CN109650388A - A kind of method and its application preparing biomass-based functional activity Carbon Materials using concentrated seawater auxiliary - Google Patents
A kind of method and its application preparing biomass-based functional activity Carbon Materials using concentrated seawater auxiliary Download PDFInfo
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- CN109650388A CN109650388A CN201910053743.8A CN201910053743A CN109650388A CN 109650388 A CN109650388 A CN 109650388A CN 201910053743 A CN201910053743 A CN 201910053743A CN 109650388 A CN109650388 A CN 109650388A
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- functional activity
- concentrated seawater
- biomass
- based functional
- carbon materials
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- 239000002028 Biomass Substances 0.000 title claims abstract description 101
- 239000013535 sea water Substances 0.000 title claims abstract description 92
- 230000005714 functional activity Effects 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims abstract description 68
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 47
- 239000000463 material Substances 0.000 claims abstract description 28
- 238000004140 cleaning Methods 0.000 claims abstract description 21
- 239000003990 capacitor Substances 0.000 claims abstract description 18
- 239000012620 biological material Substances 0.000 claims abstract description 17
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 16
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011148 porous material Substances 0.000 claims abstract description 13
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 12
- 238000010612 desalination reaction Methods 0.000 claims abstract description 10
- 235000002639 sodium chloride Nutrition 0.000 claims description 53
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 38
- 239000000047 product Substances 0.000 claims description 32
- 150000003839 salts Chemical class 0.000 claims description 31
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 26
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 22
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 22
- 239000011780 sodium chloride Substances 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 13
- 239000001110 calcium chloride Substances 0.000 claims description 12
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 12
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 12
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 12
- 229910001868 water Inorganic materials 0.000 claims description 12
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 11
- 239000000706 filtrate Substances 0.000 claims description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000000197 pyrolysis Methods 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 241000931705 Cicada Species 0.000 claims description 4
- 239000002135 nanosheet Substances 0.000 claims description 4
- 241000251468 Actinopterygii Species 0.000 claims description 3
- 235000017060 Arachis glabrata Nutrition 0.000 claims description 3
- 244000105624 Arachis hypogaea Species 0.000 claims description 3
- 235000010777 Arachis hypogaea Nutrition 0.000 claims description 3
- 235000018262 Arachis monticola Nutrition 0.000 claims description 3
- 235000013527 bean curd Nutrition 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 235000020232 peanut Nutrition 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 238000002955 isolation Methods 0.000 claims description 2
- 238000004088 simulation Methods 0.000 claims description 2
- 239000010902 straw Substances 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims 1
- 229920002678 cellulose Polymers 0.000 claims 1
- 238000005363 electrowinning Methods 0.000 claims 1
- 239000003610 charcoal Substances 0.000 abstract description 48
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 15
- 230000008569 process Effects 0.000 abstract description 15
- 229910052799 carbon Inorganic materials 0.000 abstract description 14
- 239000012190 activator Substances 0.000 abstract description 12
- 239000000460 chlorine Substances 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052801 chlorine Inorganic materials 0.000 abstract description 6
- 230000009102 absorption Effects 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 239000003463 adsorbent Substances 0.000 abstract description 5
- 230000004060 metabolic process Effects 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 230000005518 electrochemistry Effects 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 27
- 238000002360 preparation method Methods 0.000 description 20
- 239000002699 waste material Substances 0.000 description 20
- 239000000126 substance Substances 0.000 description 14
- 239000003792 electrolyte Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- 239000007772 electrode material Substances 0.000 description 8
- 238000010792 warming Methods 0.000 description 8
- 238000000498 ball milling Methods 0.000 description 7
- 238000004108 freeze drying Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 5
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052740 iodine Inorganic materials 0.000 description 5
- 239000011630 iodine Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000002336 sorption--desorption measurement Methods 0.000 description 5
- 241001131796 Botaurus stellaris Species 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 150000002926 oxygen Chemical class 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 241001412225 Firmiana simplex Species 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005067 remediation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 240000000560 Citrus x paradisi Species 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera 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
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- -1 after drying Substances 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001599 direct drying Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 229940101209 mercuric oxide Drugs 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000000618 nitrogen fertilizer Substances 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010907 stover Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Classifications
-
- 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
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
- B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
- C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/44—Raw materials therefor, e.g. resins or coal
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Power Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Environmental & Geological Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of methods for assisting preparing biomass-based functional activity Carbon Materials using concentrated seawater, be biological material is uniformly mixed with concentrated seawater, it is dry after be made under anaerobic through high temperature cabonization, cleaning solution can be mixed with biological material again and recycled gained for the first time.Carbon Materials produced by the present invention can be used as electrode of super capacitor, adsorbent material etc..The present invention solve seawater after desalination be difficult to handle and active carbon prepare needed for expensive two difficult points of activator, simultaneously, scrub raffinate of the present invention can propose bromine technique and combine with chlorine industry, Hou's process for soda production and seawater prepares other products, reach and has economized on resources, controls economic cost, pollution is reduced, the purpose of metabolism and green circulation economy technique between realization industry.The method that the present invention prepares biomass-based functional activity charcoal is easy to operate, low in cost and carbon material large specific surface area obtained, and pore structure is more, and electrochemistry, absorption and catalytic performance are excellent.
Description
Technical field
The present invention relates to the preparation method and application of biology base function Carbon Materials, it is more particularly related to a kind of
The method of biomass-based functional activity Carbon Materials is prepared as activator, pore creating material auxiliary simultaneously using concentrated seawater and its is answered
With the method for the present invention can also be achieved circulation preparation, and biomass-based functional activity Carbon Materials obtained can be applied to super capacitor
The fields such as device and adsorbent material, catalysis material.
Background technique
With the development of economy, freshwater resources consume at an amazing speed, and shortage of fresh water will be global face
The major issue faced, sea water desalination are to solve one of the effective way of water shortage.Concentrated seawater is the final stage in sea water desalination
High concentration salt water obtained, composition are mainly NaCl, and furthermore it is also enriched in multiple element heavy metal, nutrition class salt, micro has
Machine compound, organic pollutant and pathogenic bacteria.Currently, being broadly divided into two classes to concentrated seawater processing both at home and abroad, one kind is concentration
Preparing salt by working up seawater, such as extracts bromine simple substance, and yield is lower；One kind is to mix to be discharged into ocean or direct emission enters with power plant cooling water
Sea, but discharge into sea may can cause certain negative effect to the marine eco-environment.The economization of a large amount of concentrated seawaters,
High efficiency processing will be reduced production cost, realize sustainable development urgent problem to be solved.It is dense after effectively utilizing desalination
Salt water, concentrated seawater resource utilization is following important one of the developing direction after realizing sea water desalination.
Biomass-based functional activity Carbon Materials are using the agricultural such as bark, stalk waste as raw material high-temperature calcination under anoxic conditions
Be made, have the characteristics that Environmental compatibility is good, low in cost, large specific surface area, porous structure, be widely used in energy storage with
The fields such as environment remediation.Currently, biomass-based charcoal is applied to supercapacitor, absorption aspect needs to have porous knot abundant
Structure, this just proposes requirement to preparation method.Biomass-based charcoal is prepared at present mostly uses KOH, H3PO4Or ZnCl2The side such as activation
Method prepares biomass-based charcoal after overpickling, not only needs the activator of a large amount of valuableness in the process, results in waste of resources
A large amount of contaminated wastewater environment are also generated simultaneously, are lived then finding the biomass-based function for preparing that one kind is efficient, green, economic
The method of property Carbon Materials is particularly important.
Based on the above reasons, the application is proposed.
Summary of the invention
Technology based on the above background, the present invention is primarily to seawater is difficult to handle after solution desalination and prepared by active carbon
Two difficult points of activator of required valuableness, the purpose of the present invention is to provide it is a kind of using concentrated seawater auxiliary prepare it is biomass-based
The method and its application of functional activity Carbon Materials, also make while solving concentrated seawater bring environmental problem its change give up into
Treasured is used to prepare the biomass-based functional activity charcoal of low price high level.In addition, the method for the present invention is simple, low in cost, generation is given up
Liquid is recyclable to be subject to many-sided utilization, and the concentration of treated waste liquid salt is higher, can use again as biomass activator
Circular economy is generated in the preparation of biomass-based functional activity Carbon Materials；And biomass-based functional activity made from the method for the present invention
Carbon Materials can be applied to the fields such as supercapacitor and adsorbent material, catalysis.
Above-mentioned first purpose of the invention, adopts the following technical scheme that realization:
A method of prepare biomass-based functional activity Carbon Materials using concentrated seawater auxiliary, be by biological material and
Concentrated seawater is sufficiently mixed stir evenly, dry after under anaerobic through high temperature cabonization be made.
The present invention method described above for assisting preparing biomass-based functional activity Carbon Materials using concentrated seawater, specifically
Include the following steps:
(1) by biological material after broken, cleaning under the conditions of temperature is 40~150 DEG C dry 2~36h, then will
Biological material after drying is uniformly mixed with concentrated seawater, obtains mixture 1；Again by the dry 4~56h of gained mixture 1, obtain
To mixture 2；
(2) mixture 2 obtained by step (1) is placed in tube furnace or Muffle furnace, is heated under anaerobic
500~1000 DEG C, 0.5~6h of heat preservation carries out high temperature pyrolysis, is then down to room temperature naturally, obtains carbonized product；
(3) carbonized product obtained by step (2) cleaned using dilute HCl or distilled water repeatedly, filtered repeatedly, until gained is filtered
Liquid pH is 6.0~7.5, will finally filter insoluble matter dry 8~12h under the conditions of 40~120 DEG C, and obtain with porous nano
The target organism matter base functional activity Carbon Materials of chip architecture.
Further, above-mentioned technical proposal further includes step (4): gained cleaning solution for the first time is filtered in recycling step (3) cleaning
It is used as activator and pore creating material again, for being mixed with biological material, is recycled and finally prepares biomass-based function
It can absorbent charcoal material.
Further, above-mentioned technical proposal, step (1) described concentrated seawater can be the sea of the concentration after practical sea water desalination
Water is also possible to the concentrated seawater simulated according to the fixation proportioning components of practical seawater.The concentrated seawater by NaCl,
MgCl2、MgSO4、CaCl2、KCl、NaHCO3, NaBr and H2O composition, according to its different proportion in desalination process and sea area and
Concentration slightly has difference.
Preferably, above-mentioned technical proposal, in terms of 8 times of simulation concentrated seawaters of 1L, the simulated seawater includes following content
Each component: 195.0~258.2g/L of NaCl；MgCl216.5~22.5g/L；MgSO424.0~31.2g/L；CaCl2
5.5~10.5g/L；4.7~6.4g/L of KCl；NaHCO3: 1.4~1.8g/L；0.54~0.8g/L of NaBr.
Further, above-mentioned technical proposal, the biological material can be bark, fish scale, cicada slough, bean curd, pericarp, grape
Any one of sugar, straw, peanut shell etc..
Further, above-mentioned technical proposal, the concentration range of the concentrated seawater are 2~8 times of concentrated seawaters.
Further, the amount ratio of above-mentioned technical proposal, the biological material and concentrated seawater is preferably (1~10) g:
(50~500) ml.
Further, above-mentioned technical proposal, the breaking method of step (1) described biological material are mainly broken using physics
The biological material is broken into little particle or powder, for example uses ball-milling method by biological material grinds final states by method.
Further, above-mentioned technical proposal, the blending manner of step (1) biological material and concentrated seawater, can adopt
It is mixed with stirring at normal temperature method, mixing time is 2~72h；It is also possible to for mixture being placed in hydrothermal reaction kettle, 80~
2h~48h is kept the temperature under the conditions of 180 DEG C to be mixed.
Further, above-mentioned technical proposal, the drying mode of step (1) mixture 1 can be freeze-drying can also be with
It is oven drying.
Further, above-mentioned technical proposal, step (2) the tube furnace heating rate are 2~10 DEG C/min.
Further, above-mentioned technical proposal, the pyrolysis of step (2) high temperature can be in the atmosphere for having inert gas, can also
To be that isolation air is calcined after sample covers sea salt.
Preferably, above-mentioned technical proposal, the inert gas can be N2Either Ar.
The above-mentioned preparation method principle of the present invention is as follows: concentrated seawater is uniformly mixed with biomass, after drying, biomass
It is sealed in concentrated seawater salt crystal, during high temperature pyrolysis, inorganic salts can play support to the pore structure of biomass
Effect, and the salt in concentrated seawater can be effectively avoided biomass-based functional activity charcoal and be adhered to form porous nano-sheet
Structure.
Cleaning carbonized product obtains in the above-mentioned the step of preparing biomass-based functional activity Carbon Materials method (3) of the present invention
Scrub raffinate contains a large amount of NaCl and NaBr for the first time, and salinity is higher than concentrated seawater, thus more for resource utilization
Value.Therefore, the present invention also provides the method that the above-mentioned scrub raffinate for the first time containing based on NaCl is carried out secondary treatment,
To realize recycling for waste liquid, energy saving, resource is fully utilized, while also reducing cost, specific to locate
Reason method is as follows:
The ingredient of scrub raffinate is similar with concentrated seawater for the first time, and the concentration of its salt is higher, can be again as biology
Matter activator is used for the preparation of biomass-based functional activity Carbon Materials, metabolism and green circulation economy technique between realization industry；
In addition, the present invention is combined is passed through CO with reference to Hou's process for soda production in scrub raffinate for the first time2And NH3Prepare Na2CO3And NH4Cl, can be into
One step recycles waste liquid；NaOH, Cl are produced by being electrolysed scrub raffinate for the first time in conjunction with reference chlorine industry2And H2, further
Produce the industry of a series of chemical products；Bromine is mentioned in conjunction with reference preparing salt by working up seawater and seawater, applied to will can industrially wash for the first time
Wash waste liquid and introduce salt pan, after be exposed to the sun and evaporate water in the case where shining upon, leave crude salt, separate the bittern mother obtained after salt crystals
Liquid is passed through Cl2Br is mentioned for seawater afterwards.The waste liquid for preparing biomass-based charcoal Efficient Cycle is obtained using the above method to utilize, it is real
The circulation preparation path of green is showed.Above-mentioned each processing Method And Principle is as follows:
A. scrub raffinate utilizes again for the first time
The waste liquid for washing charcoal sample for the first time contains a large amount of salt, and salinity is higher, and ingredient and concentrated seawater are substantially
It is identical, the preparation of biomass-based functional activity Carbon Materials can be used for as activator again, achievees the purpose that circular economy.
B. it combines and refers to Hou's process for soda production:
NaCl+CO2+NH3+H2O=NaHCO3↓+NH4Cl (can make nitrogenous fertilizer)
2NaHCO3=Na2CO3+H2O+CO2↑(CO2It is recycled) (to heat as reaction condition)
CO is passed through in waste liquid2And NH3Gas can be used for preparing soda ash and ammonium chloride.
C. chlorine industry is combined:
2H2O+2Cl-=H2↑+Cl2↑+2OH-；
2H2O+2NaCl=H2↑+Cl2↑+2NaOH；
NaOH, Cl are produced by being electrolysed scrub raffinate for the first time2And H2, further produce a series of chemical products.
D. preparing salt by working up seawater and seawater is combined to mention bromine (total anti-reaction equation that seawater mentions bromine is as follows):
Cl2+2Br-=Br2+2Cl-
Br2+SO2+2H2O=2HBr+H2SO4
Cl2+2Br-=Br2+2Cl-；
Applied to industrially salt pan can will be introduced by scrub raffinate for the first time, after shining upon lower solarization, evaporate water, leave thick
Salt；The bittern mother liquor obtained after separation salt crystals mentions bromine for seawater.
Another object of the present invention is to provide the applications of biomass-based functional activity Carbon Materials described above, can be used for making
Standby electrode of super capacitor.
Further, above-mentioned technical proposal, the electrode material for super capacitor are prepared with the following method: will be described
A little second is added after grinding uniformly according to the ratio of mass ratio 8:1:1 in biomass-based functional activity Carbon Materials, carbon black and binder
Alcohol, pressing rolls film into 1*1cm repeatedly2Thin slice, 40~150 DEG C drying, be pressed on collector of corresponding size, obtain super electricity
Container electrode.
In addition, biomass-based functional activity Carbon Materials made from the above method of the present invention also act as adsorbent material, catalysis
Agent or catalyst carrier.
The present invention is compared with prior art compared with following substantive distinguishing features and remarkable advantage outstanding:
(1) use raw material be the biomass of abundance as presoma to the present invention, using concentrated seawater as activator with
Pore creating material prepares biomass-based functional activity Carbon Materials, the high-concentration waste liquid after washing again using or can be used for preparing other
Chemical products, three, which combines body, realizes change waste becoming treasure, the theory of green circulation economy.
(2) present invention impregnates biomass using the concentrated seawater after sea water desalination, using freezing or direct drying method, makes
It obtains salt in concentrated seawater to be present in solid form in biomass presoma, selects suitable pyrolysis temperature calcining preparation biomass
Base functional activity charcoal, a large amount of inorganic salts in concentrated seawater serve as activator in the process and reach biomass pore-creating purpose.
(3) method that the present invention prepares biomass-based functional activity charcoal, at low cost, yield is high, has porous knot abundant
Structure.Inorganic salts in seawater are filled into biomass hole, and in high-temperature calcination, inorganic salts can play the pore structure of biomass
The effect of support can improve pore structure and increase the quantity in hole, and inorganic salts can effectively avoid biomass-based functional activity
Charcoal is adhered to form porous nano chip architecture, is adapted for use as the fields such as supercapacitor and absorption.
(4) utilization again of washing water for the first time of the invention, washing water is mentioned with chlorine industry, Hou's process for soda production and seawater for the first time
Bromine technique combines, and has reached and has economized on resources, controls economic cost, reduces the purpose of pollution, realize metabolism between industry and
Green circulation economy technique.Therefore the cost-effective processing of waste liquid of the present invention, so that biomass-based functional activity of the invention
Charcoal prepares to form an efficient, economic, free of contamination preparation method.
(5) biomass-based functional activity charcoal large specific surface area prepared by the present invention, specific surface area are up to 1023.87m2/ g,
Porous structure is more, is applied to preparation supercapacitor, improves the specific capacitance of supercapacitor, enhances supercapacitor
Chemical property.In addition, biomass-based functional activity Carbon Materials prepared by the present invention also have excellent absorption property, it is expected to
Applied to fields such as absorption, catalysis.
Detailed description of the invention
Fig. 1 (a), (b) are respectively that Example 1 and Example 2 of the present invention utilizes biomass-based function made from concentrated seawater
The SEM of active carbon schemes；
Fig. 2 (a), (b) are respectively that Example 1 and Example 2 of the present invention utilizes biomass-based function made from concentrated seawater
The N of active carbon2Adsorption desorption curve and graph of pore diameter distribution；
Fig. 3 (a), (b) are respectively that Example 1 and Example 2 of the present invention utilizes biomass-based function made from concentrated seawater
Active carbon is as electrode of super capacitor in different multiplying constant current charge-discharge diagram；
Fig. 4 (a), (b) be respectively the embodiment of the present invention 8 using biomass-based functional activity charcoal made from concentrated seawater as
Oxygen reduction catalyst cyclic voltammogram and linear sweep voltammetry curve graph under the conditions of saturated oxygen；
Fig. 5 is for the method for the invention for utilizing concentrated seawater to prepare biomass-based functional activity charcoal and different application and for the first time
Cyclic utilization of washing wastewater route map.
Specific embodiment
Invention is further described in detail with specific implementation case with reference to the accompanying drawing.The implementation case is with this hair
Implemented under premised on bright technology, provides detailed embodiment and specific operating process now to illustrate that the present invention has wound
The property made, but protection scope of the present invention case study on implementation not limited to the following.
The information for including according to the application, to those skilled in the art can be easily to essence of the invention
Really description carries out various changes, without departing from spirit and scope of the appended claims.It should be understood that the scope of the present invention is not
Process, property defined by being confined to or component, because these embodiments and other descriptions are just for the sake of schematic
Illustrate certain aspects of the present disclosure.In fact, this field or those skilled in the relevant art obviously can be to embodiment party of the present invention
The various changes that formula is made all cover within the scope of the appended claims.
It is not intended to limit the scope of the invention for a better understanding of the present invention, expression dosage used in this application,
All numbers of percentage and other numerical value, are understood to be modified with word " about " in all cases.Therefore,
Unless stated otherwise, otherwise digital parameters listed in specification and appended book are all approximations, may
It can be changed according to the difference for the desirable properties for attempting to obtain.Each digital parameters at least should be considered as according to being reported
Effective digital and obtained by the conventional method of rounding up.
Testing the electrolyte used in electrode material chemical property in the following each embodiments of the present invention can be organic electrolysis
Any one of liquid, ionic liquid or aqueous solution, aqueous solution can be acid solution, aqueous slkali or neutral electrolyte.
Embodiment 1
A kind of method for assisting preparing biomass-based functional activity Carbon Materials using concentrated seawater of the present embodiment is specific to wrap
Include following steps:
(1) the Chinese parasol tree bark after distilled water cleaning repeatedly is placed in 60 DEG C of baking ovens dry 12h, uses ball milling later
Machine 350rmp ball milling 2h, for use.
(2) match 8 times of concentrated seawaters of 100mL: adding quality respectively is NaCl:21.0g；MgCl2: 2.2g；MgSO4:
2.54g；CaCl2: 0.942g；KCl:0.612g；NaHCO3: 0.159g；NaBr:0.071g is settled to 100mL later.
(3) the Chinese parasol tree bark after taking 10g step (1) ball milling mix stirring with 8 times of concentrated seawaters of step (2) 100mL
It mixes overnight；It is rapidly added liquid nitrogen after stirring, is placed in freeze drier and is freeze-dried 48h；Sample after freeze-drying is set
700 DEG C are warming up to 4 DEG C/min under 100mL/min ar gas environment in tube furnace, in 700 DEG C of heat preservation 2h, is then dropped naturally
It warms to room temperature, obtains carbonized product；Obtained carbonized product is multiple using dilute hydrochloric acid and distilled water filtering cleaning, until filtrate pH
About 7,60 DEG C of dry 10h in baking oven are subsequently placed in, the target organism matter base functional activity charcoal with porous structure is obtained, are named
For BC-7.
Take 80mg the present embodiment biomass-based functional activity charcoal (biomass carbon) obtained above, 10mg PTFE and 10mg
A little ethyl alcohol is added according to the ratio of mass ratio 8:1:1 in carbon black after grinding uniformly, pressing rolls film into 1*1cm2Thin slice, 60 DEG C
Drying, is pressed on collector of corresponding size, and super-capacitor pole piece is made.By electrode material, mercury/mercuric oxide electrode and platinized platinum
Respectively as working electrode, reference electrode and to electrode assembling at three-electrode system, electricity is tested in 6mol/L KOH electrolyte
Pole material electrochemical performance.
The waste liquid that step (3) is washed to carbonized product for the first time, combines with Hou's process for soda production, is passed through CO after concentrated2、NH3
Gas is used to prepare soda ash and ammonium chloride, efficiently recycles to realize.
Attached drawing 1 (a) and attached drawing 2 are the scanning electron microscope (SEM) of biomass-based functional activity charcoal prepared by the present embodiment, N2
Adsorption desorption curve and pore-size distribution can be seen that porous nano sheet structure, N is presented in biomass-based functional activity charcoal from SEM figure2
Adsorption desorption curve shows that the biomass-based functional activity charcoal is grade pore structure, and specific surface area is up to 227.57m2/ g, Kong Rongwei
0.252cm3/g.Attached drawing 3 (a) is that biomass-based functional activity charcoal manufactured in the present embodiment is applied to as super capacitor material
The constant current charge-discharge figure of 6mol/L KOH electrolyte, the specific capacitance of display are 154.8F/g, have good charge-discharge performance
And cyclical stability.
Embodiment 2
A kind of method for assisting preparing biomass-based functional activity Carbon Materials using concentrated seawater of the present embodiment is specific to wrap
Include following steps:
(1) prepare 8 times of concentrated seawaters of 100mL: adding quality respectively is NaCl:21.7g；MgCl2: 2g；MgSO4:
2.72g；CaCl2: 0.936g；KCl:0.592g；NaHCO3: 0.168g；NaBr:0.064g is settled to 100mL later.
(2) the 8 times of concentrated seawaters for the 50mL that 5g fish scale and step (1) are prepared be mixed overnight, stirring terminates
After be immediately placed in hydrothermal reaction kettle, keep the temperature 12h under the conditions of 160 DEG C.To obtaining that liquid nitrogen is added in filtrate, it is placed in freeze-drying
In machine after drying for 24 hours；Sample after freeze-drying is placed in tube furnace under 100mL/min ar gas environment with 5 DEG C/min heating
Rate is warming up to 800 DEG C, in 800 DEG C of heat preservation 2h, is then down to room temperature naturally, obtains carbonized product.Obtained carbonized product makes
Repeatedly with dilute hydrochloric acid and distilled water filtering cleaning, until filtrate pH is about 7,60 DEG C of dry 8h in baking oven are subsequently placed in, mesh is made
Biomass-based functional activity charcoal is marked, FC-8 is named as.
The technological parameter and process of the present embodiment preparation super-capacitor pole piece are substantially the same manner as Example 1, and difference only exists
In: biomass carbon is electrolysed using biomass-based functional activity charcoal FC-8 made from the present embodiment, electrode material in 6mol/L KOH
Chemical property is tested in liquid.
The present embodiment cleans the waste liquid of carbonized product for the first time, with reference to chlorine industry, is produced by being electrolysed scrub raffinate for the first time
NaOH、Cl2And H2Further produce a series of chemical products.
Attached drawing 1 (b) and attached drawing 2 be biomass-based functional activity charcoal prepared in the present embodiment scanning electron microscope (SEM),
N2Adsorption desorption curve and pore-size distribution can be seen that porous nano-sheet is presented in biomass-based functional activity charcoal obtained from SEM figure
Shape structure, N2Adsorption desorption curve shows that the biomass-based functional activity charcoal is grade pore structure, and specific surface area is up to 1023.87m2/
G, Kong Rongwei 0.73cm3/g.Attached drawing 3 (b) is biomass-based functional activity charcoal manufactured in the present embodiment as super capacitor equipment
Material is applied to the constant current charge-discharge figure of 6mol/L KOH electrolyte, and the specific capacitance of display is electric current of the 187.2F/g in 0.5A/g
Density has good charge-discharge performance.
Embodiment 3
A kind of method for assisting preparing biomass-based functional activity Carbon Materials using concentrated seawater of the present embodiment is specific to wrap
Include following steps:
(1) prepare 8 times of concentrated seawaters of 100mL: adding quality respectively is NaCl:21.2g；MgCl2: 2.1g；MgSO4:
2.54g；CaCl2: 0.925g；KCl:0.61g；NaHCO3: 0.172g；NaBr:0.071g is settled to 100mL later.
(2) the 8 times of concentrated seawaters for the 50mL that 3g bean curd and step (1) are prepared be mixed overnight, it is fast after stirring
Speed is placed in 120 DEG C of heat preservation 14h in hydrothermal reaction kettle.It obtains that liquid nitrogen is added in filtrate, is placed in freeze drier after drying for 24 hours；
Sample after freeze-drying, which is placed in tube furnace, is warming up to 900 DEG C under 100mL/min nitrogen environment with 2 DEG C/min, at 900 DEG C
4h is kept the temperature, room temperature is then down to naturally, obtains carbonized product.Obtained carbonized product is multiple using distilled water filtering cleaning, directly
It is about 6.5 to filtrate pH, is subsequently placed in 90 DEG C of dry 6h in baking oven, target organism matter base functional activity charcoal is made.
(3) collection step (2) is cleaned, filtering gained cleans the waste liquid of carbonized product, ingredient and concentrated seawater phase for the first time
Seemingly, concentrated seawater activator and pore creating material it is used as again to be used to recycle and prepare biomass-based functional activity charcoal.
The present embodiment prepares the technological parameter of super-capacitor pole piece and the basic phase of preparation step of process and embodiment 1
Together, difference is only that: biomass carbon is using biomass-based functional activity charcoal made from the present embodiment, and electrode material is in 6mol/L
Chemical property is tested in KOH electrolyte.The biomass-based functional activity Carbon Materials of this example preparation are used for super capacitor equipment
In material, charge-discharge performance and cyclical stability and 1 test result of embodiment are essentially identical.
Embodiment 4
A kind of method for assisting preparing biomass-based functional activity Carbon Materials using concentrated seawater of the present embodiment is specific to wrap
Include following steps:
(1) prepare 4 times of concentrated seawaters of 200mL: adding quality respectively is NaCl:22.1g；MgCl2: 1.9g；MgSO4:
2.42g；CaCl2: 0.954g；KCl:0.601g；NaHCO3: 0.172g；NaBr:0.059g is settled to 200mL later.
(2) 4h is mixed in the 4 times of concentrated seawaters for the 200mL that 5g pomelo peel and step (1) are prepared, mixed liquor is placed in baking
60 DEG C of dryings are for 24 hours in case；After drying in sample 100ml crucible, upper layer covers 15g sea salt.Sample is placed in Muffle furnace with 10
DEG C/min is warming up to 800 DEG C, in 800 DEG C of heat preservation 2h, cooled to room temperature obtains carbonized product.Obtained carbonized product makes
Repeatedly with dilute hydrochloric acid and distilled water filtering cleaning, until filtrate pH is about 7, dry 8h is subsequently placed in baking oven under the conditions of 100 DEG C,
Target organism matter base functional activity charcoal is made.
(3) collection step (2) is cleaned, filtering gained cleans the waste liquid of carbonized product, ingredient and concentrated seawater phase for the first time
Seemingly, bromine is mentioned in conjunction with preparing salt by working up seawater and seawater, leaves crude salt after scrub raffinate evaporation for the first time；The bittern obtained after separation salt crystals
Mother liquor is passed through Cl2Bromine is mentioned for seawater.
The present embodiment prepares the technological parameter of super capacitor material and the basic phase of preparation step of process and embodiment 1
Together, difference is only that: biomass carbon is using biomass-based functional activity charcoal made from the present embodiment, and electrode material is in 1mol/L
H2SO4Chemical property is tested in electrolyte.The biomass-based functional activity charcoal of present case preparation is used to prepare super capacitor equipment
Material, specific capacitance is higher and has good cyclical stability.
Embodiment 5
A kind of method for assisting preparing biomass-based functional activity Carbon Materials using concentrated seawater of the present embodiment is specific to wrap
Include following steps:
(1) prepare 2 times of concentrated seawaters of 400mL: adding quality respectively is NaCl:23.1g；MgCl2: 2.1g；MgSO4:
2.6g；CaCl2: 0.98g；KCl:0.723g；NaHCO3: 0.181g；NaBr:0.061g is settled to 400mL later.
(2) 2h is mixed in the 4 times of concentrated seawaters for the 400mL that 5g glucose and step (1) are prepared, mixed liquor is placed in baking
80 DEG C of dry 20h in case；After drying in sample 100ml crucible, upper layer covers 15g sea salt, and the sample that will be covered with sea salt is placed in
900 DEG C are being warming up to 4 DEG C/min in Muffle furnace, in 900 DEG C of heat preservation 2h, cooled to room temperature obtains carbonized product.It obtains
Carbonized product it is multiple using dilute hydrochloric acid and distilled water filtration washing, until filtrate pH is about 6.5, be subsequently placed in 120 in baking oven
DEG C dry 6h, obtains biomass-based functional activity charcoal.
(3) collection step (2) is cleaned, filtering gained cleans the waste liquid of carbonized product for the first time, in conjunction with preparing salt by working up seawater and seawater
Bromine is mentioned, leaves crude salt after scrub raffinate evaporation for the first time；Furthermore the bittern mother liquor for separating the upper layer obtained after salt crystals is passed through Cl2
Afterwards for extracting bromine.
The present embodiment prepares the technological parameter of super capacitor material and the basic phase of preparation step of process and embodiment 1
Together, difference is only that: biomass carbon is using biomass-based functional activity charcoal made from the present embodiment, reference electrode Ag/
AgNO3, electrode material is in 1.0mol/L TEABF4Chemical property is tested in/PC electrolyte.Present case is prepared biomass-based
Functional activity charcoal is used as super capacitor material, in 1.0mol/L TEABF4Good high rate performance is shown in/PC electrolyte
And cyclical stability.
Embodiment 6
A kind of method for assisting preparing biomass-based functional activity Carbon Materials using concentrated seawater of the present embodiment is specific to wrap
Include following steps:
(1) prepare 2 times of concentrated seawaters of 400mL: adding quality respectively is NaCl:22.5g；MgCl2: 2.2g；MgSO4:
2.4g；CaCl2: 0.95g；KCl:0.62g；NaHCO3: 0.173g；NaBr:0.066g is settled to 100mL later.
(2) 2h is mixed in the 2 times of concentrated seawaters for the 400mL that 4g corn stover and step (1) are prepared, mixed liquor is placed in
80 DEG C of dry 20h in baking oven；After drying in sample 100ml crucible, upper layer covers 15g sea salt, it is therefore an objective to completely cut off air.Sample is set
950 DEG C are being warming up to 5 DEG C/min in Muffle furnace, in 950 DEG C of heat preservation 4h, cooled to room temperature.Product uses distilled water
Filtration washing is multiple, until filtrate pH is about 6.5, is subsequently placed in 150 DEG C of dry 4h in baking oven, obtains biomass-based functional activity
Charcoal.
The present embodiment prepares the technological parameter of super capacitor material and the basic phase of preparation step of process and embodiment 1
Together, difference is only that: biomass carbon is using biomass-based functional activity charcoal made from the present embodiment, reference electrode Ag/
AgNO3, electrode material is in 1.0mol/L TEABF4Chemical property is tested in/AC electrolyte.Present case is prepared biomass-based
Functional activity charcoal is used as super capacitor material, in 1.0mol/L TEABF4Specific capacitance with higher and good in/AC electrolyte
Good high rate performance.
The scrub raffinate of carbonized product is cleaned in collection step (2) cleaning, filtering gained for the first time, contains higher concentration
Salt may act as the preparation that concentrated seawater is used as activator again, pore creating material is used for biomass-based functional activity charcoal, reach circulation benefit
Purpose.
Embodiment 7
The present embodiment using concentrated seawater assist prepare biomass-based functional activity Carbon Materials method, specifically include as
Lower step:
(1) prepare 8 times of concentrated seawaters of 100mL: adding quality respectively is NaCl:22.4g；MgCl2: 2.3g；MgSO4:
2.16g；CaCl2: 0.965g；KCl:0.63g；NaHCO3: 0.181g；NaBr:0.082g is settled to 100mL later.
(2) the 8 times of concentrated seawaters for the 50mL that peanut shell powder after 4g ball milling and step (1) are prepared be mixed
Night is rapidly added liquid nitrogen after stirring, is placed in freeze drier and dries for 24 hours；Sample after freeze-drying is placed in tube furnace
800 DEG C are warming up to 4 DEG C/min under 100mL/min nitrogen atmosphere, in 800 DEG C of heat preservation 2h, room temperature is then down to naturally, obtains carbon
Change product.Obtained carbonized product is multiple using dilute hydrochloric acid and distilled water filtering cleaning, until filtrate pH is about 6.5, then sets
Target organism matter base functional activity charcoal is made in 80 DEG C of dry 10h in baking oven.
Iodine sorption value is an important indicator for measuring quality of activated carbon superiority and inferiority, and iodine sorption value is higher, and quality of activated carbon is got over
It is good.The measurement of the iodine sorption value of the biomass-based functional activity charcoal of the present embodiment refers to national standard " the wooden work of GB/T 12496.8-2015
Property charcoal test method iodine sorption value measurement ", the iodine sorption value of measurement is 802mg/g.Illustrate the biology of the method for the present invention preparation
Matter base functional activity charcoal is that a very promising adsorbent material is used in environment remediation field, removes environmental contaminants, such as
Heavy metal, fuel and organic matter etc..
The present embodiment cleans the waste liquid of biomass-based functional activity charcoal for the first time, with reference to chlorine industry, is washed for the first time by electrolysis
It washs waste liquid and produces NaOH, Cl2And H2The industry for further producing a series of chemical products, achievees the purpose that circular economy.
Embodiment 8
A kind of method for assisting preparing biomass-based functional activity Carbon Materials using concentrated seawater of the present embodiment is specific to wrap
Include following steps:
(1) cicada slough after distilled water cleaning repeatedly is placed in 60 DEG C of baking ovens dry 12h, uses ball mill later
350rmp ball milling 2h, for use.
(2) match 8 times of concentrated seawaters of 100mL: adding quality respectively is NaCl:21.4g；MgCl2: 2.7g；MgSO4:
2.43g；CaCl2: 0.922g；KCl:0.636g；NaHCO3: 0.161g；NaBr:0.076g is settled to 100mL later.
(3) cicada slough after 1g ball milling is mixed with 8 times of concentrated seawaters of 50ml that step (2) is prepared, stirs 2h under room temperature,
Then liquid-nitrogen freeze drying is added for 24 hours, is warming up to 800 DEG C under 100mL/min nitrogen atmosphere with 5 DEG C/min, kept the temperature at 800 DEG C
Then 2h is down to room temperature naturally, obtain carbonized product.Obtained carbonized product is stirred overnight using 1mol/L HCl, is then used
A large amount of distilled water cleanings are repeatedly until pH is about that 7,60 DEG C of vacuum drying 10h obtain target organism matter base functional activity Carbon Materials.
Take the 5wt% of 5mg the present embodiment biomass-based functional activity Carbon Materials (being used as catalyst) obtained above, 50ul
Nafion solution mixed with the ethyl alcohol of 1mL, the slurry of 20ul drop is spontaneously dried into shape in glassy carbon electrode surface after ultrasonic treatment
At uniform catalyst layer.Using glass-carbon electrode, silver/silver chlorate and platinized platinum as working electrode, reference electrode and to electrode
It is assembled into three-electrode system, silver/silver chloride electrode is converted into relative to reversible hydrogen electrode (RHE), is electrolysed in 0.1mol/L KOH
Chemical property is tested in liquid.
The waste liquid that step (3) is washed to carbonized product for the first time is passed through CO after concentrated with reference to Hou's process for soda production is combined2、NH3
Gas is used to prepare soda ash and ammonium chloride, efficiently recycles to realize.
Attached drawing 4a is biomass-based functional activity charcoal prepared in the present embodiment in 0.1mol/L KOH electrolyte
The cyclic voltammogram of 50mv/s is measured under the conditions of saturated oxygen, as can be seen from the figure apparent cathodic reduction peak, illustrates this material
Material has stronger oxygen reducing ability, can be used as the cathod catalyst of fuel cell and metal-air battery.Attached drawing 4b is this reality
Apply in example different rotating speeds under the conditions of saturated oxygen in 0.1mol/L KOH electrolyte of prepared biomass-based functional activity charcoal
Lower test linear scan voltammogram, calculating electron transfer number is 3.9, which shows good hydrogen reduction catalytic performance.
Claims (10)
1. a kind of method for assisting preparing biomass-based functional activity Carbon Materials using concentrated seawater, it is characterised in that: be that will give birth to
Material and concentrated seawater are sufficiently mixed stir evenly, dry after be made under anaerobic through high temperature cabonization.
2. the method according to claim 1 for assisting preparing biomass-based functional activity Carbon Materials using concentrated seawater,
Be characterized in that: the method specifically comprises the following steps:
(1) biological material is dried under the conditions of temperature is 40~150 DEG C 2~36h after broken, cleaning, then will dried
Biological material afterwards is uniformly mixed with concentrated seawater, obtains mixture 1；Again by the dry 4~56h of gained mixture 1, mixed
Close object 2；
(2) mixture 2 obtained by step (1) is placed in tube furnace or Muffle furnace, it is heated to 500 under anaerobic~
1000 DEG C, 0.5~6h of heat preservation carries out high temperature pyrolysis, is then down to room temperature naturally, obtains carbonized product；
(3) carbonized product obtained by step (2) cleaned using dilute HCl or distilled water repeatedly, filtered repeatedly, until gained filtrate pH
It is 6.0~7.5, will finally filters insoluble matter dry 8~12h under the conditions of 40~120 DEG C, and obtain with porous nano-sheet knot
The target organism matter base functional activity Carbon Materials of structure.
3. the method according to claim 2 for assisting preparing biomass-based functional activity Carbon Materials using concentrated seawater,
Be characterized in that: the method also includes step (4): cleaning solution is used as activation again for the first time for recycling step (3) cleaning, filtering gained
Agent and pore creating material are recycled for mixing with biological material and finally prepare biomass-based functional activity Carbon Materials.
4. the method according to claim 2 or 3 for assisting preparing biomass-based functional activity Carbon Materials using concentrated seawater,
It is characterized by: step (1) described concentrated seawater is the concentrated seawater after practical sea water desalination or consolidating according to practical seawater
Determine the concentrated seawater that proportioning components are simulated；The concentrated seawater is by NaCl, MgCl2、MgSO4、CaCl2、KCl、NaHCO3、
NaBr and H2O composition.
5. the method according to claim 4 for assisting preparing biomass-based functional activity Carbon Materials using concentrated seawater,
Be characterized in that: in terms of 8 times of simulation concentrated seawaters of 1L, the simulated seawater includes each component of following content: NaCl 195.0
~258.2g/L；MgCl216.5~22.5g/L；MgSO424.0~31.2g/L；CaCl25.5~10.5g/L；KCl 4.7
~6.4g/L；NaHCO31.4~1.8g/L；0.54~0.8g/L of NaBr.
6. the method according to claim 2 or 3 for assisting preparing biomass-based functional activity Carbon Materials using concentrated seawater,
It is characterized by: the biological material can for bark, fish scale, cicada slough, bean curd, pericarp, straw, peanut shell, leaf,
Any one of glucose and cellulose etc.；The concentration range of the concentrated seawater is 2~8 times of concentrated seawaters.
7. the method according to claim 2 for assisting preparing biomass-based functional activity Carbon Materials using concentrated seawater,
Be characterized in that: the amount ratio of the biological material and concentrated seawater is preferably (1~10) g:(50~500) ml.
8. the method according to claim 2 for assisting preparing biomass-based functional activity Carbon Materials using concentrated seawater,
Be characterized in that: step (2) high temperature pyrolysis be in the atmosphere for having inert gas or sample covering sea salt after isolation air into
Row calcining.
9. the method according to claim 2 for assisting preparing biomass-based functional activity Carbon Materials using concentrated seawater,
It is characterized in that: being passed through CO into step (3) cleaning, filtering gained for the first time cleaning solution2And NH3It is used to prepare Na2CO3And NH4Cl；Or
By gained cleaning solution Electrowinning NaOH, Cl for the first time2And H2；Or gained is mentioned into bromine after cleaning solution is used to prepare crude salt for the first time.
10. biomass-based functional activity Carbon Materials made from method as claimed in claim 1 or 2 are as electrode of super capacitor, suction
The application of enclosure material, catalysis material.
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