CN113457627A - Polybenzoxazinyl derived carbon material for adsorbing carbonyl sulfide and preparation method and application thereof - Google Patents
Polybenzoxazinyl derived carbon material for adsorbing carbonyl sulfide and preparation method and application thereof Download PDFInfo
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- CN113457627A CN113457627A CN202110808402.4A CN202110808402A CN113457627A CN 113457627 A CN113457627 A CN 113457627A CN 202110808402 A CN202110808402 A CN 202110808402A CN 113457627 A CN113457627 A CN 113457627A
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- carbonyl sulfide
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- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000001179 sorption measurement Methods 0.000 claims abstract description 19
- 239000000571 coke Substances 0.000 claims abstract description 18
- -1 amine compound Chemical class 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 32
- 239000007789 gas Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 26
- 229920000642 polymer Polymers 0.000 claims description 24
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 22
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- 238000000197 pyrolysis Methods 0.000 claims description 10
- 229920000428 triblock copolymer Polymers 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 238000003763 carbonization Methods 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 229940015043 glyoxal Drugs 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 claims description 2
- 229960001553 phloroglucinol Drugs 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 7
- 239000006227 byproduct Substances 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 7
- 239000003463 adsorbent Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000010000 carbonizing Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000008098 formaldehyde solution Substances 0.000 description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical group [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/07—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of solid raw materials consisting of synthetic polymeric materials, e.g. tyres
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/32—Purifying combustible gases containing carbon monoxide with selectively adsorptive solids, e.g. active carbon
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Abstract
The invention discloses a polybenzoxazine-based derived carbon material for adsorbing carbonyl sulfide, and a preparation method and application thereof. The polybenzoxazine-based derivative carbon material has the advantages of large specific surface area, developed micropore pores, high mechanical strength and the like, and has a good adsorption effect on carbonyl sulfide in coke oven gas. The invention has the advantages of simple preparation method, low raw material cost, no by-product and the like, and has potential industrial application value.
Description
Technical Field
The invention relates to the technical field of adsorption and separation of carbonyl sulfide in coke oven gas, and particularly relates to a polybenzoxazinyl derived carbon material for adsorbing carbonyl sulfide and a preparation method and application thereof.
Background
The benzoxazine is a high-molecular oxazine ring aromatic polymer with good thermal stability and high carbon residue rate, and has the advantages of mild polymerization process conditions, no need of adding strong corrosive strong acid or strong base for catalysis, no by-product in the reaction, no release of small molecules and the like, so that the benzoxazine is taken as an ideal precursor. The benzoxazine monomer is subjected to ring-opening polymerization under catalysis or heating conditions to generate a polymer containing nitrogen and similar to a phenolic resin structure, namely polybenzoxazine, the polybenzoxazine resin is used as novel phenolic resin, and compared with the advantages of the traditional phenolic resin, the polybenzoxazine resin has the most remarkable characteristic of strong designability of a molecular structure, and different phenol compounds or amine compounds can be selected according to application requirements to synthesize the benzoxazine with different structures, so that the aim of further improving the comprehensive performance of a target product is fulfilled.
With the rapid development of modern chemical industry and the increasing increase of people's life, natural gas, petroleum gas, coke oven gas, water gas, semi-water gas and the like are widely applied to various chemical processes and people's daily life, and generally, the gases contain sulfides except general inorganic sulfur such as SO2、SO3、H2S, etc., and organic sulfur which is generally difficult to remove, such as COS and CS2Etc., wherein the chemical activity ratio of COS is H2S is much less chemically active and is both acidic and polar than H2S is weak, and easily causes catalyst poisoning and deactivation, and has a corrosive effect on industrial production equipment. But is generally used for removing H2The S method cannot effectively remove COS completely. Industrial methods for removing COS are largely divided into dry and wet methods, wherein dry means that CO is adsorbed by using an adsorbent and a catalystThe process of directly removing or converting S into other inorganic sulfur and then removing mainly comprises a reduction method, a hydrolysis method, an adsorption method, a photolysis method, an oxidation method and the like, and has the advantages of high desulfurization precision, low operation cost and the like, wherein the adsorption method, namely the method for treating COS after concentrated adsorption by using an adsorbent, is the most widely applied in industry.
The invention discloses a preparation method of a nitrogen and oxygen co-doped porous carbon material based on bio-based benzoxazine in patent CN 108640113A, which takes vanillin, 4-diaminodiphenyl ether and paraformaldehyde as raw materials, prepares the nitrogen and oxygen co-doped porous carbon material through processes of soft template, activation and the like, is used for an electrode of a super capacitor, has good cyclic charge and discharge performance, but has more complicated preparation method and higher cost, and has larger difficulty in practical application in industrial production.
The invention patent CN 109748279A discloses a microporous carbon material based on a benzoxazine porous polymer and a preparation method and application thereof, the method comprises the steps of firstly adding amine, phenol and paraformaldehyde into an organic solvent, stirring, heating, refluxing and reacting to synthesize the benzoxazine porous polymer, then mixing and impregnating the obtained polymer and an activating agent, and finally carrying out activation, acid washing, water washing and drying to obtain the microporous carbon material capable of efficiently adsorbing carbon dioxide.
In view of the technical background, the invention prepares the polybenzoxazinyl derivative carbon material for adsorbing carbonyl sulfide by simpler operation, has higher removal rate of carbonyl sulfide in coke oven gas, and has great environmental protection significance and economic significance.
Disclosure of Invention
Aiming at the defects of the adsorption material in the existing industrial production, the invention aims to provide a polybenzoxazinyl derived carbon material for adsorbing carbonyl sulfide and a preparation method thereof. The adsorbing material used in the invention is prepared by polymerizing a phenol compound and an aldehyde compound in one step and carbonizing and pyrolyzing at high temperature, has a good adsorbing effect on carbonyl sulfide in simulated coke oven gas, obviously improves the adsorbing capacity of a polymer carbon material on the carbonyl sulfide gas, and has potential industrial value in terms of environmental protection and economic benefit.
The preparation method of the polybenzoxazine-based derived carbon material for adsorbing carbonyl sulfide is characterized in that an amine compound is used as a curing agent, a polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer F127 is used as a soft template agent, a phenol compound and an aldehyde compound are subjected to one-step polymerization reaction in the presence of the curing agent and the soft template agent, and finally, the polybenzoxazine-based derived carbon material is prepared through high-temperature carbonization and pyrolysis.
The preparation method of the polybenzoxazinyl derivative carbon material for adsorbing carbonyl sulfide is characterized by comprising the following specific preparation steps:
1) firstly, adding a phenol compound into deionized water, stirring at room temperature until the phenol compound is completely dissolved, and marking as a solution A; adding the polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer F127 into ethanol, stirring at room temperature until the copolymer is completely dissolved, and marking as solution B for later use;
2) and adding the solution B into the solution A, stirring until the solution B is completely dissolved, then adding an aldehyde compound, stirring until the aldehyde compound is completely dissolved, adding an amine compound, stirring for reacting for a period of time, then transferring to a hydrothermal reaction kettle for carrying out one-step polymerization reaction, and finally carrying out high-temperature carbonization pyrolysis treatment on the obtained polymer to generate the polybenzoxazinyl derivative carbon material.
The preparation method of the polybenzoxazinyl derivative carbon material for adsorbing carbonyl sulfide is characterized in that in the step 1), the aldehyde compound is at least one of formaldehyde, acetaldehyde and glyoxal, the phenol compound is at least one of phenol, resorcinol and phloroglucinol, and the amine compound is at least one of 1, 2-ethylenediamine, diethylamine and triethylamine.
The preparation method of the polybenzoxazinyl derivative carbon material for adsorbing carbonyl sulfide is characterized in that in the step 2), the molar ratio of the phenol compound in the solution A to the polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer F127 in the solution B is 200:1-300: 1; in the step 2), the volume ratio of the deionized water in the solution A to the ethanol in the solution B is 1:1-1.5: 1.
The preparation method of the polybenzoxazinyl derivative carbon material for adsorbing carbonyl sulfide is characterized in that in the step 2), the molar ratio of the aldehyde compound to the phenol compound in the solution A is 1-3: 1; in the step 2), the molar ratio of the amine compound to the phenol compound in the solution A is 1: 40-60.
The preparation method of the polybenzoxazinyl derivative carbon material for adsorbing carbonyl sulfide is characterized in that in the step 2), the temperature of stirring reaction after adding the amine compound is 30-50 ℃, and the stirring reaction time is 1-4 h; the temperature for one-step polymerization reaction in the hydrothermal reaction kettle is 90-110 ℃, and the time for one-step polymerization reaction is 2-4 h.
The preparation method of the polybenzoxazinyl derivative carbon material for adsorbing carbonyl sulfide is characterized in that in the step 2), the high-temperature carbonization pyrolysis treatment process comprises the following steps: and (3) after the polymer is completely dried in an oven, transferring the polymer to a high-temperature furnace, heating to a pyrolysis temperature of 800-1100 ℃ in a nitrogen atmosphere, and then keeping the constant temperature at the pyrolysis temperature for 2-4 h.
A carbonyl sulfide adsorbing polybenzoxazinyl derivative carbon material prepared according to the above method.
The application of the polybenzoxazine-based derived carbon material in the adsorption of carbonyl sulfide in coke oven gas is characterized in that the polybenzoxazine-based derived carbon material is used as an adsorption material, the adsorption material is loaded into a fixed bed reactor, coke oven gas containing carbonyl sulfide is introduced into the fixed bed reactor, and the carbonyl sulfide in the coke oven gas is removed; the temperature in the removing process is 20-50 ℃, and the pressure is normal pressure; the ratio of the volume flow of the coke oven gas introduced into the fixed bed reactor to the filling mass of the adsorbing material in the fixed bed reactor is 2-10:1, the unit of the volume flow is mL/min, and the unit of the mass is g.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the polybenzoxazinyl derivative carbon material for adsorbing carbonyl sulfide has a good adsorption effect on carbonyl sulfide in a simulated coke oven gas mixed gas at the room temperature of 25 ℃, the pressure of the mixed gas of the normal pressure and the volume flow of the mixed gas of 20-100 mL/min, so that the adsorption capacity of the polymer carbon material on the carbonyl sulfide gas is obviously improved, and the polybenzoxazinyl derivative carbon material has potential industrial values in terms of environmental protection and economic benefits.
(2) The adsorbing material for removing carbonyl sulfide in coke oven gas disclosed by the invention is simple in preparation process, safe and environment-friendly in preparation process, low in production cost and suitable for removing carbonyl sulfide in an industrial process.
(3) The preparation method of the adsorbing material is characterized in that the adsorbing material is prepared by polymerizing the phenol compound and the aldehyde compound in one step and carbonizing and pyrolyzing the phenol compound and the aldehyde compound at high temperature.
Drawings
FIG. 1 shows N in an adsorbent obtained in example 3 of the present invention2Adsorption curve diagram;
FIG. 2 is a scanning electron microscope photograph of an adsorbent obtained in example 3 of the present invention;
FIG. 3 is a graph showing the relationship between the outlet concentration of carbonyl sulfide and the initial concentration ratio of carbonyl sulfide over time, when the adsorbing materials selected in the desulfurization adsorption experiment of the present invention were prepared in examples 1 to 3, respectively.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1:
a polybenzoxazinyl derived carbon material for adsorbing carbonyl sulfide, which is prepared by the following steps:
1) firstly, adding 3.0 g of resorcinol into 10.0 mL of deionized water, stirring at room temperature until the resorcinol is completely dissolved, and marking as a solution A; adding 1.4 g of polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer F127 (average relative molecular weight is 13000) into 10.0 mL of ethanol, stirring at room temperature until the copolymer is completely dissolved, and marking as solution B for later use;
2) and adding the solution B into the solution A, stirring until the solution B is completely dissolved, then adding 5.4 mL of formaldehyde solution with the mass fraction of 37%, then adding 36.5 uL of 1, 2-ethylenediamine, stirring and reacting at the temperature of 35 ℃ for 2 hours until the solution becomes milky white liquid, transferring the milky white liquid into a hydrothermal reaction kettle for one-step polymerization at the hydrothermal reaction temperature of 100 ℃ for 3 hours, drying the obtained polymer in an oven at the temperature of 80 ℃ for 8 hours, finally heating the obtained polymer to 1000 ℃ at the heating rate of 5 ℃/min in a nitrogen atmosphere, and carbonizing and pyrolyzing the obtained polymer at the high temperature of 1000 ℃ for 3 hours to obtain the polybenzoxazinyl derivative carbon material.
Example 2:
a polybenzoxazinyl derived carbon material for adsorbing carbonyl sulfide, which is prepared by the following steps:
1) firstly, adding 3.0 g of resorcinol into 10.0 mL of deionized water, stirring at room temperature until the resorcinol is completely dissolved, and marking as a solution A; adding 1.4 g of polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer F127 (average relative molecular weight is 13000) into 10.0 mL of ethanol, stirring at room temperature until the copolymer is completely dissolved, and marking as solution B for later use;
2) and adding the solution B into the solution A, stirring until the solution B is completely dissolved, then adding 5.4 mL of formaldehyde solution with the mass fraction of 37%, then adding 56.2 uL of diethylamine, stirring to react at 35 ℃ for 2 hours until the solution becomes yellow liquid, transferring the solution to a hydrothermal reaction kettle for one-step polymerization, wherein the hydrothermal reaction temperature is 100 ℃ for 3 hours, putting the obtained polymer into an oven for drying at 80 ℃ for 8 hours, finally heating the obtained polymer to 1000 ℃ at the heating rate of 5 ℃/min in a nitrogen atmosphere, and carbonizing and pyrolyzing the polymer at 1000 ℃ for 3 hours to obtain the polybenzoxazinyl derivative carbon material.
Example 3:
a polybenzoxazinyl derived carbon material for adsorbing carbonyl sulfide, which is prepared by the following steps:
1) firstly, adding 3.0 g of resorcinol into 10.0 mL of deionized water, stirring at room temperature until the resorcinol is completely dissolved, and marking as a solution A; adding 1.4 g of polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer F127 (average relative molecular weight is 13000) into 10.0 mL of ethanol, stirring at room temperature until the copolymer is completely dissolved, and marking as solution B for later use;
2) and adding the solution B into the solution A, stirring until the solution B is completely dissolved, then adding 5.4 mL of formaldehyde solution with the mass fraction of 37%, then adding 75.9 uL of triethylamine, stirring and reacting at 35 ℃ for 2 hours until the solution becomes milky white liquid, transferring the milky white liquid into a hydrothermal reaction kettle for one-step polymerization, wherein the hydrothermal reaction temperature is 100 ℃ for 3 hours, putting the obtained polymer into an oven for drying at 80 ℃ for 8 hours, finally heating the obtained polymer to 1000 ℃ at the heating rate of 5 ℃/min in a nitrogen atmosphere, and carbonizing and pyrolyzing the obtained polymer at the high temperature of 1000 ℃ for 3 hours to generate the polybenzoxazinyl derivative carbon material.
The adsorption material finally prepared in the embodiment 3 of the invention is subjected to BET characterization, and the specific surface area is 477.45 m2(g) adsorbing Material obtained in example 3 of the present invention, N2The adsorption profile is shown in figure 1. FIG. 1 illustrates that the polybenzoxazinyl derived carbon material obtained in example 3 conforms to the typical N form H12Adsorption curve, which shows that it has rich pore structure, especially micropore distribution. Fig. 2 shows a scanning electron microscope image of the adsorbent obtained in example 3 of the present invention. FIG. 2 illustrates that the polybenzoxazine based derivatized carbon material obtained in example 3 has a cross-linked spherical morphology with a large specific surface area.
Comparative example 1:
a polybenzoxazinyl derived carbon material for adsorbing carbonyl sulfide, which is prepared by the following steps:
1) firstly, adding 3.0 g of resorcinol into 10.0 mL of deionized water, stirring at room temperature until the resorcinol is completely dissolved, and marking as a solution A; adding 1.4 g of polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer F127 (average relative molecular weight is 13000) into 10.0 mL of ethanol, stirring at room temperature until the copolymer is completely dissolved, and marking as solution B for later use;
2) and adding the solution B into the solution A, stirring until the solution B is completely dissolved, then adding 5.4 mL of formaldehyde solution with the mass fraction of 37%, then adding 5.0 mol/L of sodium hydroxide solution, adjusting the pH to be about 9, stirring and reacting at the temperature of 35 ℃ for 2 hours until the solution becomes milky liquid, continuing stirring, aging for 12 hours, putting the obtained polymer into an oven for drying at the temperature of 80 ℃ for 8 hours, finally heating the obtained polymer to 1000 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere, and carbonizing and pyrolyzing at the high temperature of 1000 ℃ for 3 hours to generate the polybenzoxazinyl derived carbon material.
Application example 1:
when the adsorbing material is applied to removing carbonyl sulfide in coke oven gas, the experimental process is as follows: firstly, 1.0 g of adsorbing material is weighed and filled in a fixed bed reactor, then the fixed bed reactor is connected with a gas chromatograph to detect the concentration of carbonyl sulfide in gas at the outlet of the fixed bed reactor, the testing temperature is 25 ℃, the pressure is normal pressure, and simulated coke oven gas with the flow rate of 20 mL/min is introduced into the fixed bed reactor. Wherein, the gas components of the simulated coke oven gas are as follows: COS concentration is 300 mg/m3Volume fraction of CO is 1.01%, CO2The volume fraction is 30 percent, and the rest is N2。
When the adsorbing materials selected according to the above experimental procedures were the adsorbing materials prepared in examples 1 to 3 and comparative example 1, respectively, the relationship between the exit concentration of cos and the initial concentration ratio in the outlet gas of the fixed-bed reactor as a function of time is summarized in fig. 3.
As can be seen from fig. 3, the adsorbent of example 3 has the best experimental effect, and the removal rate of COS in 6 hours by the adsorbent of example 3 is more than 95%. The experimental effect of the adsorbing material of the comparative example 1 is slightly worse than that of the adsorbing material of the example 1, but compared with the comparative example 1, in the preparation method of the adsorbing material of the example 1, after the amine curing agent is added, the time for the polymerization reaction of the phenol compound and the aldehyde compound is obviously shortened, and the preparation method of the adsorbing material is simpler and more efficient.
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.
Claims (9)
1. A preparation method of a polybenzoxazine-based derived carbon material for adsorbing carbonyl sulfide is characterized in that an amine compound is used as a curing agent, a polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer F127 is used as a soft template agent, a phenol compound and an aldehyde compound are subjected to one-step polymerization reaction in the presence of the curing agent and the soft template agent, and finally, the polybenzoxazine-based derived carbon material is prepared through high-temperature carbonization and pyrolysis.
2. The method for preparing a carbonyl sulfide adsorbing polybenzoxazine based derivative carbon material according to claim 1, which comprises the following steps:
1) firstly, adding a phenol compound into deionized water, stirring at room temperature until the phenol compound is completely dissolved, and marking as a solution A; adding the polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer F127 into ethanol, stirring at room temperature until the copolymer is completely dissolved, and marking as solution B for later use;
2) and adding the solution B into the solution A, stirring until the solution B is completely dissolved, then adding an aldehyde compound, stirring until the aldehyde compound is completely dissolved, adding an amine compound, stirring for reacting for a period of time, then transferring to a hydrothermal reaction kettle for carrying out one-step polymerization reaction, and finally carrying out high-temperature carbonization pyrolysis treatment on the obtained polymer to generate the polybenzoxazinyl derivative carbon material.
3. The method for preparing a polybenzoxazine based derived carbon material for adsorbing carbonyl sulfide according to claim 2, wherein in step 1), the aldehyde compound is at least one of formaldehyde, acetaldehyde and glyoxal, the phenol compound is at least one of phenol, resorcinol and phloroglucinol, and the amine compound is at least one of 1, 2-ethylenediamine, diethylamine and triethylamine.
4. The method for preparing a carbonyl sulfide adsorbing polybenzoxazine based derivative carbon material according to claim 2, wherein in step 2), the molar ratio of the phenolic compound in the solution A to the polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer F127 in the solution B is 200:1 to 300: 1; in the step 2), the volume ratio of the deionized water in the solution A to the ethanol in the solution B is 1:1-1.5: 1.
5. The method for preparing a carbonyl sulfide adsorbing polybenzoxazine based derivative carbon material according to claim 2, wherein in the step 2), the molar ratio of the aldehyde compound to the phenol compound in the solution A is 1-3: 1; in the step 2), the molar ratio of the amine compound to the phenol compound in the solution A is 1: 40-60.
6. The method for preparing a polybenzoxazinyl derived carbon material for absorbing carbonyl sulfide as claimed in claim 2, wherein in the step 2), the temperature of stirring reaction after adding the amine compound is 30-50 ℃, and the stirring reaction time is 1-4 h; the temperature for one-step polymerization reaction in the hydrothermal reaction kettle is 90-110 ℃, and the time for one-step polymerization reaction is 2-4 h.
7. The method for preparing a carbonyl sulfide adsorbing polybenzoxazine based derivative carbon material according to claim 2, wherein in the step 2), the high temperature carbonization pyrolysis treatment process comprises: and (3) after the polymer is completely dried in an oven, transferring the polymer to a high-temperature furnace, heating to a pyrolysis temperature of 800-1100 ℃ in a nitrogen atmosphere, and then keeping the constant temperature at the pyrolysis temperature for 2-4 h.
8. A carbonyl sulfide adsorbing polybenzoxazine based derivative carbon material prepared according to the method of any one of claims 1 to 7.
9. The application of the polybenzoxazine based derived carbon material in the adsorption of carbonyl sulfide in coke oven gas as claimed in claim 8, wherein the polybenzoxazine based derived carbon material is used as an adsorption material, the adsorption material is loaded in a fixed bed reactor, coke oven gas containing carbonyl sulfide is introduced into the fixed bed reactor, and the process of removing carbonyl sulfide in coke oven gas is carried out; the temperature in the removing process is 20-50 ℃, and the pressure is normal pressure; the ratio of the volume flow of the coke oven gas introduced into the fixed bed reactor to the filling mass of the adsorbing material in the fixed bed reactor is 2-10:1, the unit of the volume flow is mL/min, and the unit of the mass is g.
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