable application prospect in industrial dechlorination agents.
Drawings
FIG. 1 is a schematic diagram of a high specific surface area, high chlorine capacity dechlorination performance evaluation apparatus of the dechlorination agent of the present invention, wherein 1: a nitrogen cylinder; 2: a hydrogen chloride gas bottle; 3,4: a mass flowmeter; 5: a mixer; 6,12: a filter; 7,13,15,16: a needle valve; 8,11: a volumetric flowmeter; 9: u-shaped tubular resistance furnace; 10: a thermometer; 14: a tail gas absorption tank.
Detailed Description
The technical scheme of the invention is further specifically described by the following specific examples. It should be understood that the practice of the invention is not limited to the following examples, but is intended to be within the scope of the invention in any form and/or modification thereof.
In the present invention, unless otherwise specified, all parts and percentages are by weight, and the equipment, materials, etc. used are commercially available or are conventional in the art. The methods in the following examples are conventional in the art unless otherwise specified.
Example 1
The preparation method of the dechlorinating agent with high specific surface area and high chlorine capacity comprises the following specific steps:
(1) Resorcinol and template polyethylene glycol-2000 were dissolved in 100mL of absolute ethanol, and then crosslinker N, N-methylenebisacrylamide and sodium hydroxide solids were added thereto, wherein the molar ratio of resorcinol to polyethylene glycol-2000 was 1:0.05, resorcinol to N, N-methylenebisacrylamide molar ratio of 1:0.06, resorcinol to sodium hydroxide molar ratio of 1:2.2, fully stirring until the components are completely dissolved;
(2) A proper amount of 37wt% formaldehyde solution is measured and poured into a separating funnel, so that the mol ratio of resorcinol to formaldehyde is as follows: 1:2, slowly dripping the mixture into the liquid obtained in the step (1) at the constant temperature of a water bath at 40 ℃ under mechanical stirring, and continuously stirring for 30min after the dripping is completed to obtain yellow sol liquid;
(3) KCl solid and CaCl 2 solid are dissolved in 75% ethanol water solution and poured into a separating funnel, and the molar ratio of resorcinol to KCl to CaCl 2 is as follows: 1:1.2: slowly dripping the mixture into the liquid obtained in the step (2) under the conditions of constant temperature of water bath and mechanical stirring at the temperature of 1, pouring the mixture into a culture dish, putting the culture dish into a baking oven, evaporating the solvent at the constant temperature of 60 ℃, and then transferring the culture dish into a blast baking oven, and drying the mixture at the constant temperature of 150 ℃ for 4 hours to obtain a solid sample;
(4) Crushing and grinding the solid sample obtained in the step (3) to about 100 meshes, putting the crushed and ground solid sample into a horizontal tube type heating furnace for carbonization treatment, wherein the protective gas is nitrogen (N 2 is more than or equal to 99.999 percent), the gas flow is 200mL/min, heating the solid sample from room temperature to 900 ℃ at a heating rate of 2 ℃/min for 5 hours, and naturally cooling the solid sample to the room temperature to obtain the mesoporous K 2 O-CaO-C composite material, namely: dechlorination adsorbent. The specific surface area, average pore size and pore volume of the dechlorinated adsorbent were measured using a NOVA4000 auto-adsorbent from Kang Da in the united states.
Dechlorination performance detection test of dechlorination agent dechlorination performance of dechlorination agent prepared by adopting a fixed bed dynamic adsorption device, and a schematic diagram of an experimental device is shown in figure 1. The evaluation equipment comprises a mixer 5, a U-shaped tubular resistance furnace 9 and a tail gas absorption tank 14 which are connected through pipelines, wherein a nitrogen bottle 1 and a hydrogen chloride bottle 2 enter the mixer 5 through respective mass flow meters 3 and 4 respectively, a thermometer 10 is arranged on the U-shaped tubular resistance furnace 9,U through a volume flow meter 8 after mixing, an outlet pipeline of the U-shaped tubular resistance furnace 9 is connected with the tail gas absorption tank 14 through a volume flow meter 11, a branch pipeline is arranged at the outlet of the mixer 5, a filter 6 and a needle valve 7 are sequentially arranged on the branch pipeline, and the terminal of the branch pipeline is connected with the concentration detection of hydrogen chloride at an adsorption inlet; the volume flowmeter 11 is provided with a branch pipeline on a pipeline connected with the tail gas absorption tank 14, the branch pipeline is sequentially provided with a filter 12 and a needle valve 13, the terminal of the branch pipeline is connected with the concentration detection of hydrogen chloride at the absorption outlet, the terminal of the branch pipeline is provided with a secondary branch pipeline, the secondary branch pipeline is provided with a needle valve 16, one section of the secondary branch pipeline is communicated with the tail gas absorption tank 14, and the other section of the secondary branch pipeline is provided with a needle valve 15 and is communicated with the concentration detection of hydrogen chloride at the absorption inlet.
10.0G of mesoporous K 2 O-CaO-C composite material is subjected to tabletting and crushing (about 20 meshes of particles) treatment and is filled into a U-shaped quartz tube, the rest space is filled with quartz sand and quartz cotton, and the concentration of hydrogen chloride in mixed gas of nitrogen and hydrogen chloride is as follows: 200ppm, the flow rate of the mixed gas is: 300mL/min, the constant temperature of the resistance furnace at 40 ℃, the self-priming hydrogen chloride gas detector is connected behind the U-shaped tubular resistance furnace, a high report value of 1ppm is set for reminding experimenters, the timing is started from the mixed gas inlet, when the concentration of the hydrogen chloride at the outlet reaches 1ppm, the timing and the adsorption performance test are stopped, the time difference between the two is the penetration time, and the capacity of the adsorbent for absorbing the hydrogen chloride is calculated, namely: penetrating the chlorine vessel.
Wherein, the formula of calculation of penetration chlorine capacity is:
Example 2
Template F127 was used instead of polyethylene glycol-2000 as template in example 1, and the other steps were the same as in example 1.
Example 3
The procedure of example 1 was followed except that the crosslinking agent N, N-methylenebisacrylamide of example 1 was replaced with bismaleimide as a crosslinking agent.
Example 4
The molar ratio of resorcinol to polyethylene glycol-2000 is 1:0.08 instead of example 1 the molar ratio of resorcinol to polyethylene glycol-2000 is 1:0.05, the other steps are the same as in example 1.
Example 5
The molar ratio of resorcinol to N, N-methylene bisacrylamide is 1:0.08 instead of example 1 the molar ratio of resorcinol to N, N-methylenebisacrylamide was 1:0.06, the other steps are the same as in example 1.
Example 6
Resorcinol, KCl and CaCl 2 are used in the following molar ratio: 1:1.5:1.5 instead of resorcinol, KCl, caCl 2 in example 1, the molar ratio was: 1:1.2:1, the other steps are the same as in example 1.
Example 7
The procedure of example 1 was followed except that the drying was carried out at a constant temperature of 130℃for 6 hours instead of 150℃for 4 hours in example 1.
Example 8
The procedure of example 1 was repeated except that the shielding gas was helium instead of nitrogen in example 1.
Example 9
The procedure of example 1 was followed except that the temperature rise rate of 2℃per minute was increased to 700℃instead of increasing the temperature rise rate of 2℃per minute to 900℃in example 1.
Comparative example 1
The concentration of hydrogen chloride is as follows: 400ppm instead of the hydrogen chloride concentration in example 1: 200ppm, the other steps are as in example 1.
Performance test results specific surface area, pore volume and pore diameter of the dechlorinating agent prepared in examples 1 to 9 and comparative example 1 were measured, and the results of the hydrogen chloride adsorption performance test are shown in Table 1.
TABLE 1 BET parameters and adsorption Performance parameters of the dechlorinating agents prepared in examples 1 to 9 of the present invention and comparative example 1
As can be seen from Table 1, the mesoporous K 2 O-CaO-C composite material of the invention has higher adsorption capacity and excellent adsorption performance on hydrogen chloride gas. The adsorption effect of the adsorbent prepared by replacing the template agent in the example 2 and replacing the cross-linking agent in the example 3 is equivalent to that of the adsorbent prepared in the example 1; compared with the adsorbent prepared by changing the addition amount of the template agent in the example 4 and the addition amount of the cross-linking agent in the example 5 and the adsorbent prepared by changing the addition amount of the cross-linking agent in the example 1, the characterization of the specific surface area, the pore diameter and the air-volume performance is almost the same, and the penetration chlorine volume is higher than 50%; example 6 adsorbent prepared by increasing the amount of alkaline metal added, although the specific surface area is reduced, the penetration time of hydrogen chloride is obviously delayed, and the penetration chlorine capacity is even higher than 60%; examples 7, 8, and 9 are adsorbents prepared from optimized carbonization conditions, and have higher penetration chlorine than example 1; comparative example 1 shows that the adsorbent prepared by the invention has good adsorption performance on high-concentration hydrogen chloride as well as the concentration of hydrogen chloride is improved during performance test.
In this specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, so that the same or similar parts between the embodiments are referred to each other. For the device disclosed in the embodiment, since it corresponds to the method disclosed in the embodiment, the description is relatively simple, and the relevant points refer to the description of the method section.
The dechlorination agent with high specific surface area and high chlorine capacity and the preparation method thereof are described in detail. The principles and embodiments of the present invention have been described herein with reference to specific examples, the description of which is intended only to facilitate an understanding of the method of the present invention and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.
Claims (8)
1. The preparation method of the dechlorinating agent with high specific surface area and high chlorine capacity is characterized by comprising the following steps:
Step one: resorcinol, a template agent, a cross-linking agent and sodium hydroxide solid are dissolved in proper amount of absolute ethyl alcohol, and the mol ratio of resorcinol to the template agent is 1: (0.01-0.1), wherein the mol ratio of resorcinol to the cross-linking agent is 1: (0.01-0.1), wherein the mol ratio of resorcinol to sodium hydroxide is 1: (2-3);
step two: pouring 35-40 wt% of formaldehyde aqueous solution into a separating funnel under the conditions of constant temperature and stirring in a water bath at 30-50 ℃, adding the formaldehyde aqueous solution into the liquid in the step one, and continuing stirring for 30min after the dripping is finished, wherein the molar ratio of resorcinol to formaldehyde is as follows: 1: (1-3);
Step three: dissolving M xCly solid in 70-80 wt% ethanol water solution, keeping the temperature in a water bath at 30-50 ℃, adding the solution into the liquid obtained in the second step under stirring, stirring for 2 hours, pouring the solution into a culture dish, putting the culture dish into a 40-70 ℃ oven, evaporating the solution, transferring the culture dish into a blast oven, and drying the culture dish at the constant temperature of 120-180 ℃ for 3-6 hours to obtain a solid sample;
The M xCly solid is KCl and CaCl 2, and the mol ratio of resorcinol to KCl to CaCl 2 is: 1: (1-2): (1-2);
Step four: crushing and grinding the solid sample to 80-120 meshes, and putting the solid sample into a horizontal tube type heating furnace for carbonization treatment to obtain the mesoporous composite material, namely the dechlorinated adsorbent.
2. The method of manufacturing according to claim 1, characterized in that: the template agent is one or more of P123, F127, F108, polyethylene glycol-2000, polyethylene glycol-4000, 18-crown ether-6, hexadecylamine, hexadecyl trimethyl ammonium bromide, trioctylmethyl ammonium chloride and tetrabutyl ammonium bromide.
3. The method of manufacturing according to claim 1, characterized in that: the mol ratio of the resorcinol to the template agent is 1: (0.03 to 0.06).
4. The method of manufacturing according to claim 1, characterized in that: the cross-linking agent is one or more of diethylenetriamine, triethylenetetramine, hexamethylenetetramine, N-methylene bisacrylamide, p-benzoyl quinone dioxime, propylene diamine, trimethylolpropane, bismaleimide, divinylbenzene and trimethylcyclohexane.
5. The method of manufacturing according to claim 1, characterized in that: the mol ratio of resorcinol to the crosslinking agent is 1: (0.05 to 0.1).
6. The method of manufacturing according to claim 1, characterized in that: the carbonization treatment conditions are as follows: the protective gas is inert gas with the purity of more than or equal to 99.999%, the gas flow is 100-500 mL/min, the temperature is raised to 700-1000 ℃ from the room temperature at the heating rate of 1-3 ℃/min for 3-8 hours, and then the temperature is naturally lowered to the room temperature.
7. The method of manufacturing according to claim 6, wherein: the inert gas is one of nitrogen, helium and argon.
8. A dechlorination agent having a high specific surface area and a high chlorine capacity obtained by the production method of claim 1.
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