CN117623302A - Preparation method and application of heteroatom doped biochar - Google Patents
Preparation method and application of heteroatom doped biochar Download PDFInfo
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- 125000005842 heteroatom Chemical group 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000008367 deionised water Substances 0.000 claims abstract description 32
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 239000002019 doping agent Substances 0.000 claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 16
- 230000007935 neutral effect Effects 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 16
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052796 boron Inorganic materials 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 13
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 7
- 230000001681 protective effect Effects 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 125000004437 phosphorous atom Chemical group 0.000 claims abstract description 5
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 5
- 230000003213 activating effect Effects 0.000 claims abstract description 4
- 238000000227 grinding Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 30
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 15
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 8
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000002028 Biomass Substances 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- MHJAJDCZWVHCPF-UHFFFAOYSA-L dimagnesium phosphate Chemical compound [Mg+2].OP([O-])([O-])=O MHJAJDCZWVHCPF-UHFFFAOYSA-L 0.000 claims description 4
- 229910000395 dimagnesium phosphate Inorganic materials 0.000 claims description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 4
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 4
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 4
- 235000011151 potassium sulphates Nutrition 0.000 claims description 4
- JVUYWILPYBCNNG-UHFFFAOYSA-N potassium;oxido(oxo)borane Chemical compound [K+].[O-]B=O JVUYWILPYBCNNG-UHFFFAOYSA-N 0.000 claims description 4
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 4
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- VLCLHFYFMCKBRP-UHFFFAOYSA-N tricalcium;diborate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]B([O-])[O-].[O-]B([O-])[O-] VLCLHFYFMCKBRP-UHFFFAOYSA-N 0.000 claims description 4
- NFMWFGXCDDYTEG-UHFFFAOYSA-N trimagnesium;diborate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]B([O-])[O-].[O-]B([O-])[O-] NFMWFGXCDDYTEG-UHFFFAOYSA-N 0.000 claims description 4
- 229910000404 tripotassium phosphate Inorganic materials 0.000 claims description 4
- 235000019798 tripotassium phosphate Nutrition 0.000 claims description 4
- 229910021538 borax Inorganic materials 0.000 claims description 3
- 235000011132 calcium sulphate Nutrition 0.000 claims description 3
- ILOKQJWLMPPMQU-UHFFFAOYSA-N calcium;oxido(oxo)borane Chemical compound [Ca+2].[O-]B=O.[O-]B=O ILOKQJWLMPPMQU-UHFFFAOYSA-N 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 3
- 235000019800 disodium phosphate Nutrition 0.000 claims description 3
- QQFLQYOOQVLGTQ-UHFFFAOYSA-L magnesium;dihydrogen phosphate Chemical compound [Mg+2].OP(O)([O-])=O.OP(O)([O-])=O QQFLQYOOQVLGTQ-UHFFFAOYSA-L 0.000 claims description 3
- 229910000401 monomagnesium phosphate Inorganic materials 0.000 claims description 3
- 235000019785 monomagnesium phosphate Nutrition 0.000 claims description 3
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 3
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 3
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 3
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 3
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 claims description 3
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 3
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 claims description 3
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims description 3
- 239000012190 activator Substances 0.000 claims description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 2
- 235000019797 dipotassium phosphate Nutrition 0.000 claims description 2
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 2
- 150000001642 boronic acid derivatives Chemical group 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 59
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 8
- 239000003546 flue gas Substances 0.000 abstract description 8
- 239000011574 phosphorus Substances 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 7
- 238000000197 pyrolysis Methods 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011593 sulfur Substances 0.000 abstract description 4
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 14
- 238000001914 filtration Methods 0.000 description 12
- 239000004570 mortar (masonry) Substances 0.000 description 12
- 239000011148 porous material Substances 0.000 description 12
- 239000012257 stirred material Substances 0.000 description 12
- 238000003775 Density Functional Theory Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 235000012054 meals Nutrition 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical group [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 2
- 235000017491 Bambusa tulda Nutrition 0.000 description 2
- 241001330002 Bambuseae Species 0.000 description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 2
- 235000011613 Pinus brutia Nutrition 0.000 description 2
- 241000018646 Pinus brutia Species 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000011425 bamboo Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012900 molecular simulation Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- 230000009897 systematic effect Effects 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 238000010200 validation analysis Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method of heteroatom doped biochar, which comprises the following steps: placing 1 part of carbon source material, 1-6 parts of activating agent and 0.5-1.5 parts of heteroatom doping agent into a grinder for physical grinding and fully mixing; heating the mixture to 600-1000deg.C under protective gas environment for 45-90min; naturally cooling, and stirring the carbonized black material with deionized water at normal temperature for 10-20 hours; repeatedly washing the solid substance with deionized water until the solution is neutral; and (5) drying the washed material in an oven to obtain the heteroatom doped biochar. The hetero atom doping agent is selected from boron atom, phosphorus atom and sulfur atom doping agent, and can be used for preparing corresponding boron doped biochar, phosphorus doped biochar and sulfur doped biochar respectively, and the specific doping of the biochar is thatThe form is monomer, the preparation adopts a one-step pyrolysis method, no acid-base solvent participates in the whole process, the process is simple, the environment is friendly, and the prepared heteroatom doped biochar is not only rich in a large amount of ultra-microporous structures, but also has rich surface functional groups, and can realize flue gas CO 2 High performance adsorption.
Description
Technical Field
The invention relates to the technical field of doped biochar preparation, in particular to a preparation method and application of heteroatom doped biochar.
Background
CO 2 Is causing a series of problems such as global warming. Although corresponding measures for carbon emission reduction are proposed worldwide, the publication of IEA was made on the basis of 2022 CO 2 Emissions report 2022 worldwide CO 2 The discharge amount exceeds 368 hundred million tons, and the history is high. Wherein the emission of the power industry accounts for 39.3% of the total emission. Thus reducing CO in the global power industry 2 The discharge is imperative. Among them, the solid adsorption method is considered as one of the most promising carbon trapping technologies in the future due to the advantages of low trapping energy consumption, good thermal stability, excellent cycle performance, high selectivity and the like.
Has been widely used for CO at present 2 The solid adsorbent is selected from zeolite molecular sieve, organic metal frame, mesoporous silicon, alkali metal carbonate, porous carbon material, organic polymer, etc. The biggest commonality of these materials is the rich pore structure that is common to CO 2 Is typical of physical adsorption, CO 2 The concentration and adsorption temperature have a great influence on physical adsorption. CO in flue gas 2 The concentration is low, the adsorption temperature is relatively high, so that the mere dependence on the abundant pore structure is obviously insufficient for realizing CO in the flue gas 2 Is a high performance trap of (a). Many functionalized materials have been developed for low concentration CO at high temperatures 2 The high-efficiency trapping of the (2) is realized by changing the polarity of the material by changing the skeleton structure, the electronic arrangement and the like of the original material, thereby improving the CO doping technology 2 Is a trapping property of the (c). The heteroatom doped biochar combines the advantages of simple preparation method, wide raw material sources and low cost of the biochar and the specific absorption caused by the doping of the heteroatomsAnd is a promising solid adsorbent.
The main atoms used for doping at present are boron, nitrogen, phosphorus, sulfur and the like, and are mainly applied to the aspects of adsorption separation, organic catalysis, sensors, energy conversion, storage and the like. For CO 2 The adsorbed heteroatom doped carbon materials are mainly concentrated in nitrogen doping, and the research on doping of other atoms is limited. The main reasons are as follows: on one hand, the complex and expensive development process is caused by the complex doping forms of the heteroatoms and the lack of directional theoretical guidance. On the other hand, no systematic research on heteroatom doped biochar exists, and the prepared material has limited adsorption performance. Zaman et al [1] The sulfur-doped carbon material is prepared by using p-toluenesulfonic acid as a precursor and sodium chloride as a pore-forming agent, but the maximum CO of the material is 0.15bar at 25 DEG C 2 The adsorption amount was only 0.78mmol/g, and the adsorption amount was relatively limited.
In summary, the current research on heteroatom-doped biochar has the following two problems: firstly, because the doping forms of the hetero atoms are numerous, and each doping form has different influences on the carbon capturing performance, a large number of trial experiments are needed to optimize the performance, and a large number of trial and error times lead to higher development cost of the hetero atom doped biochar. Secondly, the research on the heteroatom doped biochar is mainly performed on nitrogen doped biochar, the research on other atom doped biochar is less, and no systematic research has revealed the influence condition of each heteroatom doped form on the biochar carbon trapping performance, so that the prepared heteroatom doped biochar carbon trapping performance is limited.
[1]Zaman A C,Karaaslan O F.Sulfur/Oxygen-Doped Porous Carbon via NaCl-Assisted Thermolysis of Molecular Precursor for CO2 Capture[J].Materials Chemistry and Physics,2021:125288.
Disclosure of Invention
In order to solve at least one of the problems existing in the preparation of heteroatom-doped biochar in the prior art, the invention provides a preparation method and application of heteroatom-doped biochar, the preparation adopts a one-step pyrolysis method, the whole process has no acid-base solvent participation, the process is simple, the environment is friendly, and the prepared heteroatom-doped biochar is greenThe charcoal is not only rich in a large amount of ultra-microporous structures, but also has rich surface functional groups, and can realize the CO of flue gas 2 High performance adsorption.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the first aspect of the invention provides a method for preparing heteroatom-doped biochar, comprising the following steps:
s1, placing 1 part of carbon source material, 1-6 parts of activating agent and 0.5-1.5 parts of heteroatom doping agent into a grinder for physical grinding and fully mixing;
s2, heating the mixture to 600-1000 ℃ in a protective gas environment and keeping the temperature for 45-90min;
s3, naturally cooling after the step S2 is completed, and stirring the carbonized black material with deionized water at normal temperature for 10-20 hours;
s4, repeatedly washing the solid matters with deionized water until the solution is neutral after the step S3 is completed;
s5, drying the washed material in a baking oven to obtain heteroatom doped biochar; in some embodiments, the washed material is dried in an oven at 105 ℃ for 12 hours.
In some embodiments of the invention, the heteroatom dopant is one of a boron atom dopant, a phosphorus atom dopant, a sulfur atom dopant.
In some embodiments of the invention, the boron atom dopant is a borate, preferably one of potassium metaborate, potassium borate, sodium metaborate, sodium borate, calcium metaborate, calcium borate, magnesium borate.
In some embodiments of the invention, the phosphorus atom dopant is a phosphate, preferably one of tripotassium phosphate, monopotassium phosphate, potassium phosphate, sodium phosphate monobasic, sodium phosphate dibasic, magnesium phosphate monobasic, magnesium phosphate dibasic.
In some embodiments of the invention, the sulfur atom dopant is a sulfate, preferably one of potassium sulfate, sodium sulfate, calcium sulfate, magnesium sulfate.
In some embodiments of the invention, the carbon source material is a biomass carbon source material, such as corncob meal, wood meal, bamboo meal, agricultural waste, straw meal, and the like.
In some embodiments of the invention, the activator is potassium carbonate.
In some embodiments of the invention, the shielding gas environment in step S2 is: the protective gas is nitrogen, the flow is 100-200mL/min, and the heating rate is 5-10 ℃/min. In some embodiments of the invention, the mixture is heated to 800 ℃ under a nitrogen atmosphere of 100-200mL/min at a ramp rate of 5-10 ℃/min and held for 1 hour.
In a second aspect the present invention provides heteroatom doped biochar prepared according to the method of the first aspect.
A third aspect of the invention provides the use of a heteroatom doped biochar according to the second aspect in carbon capture, such as CO in flue gas 2 Is adsorbed by the adsorbent.
The invention also provides a method for directionally designing the heteroatom doped biochar, which comprises the following steps: firstly, constructing different heteroatom morphology doped biochar molecular models, and calculating CO on different biochar models by DFT 2 Adsorption energy, N 2 Adsorption energy and CO 2 /N 2 Theoretical selectivity. According to CO 2 The size of adsorption energy and theoretical selectivity screens out the proper specific doping form.
Then, according to the specific doping form screened by DFT calculation, constructing a nanoscale porous material model, and simulating CO on different nanoscale porous material models by adopting GCMC 2 And (5) adsorbing the performance data such as isotherms, and further verifying the result of DFT calculation screening.
Finally, adopting a one-step pyrolysis method to directionally prepare the biochar doped with the heteroatom morphology.
The beneficial effects of the invention are that
Compared with the prior art, the invention has the following beneficial effects: the invention provides a heteroatom doped biochar directional design thought and a method based on DFT screening, and adopts DFT theory to calculate through CO 2 Adsorption energy, N 2 Adsorption energy and CO 2 /N 2 Three aspects of theoretical selectivity screen heteroatom doped form BCO with excellent adsorption performance from molecular atom angle 2 P-C and C-S-C, providing specific doping directions for subsequent studies. Subsequently, the GCMC molecular simulation is adopted to dope the CO on the biochar in the three forms on the nanometer scale through calculation 2 Adsorption isotherms and the like further verify the results of DFT calculation, CO 2 Adsorption isotherm results show that the doping of hetero atoms can improve the CO of the biochar under low pressure 2 Adsorption capacity. According to the specific doping form screened by DFT calculation, the monomer is finally adopted to directionally prepare the biochar doped with the doping form screened by the previous method by adopting one-step pyrolysis method, so that excellent CO is realized 2 And (5) adsorption. The theoretical calculation guiding experiment provided by the invention realizes the directional preparation of the heteroatom doping, reduces the trial-and-error times of the experiment, and reduces the development cost of the material.
The heteroatom doped biochar prepared by the invention takes waste biomass carbon source materials such as corncobs as raw materials, the activating agent and the doping agent are cheap chemicals, the activation and the modification can be realized in one step, and the preparation cost is low.
The one-step pyrolysis method adopted by the invention has no acid-base solvent participation in the whole process, the process is simple, the environment is friendly, the prepared heteroatom doped biochar is not only rich in a large number of ultra-microporous structures, but also has rich surface functional groups, and the heteroatom doped biochar prepared by the invention has excellent CO 2 Adsorption performance and CO 2 /N 2 Selectivity and excellent cycle performance, can realize the CO of the flue gas 2 High-performance adsorption and can be reused.
Drawings
FIG. 1 is an SEM image of biochar prepared in example 1, example 5, example 8 and comparative example 1 of the present invention; wherein A corresponds to the results of example 1, B corresponds to the results of example 5, C corresponds to the results of example 8, and D corresponds to the results of example 1;
FIG. 2 shows the adsorption amounts and CO at 37℃of biochar prepared in example 1, example 5, example 8 and comparative example 1 according to the present invention 2 /N 2 A selective comparison graph;
FIG. 3 shows the adsorption amount and CO at 55℃of biochar prepared in example 1, example 5, example 8 and comparative example 1 according to the present invention 2 /N 2 A selective comparison graph;
FIG. 4 shows the adsorption amount and CO at 72℃of biochar prepared in example 1, example 5, example 8 and comparative example 1 according to the present invention 2 /N 2 A selective comparison graph;
FIG. 5 is a graph showing the cycle performance test of the boron doped biochar prepared in example 1 of the present invention;
FIG. 6 is a graph showing the cycle performance test of the phosphorus-doped biochar prepared in example 5 of the present invention;
FIG. 7 is a graph showing the cycle performance test of sulfur-doped biochar prepared in example 8 of the present invention;
FIG. 8 is a schematic diagram of the concept of the directional design of the heteroatom-doped biochar and the corresponding preparation method in the invention;
FIG. 9 shows the CO of the different heteroatom morphology doped biochar calculated by DFT in the present invention 2 Adsorption energy, N 2 Adsorption energy and theoretical selectivity;
FIG. 10 is a graph showing the CO at 25℃and 0-1bar for various heteroatom-doped biochar obtained by GCMC simulation in accordance with the present invention 2 Adsorption isotherms.
Detailed Description
The following examples are presented herein to demonstrate preferred embodiments of the present invention. It will be appreciated by those skilled in the art that the techniques disclosed in the examples which follow represent techniques discovered by the inventor to function in the practice of the invention, and thus can be considered to constitute preferred modes for its practice. Those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments which are disclosed and still obtain a like or similar result without departing from the spirit or scope of the invention. Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. Such equivalents are intended to be encompassed by the claims.
A preparation method of heteroatom doped biochar comprises the following steps:
s1, 1 part of biomass carbon source material, 1-6 parts of potassium carbonate and 0.5-1.5 parts of heteroatom doping agent: placing one of sulfate, phosphate and borate into a grinder for physical grinding and fully mixing;
s2, heating the mixture to 600-1000 ℃ at a heating rate of 5-10 ℃/min under a nitrogen atmosphere of 100-200mL/min and keeping the temperature for 45-90min;
s3, naturally cooling, and stirring the carbonized black material with deionized water at normal temperature for 10-20 hours;
s4, repeatedly washing the solid matters with deionized water until the solution is neutral;
s5, placing the washed material in an oven at 105 ℃ for drying for 12 hours to obtain the heteroatom doped biochar.
Wherein the borate can be one of potassium metaborate, potassium borate, sodium metaborate, sodium borate, calcium metaborate, calcium borate and magnesium borate; the phosphate can be one of tripotassium phosphate, monopotassium phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, sodium hydrogen phosphate, magnesium dihydrogen phosphate and magnesium hydrogen phosphate; the sulfate may be one of potassium sulfate, sodium sulfate, calcium sulfate, and magnesium sulfate.
Example 1
Firstly, 5g of corncob powder, 5g of potassium metaborate and 15g of potassium carbonate are physically ground in a mortar for 30 minutes to be fully mixed; the mixture was then heated to 800℃under a nitrogen atmosphere at a rate of 10℃per minute for 1 hour. After natural cooling, the carbonized black material is transferred to a beaker, 200mL of deionized water is added, and the mixture is stirred for 12 hours at normal temperature. And repeatedly washing and suction-filtering the stirred material with 1000mL of deionized water until the solution is neutral. And finally, drying the washed material in an oven at 105 ℃ for 12 hours to obtain the boron doped biochar.
Example 2
Firstly, 5g of corn stalk powder, 7.5g of magnesium borate and 30g of potassium carbonate are physically ground in a mortar for 30 minutes to be fully mixed; the mixture was then heated to 600℃under a nitrogen atmosphere of 100mL/min at a rate of 10℃per minute and maintained for 1 hour. After natural cooling, the carbonized black material is transferred to a beaker, 200mL of deionized water is added, and the mixture is stirred for 12 hours at normal temperature. And repeatedly washing and suction-filtering the stirred material with 1000mL of deionized water until the solution is neutral. And finally, drying the washed material in an oven at 105 ℃ for 12 hours to obtain the boron doped biochar.
Example 3
Firstly, 5g of wood chips, 2.5g of sodium metaborate and 5g of potassium carbonate are physically ground in a mortar for 30 minutes to carry out full mixing; the mixture was then heated to 800℃under a nitrogen atmosphere at a rate of 10℃per minute for 1 hour. After natural cooling, the carbonized black material is transferred to a beaker, 200mL of deionized water is added, and the mixture is stirred for 12 hours at normal temperature. And repeatedly washing and suction-filtering the stirred material with 1000mL of deionized water until the solution is neutral. And finally, drying the washed material in an oven at 105 ℃ for 12 hours to obtain the boron doped biochar.
Example 4
Firstly, 5g of pine powder, 5g of calcium borate and 25g of potassium carbonate are physically ground in a mortar for 30 minutes to be fully mixed; the mixture was then heated to 800℃under a nitrogen atmosphere of 100mL/min at a heating rate of 8℃per minute and maintained for 1 hour. After natural cooling, the carbonized black material is transferred to a beaker, 200mL of deionized water is added, and the mixture is stirred for 12 hours at normal temperature. And repeatedly washing and suction-filtering the stirred material with 1000mL of deionized water until the solution is neutral. And finally, drying the washed material in an oven at 105 ℃ for 12 hours to obtain the boron doped biochar.
Example 5
First, 5g of corncob meal, 5g of tripotassium phosphate and 15g of potassium carbonate were physically ground in a mortar for 30 minutes to perform sufficient mixing. The mixture was then heated to 800℃under a nitrogen atmosphere at a rate of 10℃per minute for 1 hour. After natural cooling, the carbonized black material is transferred to a beaker, 200mL of deionized water is added, and the mixture is stirred for 12 hours at normal temperature. And repeatedly washing and suction-filtering the stirred material with 1000mL of deionized water until the solution is neutral. Finally, the washed material is put into a baking oven at 105 ℃ to be dried for 12 hours, and the phosphorus doped biochar can be obtained.
Example 6
First, 5g of bamboo powder, 7.5g of sodium dihydrogen phosphate and 25g of potassium carbonate were physically ground in a mortar for 30 minutes to perform sufficient mixing. The mixture was then heated to 1000 ℃ under a nitrogen atmosphere at a rate of 10 ℃/min for 1 hour. After natural cooling, the carbonized black material is transferred to a beaker, 200mL of deionized water is added, and the mixture is stirred for 12 hours at normal temperature. And repeatedly washing and suction-filtering the stirred material with 1000mL of deionized water until the solution is neutral. Finally, the washed material is put into a baking oven at 105 ℃ to be dried for 12 hours, and the phosphorus doped biochar can be obtained.
Example 7
First, 5g of bark powder, 2.5g of magnesium hydrogen phosphate and 7.5g of potassium carbonate were physically ground in a mortar for 30 minutes to perform sufficient mixing. The mixture was then heated to 800℃under a nitrogen atmosphere at a rate of 10℃per minute for 1 hour. After natural cooling, the carbonized black material is transferred to a beaker, 200mL of deionized water is added, and the mixture is stirred for 12 hours at normal temperature. And repeatedly washing and suction-filtering the stirred material with 1000mL of deionized water until the solution is neutral. Finally, the washed material is put into a baking oven at 105 ℃ to be dried for 12 hours, and the phosphorus doped biochar can be obtained.
Example 8
First, 5g of wheat straw powder, 5g of potassium sulfate and 15g of potassium carbonate were physically ground in a mortar for 30 minutes to perform sufficient mixing. The mixture was then heated to 700 ℃ under a nitrogen atmosphere at 100mL/min at a rate of 10 ℃/min and maintained for 1 hour. After natural cooling, the carbonized black material is transferred to a beaker, 200mL of deionized water is added, and the mixture is stirred for 12 hours at normal temperature. And repeatedly washing and suction-filtering the stirred material with 1000mL of deionized water until the solution is neutral. And finally, drying the washed material in an oven at 105 ℃ for 12 hours to obtain the sulfur-doped biochar.
Example 9
First, 5g of corncob meal, 6g of sodium sulfate and 25g of potassium carbonate were physically ground in a mortar for 30 minutes to perform sufficient mixing. The mixture was then heated to 800℃under a nitrogen atmosphere at a rate of 10℃per minute for 1 hour. After natural cooling, the carbonized black material is transferred to a beaker, 200mL of deionized water is added, and the mixture is stirred for 12 hours at normal temperature. And repeatedly washing and suction-filtering the stirred material with 1000mL of deionized water until the solution is neutral. And finally, drying the washed material in an oven at 105 ℃ for 12 hours to obtain the sulfur-doped biochar.
Example 10
5g of pine wood flour, 3g of calcium sulfate and 6g of potassium carbonate were first physically ground in a mortar for 30 minutes to allow for adequate mixing. The mixture was then heated to 1000 ℃ under a nitrogen atmosphere at a rate of 10 ℃/min for 1 hour. After natural cooling, the carbonized black material is transferred to a beaker, 200mL of deionized water is added, and the mixture is stirred for 12 hours at normal temperature. And repeatedly washing and suction-filtering the stirred material with 1000mL of deionized water until the solution is neutral. And finally, drying the washed material in an oven at 105 ℃ for 12 hours to obtain the sulfur-doped biochar.
Example 11
5g Huang Zhufen g magnesium sulfate and 20g potassium carbonate were first physically ground in a mortar for 30 minutes for thorough mixing. The mixture was then heated to 800℃under a nitrogen atmosphere at a rate of 10℃per minute for 1 hour. After natural cooling, the carbonized black material is transferred to a beaker, 200mL of deionized water is added, and the mixture is stirred for 12 hours at normal temperature. And repeatedly washing and suction-filtering the stirred material with 1000mL of deionized water until the solution is neutral. And finally, drying the washed material in an oven at 105 ℃ for 12 hours to obtain the sulfur-doped biochar.
Comparative example 1
First, 5g of corncob meal and 15g of potassium carbonate were physically ground in a mortar for 30 minutes to perform sufficient mixing. The mixture was then heated to 800℃under a nitrogen atmosphere at a rate of 10℃per minute for 1 hour. After natural cooling, the carbonized black material is transferred to a beaker, 200mL of deionized water is added, and the mixture is stirred for 12 hours at normal temperature. And repeatedly washing and suction-filtering the stirred material with 1000mL of deionized water until the solution is neutral. And finally, drying the washed material in an oven at 105 ℃ for 12 hours to obtain the original biochar.
Performance testing and characterization
(1) SEM test of biochar prepared in example 1, example 5, example 8 and comparative example 1 was performed, and the results are shown in FIG. 1.
As can be seen from fig. 1, the heteroatom dopant has a certain promoting effect on the morphology of the pores. Both boron-doped and phosphorus-doped biochar present a block shape with a large number of round holes, while sulfur-doped biochar present a multi-layered chip shape with a large number of holes. From fig. 1, it can be seen that the pores of the original biochar are not completely etched, and it is presumed that the specific surface area thereof is relatively low.
(2) The biochar prepared in example 1, example 5, example 8 and comparative example 1 were subjected to pore structure characterization, and the results are shown in table 1.
TABLE 1 pore Structure characterization results of biochar
As can be seen from table 1 above: the heteroatom dopant can increase the specific surface area and the total pore volume of the biochar, which verifies the assumption that the original biochar has the lowest specific surface area in SEM test. The ultra-micropore area and the ultra-micropore volume of the boron-doped biochar and the phosphorus-doped biochar are relatively similar to those of the original biochar. While sulfur-doped biochar has a minimum ultramicropore structure despite its highest specific surface area and total pore volume. From the pore structure distribution, it is speculated that boron-doped and phosphorus-doped biochar will have higher CO than sulfur-doped biochar due to the more micropores available 2 Adsorption amount.
(3) XPS surface element tests were performed on biochar prepared in example 1, example 5, example 8 and comparative example 1, and the results are shown in Table 2.
TABLE 2 XPS element distribution of biochar
It can be seen from table 2 that all three kinds of heteroatom doped biochar prepared in example 1, example 5 and example 8 are doped with the corresponding elements, indicating that the heteroatom doping was successful. Wherein the sulfur and boron doping levels are relatively high and the phosphorus doping ratio is low. The original biochar prepared in comparative example 1 was free of other heteroatom doping.
(4) The biochars prepared in example 1, example 5, example 8 and comparative example 1 were tested for CO2 adsorption performance and CO2/N2 selectivity at temperatures of 37 ℃, 55 ℃ and 72 ℃ respectively using a thermogravimetric analyzer.
The specific test flow is as follows: firstly, adding about 5mg of biochar into a crucible, and adding 100mL/min of N 2 Degassing at 100deg.C for 20 min to remove impurities in biochar, wherein the mass is denoted as m 1 . Then the temperature is adjusted to the target adsorption temperature, and the mass at the moment is recorded as m 2 . After reaching the target adsorption temperature, pure nitrogen is switched into 100mL/min of pure CO 2 Performing adsorption experiment for 1 hour, and recording the mass after adsorption as m 3 . Calculating N of biochar by adopting formulas (1) and (2) 2 And CO 2 Adsorption quantity (Q) N2 And Q CO2 )：
CO of biochar prepared in example 1, example 5, example 8 and comparative example 1 2 Adsorption amount, N 2 Adsorption amount and CO 2 /N 2 The selectivity results are shown in figures 2 to 4.
From FIGS. 2 to 4, it can be seen that the CO of the phosphorus-doped and boron-doped biochar is reduced at the same adsorption temperature 2 The adsorption quantity is higher than that of the original biochar. Wherein the phosphorus doped biochar is CO at 72 ℃ and 1bar 2 The adsorption capacity is 1.34mmol/g, which is 10.7% higher than that of the original biochar, and is also higher than most of the studies published at present. As can be seen from the results of the pore structure analysis, the phosphorus-doped and boron-doped biochar is resistant to CO 2 The increase in adsorption is mainly due to doping of the heteroatoms. In addition, CO 2 And N 2 The ratio of the adsorption amounts is defined as CO 2 /N 2 Selectivity. It can be seen that at all temperatures, the three heteroatom-doped biochar has higher selectivity than the original biochar, which is mutually verified with the previous calculation result of DFT, and means that the heteroatom-doped biochar can show better CO in actual flue gas than the original biochar 2 Trapping performance.
(5) The cycle performance of the boron-doped biochar, the phosphorus-doped biochar and the sulfur-doped biochar prepared in example 1, example 5 and example 8 was tested, and the test curve results are shown in fig. 5 to 7.
As can be seen from FIG. 5, the mass increase of the boron doped biochar after being subjected to multi-temperature section adsorption is only 0.19%, and CO is basically realized 2 And shows better chemical stability. In addition, the second CO of the boron doped biochar 2 The adsorption amount is up to 113.4mg/g, which is reduced by 0.4% compared with the first 113.9mg/g, and the cycle performance is excellent.
As can be seen from FIG. 6, the mass increase of the phosphorus-doped biochar after being subjected to multi-temperature-section adsorption is only 0.54%, and CO is basically realized 2 And shows better chemical stability. Secondary CO of phosphorus doped biochar 2 The adsorption amount reaches 113.7mg/g, which is reduced by 0.7% compared with 114.5mg/g of the first time, and the catalyst also shows excellent cycle performance.
As can be seen from FIG. 7, the sulfur-doped biochar has a low adsorption capacity due to a small distribution of ultra-micropores, but has a mass increase of only 0.11% after undergoing multi-temperature-zone adsorption, and realizes CO 2 Is completely desorbed and showsBetter chemical stability. Secondary CO of sulfur-doped biochar 2 The adsorption amount was reduced by only 0.6% compared to the first time, and also exhibited excellent cycle performance.
In conclusion, the heteroatom-doped biochar has excellent chemical stability and cycle stability while having excellent adsorption performance, and can be recycled for multiple times in practical application.
(6) Heteroatom doped biochar orientation design and validation, see fig. 8-10.
The idea of the directional design of the heteroatom doped biochar and the corresponding preparation method are shown in fig. 8, and the method comprises the following steps: first calculate the CO by DFT theory 2 Adsorption energy, N 2 Adsorption energy and CO 2 /N 2 Three aspects of theoretical selectivity screen heteroatom doped form BCO with excellent adsorption performance from molecular atom angle 2 P-C and C-S-C, as shown in FIG. 9, provide specific doping directions for subsequent studies. Subsequently, the GCMC molecular simulation is adopted to dope the CO on the biochar in the three forms on the nanometer scale through calculation 2 Adsorption isotherms and the like further verify the results of DFT calculation, CO 2 Adsorption isotherm results show that the doping of hetero atoms can improve the CO of the biochar under low pressure 2 Adsorption capacity, as shown in figure 10.
Finally, preparing the biochar doped with the doping forms screened by the method by adopting a one-step pyrolysis method.
The test results related to the previous examples show that the heteroatom doped biochar prepared by the invention has excellent CO 2 Adsorption performance and CO 2 /N 2 Selectivity, excellent circulation performance and capability of recycling CO in flue gas 2 High performance adsorption aspects.
All documents mentioned in this application are incorporated by reference as if each were individually incorporated by reference. Further, after reading the above teachings of the present invention, those skilled in the art may make various changes or modifications to the present invention, which equivalent forms also fall within the scope of the claims appended hereto.
Claims (10)
1. The preparation method of the heteroatom doped biochar is characterized by comprising the following steps of:
s1, placing 1 part of carbon source material, 1-6 parts of activating agent and 0.5-1.5 parts of heteroatom doping agent into a grinder for physical grinding and fully mixing;
s2, heating the mixture to 600-1000 ℃ in a protective gas environment and keeping the temperature for 45-90min;
s3, naturally cooling after the step S2 is completed, and stirring the carbonized black material with deionized water at normal temperature for 10-20 hours;
s4, repeatedly washing the solid matters with deionized water until the solution is neutral after the step S3 is completed;
s5, drying the washed material in an oven to obtain the heteroatom doped biochar.
2. The method for preparing the heteroatom-doped biochar according to claim 1, wherein the method comprises the following steps: the heteroatom dopant is one of boron atom dopant, phosphorus atom dopant and sulfur atom dopant.
3. The method for preparing the heteroatom-doped biochar according to claim 2, wherein the method comprises the following steps: the boron atom dopant is borate: one of potassium metaborate, potassium borate, sodium metaborate, sodium borate, calcium metaborate, calcium borate and magnesium borate.
4. The method for preparing the heteroatom-doped biochar according to claim 2, wherein the method comprises the following steps: the phosphorus atom dopant is phosphate: one of tripotassium phosphate, monopotassium phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, sodium hydrogen phosphate, magnesium dihydrogen phosphate and magnesium hydrogen phosphate.
5. The method for preparing the heteroatom-doped biochar according to claim 2, wherein the method comprises the following steps: the sulfur atom dopant is sulfate: potassium sulfate, sodium sulfate, calcium sulfate, magnesium sulfate.
6. The method for preparing the heteroatom-doped biochar according to claim 1, wherein the method comprises the following steps: the carbon source material is a biomass carbon source material.
7. The method for preparing the heteroatom-doped biochar according to claim 1, wherein the method comprises the following steps: the activator is potassium carbonate.
8. The method for preparing the heteroatom-doped biochar according to claim 1, wherein the method comprises the following steps: the protective gas environment in the step S2 is as follows: the protective gas is nitrogen, the flow is 100-200mL/min, and the heating rate is 5-10 ℃/min.
9. Heteroatom-doped biochar prepared according to the method of any one of claims 1-8.
10. Use of the heteroatom-doped biochar of claim 9 for carbon capture.
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