CN105502387B - The method that activated carbon is prepared using the corn cob residue after xylitol preparation technology - Google Patents
The method that activated carbon is prepared using the corn cob residue after xylitol preparation technology Download PDFInfo
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- CN105502387B CN105502387B CN201510961373.XA CN201510961373A CN105502387B CN 105502387 B CN105502387 B CN 105502387B CN 201510961373 A CN201510961373 A CN 201510961373A CN 105502387 B CN105502387 B CN 105502387B
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- corncob
- hemicellulose
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 190
- 240000008042 Zea mays Species 0.000 title claims abstract description 45
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 title claims abstract description 45
- 235000002017 Zea mays subsp mays Nutrition 0.000 title claims abstract description 45
- 235000005822 corn Nutrition 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 24
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 title claims abstract description 21
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000000811 xylitol Substances 0.000 title claims abstract description 21
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 title claims abstract description 21
- 235000010447 xylitol Nutrition 0.000 title claims abstract description 21
- 229960002675 xylitol Drugs 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000005516 engineering process Methods 0.000 title abstract description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000001784 detoxification Methods 0.000 claims abstract description 36
- 229920002488 Hemicellulose Polymers 0.000 claims abstract description 25
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 24
- 239000002699 waste material Substances 0.000 claims abstract description 17
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004327 boric acid Substances 0.000 claims abstract description 15
- 239000003610 charcoal Substances 0.000 claims abstract description 9
- 238000007654 immersion Methods 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 8
- 238000009413 insulation Methods 0.000 claims abstract description 5
- 230000007935 neutral effect Effects 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims abstract description 4
- 238000003763 carbonization Methods 0.000 claims abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 20
- 238000004061 bleaching Methods 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 230000000694 effects Effects 0.000 claims description 12
- 230000007062 hydrolysis Effects 0.000 claims description 12
- 238000006460 hydrolysis reaction Methods 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000012491 analyte Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 3
- 238000003801 milling Methods 0.000 claims description 3
- 239000002893 slag Substances 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 108010009736 Protein Hydrolysates Proteins 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 11
- 229910052799 carbon Inorganic materials 0.000 abstract description 9
- HEBKCHPVOIAQTA-NGQZWQHPSA-N d-xylitol Chemical compound OC[C@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-NGQZWQHPSA-N 0.000 abstract description 8
- 238000000605 extraction Methods 0.000 abstract description 5
- 238000007873 sieving Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 24
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 18
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 16
- 238000001816 cooling Methods 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- 238000005903 acid hydrolysis reaction Methods 0.000 description 11
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 9
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 150000002989 phenols Chemical class 0.000 description 9
- 238000004042 decolorization Methods 0.000 description 8
- 235000015099 wheat brans Nutrition 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 5
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 5
- -1 energy consumption Substances 0.000 description 5
- 239000000413 hydrolysate Substances 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000000855 fermentation Methods 0.000 description 3
- 230000004151 fermentation Effects 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012935 Averaging Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 1
- 240000007049 Juglans regia Species 0.000 description 1
- 235000009496 Juglans regia Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- 238000011481 absorbance measurement Methods 0.000 description 1
- LPQOADBMXVRBNX-UHFFFAOYSA-N ac1ldcw0 Chemical compound Cl.C1CN(C)CCN1C1=C(F)C=C2C(=O)C(C(O)=O)=CN3CCSC1=C32 LPQOADBMXVRBNX-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229930014669 anthocyanidin Natural products 0.000 description 1
- 150000001452 anthocyanidin derivatives Chemical class 0.000 description 1
- 235000008758 anthocyanidins Nutrition 0.000 description 1
- 150000001480 arabinoses Chemical class 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 235000003599 food sweetener Nutrition 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002972 pentoses Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000003765 sweetening agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
Landscapes
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses the method that the corn cob residue after a kind of utilization xylitol preparation technology prepares activated carbon, including：（1）The waste residue after hemicellulose is extracted from corncob, sieving, addition mass fraction is 40 65% phosphoric acid solution and the boric acid of set amount, mixes, is soaked in 70 90 DEG C；（2）Immersion sample is taken out, is then placed in Muffle furnace, in 450 550 DEG C of the 2h of lower insulation 0.5；（3）By step（2）Corn cob residue after middle carbonization is ground, cleaning to neutrality；（4）By step（3）In neutral active charcoal dry, grinding；5）By gained activated carbon HCl solution pair（4）In obtained activated carbon activated after produce.This uses simple chemicals logos, and the corn cob residue after extraction hemicellulose is prepared into powdered active carbon, for extracting decolouring detoxification when hemicellulose prepares xylo-oligosaccharide from corn core raw material, realizes the higher value application of corn core raw material.
Description
Technical field
The invention belongs to the field of the recycling of agricultural wastes, and in particular to one kind utilizes xylitol preparation technology
The method that corn cob residue afterwards prepares activated carbon.
Background technology
Contain substantial amounts of hemicellulose in corncob, be the important source material for preparing xylo-oligosaccharide and xylitol at present.Using
Sour water solution or the method for basic hydrolysis, separate the hemicellulose in corncob and prepare the sweeteners such as xylo-oligosaccharide, xylitol,
The need for modern people's high-quality life can be met.The production technology of xylo-oligosaccharide and xylitol is prepared with corncob, mainly
Using chemistry and biological means, the hemicellulose pentosan in corncob is extracted, decolouring detoxification is then carried out, then by chemistry
Method, bioanalysis, or biochemical process degrade pentosan to small molecule xylo-oligosaccharide, or continue to prepare after xylo-oligosaccharide is hydrogenated with
Xylitol.Substantial amounts of corn cob residue can be produced by preparing the process of xylo-oligosaccharide and xylitol, and main component is cellulose and wood
Element, the major way of processing waste residue is that burning generation heat is generated electricity at present, but this processing mode added value is than relatively low.
The content of the invention
The present invention provides the method that the corn cob residue after a kind of utilization xylitol preparation technology prepares activated carbon.
The present invention provides a kind of using dilute sulfuric acid pyrohydrolysis corncob, extracts hemicellulose glycan and prepares after xylitol
It is found that the aperture of activated carbon prepared by the corn cob residue is just adapted in the method that waste residue prepares activated carbon, the present invention simultaneously
The detoxification of hydrolyzate after corncob hydrolysis is decolourized, and the decolorizing effect of the merchandise active carbon prepared compared with other raw materials is more excellent,
And the activated carbon cost prepared in the present invention is very low, only 1/3rd of homogenous quantities merchandise active carbon price fit very much
The substantial amounts of decolouring detoxification production process that xylose and xylitol are prepared with corncob before being fated.
The present invention uses following technical scheme：
A kind of corn cob residue after xylitol preparation technology is preparing the application of activated carbon, the system of the corn cob residue
Standby technique is, using corncob as raw material, corn cob residue to be prepared using dilute sulfuric acid hydrolysis of corncob, and concrete technology condition is：
Hydrolysis temperature is 90~150 DEG C, and hydrolysis time is 1~3h, feed liquid (corncob：Dilution heat of sulfuric acid) than being 1:4~8, dilute sulfuric acid
The mass fraction of solution is 0.5~2%, and hydrolysis obtains Corncob hydrolysate after terminating, and is separated by filtration, obtains containing hemicellulose
The hydrolyzate and corn cob residue mixture of analyte, wherein corn cob residue mixture are dried to obtain corn cob residue.
A kind of corn cob residue after xylitol preparation technology is preparing the application of activated carbon, specific application process：
(1) the waste residue after extraction hemicellulose poly-pentose is taken from corncob, dry, sieving, addition mass fraction is 40-
65% phosphoric acid solution and the boric acid of set amount, are well mixed, and are soaked 1-2.5 hours in 70-90 DEG C；
(2) immersion sample is taken out, is then placed in Muffle furnace, lower insulation 0.5-2 hours of 400-550 DEG C；
(3) corn cob residue after being carbonized in step (2) is ground, phosphoric acid is reclaimed in cleaning to neutrality；
(4) the neutral active charcoal in step (3) is dried, ground, you can obtain Powdered Activated Carbon.
(5) after the middle gained activated carbon of step (4) is activated with HCl solution to the powdered active carbon obtained in (4)
Produce.
In step (1), phosphoric acid solution and boric acid are added after the net screening for crossing 20-40 mesh.
In step (1), the quality of waste residue and the volume ratio of phosphoric acid solution are 1g：(1.5~5) ml.Tested by many experiments
Card and analysis, the present invention use above-mentioned impregnating ratio, the acid of cellulose and lignin can be promoted to hydrolyze to form larger topological structure
Staggered floor graphite microcrystal, and have more phosphoric acid esterification occurs therewith and be combined, be conducive to increase and the shape of specific surface area
Into the activated carbon in specific aperture.Inappropriate impregnating ratio, will be unfavorable for formation and the reduction activity of activated carbon in the present invention
The yield of charcoal.
In step (1), the addition of boric acid is the 0.5~3.5% of slag quality.Given up according to corncob after cellulose is extracted
The distinctive property of slag, the present invention soaks waste residue jointly using boric acid and phosphoric acid so that the given activity charcoal finally prepared
The detoxification that aperture and specific surface area are more suitable for Corncob hydrolysate is decolourized.Using above-mentioned boric acid quality, with both phosphoric acid to waste residue
Generation synergistic function, improves the performance for the activated carbon being made using waste residue as raw material.
In step (3), the milling time is 3~5 minutes.
In step (3), the cleaning to neutral concrete operation step is：By the stalk waste residue and water 1g after grinding:(4
~5) ml ratio be cleaned multiple times to neutrality.
The 70-75% of recyclable phosphoric acid during first and second cleaning, after third time is cleaned, the rate of recovery of phosphoric acid can reach
More than 99%, cleaning phosphorus acid content hereafter reaches less than 0.5%, behind cleaning can be without recycling phosphoric acid.
In step (4), the drying temperature is 100~110 DEG C.
In step (4), the milling time is 3~5 minutes, and corn cob residue prepares the pick-up rate of activated carbon in 44-
48%.
In step (5), the activated carbon activation refers to the activated carbon in step (4) in 0.8~1.1mol/L (preferably
Seethe with excitement 1~1.5h (preferably 1h) in HCl solution 1mol/L), rinses filtrate in neutrality with water afterwards, dry at 100~110 DEG C
Dry 6~9h (preferably 105 DEG C and 8h) is to obtain activated carbon.Compared with the active carbon powder in step (4), after overactivation
The aperture of activated carbon be basically unchanged, but specific surface area improves 30% or so, strengthens the detoxification decolorizing effect of Corncob hydrolysate.
Bleaching process is that pigment in the master operation of xylose alcohol production, hydrolyzate has natural pigment in raw material and in life
The pigment generated in production, natural pigment exists such as anthocyanidin with glycocide, and a sugar can be hydrolyzed into acid medium
With a non-saccharide body, in green in alkalescence, nitrogenous coloring matter is also produced when protein and acid hydrolysis, carbohydrate is in alkali
Property in also decompose generation pigment, sugar heating when can also produce burnt sugar coloring.These factors all can deepen the color and luster of hydrolyzate, influence
The quality of xylitol products, it is necessary to carry out decolorization.Routinely the decoloring ability of activated carbon is typically the activity of unit volume
Carbon can take off the blue solution of methyl of how many volume, and the activated carbon for being used for xylitol hydrolyzate decolorizing can not be surveyed with this conventional method
Examination, it is necessary to compared in production with the ability of activated carbon Direct Dehydration solution liquid, to determine the quality of activated carbon quality.
Hemicellulose can obtain the hemicellulose hydrolysate containing monose such as xylose, arabinoses through hydrolysis, available for micro- life
Thing fermentation obtains xylitol, ethanol and other useful products.But also generated in hydrolytic process a certain amount of furfural, acetic acid,
Phenols etc. suppresses the toxicant of hydrolyzate fermentation.How detoxification to be pre-processed to hydrolyzate before fermentation, to improving hydrolyzate hair
Ferment performance, raising product yield are extremely important.
The present invention also provides a kind of preparation of the corn cob residue after xylitol preparation technology active carbon method and is prepared into
The activated carbon arrived, application of the activated carbon in corncob prepares the decolouring During Detoxification of xylitol technique, the activated carbon
It is that decolouring detoxification is carried out to the above-mentioned hydrolyzate containing hemicellulose analyte.
The present invention also provides a kind of decolouring detoxification process, comprises the following steps：Described is contained using described activated carbon
The hydrolyzate for having hemicellulose analyte carries out decolouring detoxification, and the addition of activated carbon is the 0.1%~1% of hydrolyzate quality,
Bleaching temperature is 30~40 DEG C, and bleaching time is 1.5~3h.
The beneficial effects of the invention are as follows：
(1) because the raw material of the activated carbon of the present invention uses the corncob mixed sludge of extraction hemicellulose, in system
During standby xylitol, corncob has passed through dilute acid pretreatment, acetyl group during dilute acid hydrolysis corncob on chief destructive hemicellulose,
Uronic acid substituent, generation acetic acid and other organic acids.The acidic materials destruction native cellulose and lignin of generation are complicated
Rigid structure, while contributing to the connection of ehter bond destroyed on fibrous raw material cell membrane, causes cell expansion so that corncob knot
Structure becomes loose, and the formation to activated carbon serves certain catalytic action in advance so that the structure of corncob is active to prepare
Charcoal provides a good basis.
(2) present invention prepares the activated carbon with certain performance using the corn cob residue after hemicellulose is extracted, and it is obtained
Yield is higher, reaches 42~45%, and using V-Sorb 2800p specific surface areas and Porosimetry, gained activated carbon is compared
Surface area test, the specific surface area for measuring activated carbon is 890-1080m2/ g, the activated carbon specific surface area after hydrochloric acid activation is
1187-1440m2/ g, pore structure is flourishing, and the average pore size for measuring activated carbon is 5~25nm, can specificity to be used for corncob dilute
The decolouring detoxification of hydrolyzate, meets the application request of enterprises during acidity extraction hemicellulose glycan.
In addition, the shortcoming of the activated carbon manufactured using traditional material (full stalk of coconut husk, walnut shell, bamboo, corn etc.) is living
The consumption of the chemical reagent such as energy consumption, phosphoric acid of agent amount and water is big, and the rate of recovery is low, and the waste water and gas of generation causes one to environment
Fixed harm.The characteristic of the corn cob residue of hemicellulose is extracted according to the present invention, the phosphoric acid that the present invention is used is consumed in 1.3-
1.6% (preparing the acid consumption per kg activated carbons), phosphoric acid consumption is considerably less, and for compared with low-temperature activation, it is not necessary to higher temperatures, phosphoric acid
Low consumption and not only substantially reduce production cost and energy consumption compared with low-temperature activation, and protect environment, realize enterprises
Clean manufacturing, also achieve turning waste into wealth for corn wheat bran.
(3) present invention is met application request, realized in enterprise using a kind of distinctive waste material in enterprise
Portion's resources circulation, realizes the comprehensive reutilization of waste, improves enterprise's level of production, saves the energy, cleaning resource, protection
Environment, meets the relevant policies regulation of country.
(4) invention uses simple chemicals logos, the corn cob residue after extraction hemicellulose is prepared into powdered
Activated carbon, for extracting decolouring detoxification when hemicellulose prepares xylo-oligosaccharide from corn core raw material, so can be achieved corn
The higher value application of core raw material, can reduce enterprise's production cost, realize energy-saving and emission-reduction again.The present invention is prepared during activated carbon,
The rate of recovery of phosphoric acid can reach more than 99%, therefore no acidic waste water, waste gas are discharged, and meet national energy-saving environmental protection policy.
Embodiment
With reference to embodiment, the present invention is further described.
The preparation technology of corn cob residue is, using corncob as raw material, corn to be prepared using dilute sulfuric acid hydrolysis of corncob
Core waste residue, concrete technology condition is：Hydrolysis temperature is 90~150 DEG C, and hydrolysis time is 1~3h, and solid-liquid ratio is 1:5, dilute sulfuric acid
The mass fraction of solution is 0.5~2%, and hydrolysis obtains Corncob hydrolysate after terminating, and is separated by filtration, obtains containing hemicellulose
The hydrolyzate and corn cob residue mixture of analyte, wherein corn cob residue mixture are dried to obtain corn cob residue.
Embodiment 1
4g corn wheat brans are added in crucible, 0.04g boric acid, 50% phosphatase 11 0ml is taken, uniform in automatic stirrer is stirred
Mix down, soaked 1.5 hours in 80 DEG C of thermostat water baths；Take out in immersion sample, the Muffle furnace for being then placed in 450 DEG C and be incubated 1
After hour, cooling is taken out, is then slightly ground 3 minutes, with hot wash to neutrality, is dried at 105 DEG C, cooling is ground to powder
End, obtains Powdered Activated Carbon 1.8831g, specific surface area 898m2/ g, Powdered Activated Carbon is seethed with excitement 1h in 1mol/L HCl solution,
Filtrate is rinsed in neutrality with water afterwards, is to obtain activated carbon in 105 DEG C of dry 8h, is measured specific surface area 1139m2/ g,
Aperture averaging is 5~15nm, and activated carbon pick-up rate is 45.8%, and phosphoric acid consumption is 1.25%.
By the activated carbon application in the decolouring detoxification of corncob dilute acid hydrolysis liquid, the addition of activated carbon is hydrolyzate matter
The 0.5% of amount, bleaching temperature is 35 DEG C, and bleaching time is 1.5h, and decolouring detoxification efficiency is excellent, wherein, percent of decolourization is
92.85%, acetic acid clearance is 96.5%, and furfural clearance is 100%, phenolic compound removal efficiency R280Value 0.003, wood
Sugared loss late is less, and only 5.05%.
Embodiment 2
4g corn wheat brans are added in crucible, 0.05g boric acid, 50% phosphoric acid 8ml, in the uniform stirring of automatic stirrer is taken
Under, soaked 1.5 hours in 80 DEG C of thermostat water baths；Immersion sample is taken out, insulation 1 in 450 DEG C of Muffle furnace is then placed in small
Shi Hou, takes out cooling, then slightly grinds 4 minutes, with hot wash to neutrality, is dried at 105 DEG C, cooling is ground to powder
End, obtains activated carbon 1.848g, specific surface area 937m2/ g, Powdered Activated Carbon is seethed with excitement 1h in 1mol/L HCl solution, afterwards
Filtrate is rinsed in neutrality with water, is to obtain activated carbon in 105 DEG C of dry 8h, is measured specific surface area 1143m2/ g, aperture
5~15nm of average out to, activated carbon pick-up rate is 46.2%, and phosphoric acid consumption is 1.29%.
By the activated carbon application in the decolouring detoxification of corncob dilute acid hydrolysis liquid, the addition of activated carbon is hydrolyzate matter
The 0.8% of amount, bleaching temperature is 37 DEG C, and bleaching time is 2h, and decolouring detoxification efficiency is excellent.Wherein, percent of decolourization is 97.9%, second
Sour clearance is 95.4%, and furfural clearance is 99%, phenolic compound removal efficiency R280Value 0.004, xylose loss late compared with
It is few, only 4.96%.
Embodiment 3
4g corn wheat brans are added in crucible, 0.06g boric acid is taken, 50% phosphatase 11 0ml, in Muffle furnace 500 degrees Celsius plus
After hot 1 hour, slightly grind 4.5 minutes, it is neutral with hot wash paper, dried under 105 degree, be ground to powder, obtain active
Charcoal 1.768g, specific surface area 1080m2/ g, Powdered Activated Carbon is seethed with excitement 1h in 1mol/L HCl solution, rinsed afterwards with water
Filtrate is to obtain activated carbon in 105 DEG C of dry 8h, measures specific surface area 1435m in neutrality2/ g, aperture averaging be 5~
15nm, activated carbon pick-up rate is 44.2%, and phosphoric acid consumption is 1.29%.
By the activated carbon application in the decolouring detoxification of corncob dilute acid hydrolysis liquid, the addition of activated carbon is hydrolyzate matter
The 0.6% of amount, bleaching temperature is 40 DEG C, and bleaching time is 2h, and decolouring detoxification efficiency is excellent.Wherein, percent of decolourization is 97.35%,
Acetic acid clearance is 98.56%, and furfural clearance is 99.02%, phenolic compound removal efficiency R280Value 0.004, xylose loss
Rate is less, and only 5.06%.
Comparative example 1
4g corn wheat brans are added in crucible, 0.04g boric acid, 50% phosphatase 11 0ml is taken, uniform in automatic stirrer is stirred
Mix down, soaked 1.5 hours in 80 DEG C of thermostat water baths；Take out in immersion sample, the Muffle furnace for being then placed in 600 DEG C and be incubated 1
After hour, cooling is taken out, is then slightly ground 3 minutes, with hot wash to neutrality, is dried at 105 DEG C, cooling is ground to powder
End, obtains Powdered Activated Carbon 1.32g, specific surface area 1389m2/ g, Powdered Activated Carbon is seethed with excitement 1h in 1mol/L HCl solution,
Filtrate is rinsed in neutrality with water afterwards, is to obtain activated carbon in 105 DEG C of dry 8h, is measured specific surface area 1578m2/ g,
Aperture is 40nm~50nm, and activated carbon pick-up rate is 33%.
By the activated carbon application in the decolouring detoxification of corncob dilute acid hydrolysis liquid, the addition of activated carbon is hydrolyzate matter
The 0.5% of amount, bleaching temperature is 35 DEG C, and bleaching time is 1.5h, and decolouring detoxification efficiency is undesirable, hence it is evident that not as in embodiment 1
Good decolorizing effect.Wherein, percent of decolourization is 60.36%, and acetic acid clearance is 42.25%, and furfural clearance is 37.75%, phenol
Class compound removal efficiency R280Value 0.6, xylose loss late is more, is 15.61%.
Comparative example 2
4g corn wheat brans are added in crucible, 0.04g boric acid, 50% phosphatase 11 0ml is taken, uniform in automatic stirrer is stirred
Mix down, soaked 1.5 hours in 80 DEG C of thermostat water baths；Take out in immersion sample, the Muffle furnace for being then placed in 385 DEG C and be incubated 1
After hour, cooling is taken out, is then slightly ground 3 minutes, with hot wash to neutrality, is dried at 105 DEG C, cooling is ground to powder
End, obtains Powdered Activated Carbon 1.27g, specific surface area 598m2/ g, Powdered Activated Carbon is seethed with excitement 1h in 1mol/L HCl solution, it
Filtrate is rinsed in neutrality with water afterwards, is to obtain activated carbon in 105 DEG C of dry 8h, is measured specific surface area 643m2/ g, aperture
For 5~15nm, activated carbon pick-up rate is 31.75%.
By the activated carbon application in the decolouring detoxification of corncob dilute acid hydrolysis liquid, the addition of activated carbon is hydrolyzate matter
The 0.5% of amount, bleaching temperature is 35 DEG C, and bleaching time is 1.5h, and decolouring detoxification efficiency is undesirable, hence it is evident that not as in embodiment 1
Good decolorizing effect.Wherein, percent of decolourization is 45.86%, and acetic acid clearance is 23.88%, and furfural clearance is 34.55%, phenol
Class compound removal efficiency R280Value 0.5, xylose loss late is more, is 19.29%.
Comparative example 3
4g corn wheat brans are added in crucible, 0.04g boric acid, 50% phosphoric acid 6ml, in the uniform stirring of automatic stirrer is taken
Under, soaked 1.5 hours in 80 DEG C of thermostat water baths；Immersion sample is taken out, insulation 1 in 450 DEG C of Muffle furnace is then placed in small
Shi Hou, takes out cooling, then slightly grinds 3 minutes, with hot wash to neutrality, is dried at 105 DEG C, cooling is ground to powder
End, obtains Powdered Activated Carbon 1.35g, specific surface area 709m2/ g, Powdered Activated Carbon is seethed with excitement 1h in 1mol/L HCl solution, it
Filtrate is rinsed in neutrality with water afterwards, is to obtain activated carbon in 105 DEG C of dry 8h, is measured specific surface area 725m2/ g, aperture
For 5~15nm, activated carbon pick-up rate is 33.75%.
By the activated carbon application in the decolouring detoxification of corncob dilute acid hydrolysis liquid, the addition of activated carbon is hydrolyzate matter
The 0.5% of amount, bleaching temperature is 35 DEG C, and bleaching time is 1.5h, and decolouring detoxification efficiency is undesirable, hence it is evident that not as in embodiment 1
Good decolorizing effect.Wherein, percent of decolourization is 44.09%, and acetic acid clearance is 22.74%, and furfural clearance is 35.32%, phenol
Class compound removal efficiency R280Value 0.5, xylose loss late is more, is 18.34%.
Comparative example 4
4g corn wheat brans are added in crucible, 0.0195g boric acid, 50% phosphatase 11 0ml, in the uniform of automatic stirrer is taken
Under stirring, soaked 1.5 hours in 80 DEG C of thermostat water baths；Immersion sample is taken out, is then placed in 450 DEG C of Muffle furnace and is incubated
After 1 hour, cooling is taken out, is then slightly ground 3 minutes, with hot wash to neutrality, is dried at 105 DEG C, cooling is ground to
Powder, obtains Powdered Activated Carbon 1.43g, specific surface area 710m2/ g, Powdered Activated Carbon is seethed with excitement 1h in 1mol/L HCl solution,
Filtrate is rinsed in neutrality with water afterwards, is to obtain activated carbon in 105 DEG C of dry 8h, is measured specific surface area 763m2/ g, hole
Footpath is 5~15nm, and activated carbon pick-up rate is 35.75%.
By the activated carbon application in the decolouring detoxification of corncob dilute acid hydrolysis liquid, the addition of activated carbon is hydrolyzate matter
The 0.5% of amount, bleaching temperature is 35 DEG C, and bleaching time is 1.5h, and decolouring detoxification efficiency is undesirable, hence it is evident that not as in embodiment 1
Good decolorizing effect.Wherein, percent of decolourization is 49.59%, and acetic acid clearance is 24.84%, and furfural clearance is 35.39%, phenol
Class compound removal efficiency R280Value 0.5, xylose loss late is more, is 18.84%.
To sum up, there is significant difference in the decolouring detoxification efficiency of different activated carbons, wherein the activated carbon in the present invention is de-
Color detoxification efficiency is optimal.
Wherein, the measure of phenolic compound:Hydrolysising original liquid and detoxification liquid are existed with the ultraviolet specrophotometers of UV-min 1240
Carry out absorbance measurement under 280nm wavelength, hydrolyzate and detoxification liquid after 100 times of distilled water diluting with light absorption value is surveyed, and distilled water is
Blank control.R of the activated carbon to phenolic compound can be estimated roughly according to below equation280Value, this ratio is represented pair
The removal effect of phenolic compound, when ratio is 1, illustrates do not have removal effect to phenolic compound；Ratio is smaller, removal
Phenolic compound is also more.R280=detoxification liquid light absorption value/hydrolysising original liquid light absorption value.
Claims (6)
1. a kind of method that corn cob residue prepares activated carbon, it is characterized in that, comprise the following steps：
（1）It the waste residue after hemicellulose is extracted from corncob, dry, pulverize, add mass fraction molten for 40-65% phosphoric acid
The boric acid of liquid and set amount, is well mixed, and is soaked 1-2.5 hours in 70-90 DEG C；
The preparation of corn cob residue comprises the following steps：Corncob is hydrolyzed using dilute sulfuric acid, hydrolysis temperature is 90 ~ 150
DEG C, hydrolysis time is 1 ~ 3h, and solid-liquid ratio is 1:4 ~ 8, the mass fraction of dilution heat of sulfuric acid is 0.5 ~ 2%, and hydrolysis is obtained after terminating
Corncob hydrolysate, is separated by filtration, and obtains the hydrolyzate containing hemicellulose analyte and corn cob residue mixture, wherein beautiful
Rice core waste residue mixture is dried to obtain corn cob residue；
The quality of waste residue and the volume ratio of phosphoric acid solution are 1g：（1.5~5）ml；The addition of boric acid for slag quality 0.5 ~
3.5%；
（2）Immersion sample is taken out, is then placed in Muffle furnace, lower insulation 0.5-2 hours of 450-550 DEG C；
（3）By step（2）Corn cob residue after middle carbonization is ground, cleaning to neutrality, reclaims phosphoric acid；
（4）By step（3）In neutral active charcoal dry, grinding, that is, obtain Powdered Activated Carbon；
（5）By step（4）Middle gained activated carbon HCl solution pair（4）In obtained powdered active carbon activated after produce.
2. the method as described in claim 1, it is characterized in that：Step（3）In, the milling time is 3 ~ 5 minutes；It is described clear
Being washed till the concrete operation step of neutrality is：By the stalk waste residue and water 1g after grinding:（4~ 5）Ml ratio is cleaned multiple times
To neutrality.
3. the method as described in claim 1, it is characterized in that：Step（4）In, the drying temperature is 100 ~ 110 DEG C；It is described to grind
Consume time as 3 ~ 5 minutes.
4. the method as described in claim 1, it is characterized in that：Step（5）In, step（4）In activated carbon in 0.8 ~ 1.1mol/
Seethe with excitement 1 ~ 1.5h in L HCl solution, rinses filtrate in neutrality with water afterwards, is to obtain activity in 100 ~ 110 DEG C of dry 6 ~ 9h
Charcoal.
5. a kind of method that activated carbon prepares the decolouring detoxification of xylitol technique in corncob, it is characterized in that, comprise the following steps：
The activated carbon is prepared according to the method described in claim 1；
Then decolouring detoxification is carried out to the hydrolyzate containing hemicellulose analyte described in claim 1.
6. a kind of decolouring detoxification process, it is characterized in that, comprise the following steps：Using according to the method system described in claim 1
Standby obtained activated carbon carries out decolouring detoxification, activity to the hydrolyzate containing hemicellulose analyte described in claim 1
The addition of charcoal is the 0.1% ~ 1% of hydrolyzate quality, and bleaching temperature is 30 ~ 40 DEG C, and bleaching time is 1.5 ~ 3h.
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