CN105688856A - Decorating method of porous carbon microsphere quaternization - Google Patents
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- 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
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- G01N30/02—Column chromatography
Abstract
The invention provides a decorating method of porous carbon microsphere quaternization. Quaternization porous carbon microspheres are used for correspondingly fixing an ion spectrum and have the advantages that the preparation process is simple, filler is uniform in granularity, and negative ion spectrum columns are controllable in capacity and resistant to pressure, acid and alkali.
Description
Technical field
The present invention relates to a kind of novel anionic chromatographic column and preparation method thereof, particularly relate to porous carbon microsphere preparation and efficient quaternised method and the method using quaternized porous carbon microsphere as the fixing facies analysis conventional anion of anion chromatographic。
Background technology
Along with developing rapidly of science and technology, chromatography of ions is as the important branch of chromatography, and oneself is through being widely used in the fields such as environmental monitoring, electric power and energy industry, electron trade, food and beverage industry, chemical industry, pharmaceutical industry and life sciences。The same with other chromatograph branches, chromatographic column, as the split site of each target analytes, is the core of whole piece-rate system, the study hotspot of chromatograph worker especially。The filler of ion chromatographic column can be made up of substrate and functional group two parts, and the substrate as filler mainly includes machine polymeric matrix and the big class of inorganic matrix two。Owing to being capable of withstanding by very wide pH value range, the application of organic polymer ion crossover fixation phase is relatively wide, is the main stuffing of current commercialization ion chromatographic column。But organic polymer has Swelling, mechanical strength is not high, and preparation process needs to consume a large amount of organic reagent, so development has the Novel ion chromatographic stationary phases of PH toleration, high mechanical properties and environmental protection concurrently highly significant。
Porous carbon microsphere is spherical or almost spherical, rich in a kind of new carbon in micron number magnitude of duct, particle size distribution。Due to its rich in duct, mechanical strength is high, density is little, acid-fast alkali-proof, without swelling, be therefore the potential substrate of one preparing the fixing phase of chromatography of ions。At present, preparing porous carbon microsphere traditional method is hard template method, namely with monodispersed silicon ball for template, its surface is made uniformly to adhere to Organic substance by the mode impregnated, then in atmosphere of inert gases, high-temperature calcination makes Organic substance graphitization, then adds heat soaking with Fluohydric acid. and remove sol-gel and obtain porous carbon microsphere。But this method process is loaded down with trivial details, equipment requirements is high, and used organic solvent and Fluohydric acid. environment and people is all harmful。In recent years, safety non-toxic, technological process be simple, product purity advantages of higher owing to having for hydro-thermal method, and receives significant attention。Water soluble carbohydrates (such as glucose, sucrose etc.) can obtain solid carbon microsphere by hydro-thermal reaction, can obtain porous carbon microsphere again through high-temperature heat treatment, and this method has simplicity, the feature such as quick, green。
The quaternised modified of porous carbon microsphere currently mainly adopts covalent bond or non-covalent bond method。For non-covalent bond method, modifier molecules is adsorbed on carbosphere surface by active forces such as hydrogen bond, π-pi-electron accumulation, electrostatic interaction, Van der Waals force and hydrophilic/hydrophobic interactions。Owing to the active force between interface is relatively weak, the bonding force strength ratio covalent bond effect of non-covalent bond is little a lot, it is easy to come off。Covalent bond is modified method and is generally first used quaternizing agent (such as iodomethane) with needs, and the amido generation substitution reaction modified with carbosphere surface generates quaternary ammonium salt, but this method effective percentage is not high and the shortcoming of use poisonous reagent。
The invention provides a kind of quaternised new method of porous carbon microsphere, and quaternised porous carbon microsphere is applied in chromatography of ions as chromatographic stationary phases first。This method utilizes the carboxyl on porous carbon microsphere surface and hydroxyl after strong acid oxidation, with methylamine and 1,4-butanediol diglycidyl ether is copolymerized, introduce the macromolecule layer containing quaternary ammonium group, constantly circulate this process and can effectively regulate the content of quaternary ammonium salt, thus controlling the ion exchange capacity of carbosphere。
Summary of the invention
The present invention provides a kind of quaternised method of modifying of porous carbon microsphere, and quaternised porous carbon microsphere is applied in chromatography of ions as chromatographic stationary phases, having preparation technology simple, packing material size is uniform, anion chromatographic column column capacity is controlled, pressure, the characteristic of acid and alkali-resistance。
The present invention prepares the carbon ball of rich surface hydroxyl and carboxyl by the hydro-thermal reaction of sucrose, then 1000 DEG C of high-temperature process carbon balls in nitrogen atmosphere, make its progressively graphitization finally give the porous carbon microsphere that mean diameter is 3.8 μm, then aoxidize it with concentrated sulphuric acid and concentrated nitric acid mixed liquor。The carboxyl formed after utilizing porous carbon microsphere surface to be aoxidized by strong acid and hydroxyl, be copolymerized with methylamine water solution and BDO diglycidyl ether, introduces the macromolecule layer containing quaternary ammonium group, thus opening the quaterisation of carbosphere。
Described preparation process is:
(1) the carbon ball that sucrose solution hydro-thermal reaction is prepared is put in tube furnace, pass into nitrogen and keep high temperature, prepare required porous carbon microsphere；
(2) porous carbon microsphere is added in concentrated sulphuric acid and the concentrated nitric acid mixed liquor of 30-100ml, be stirred at reflux。After question response terminates, filter and with deionized water wash product to neutral, put in baking oven and dry；
(3) by the methylamine of 20-60ml and BDO diglycidyl ether mix homogeneously, 2-4g porous carbon microsphere, ultrasonic disperse are added；
(4) by after above-mentioned solution reacting by heating 15-60min under magnetic stirring, filter with deionized water wash；
(5) add BDO diglycidyl ether to mix with porous carbon microsphere, under magnetic agitation after reacting by heating 15-60min, filter with deionized water wash；
(6) add methylamine water solution to mix with porous carbon microsphere, under magnetic agitation after reacting by heating 15-60min, filter with deionized water wash；
(7) (4), (5) two-step reaction alternate cycles are carried out n time, the porous carbon microsphere of surface grafting n strata cationic layer, N ∈ Z and N >=1 can be obtained；
(8) with deionized water for homogenate, under 40Mpa, wet method dress post is adopted；
(9) with NaOH solution for leacheate, it is suppressed that seven kinds of conventional anion are detected by electric conductivity detector。
The present invention, with methylamine, BDO diglycidyl ether for monomer, is copolymerized introducing quaternary ammonium salt with the carboxyl on porous carbon microsphere surface and hydroxyl。
As further optimization, the concrete operation step of above-mentioned steps of the present invention is as follows:
Step 1: 6.1g carbon ball sucrose solution hydro-thermal reaction prepared is put in tube furnace, nitrogen is passed into the speed of 30ml/min, arranging temperature control program after half an hour is: from room temperature to the heating rate of 1000 DEG C be 8 DEG C/min, 1000 DEG C keep 2h, from 1000 DEG C to the rate of temperature fall of room temperature be 10 DEG C/min。After calcining, original surface has the solid carbon ball of a lot of oxy radical to be changed into the graphited porous carbon microsphere in surface, and its Quality Down is to 3.5g。
Step 2: joined by porous carbon microsphere prepared by 3.5g step 1 in 30-100ml concentrated sulphuric acid and concentrated nitric acid mixed liquor, after heated and stirred backflow 1-3h, filtration washing product is to neutral。
Step 3: products therefrom in step 2 is added in the 20-60ml methylamine (2%, the v/v) mixed liquor with BDDE (8%, v/v), ultrasonic disperse。
Step 4: after above-mentioned solution under magnetic stirring 60 DEG C of reacting by heating 15-60min, filter with deionized water wash。
Step 5: add 20-60ml1,4-butanediol diglycidyl ether (60%, v/v) and mix with carbosphere, after heating 60 DEG C of reaction 15-60min, filters repeatedly with deionized water wash under magnetic agitation。
Step 6: add 60ml methylamine water solution (40%, v/v) and mix with carbosphere, after heating 60 DEG C of reaction 15-60min, filters repeatedly with deionized water wash under magnetic agitation。
Step 7: alternate cycles carries out step 4 and step 5 two-step reaction for four times, can obtain the carbosphere of surface grafting 5 number of plies polycation layer。
Step 8: with deionized water for homogenate, under 40MPa pressure, wet method dress post, can terminate when effluent is about 300ml。
Step 9: with 20mMNaOH solution for leacheate, (concentration is F respectively for seven kinds of Common Anions of 50mA Suppressor conductivity detection-2ppm, Cl-5ppm, NO2 -10ppm, Br-10ppm, NO3 -10ppm)。
Beneficial effects of the present invention is as follows:
The method applied in the present invention is simple to operate, reaction condition is gentle, consuming time few, react in aqueous, environmental pollution is little。
The quaterisation of the porous carbon microsphere in the present invention, based on the oxidized carboxyl obtained in its surface and hydroxyl, is copolymerized with methylamine water solution and BDO diglycidyl ether, has the advantage that reaction is efficient and controlled。
Gained of the present invention quaternized porous carbon microsphere Heat stability is good, rich in duct, high pressure resistant, acid-fast alkali-proof, and quaternary ammonium salt content is controlled, thus be successfully applied to anion chromatographic fixing mutually in。
The anion chromatographic column prepared by quaternized porous carbon microsphere in the present invention has highly controllable ion exchange capacity, it is possible to separate seven kinds of common aniones preferably。
The present invention can facilitate, the effective quaternization degree controlling porous carbon microsphere, thus regulating the ion exchange capacity of carbosphere ion chromatographic column。Meanwhile, prepared quaternized carbosphere good thermal stability, pressure, acid and alkali-resistance, it is possible to use high concentration highly basic to do leacheate, conventional anion is had good separating power。
Accompanying drawing explanation
SEM figure (amplifying 45000 times) of the monodisperse porous carbosphere of Fig. 1；
The schematic diagram of the quaternized modification of Fig. 2 carbosphere；
Five kinds of general inorganic aniones of Fig. 3 are at the fixing chromatographic fractionation figure gone up mutually of porous carbon microsphere type chromatography of ions；
(chromatographic peak is from left to right followed successively by F-, Cl-, NO2 -, Br-, NO3 -)。
Detailed description of the invention
Below in conjunction with accompanying drawing, embodiments of the invention are further elaborated:
Embodiment 1: the quaternized porous carbon microsphere of surface grafting 2 number of plies polycation layer
(1) 17g sucrose and 50mg sodium polyacrylate are dissolved in 35ml deionized water and form solution, it is transferred in the water heating kettle containing politef internal memory, it is then placed in baking oven, arrange 200 DEG C, water heating kettle is taken out after reaction 18h, product is filtered, filters repeatedly by deionized water and washing with alcohol, finally dry to obtain the single dispersing carbosphere of particle diameter about 3.8 μm。
(2) gained carbon ball (6.0g) in (1) is put in tube furnace, nitrogen is passed into the speed of 30ml/min, arranging temperature control program after half an hour is: from room temperature to the heating rate of 1000 DEG C be 8 DEG C/min, 1000 DEG C keep 2h, from 1000 DEG C to the rate of temperature fall of room temperature be 10 DEG C/min。Porous carbon microsphere is obtained through calcining。
(3) joining in 40ml concentrated sulphuric acid and concentrated nitric acid mixed liquor by the porous carbon microsphere of preparation in (2), after heated and stirred backflow 1h, filtration washing product is to neutral。
(4) porous carbon microsphere of oxidation acidified in (3) is joined in the mixed liquor of 20ml methylamine (2%, v/v) and BDDE (8%, v/v), ultrasonic disperse。Then, under magnetic stirring after 60 DEG C of reacting by heating 1h, filter with deionized water wash。
(5) 20ml1,4-butanediol diglycidyl ether (60%, v/v) mixes with carbosphere, after heating 60 DEG C of reaction 60min, filters with deionized water wash under magnetic agitation。
(6) add 20ml methylamine water solution (40%, v/v) to mix with carbosphere, after heating 60 DEG C of reaction 1h under magnetic agitation, filter with deionized water wash。
(7) again add 20ml1,4-butanediol diglycidyl ether (60%, v/v) to mix with carbosphere, after heating 60 DEG C of reaction 60min under magnetic agitation, filter with deionized water wash。
(8) product is put into baking oven is dried to obtain the quaternized carbosphere of surface grafting two number of plies polycation layer。
Embodiment 2: the quaternized porous carbon microsphere of surface grafting 4 number of plies polycation layer
Step as implemented shown in 1, the difference is that will (6) (7) two step in triplicate after in enforcement (8)。
Embodiment 3: quaternized carbosphere ion is applied in chromatography of ions as chromatographic stationary phases to separate common seven kinds of aniones
Take the quaternary ammoniated porous carbon microsphere of 2.5g and join in 50ml deionized water, ultrasonic make carbon ball fully dispersed。Dispersion liquid is added in packing column machine, keep 40MPa pressure dress post, with deionized water for effluent, treat that final effluent is more than 200ml, terminate dress post process, take off column jecket。The ion chromatographic column installed is connected on Sheng writing brush SC-14A ion chromatograph, is that leacheate rinses chromatographic column 48h with the flow velocity of 0.10ml/min with 10mMNaOH aqueous solution。Then progressively regulating flow velocity to 1.0ml/min, use and contain writing brush anion suppressor, arrange suppression electric current 40mA, band baseline is walked after putting down, and starts test sample, and the measurement result of seven kinds of aniones is as shown in Figure 3。Ion and concentration that its chromatograph is corresponding are from left to right followed successively by: F-2ppm, Cl-5ppm, NO2 -10ppm, Br-10ppm, NO3 -10ppm。
Present implementation is simple to operate, process control, with low cost, experiment favorable reproducibility, it is possible to separate common five kinds of aniones preferably。
Above-described is only the preferred embodiment of the present invention; it should be pointed out that, for those of ordinary skill in the art, under the premise without departing from core technical features of the present invention; can also making some improvements and modifications, these improvements and modifications also should be regarded as protection scope of the present invention。
Claims (7)
1. the quaternised method of modifying of porous carbon microsphere, it is characterized in that, the strong oxidizing property utilizing concentrated sulphuric acid and concentrated nitric acid introduces carboxyl and hydroxyl on porous carbon microsphere surface, again with methylamine water solution and 1,4-butanediol diglycidyl ether is copolymerized, and introduces the macromolecule layer containing quaternary ammonium group, thus opening the quaterisation of porous carbon microsphere, may finally the positive charge macromolecule layer of scion grafting multilamellar as required, step is as follows:
(1) the carbon ball that sucrose solution hydro-thermal reaction is prepared is put in tube furnace, pass into nitrogen and keep high temperature, prepare required porous carbon microsphere；
(2) being added by porous carbon microsphere in concentrated nitric acid and concentrated sulphuric acid mixed liquor and be heated to reflux, filtration washing product is to neutral afterwards；
(3) by methylamine and BDO diglycidyl ether mix homogeneously, the porous carbon microsphere of acidified oxidation, ultrasonic disperse in (1) are added；
(4) by after step (2) solution reacting by heating 15-60min under magnetic stirring, filter with deionized water wash；
(5) add BDO diglycidyl ether to mix with porous carbon microsphere, under magnetic agitation after reacting by heating 15-60min, filter with deionized water wash；
(6) add methylamine water solution to mix with porous carbon microsphere, under magnetic agitation after reacting by heating 15-60min, filter with deionized water wash；
(7) (4), (5) two-step reaction alternate cycles are carried out n time, the porous carbon microsphere of surface grafting n strata cationic layer, N ∈ Z and N >=1 can be obtained。
2. the quaternised method of modifying of porous carbon microsphere according to claim 1, it is characterized in that, preparing of described porous carbon microsphere is as follows: with sucrose be carbon source, sodium polyacrylate is for dispersant, the hydro-thermal reaction 18h of 200 DEG C, obtain solid carbon ball, namely obtain the porous carbon microsphere that particle diameter is 3.8 μm that can be applicable to chromatography of ions through 1000 DEG C of high-temperature calcinations。
3. the quaternised method of modifying of porous carbon microsphere according to claim 1, its feature is being, the operation of step (1) is as follows: the porous carbon microsphere prepared by 3.5g joins in 30-100ml concentrated sulphuric acid and concentrated nitric acid mixed liquor, after heated and stirred backflow 1-3h, filtration washing product is to neutral。
4. the quaternised method of modifying of porous carbon microsphere according to claim 1, it is characterized in that, the operation of step (2) and (3) is as follows: 3.5g porous carbon microsphere is scattered in 20-60ml methylamine (2%, v/v) with BDDE (8%, v/v) in mixed liquor, ultrasonic disperse, under magnetic stirring after 60 DEG C of reacting by heating 15-60min, filters with deionized water wash。
5. the quaternised method of modifying of porous carbon microsphere according to claim 1, it is characterized in that, the operation of step (4) is as follows: after step (1) solution under magnetic stirring 60 DEG C of reacting by heating 15-60min, filter with deionized water wash。
6. the quaternised porous carbon microsphere of porous carbon microsphere according to claim 1 quaternised method of modifying gained is applied in chromatography of ions as chromatographic stationary phases。
7. quaternised porous carbon microsphere according to claim 6 is applied in chromatography of ions as chromatographic stationary phases, it is characterized in that, with deionized water for effluent, adopt homogenate method that quaternized porous carbon microsphere carries out dress post and obtain anion chromatographic column, and with Suppressor conductivity detection device, five kinds of Common Anions are easily separated detection。
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Cited By (6)
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| CN107555521A (en) * | 2017-10-27 | 2018-01-09 | 卢伟 | A kind of heavy metal-polluted water process multiporous biological matter microballoon and preparation method thereof |
| CN109517354A (en) * | 2018-11-22 | 2019-03-26 | 安徽汇创新材料有限公司 | A kind of fire-retardant resistance to compression composite material and preparation method for glass toughening manure pit |
| CN110624548A (en) * | 2019-09-26 | 2019-12-31 | 中国矿业大学(北京) | Preparation method of multistage iron oxide catalyst for removing heteroatoms in coal liquefied oil |
| US10836952B2 (en) | 2018-08-14 | 2020-11-17 | King Fahd University Of Petroleum And Minerals | Oil recovery methods using carboxylated pyrolyzed date leaves |
| CN112756015A (en) * | 2020-12-11 | 2021-05-07 | 安徽皖仪科技股份有限公司 | Anion exchange resin and preparation method and application thereof |
| CN116445137A (en) * | 2023-03-02 | 2023-07-18 | 西南石油大学 | Modified carbon sphere lubricant for drilling fluid and preparation method and application thereof |
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| CN107555521A (en) * | 2017-10-27 | 2018-01-09 | 卢伟 | A kind of heavy metal-polluted water process multiporous biological matter microballoon and preparation method thereof |
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| US10836952B2 (en) | 2018-08-14 | 2020-11-17 | King Fahd University Of Petroleum And Minerals | Oil recovery methods using carboxylated pyrolyzed date leaves |
| CN109517354A (en) * | 2018-11-22 | 2019-03-26 | 安徽汇创新材料有限公司 | A kind of fire-retardant resistance to compression composite material and preparation method for glass toughening manure pit |
| CN110624548A (en) * | 2019-09-26 | 2019-12-31 | 中国矿业大学(北京) | Preparation method of multistage iron oxide catalyst for removing heteroatoms in coal liquefied oil |
| CN110624548B (en) * | 2019-09-26 | 2020-09-08 | 中国矿业大学(北京) | Preparation method of multistage iron oxide catalyst for removing heteroatoms in coal liquefied oil |
| CN112756015A (en) * | 2020-12-11 | 2021-05-07 | 安徽皖仪科技股份有限公司 | Anion exchange resin and preparation method and application thereof |
| CN116445137A (en) * | 2023-03-02 | 2023-07-18 | 西南石油大学 | Modified carbon sphere lubricant for drilling fluid and preparation method and application thereof |
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Application publication date: 20160622 |