CN109158083A - A kind of preparation method and its usage of biomass-based carbon material - Google Patents
A kind of preparation method and its usage of biomass-based carbon material Download PDFInfo
- Publication number
- CN109158083A CN109158083A CN201811194726.8A CN201811194726A CN109158083A CN 109158083 A CN109158083 A CN 109158083A CN 201811194726 A CN201811194726 A CN 201811194726A CN 109158083 A CN109158083 A CN 109158083A
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- Prior art keywords
- biomass
- ionic liquid
- carbon
- preparation
- carbon material
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- 239000002028 Biomass Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000002608 ionic liquid Substances 0.000 claims abstract description 39
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229960001231 choline Drugs 0.000 claims abstract description 14
- 229940105132 myristate Drugs 0.000 claims abstract description 12
- TUNFSRHWOTWDNC-UHFFFAOYSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims description 26
- 240000008042 Zea mays Species 0.000 claims description 23
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 23
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 21
- 235000005822 corn Nutrition 0.000 claims description 21
- 238000003763 carbonization Methods 0.000 claims description 8
- 240000007594 Oryza sativa Species 0.000 claims description 5
- 235000007164 Oryza sativa Nutrition 0.000 claims description 5
- 235000009566 rice Nutrition 0.000 claims description 5
- 239000010902 straw Substances 0.000 claims description 5
- 239000003463 adsorbent Substances 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims description 2
- 239000010903 husk Substances 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 48
- 239000000463 material Substances 0.000 abstract description 24
- 238000000034 method Methods 0.000 abstract description 13
- 239000003795 chemical substances by application Substances 0.000 abstract description 7
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 abstract 1
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract 1
- 239000001569 carbon dioxide Substances 0.000 abstract 1
- 239000010907 stover Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- 239000003610 charcoal Substances 0.000 description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 238000001179 sorption measurement Methods 0.000 description 11
- 239000002699 waste material Substances 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 230000002378 acidificating effect Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 5
- 235000017491 Bambusa tulda Nutrition 0.000 description 5
- 244000082204 Phyllostachys viridis Species 0.000 description 5
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000011425 bamboo Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 244000046052 Phaseolus vulgaris Species 0.000 description 4
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 239000012190 activator Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 4
- 150000004040 pyrrolidinones Chemical class 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 3
- 244000002639 Delonix regia Species 0.000 description 3
- 235000003283 Pachira macrocarpa Nutrition 0.000 description 3
- 240000001085 Trapa natans Species 0.000 description 3
- 235000014364 Trapa natans Nutrition 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 235000009165 saligot Nutrition 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- -1 1-Methyl-2-Pyrrolidone sulfuric acid Hydrogen salt Chemical class 0.000 description 2
- 241000609240 Ambelania acida Species 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 2
- 239000010905 bagasse Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- FYWVMROQEMIMSK-UHFFFAOYSA-N butane-1-sulfonic acid;hydrogen sulfate;3-methyl-1h-imidazol-3-ium Chemical compound OS([O-])(=O)=O.C[N+]=1C=CNC=1.CCCCS(O)(=O)=O FYWVMROQEMIMSK-UHFFFAOYSA-N 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 235000009973 maize Nutrition 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 235000020238 sunflower seed Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 235000017060 Arachis glabrata Nutrition 0.000 description 1
- 244000105624 Arachis hypogaea Species 0.000 description 1
- 235000010777 Arachis hypogaea Nutrition 0.000 description 1
- 235000018262 Arachis monticola Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 240000002943 Elettaria cardamomum Species 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 240000007049 Juglans regia Species 0.000 description 1
- 235000009496 Juglans regia Nutrition 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- DHQLIBVQKUIKAZ-UHFFFAOYSA-N S(=O)(=O)(O)OS(=O)(=O)O.CN1C(CCC1)=O Chemical compound S(=O)(=O)(O)OS(=O)(=O)O.CN1C(CCC1)=O DHQLIBVQKUIKAZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- QRSFFHRCBYCWBS-UHFFFAOYSA-N [O].[O] Chemical compound [O].[O] QRSFFHRCBYCWBS-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- IMUHSLDVFHLXDW-UHFFFAOYSA-N butane-1-sulfonic acid fluoroform 1-methylimidazole Chemical compound C(F)(F)F.CN1C=NC=C1.C(CCC)S(=O)(=O)O IMUHSLDVFHLXDW-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000005300 cardamomo Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 210000000232 gallbladder Anatomy 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000012978 lignocellulosic material Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- NTSJRFHRTPPSND-UHFFFAOYSA-N methanesulfonate 1-methylpyrrolidin-1-ium-2-one Chemical compound CS([O-])(=O)=O.C[NH+]1CCCC1=O NTSJRFHRTPPSND-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- QVGXLLKOCUKJST-BJUDXGSMSA-N oxygen-15 atom Chemical compound [15O] QVGXLLKOCUKJST-BJUDXGSMSA-N 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J20/28054—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 surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/485—Plants or land vegetals, e.g. cereals, wheat, corn, rice, sphagnum, peat moss
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Materials Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a kind of preparation methods of biomass-based carbon material, and this method comprises the following steps: (1) biomass material is sufficiently impregnated with ionic liquid solution；(2) it will be carbonized impregnated of the biomass material of ionic liquid, obtain the biomass-based carbon material；It is characterized in that: the ionic liquid is choline myristate.The present invention, as carbon forming agent, can be obtained the carbon material with abundant porous structure, specific surface area is up to 1500~3100m using ionic liquid choline myristate after biomass material charing2/ g, for the maximal absorptive capacity of methylene blue up to 1500~2000mg/g, yield is up to 40% or more, and carbon monoxide and carbon dioxide content when can be substantially reduced charing in tail gas, more environmentally friendly.
Description
Technical field
The invention belongs to carbon material fields, and in particular to a kind of preparation method and its usage of biomass-based carbon material.
Background technique
Active carbon is a kind of hydrophobic group carbonaceous adsorbent material with abundant pore structure and high-specific surface area, it, which has, inhales
Attached ability is strong, and chemical stability is good, and mechanical strength is high, and the features such as facilitate regeneration, is widely used in industry, agricultural, medicine
The fields such as health and environmental protection.And increasingly improved recently as the requirement of environmental protection, so that the need of active carbon both at home and abroad
The amount of asking is increasing.
The main material for preparing active carbon at present has: timber, sawdust, shell etc., due to the reduction of wood raw material supply,
So that cost increase, Activated Carbon Production is restricted.In addition, also useful coal, sludge, plastics, petroleum coke are the work of raw material preparation
Property charcoal, but these raw materials will cause environmental pollution.Currently, biomass castoff is used to become research heat as activated carbon raw material
Point.Tzong-Horng Liou(Development of mesoporous structure and high adsorption
capacity of biomass-based activated carbon by phosphoric acid and zinc
Chloride activation, Chemical Engineering Journal, 2010,158:129-142) with bagasse and
Sunflower seed shell is that raw material prepares active carbon, (the Preparation and such as Alexandro M.M.Vargas
characterization of activated carbon from a new raw lignocellulosic material:
Flamboyant(Delonix regia)pods,Journal of Environmental Management,2011,92:
It is 178-184) that raw material prepares active carbon, (the Preparation of such as Luiz C.A.Oliveira with flame tree beanpod
activated carbons from coffee husks utilizing FeCl3and ZnCl2as activating
Agents, Journal of Hazardous Materials, 2009:165:87-94) with coffee shell be raw material preparation activity
Charcoal, Zhang Chenglu etc. (preparation method of water chestnut leather activated char, application number 200810016234.X) are prepared for active carbon with water chestnut skin,
It builds etc. (preparation method of bean tendril absorbent charcoal, application number 200810013900.4) and prepares active carbon with beans are climing for raw material.
In numerous biomass castoffs, Maize Industry biomass castoff includes corn stover, corncob cellulose and jade
Rice bract is the largest biomass castoff, and 2017 yield for being only corn in Gansu industry associated biomolecule matter waste reach
5000000 tons or more, currently with approach be primarily used to feed, less than 15%, others are dropped or burn utilization rate,
Cause the serious wasting of resources and environmental pollution.If these discarded Maize Industry associated biomolecule matter wastes can be used
Activated carbon from activated sludge is prepared, then can not only be turned waste into wealth, realizes recycling for resource, and active carbon can be used for ring
The improvement in border, such as sewage treatment, soil remediation etc. realize the purpose of waste recycling, have critically important social benefit and warp
Ji benefit.
The document for preparing biomass carbon using corn stover as primary raw material that document is published at present is more, wherein having
Representative to be summarized as follows: Chemical Journal of Chinese Universities in 2018 reports the preparation of corn stover Quito hole biomass carbon, table
Sign and chemical property, using corn stover as raw material, calcium chloride is activator, is prepared for multiporous biological matter carbon.Prepared sample
Product have biggish specific surface area, can be improved the permeability of electrolyte and increase reactivity site, and hole abundant is tied
Structure increases the free movement space of lithium ion and charge, is conducive to the raising of chemical property.Beihua University's journal in 2018
Cornstalk biological charcoal is reported to the absorption property of heavy metal cadmium, lead, prepares charcoal using corn stover, carries out absorption weight
Metal Cd2+And Pb2+Test, the adsorbance and adsorption efficiency of analysis charcoal absorption heavy metal.The result shows that charcoal is to cultivation
Pb in waste water2+And Cd2+With preferable adsorption effect, eliminating rate of absorption is respectively 85% and 98%.Used in this article at
Charcoal agent is phosphoric acid, but produces carbon rate without report.One text of the preparation of cornstalk biological charcoal and Analysis of Structural Characteristics of Xu Dongqian report,
Corn stover is utilized and is prepared for charcoal at 400 DEG C, it is lower though referred to other document report temperature, but still can obtain
Obtain relatively high yield, but only 14%.And obtained biological carbon structure is most stable, and specific surface area and pore volume are maximum,
Absorption property is best, is suitable for corn stover.The research is to explore cornstalk biological charcoal a large amount of, low power consuming, environmental-friendly
Preparation method has established certain theoretical basis.Sludge-corn stover of application chemical industry report in 2018 be pyrolyzed charcoal processed and
It is to Pb2+Characterization of adsorption, but do not refer to the production carbon rate of biomass carbon.Corn straw, biomass are retrieved in international paper
The keywords such as carbon, adsorption can also find 33800 and prepare active carbon for adsorbing about biomass castoff
Report paper perhaps patent but highest production carbon rate 20% hereinafter, the carbon forming agent used be largely inorganic salts or
Inorganic acid, such as " the Adsorption of copper and zinc by of Bioresource Technology magazine ran
biochars produced from pyrolysis of hardwood and corn straw in aqueous
Solution ", corn stalk active carbon is prepared for by different temperature and is studied for the absorption of zinc ion and copper ion, but
It is also not report production carbon rate.
Patent document CN104176736A discloses a kind of method for preparing activated carbon with ionic liquid pretreatment raw material, should
Method is first to use pyrrolidinone compounds acidic ion liquid pretreated feedstock, then by raw material and phosphoric acid using agriculture and forestry organic waste material as raw material
Mixing obtains active carbon in 300~600 DEG C of activation, and pyrrolidinone compounds acidic ion liquid is 1-Methyl-2-Pyrrolidone sulfuric acid
Hydrogen salt, 1-Methyl-2-Pyrrolidone villaumite, 1-Methyl-2-Pyrrolidone methyl sulfonate.The deficiency of this method is: through pyrroles
The pretreated raw material of alkanone class acidic ion liquid need to use phosphoric acid in activation, using this method production active carbon to environment
There is serious secondary pollution, and full text does not mention biomass carbon and produces carbon rate.
Patent document CN102774837A discloses a kind of method for preparing active carbon as activator using ionic liquid, the party
Method, then will treated first with the ionic liquid impregnation containing hexafluoro-phosphate radical or tetrafluoroborate is wooden or bamboo matter raw material
Raw material in 200~400 DEG C and 600~900 DEG C of insulation reactions, obtains active carbon respectively, contains hexafluoro-phosphate radical or tetrafluoro boric acid
The ionic liquid of root is respectively [Bmim] PF6、[Bmim]BF4.Hexafluorophosphoricacid acid ions liquid used in this method its effect with
Phosphoric acid is suitable, and raw material be using wooden or bamboo material, these two types of raw materials relative to stalk biomass waste more
It is easy carbonization, is the primary raw material of current industrially prepared active carbon.The active carbon of usually wooden or bamboo material preparation itself has
There is very high specific surface area.
Patent document CN103359729A discloses a kind of preparation method of mesoporous activated carbon, with carbohydrate, wooden
Or one of bamboo matter is used as starting material, first with acidic ion liquid or the mixed liquor of acidic ion liquid and surfactant
Starting material is impregnated, then in 150~200 DEG C of hot carbonization reactions of progress ion, obtained primary carbonizing production washes away primary carbon
Change after the adsorbed ionic liquid of product again at 500 DEG C with CO21~10h is activated, mesoporous activated carbon is obtained, the acidity selected
Ionic liquid is 1- butyl sulfonic acid -3- methylimidazolium hydrogen sulphate salt, 1- butyl sulfonic acid -3- methylimidazole fluoroform sulphonate.It should
Though the primary charing product yield of method can reach 50% or so, and carbonization temperature is lower, and there is still a need for be aided with CO2Activation is with complete
Pore-forming and reaming at microcellular structure, and the total recovery of active carbon only has 30% or so.
Currently, biomass castoff, which prepares the maximum difficulty of biomass carbon, is that production carbon rate is too low, cause to produce biology
Matter carbon is with high costs, so at present mainly using wooden or bamboo material as raw material in industrial biological matter carbon.
Summary of the invention
It is lived using pyrrolidinone compounds, imidazoles acidic ion liquid as activator or carbon forming agent preparation according to the prior art
The deficiency of property charcoal, the purpose of the present invention is to provide one kind prepared using ionic liquid choline myristate as carbon forming agent it is biomass-based
The method of carbon material.
In order to solve the above-mentioned technical problems, the present invention provides the following technical solutions:
A kind of preparation method of biomass-based carbon material, includes the following steps:
(1) biomass material is sufficiently impregnated with ionic liquid solution；
(2) it will be carbonized impregnated of the biomass material of ionic liquid, obtain the biomass-based carbon material；
It is characterized in that: the ionic liquid is choline myristate.
Preferably, in step (1), the ionic liquid solution is that the choline myristate that concentration is 3~10wt% is water-soluble
Liquid.
Preferably, in step (1), the mass percent concentration of the biomass material is 20~80wt%.
It is highly preferred that dip time be 12~for 24 hours.
Preferably, in step (2), the temperature of the charing is 500~600 DEG C, and the time of charing is 1~5h.
Preferably, after biomass material is sufficiently impregnated with ionic liquid solution, it is filtered to remove extra ionic liquid, is not necessarily to
Other biomass materials impregnated of ionic liquid that will directly obtain that handle carbonize.
Post-processing: after charing, by obtained biomass-based carbon material successively with acid solution, be washed to neutrality, it is dry.
Preferably, the biomass material is the agricultural biomass wastes such as stalk, corncob cellulose, rice hulls.
Beneficial effects of the present invention:
(1) compared with existing pyrrolidinone compounds, imidazoles acidic ion liquid, the present invention uses ionic liquid choline cardamom
Hydrochlorate as carbon forming agent, biomass material carbonize during can be obtained without using the activation of other activators have enrich it is porous
The carbon material of structure, specific surface area is up to 1500~3100m2/ g, the maximal absorptive capacity of methylene blue up to 1500~
2000mg/g is operated more simple.
(2) compared with prior art, the method for the present invention is to the agricultural biomass waste such as stalk, corncob cellulose, rice hulls
Charring rate it is high, the yield of biomass-based carbon material is up to 40% or more.
(3) compared with prior art, carbon monoxide and titanium dioxide when the method for the present invention can obviously reduce charing in tail gas
Carbon content, it is more environmentally friendly.
Detailed description of the invention
Attached drawing is used to provide further understanding of the present invention, and constitutes part of specification, with reality of the invention
It applies example to be used to explain the present invention together, not be construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the scanning electron microscope (SEM) photograph of corn biomass waste active carbon of the present invention.
Specific embodiment
Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings, it should be understood that preferred reality described herein
Apply example only for the purpose of illustrating and explaining the present invention and is not intended to limit the present invention.
The preparation method of biomass-based carbon material of the present invention, includes the following steps:
(1) biomass material is sufficiently impregnated with ionic liquid choline myristate solution；
(2) it will be carbonized impregnated of the biomass material of ionic liquid, obtain the biomass-based carbon material.
Ionic liquid choline myristate:It can make by oneself or commercially available (such as silent Buddhist nun's chemical science and technology (Shanghai)
Co., Ltd).
Biomass material of the present invention can be stalk (such as corn stover, rice straw), corncob cellulose, paddy
Shell, bagasse, shell (such as sunflower seed shell, coffee shell, palm shell, walnut shell, peanut shell, cocoanut shell, water chestnut skin) agricultural are raw
Physical obsolescence object.
To be immersed in biomass material in ionic liquid solution and facilitating subsequent filter operation, institute in dipping system
The mass percent concentration for stating biomass material can be controlled in 20~80wt%.
Preferably, the concentration of the ionic liquid solution be 3~10wt%, dip time be 12~for 24 hours.
Preferably, after biomass material is sufficiently impregnated with ionic liquid solution, it is filtered to remove extra ionic liquid, is not necessarily to
Other biomass materials impregnated of ionic liquid that will directly obtain that handle carbonize.(pass through nitrogen+air in limit oxygen
Oxygen content in control Muffle furnace is in 5~15vt%) under the conditions of carbonized, it is preferable that carbonization temperature can be controlled in 500~
600 DEG C, the time is 1~5h.
Post-processing: after charing, by obtained biomass-based carbon material successively with acid solution, be washed to neutrality, it is dry.
The hydrochloric acid solution that concentration is 5~15wt% can be selected in acid solution.
Embodiment 1
After corn stover dry (air-dry or dry under room temperature), crushing (to 30~80 mesh), it is placed in ionic liquid choline
Soak at room temperature 12h (mass percent of corn stover is 80%) in myristate aqueous solution (concentration 3wt%), filtering is placed on
In Muffle furnace, be carbonized 5h under 500 DEG C, limited oxygen condition (amount of oxygen 15%)；It is cooled to room temperature, is successively 5wt% with concentration
Hydrochloric acid, distillation be washed to neutrality；It is dried in vacuo at 110~150 DEG C, ground 160 mesh sieve is to get active carbon.
Embodiment 2
After corn stover dry (air-dry or dry under room temperature), crushing (to 30~80 mesh), in ionic liquid choline beans
Soak at room temperature 12h (mass percent of corn stover is 50%) in cool acid salt aqueous solution (concentration 5wt%), filtering is placed on horse
Not in furnace, in 550 DEG C, (amount of oxygen 10%) carbonization 3h under limited oxygen condition；It is cooled to room temperature, is successively 5wt%'s with concentration
Hydrochloric acid, distillation are washed to neutrality；It is dried in vacuo at 110~150 DEG C, ground 160 mesh sieve is to get active carbon.
Embodiment 3
After corn stover dry (air-dry or dry under room temperature), crushing (to 30~80 mesh), in ionic liquid choline beans
For 24 hours (mass percent of corn stover is 20%), filtering is placed on soak at room temperature in cool acid salt aqueous solution (concentration 10wt%)
In Muffle furnace, in 600 DEG C, (amount of oxygen 5%) carbonization 1h under limited oxygen condition；It is cooled to room temperature, is successively 15wt% with concentration
Hydrochloric acid, distillation be washed to neutrality；It is dried in vacuo at 110~150 DEG C, ground 160 mesh sieve is to get active carbon.
Analytic explanation is carried out below by structure and shape characteristic of the scanning electron microscope to activated carbon prepared by the present invention, and is led to
The experiment for crossing absorption methylene blue, is illustrated the absorption property of active carbon.
Scanning electron microscope analysis
The scanning electron microscope (SEM) photograph (SEM) of Fig. 1 corn biomass waste active carbon；From Fig. 1 it is observed that prepared by the present invention
Active carbon possess porous structure so that its have very big specific surface area (tested through specific-surface area detection instrument, which compares table
1500~3100m of area2/ g), so possessing very strong adsorption capacity.
Absorption property test
Test method: weighing activated carbon sample 15mg of the present invention, and the methylene blue solution (1520 of 15mL various concentration is added
~2030mg/L), (130r/min) reaches adsorption equilibrium after shaking 2.5h in shaking screen at 30 DEG C.
Test result: 25~30 DEG C, 0.5~2.5h of adsorption time, to the maximal absorptive capacity of methylene blue be 1500~
2000mg/g.Illustrate, active carbon prepared by the present invention has very strong adsorption capacity, can be used for drinking water, industrial water and gives up
Deep purifying life, industrial purification of water quality and the Gas Phase Adsorption of water.
Comparative example 1-6
In order to prove choline myristate ionic liquid in the present invention relative to the report that can read up the literature ionic liquid to straw
Stalk biolobic material waste it is good at carbon ability, the present invention use respectively ionic liquid 1-Methyl-2-Pyrrolidone disulfate,
[Bmim]BF4, 1- butyl sulfonic acid -3- methylimidazolium hydrogen sulphate salt, phosphoric acid, zinc chloride or calcium chloride alternate embodiment 2 gallbladder
Alkali myristate, other conditions and operation are the same as embodiment 2.As a result as follows:
Finally, it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not intended to restrict the invention,
Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features.
All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in of the invention
Within protection scope.
Claims (10)
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| CN114212789A (en) * | 2021-11-27 | 2022-03-22 | 安徽工程大学 | A method for constructing superhydrophobic biomass-based carbon materials |
| CN116902977A (en) * | 2023-07-14 | 2023-10-20 | 西安交通大学 | Preparation method of ionic activated carbon, ionic activated carbon and regeneration method |
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