CN113231018A - Preparation method of modified vinegar residue biochar for removing Cr (VI) in water body and product - Google Patents
Preparation method of modified vinegar residue biochar for removing Cr (VI) in water body and product Download PDFInfo
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- CN113231018A CN113231018A CN202110488957.5A CN202110488957A CN113231018A CN 113231018 A CN113231018 A CN 113231018A CN 202110488957 A CN202110488957 A CN 202110488957A CN 113231018 A CN113231018 A CN 113231018A
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- 239000000052 vinegar Substances 0.000 title claims abstract description 359
- 235000021419 vinegar Nutrition 0.000 title claims abstract description 358
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 238000001035 drying Methods 0.000 claims abstract description 70
- 238000005406 washing Methods 0.000 claims abstract description 63
- 239000008367 deionised water Substances 0.000 claims abstract description 55
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 55
- 238000001816 cooling Methods 0.000 claims abstract description 45
- 239000002994 raw material Substances 0.000 claims abstract description 40
- 239000002253 acid Substances 0.000 claims abstract description 37
- 238000007602 hot air drying Methods 0.000 claims abstract description 34
- 238000010000 carbonizing Methods 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 25
- 239000002245 particle Substances 0.000 claims abstract description 23
- 238000007873 sieving Methods 0.000 claims abstract description 23
- 238000002791 soaking Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000003607 modifier Substances 0.000 claims abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 50
- 238000003763 carbonization Methods 0.000 claims description 46
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 43
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- 239000011592 zinc chloride Substances 0.000 claims description 12
- 230000018044 dehydration Effects 0.000 claims description 11
- 238000006297 dehydration reaction Methods 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 6
- 231100000331 toxic Toxicity 0.000 claims description 6
- 230000002588 toxic effect Effects 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 150000002825 nitriles Chemical class 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 3
- 238000005143 pyrolysis gas chromatography mass spectroscopy Methods 0.000 claims description 3
- 239000011651 chromium Substances 0.000 description 55
- 239000000243 solution Substances 0.000 description 45
- 241000209094 Oryza Species 0.000 description 37
- 235000007164 Oryza sativa Nutrition 0.000 description 37
- 235000009566 rice Nutrition 0.000 description 37
- 239000012299 nitrogen atmosphere Substances 0.000 description 16
- 238000010298 pulverizing process Methods 0.000 description 16
- 239000000047 product Substances 0.000 description 14
- 150000003839 salts Chemical class 0.000 description 12
- 239000003513 alkali Substances 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- -1 nitrile compounds Chemical class 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- KSPIHGBHKVISFI-UHFFFAOYSA-N Diphenylcarbazide Chemical compound C=1C=CC=CC=1NNC(=O)NNC1=CC=CC=C1 KSPIHGBHKVISFI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 231100000167 toxic agent Toxicity 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 240000006394 Sorghum bicolor Species 0.000 description 1
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 1
- 206010043275 Teratogenicity Diseases 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- YFRUFKQLNSOIEO-UHFFFAOYSA-N [C-]#N.CCCC Chemical compound [C-]#N.CCCC YFRUFKQLNSOIEO-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000013124 brewing process Methods 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 231100000299 mutagenicity Toxicity 0.000 description 1
- 230000007886 mutagenicity Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000211 teratogenicity Toxicity 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/024—Compounds of Zn, Cd, Hg
- B01J20/0244—Compounds of Zn
-
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0288—Halides of compounds other than those provided for in B01J20/046
-
- 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- 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
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic 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
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
-
- 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
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
- B01J2220/4887—Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- 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
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Distillation Of Fermentation Liquor, Processing Of Alcohols, Vinegar And Beer (AREA)
- Fertilizers (AREA)
Abstract
The invention discloses a preparation method and a product of modified vinegar residue biochar for removing Cr (VI) in a water body, which comprises the steps of mixing a vinegar residue raw material with a modifier, soaking for 12 hours to obtain pretreated vinegar residue, and drying the pretreated vinegar residue by hot air at the temperature of 60-65 ℃ to constant weight to obtain dried vinegar residue; crushing the dried vinegar residue, sieving with a 80-mesh sieve to obtain vinegar residue powder with the particle size of less than 0.18mm, carbonizing, cooling to obtain vinegar residue biochar, soaking in dilute acid solution for deashing to obtain deashed vinegar residue biochar; washing the ash-removed vinegar residue biochar with deionized water to remove redundant acid, and placing the washed vinegar residue biochar in a containerAnd drying in a hot air drying box to constant weight to obtain the modified vinegar residue biochar. The modified vinegar residue biochar prepared by the invention can remove Cr (VI) in water body up to 231.62mg g‑1Compared with the original vinegar residue biochar which is not modified, the yield is improved by 23 times.
Description
The invention belongs to the technical field of Cr (VI) removal in water, and particularly relates to a preparation method and a product of modified vinegar residue biochar for removing Cr (VI) in water.
Background
Due to the increasingly prominent environmental problems, heavy metal pollution remediation has attracted attention all over the world. Chromium (Cr) is an important environmental pollutant and can be classified into trivalent chromium (Cr (iii)) and hexavalent chromium (Cr (vi)) according to valence states. Compared with Cr (III), Cr (VI) has the characteristics of high toxicity, mutagenicity, teratogenicity, carcinogenesis and the like. Cr (vi) is commonly released into the environment via factory wastewater discharge in the textile, printing, tanning, metallurgy, electroplating, battery, etc. industries and causes severe farmland and food contamination.
In recent years, biochar is considered to be a promising heavy metal adsorbent due to its good characteristics of low cost, high Specific Surface Area (SSA), high carbon (C) content, and abundant functional groups. The vinegar residue is an important agricultural byproduct in the vinegar brewing process, mainly consists of rice hulls and other components such as bran, sorghum hulls, bacterial sludge and the like. The vinegar residues have the characteristics of high water content, strong acidity, rich organic matters and the like, and the local ecology can be seriously damaged by the traditional incineration, landfill or direct placement in the environment.
Therefore, the preparation method, the product and the application of the modified vinegar residue biochar which can remove toxic heavy metals in the environment and solve the negative effect of the vinegar residue on the environment are needed in the field.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
Therefore, the invention aims to overcome the defects of the existing preparation method of the vinegar residue biochar and provide a preparation method of the modified vinegar residue biochar for removing Cr (VI) in a water body.
In order to solve the technical problems, the invention provides the following technical scheme: a preparation method of modified vinegar residue biochar for removing Cr (VI) in a water body comprises the following steps,
mixing the vinegar residue raw material with a modifier, soaking for 12h to obtain pretreated vinegar residue, and drying by hot air at the temperature of 60-65 ℃ to constant weight to obtain dried vinegar residue;
crushing the dried vinegar residue, sieving with a 80-mesh sieve to obtain vinegar residue powder with the particle size of less than 0.18mm, carbonizing, cooling to obtain vinegar residue biochar, soaking in dilute acid solution for deashing to obtain deashed vinegar residue biochar;
washing the ash-removed vinegar residue biochar with deionized water, removing redundant acid, and placing the vinegar residue biochar in a hot air drying box to be dried to constant weight to obtain the modified vinegar residue biochar; wherein,
the modifier is ZnCl2The mass ratio of the modifier to the vinegar residue raw material is 1: 1-2: 1.
As a preferable scheme of the preparation method of the modified vinegar residue biochar for removing Cr (VI) in the water body, the method comprises the following steps: and drying the mixture by hot air at the temperature of 60-65 ℃ to constant weight, wherein the weight difference of 2 hours in the drying process is not more than 0.5 percent of the weight of the vinegar residue according to the standard of drying to constant weight.
As a preferable scheme of the preparation method of the modified vinegar residue biochar for removing Cr (VI) in the water body, the method comprises the following steps: the carbonization treatment comprises physical heating carbonization and concentrated acid dehydration carbonization.
As a preferable scheme of the preparation method of the modified vinegar residue biochar for removing Cr (VI) in the water body, the method comprises the following steps: the physical heating carbonization comprises the following steps of,
carbonizing the vinegar residue powder at 700 deg.C2-2.5 h, wherein the temperature rise rate during carbonization is 10-15 ℃ min-1。
As a preferable scheme of the preparation method of the modified vinegar residue biochar for removing Cr (VI) in the water body, the method comprises the following steps: cooling to obtain the vinegar residue biochar, wherein the cooling is carried out at 10 ℃ per minute-1Cooling to 200-300 ℃, and naturally cooling to room temperature.
As a preferable scheme of the preparation method of the modified vinegar residue biochar for removing Cr (VI) in the water body, the method comprises the following steps: the soaking and deashing of the dilute acid solution comprises,
1 part by mass of the vinegar residue biochar is put into 40 parts by volume of dilute acid solution at the temperature of 30 ℃ for 180 r.min-1After shaking for 4 hours, carrying out solid-liquid separation, and reserving a solid component, namely the ash-removed vinegar residue biochar; wherein,
the dilute acid solution is dilute hydrochloric acid or dilute sulfuric acid, and is prepared by adding 1 volume part of hydrochloric acid or sulfuric acid into 3 volume parts of water, uniformly mixing and cooling.
As a preferable scheme of the preparation method of the modified vinegar residue biochar for removing Cr (VI) in the water body, the method comprises the following steps: the concentrated acid is dehydrated and carbonized, including,
mixing the vinegar residue and concentrated acid according to the mass volume ratio g: uniformly mixing the materials in a ratio of 1: 2-4 by mL, standing for 8-9 h, and finishing the dehydration and carbonization process; wherein the concentrated acid is concentrated sulfuric acid.
The invention further aims to overcome the defects of the prior art and provide a product prepared by the preparation method of the modified vinegar residue biochar for removing Cr (VI) in the water body, and the product Py-GC-MS detects no toxic nitrile substances.
The invention also aims to overcome the defects of the prior art and provides application of the modified vinegar residue biochar for removing Cr (VI) in the water body.
As a preferable aspect of the application of the present invention, wherein: the use of a composition according to any one of the preceding claims,
when the product input amount is 2 g.L-1In this case, the concentration of Cr (VI) is preferably 200-500 mg.L-1The removing time is 1-5 h
The invention has the beneficial effects that:
(1) the invention utilizes ZnCl2The capacity of removing Cr (VI) of the formed modified vinegar residue biochar is 231.62mg g-1Compared with the original vinegar residue biochar which is not modified, the yield is improved by 23 times.
(2) The modified vinegar residue biochar prepared by the invention can effectively inhibit the vinegar residue from forming toxic nitrile compounds in the carbonization process, and improves the safety of the biochar in practical application. As the vinegar residue is a fermented product, the nitrogen content of the carbonized vinegar residue is more than 10 times of that of a similar non-fermented product, however, the nitrogen can generate toxic nitrile compounds in the pyrolysis process, and when the vinegar residue is subjected to ZnCl treatment2After modification, carbonization does not generate nitrile compounds, most of the nitrogen-containing substances exist in the form of amino groups, and the amino groups can form van der Waals force or hydrogen bond with Cr (VI) to provide direct and firm adsorption sites.
(3) The modified vinegar residue biochar prepared by the invention has the characteristics of high specific surface area, pore size suitable for Cr (VI) adsorption, abundant functional groups and the like; ZnCl2The carbonization process of the vinegar residue can be promoted, so that a high-aromatized high-carbon product is formed, and the decomposition and volatilization of some heat-sensitive substances and the evaporation loss of Zn under the high-temperature condition can form a rich and developed pore structure in the modified biochar, so that an adsorption site is provided for the efficient and rapid removal of Cr (VI); meanwhile, sulfuric acid undergoes sulfonation reaction while being carbonized, so that the effective functional group content capable of combining Cr (VI) is increased, and ZnCl is added2A synergistic effect is formed, which is beneficial to the removal of Cr (VI).
(4) The main component of the vinegar residue is fermented rice hulls which contain abundant amorphous silicon dioxide, the silicon dioxide is still retained after carbonization, and silicon hydroxyl formed in the process of removing Cr (VI) can be effectively combined with Cr (VI); the modified vinegar residue biochar prepared by the invention is deashed by adopting dilute hydrochloric acid or dilute sulfuric acid, so that mineral impurities attached to the surface of the biochar can be effectively removed, the smoothness of a pore passage in the biochar is enhanced, amorphous silicon dioxide is retained, and the removal capability of the modified biochar to hexavalent chromium is improved.
(5) The invention adopts a concentrated acid dehydration carbonization mode to replace the traditional physical heating carbonization mode, can effectively reduce the energy consumption in the processing process of the biochar, and combines two steps of carbonization and deashing into one by concentrated acid treatment, so that the processing of the biochar is simpler and more convenient. The modified vinegar residue biochar disclosed by the invention is simple in preparation process, low in raw material price, easy to obtain and low in requirements on production equipment.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, specific embodiments thereof are described in detail below with reference to examples of the specification.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Determination of Cr (VI) in the present invention: the content of Cr (VI) in the filtrate was measured by 1, 5-diphenylcarbohydrazide method. Namely, the solution containing Cr (VI) is filtered through a 0.22 mu m water system microporous filter membrane, 200 mu L of filtrate is diluted to 25mL, 0.25mL of sulfuric acid solution (sulfuric acid is added into equal volume of distilled water) and 0.25mL of phosphoric acid solution (phosphoric acid is added into equal volume of distilled water) are respectively added into the filtrate, 1mL of 1, 5-diphenyl carbohydrazide solution is added into the filtrate after shaking uniformly, the mixed system is shaken uniformly and then is kept stand for 10min, and the light absorption value is measured at 540 nm.
Thermal cracking-gas chromatography-mass spectrometry (Py-GC-MS) was performed on a thermal cracker with GC-MS equipped with a UA-5MS column. The sample was pyrolyzed at 600 ℃ for 10s and then at 10 ℃ min-1The GC oven was then raised from 50 ℃ to 250 ℃ and held for 2min with heliumGas was used as carrier gas (1 mL/min). The ion range is 40 to 550 m/z.
In the invention: hot air equipment: GZX-9070MBE, Shanghai Bochen industries, Inc. medical facilities; a tube furnace: OTF-1200X, Combined Fertilizer and Crystal Material technology, Inc.; FTIR: IS50, Nicolet corporation, usa; a thermal cracker: EGA/PY-3030D, Frontier Lab, Japan; GC-MS: q P2010Ultra, Shimadzu, Japan; a chromatographic column: 30 m.times.0.25 mm.times.0.25 μm, Japanese Frontier Lab; BET equipment: ASAP2020, fangru composite research institute, ltd, han, china; a pulverizer: FZ-102, Tensted instruments, Inc., Tianjin; vinegar residue: the vinegar residue is provided by Shanxi Shuangyuan vinegar industry, Inc.
Other raw materials are not specially described and are all generally sold in the market.
Example 1:
the embodiment provides a preparation method of vinegar residue biochar, which comprises the following steps:
(1) drying and dehydrating the raw materials: hot air drying the vinegar residue at 60 deg.C to constant weight (weight difference of 2 hr is not more than 0.5% of the weight of the vinegar residue) to obtain dried vinegar residue;
(2) crushing the dried raw materials: crushing the dried vinegar residue, and sieving the crushed vinegar residue with a 80-mesh sieve to obtain vinegar residue powder with the particle size of less than 0.18 mm;
(3) carbonizing treatment: pulverizing the vinegar residue under nitrogen atmosphere at 10 deg.C/min-1Heating to 300 deg.C, maintaining for 2 hr, and heating to 10 deg.C/min-1Cooling to 150 ℃, and then naturally cooling to room temperature to prepare the vinegar residue biochar-1.
Example 2:
the embodiment provides a preparation method of vinegar residue biochar, which comprises the following steps:
(1) drying and dehydrating the raw materials: hot air drying the vinegar residue at 60 deg.C to constant weight (weight difference of 2 hr is not more than 0.5% of the weight of the vinegar residue) to obtain dried vinegar residue;
(2) crushing the dried raw materials: crushing the dried vinegar residue, and sieving the crushed vinegar residue with a 80-mesh sieve to obtain vinegar residue powder with the particle size of less than 0.18 mm;
(3) carbonizing treatment: pulverizing the vinegar residue under nitrogen atmosphere at 10 deg.C/min-1Heating to 700 deg.C, maintaining for 2 hr, and keeping at 10 deg.C/min-1Cooling to 300 ℃, and then naturally cooling to room temperature to prepare the vinegar residue biochar-2.
The biochar described in example 1 and example 2, respectively, adsorbed cr (vi) in aqueous solution under the same conditions, and the results are shown in table 1.
TABLE 1 comparison of Cr (VI) removing ability of vinegar residue biochar carbonized at different temperatures
As can be seen from Table 1, the vinegar residue biochar has a high Cr (VI) removing ability when the carbonization temperature is 700 ℃, and therefore 700 ℃ is selected as the carbonization temperature.
Example 3:
the embodiment provides a preparation method of rice husk biochar, which comprises the following steps:
(1) drying and dehydrating the raw materials: drying the rice hulls with hot air at 60 ℃ to constant weight (the weight difference of 2 hours is not more than 0.5 percent of the weight of the rice hulls) to obtain dried rice hulls;
(2) crushing the dried raw materials: crushing the dried rice hulls, and sieving the crushed rice hulls with a 80-mesh sieve to obtain vinegar residue powder with the particle size of less than 0.18 mm;
(3) carbonizing treatment: pulverizing rice hull under nitrogen atmosphere at 10 deg.C/min-1Heating to 700 deg.C, maintaining for 2 hr, and keeping at 10 deg.C/min-1And cooling to 300 ℃, and then naturally cooling to room temperature to obtain the rice hull biochar.
The biochar described in example 2 and example 3 adsorbed cr (vi) in aqueous solution under the same conditions, respectively, and the results are shown in table 2.
TABLE 2 comparison of the Cr (VI) removing abilities of the rice hull biochar and the vinegar residue biochar
As can be seen from Table 2, the vinegar residue biochar has higher Cr (VI) removing capability under the same preparation conditions and adsorption conditions. The main component of the vinegar residue is fermented rice hulls, and products formed during carbonization of the vinegar residue possibly after microbial decomposition are more beneficial to removing Cr (VI), and the table 2 proves the advantages of the vinegar residue as a raw material for preparing and removing Cr (VI) biochar.
Example 4:
the embodiment provides a preparation method of deashed vinegar residue biochar, which comprises the following steps:
(1) drying and dehydrating the raw materials: drying the rice hulls with hot air at 60 ℃ to constant weight (the weight difference of 2 hours is not more than 0.5 percent of the weight of the vinegar residue), and obtaining dry vinegar residue;
(2) crushing the dried raw materials: crushing the dried rice hulls, and sieving the crushed rice hulls with a 80-mesh sieve to obtain vinegar residue powder with the particle size of less than 0.18 mm;
(3) carbonizing treatment: pulverizing rice hull under nitrogen atmosphere at 10 deg.C/min-1Heating to 700 deg.C, maintaining for 2 hr, and keeping at 10 deg.C/min-1And cooling to 300 ℃, and then naturally cooling to room temperature to obtain the rice hull biochar.
(4) And (3) deashing treatment: 1 part by mass of the vinegar residue biochar is placed in 40 parts by volume of dilute hydrochloric acid solution (1 part of hydrochloric acid is added into 3 parts of deionized water) at 30 ℃ for 180 r.min-1After shaking for 4 hours, performing solid-liquid separation, and reserving a solid component, namely the deashed vinegar residue biochar; wherein the mass volume ratio of the vinegar residue biochar to the dilute hydrochloric acid solution is as follows in g: the mL is 1: 40.
(5) Washing treatment: and washing the deashed vinegar residue biochar with deionized water to remove redundant acid until the difference between the pH value of the washing water and the pH value of the deionized water is not more than 0.5.
(6) And (3) drying treatment: and (3) drying the washed deashed biochar in a hot air drying box at 60 ℃ until the weight is constant (the weight difference is not more than 0.02g after 2 hours), thus obtaining the deashed vinegar residue biochar-1.
Example 5:
the embodiment provides a preparation method of deashed vinegar residue biochar, which comprises the following steps:
(1) drying and dehydrating the raw materials: drying the rice hulls with hot air at 60 ℃ to constant weight (the weight difference of 2 hours is not more than 0.5 percent of the weight of the vinegar residue), and obtaining dry vinegar residue;
(2) crushing the dried raw materials: crushing the dried rice hulls, and sieving the crushed rice hulls with a 80-mesh sieve to obtain vinegar residue powder with the particle size of less than 0.18 mm;
(3) carbonizing treatment: pulverizing rice hull under nitrogen atmosphere at 10 deg.C/min-1Heating to 700 deg.C, maintaining for 2 hr, and keeping at 10 deg.C/min-1And cooling to 300 ℃, and then naturally cooling to room temperature to obtain the rice hull biochar.
(4) And (3) deashing treatment: 1 part by mass of the vinegar residue biochar is placed in 40 parts by volume of dilute sulfuric acid solution (1 part of sulfuric acid is added into 3 parts of deionized water) at 30 ℃ for 180 r.min-1After shaking for 4 hours, performing solid-liquid separation, and reserving a solid component, namely the deashed vinegar residue biochar; wherein the mass volume ratio of the vinegar residue biochar to the dilute sulfuric acid solution is as follows in g: the mL is 1: 40.
(5) Washing treatment: and washing the deashed vinegar residue biochar with deionized water to remove redundant acid until the difference between the pH value of the washing water and the pH value of the deionized water is not more than 0.5.
(6) And (3) drying treatment: and (3) drying the washed deashed biochar in a hot air drying box at 60 ℃ until the weight is constant (the weight difference is not more than 0.02g after 2 hours), thus obtaining the deashed vinegar residue biochar-2.
Example 6:
the embodiment provides a preparation method of deashed vinegar residue biochar, which comprises the following steps:
(1) drying and dehydrating the raw materials: drying the rice hulls with hot air at 60 ℃ to constant weight (the weight difference of 2 hours is not more than 0.5 percent of the weight of the vinegar residue), and obtaining dry vinegar residue;
(2) crushing the dried raw materials: crushing the dried rice hulls, and sieving the crushed rice hulls with a 80-mesh sieve to obtain vinegar residue powder with the particle size of less than 0.18 mm;
(3) carbonizing treatment: pulverizing rice hull under nitrogen atmosphere at 10 deg.C/min-1Heating to 700 deg.C, maintaining for 2 hr, and keeping at 10 deg.C/min-1And cooling to 300 ℃, and then naturally cooling to room temperature to obtain the rice hull biochar.
(4) And (3) deashing treatment: 1 part by mass of vinegar residue biochar is placed in 40 parts by volume of dilute nitric acid solution (1 part of nitric acid is added into 3 parts of deionized water)) At 30 ℃ for 180r min-1After shaking for 4 hours, performing solid-liquid separation, and reserving a solid component, namely the deashed vinegar residue biochar; wherein the mass volume ratio of the vinegar residue biochar to the dilute nitric acid solution is as follows in g: the mL is 1: 40.
(5) Washing treatment: and washing the deashed vinegar residue biochar with deionized water to remove redundant acid until the difference between the pH value of the washing water and the pH value of the deionized water is not more than 0.5.
(6) And (3) drying treatment: and (3) drying the washed deashed biochar in a hot air drying box at 60 ℃ until the weight is constant (the weight difference is not more than 0.02g after 2 hours), thus obtaining the deashed vinegar residue biochar-3.
Example 7:
the embodiment provides a preparation method of deashed vinegar residue biochar, which comprises the following steps:
(1) drying and dehydrating the raw materials: drying the rice hulls with hot air at 60 ℃ to constant weight (the weight difference of 2 hours is not more than 0.5 percent of the weight of the vinegar residue), and obtaining dry vinegar residue;
(2) crushing the dried raw materials: crushing the dried rice hulls, and sieving the crushed rice hulls with a 80-mesh sieve to obtain vinegar residue powder with the particle size of less than 0.18 mm;
(3) carbonizing treatment: pulverizing rice hull under nitrogen atmosphere at 10 deg.C/min-1Heating to 700 deg.C, maintaining for 2 hr, and keeping at 10 deg.C/min-1And cooling to 300 ℃, and then naturally cooling to room temperature to obtain the rice hull biochar.
(4) And (3) deashing treatment: 1 part by mass of vinegar residue biochar is placed in 40 parts by volume of dilute phosphoric acid solution (1 part by mass of phosphoric acid is added into 3 parts by mass of deionized water) at 30 ℃ for 180 r.min-1After shaking for 4 hours, performing solid-liquid separation, and reserving a solid component, namely the deashed vinegar residue biochar; wherein the mass volume ratio of the vinegar residue biochar to the dilute phosphoric acid solution is as follows in g: the mL is 1: 40.
(5) Washing treatment: and washing the deashed vinegar residue biochar with deionized water to remove redundant acid until the difference between the pH value of the washing water and the pH value of the deionized water is not more than 0.5.
(6) And (3) drying treatment: and (3) drying the washed deashed biochar in a hot air drying box at 60 ℃ until the weight is constant (the weight difference is not more than 0.02g after 2 hours), and preparing the deashed vinegar residue biochar-4.
Example 8:
the embodiment provides a preparation method of deashed vinegar residue biochar, which comprises the following steps:
(1) drying and dehydrating the raw materials: drying the rice hulls with hot air at 60 ℃ to constant weight (the weight difference of 2 hours is not more than 0.5 percent of the weight of the vinegar residue), and obtaining dry vinegar residue;
(2) crushing the dried raw materials: crushing the dried rice hulls, and sieving the crushed rice hulls with a 80-mesh sieve to obtain vinegar residue powder with the particle size of less than 0.18 mm;
(3) carbonizing treatment: pulverizing rice hull under nitrogen atmosphere at 10 deg.C/min-1Heating to 700 deg.C, maintaining for 2 hr, and keeping at 10 deg.C/min-1And cooling to 300 ℃, and then naturally cooling to room temperature to obtain the rice hull biochar.
(4) And (3) deashing treatment: 1 part by mass of vinegar residue biochar is put into 40 parts by volume of deionized water at the temperature of 30 ℃ for 180 r.min-1After shaking for 4 hours, performing solid-liquid separation, and reserving a solid component, namely the deashed vinegar residue biochar; wherein the mass volume ratio of the vinegar residue biochar to the deionized water is as follows in g: the mL is 1: 40.
(5) Washing treatment: and washing the deashed vinegar residue biochar with deionized water until the difference between the pH value of the washing water and the pH value of the deionized water is not more than 0.5.
(6) And (3) drying treatment: and (3) drying the washed deashed biochar in a hot air drying box at 60 ℃ until the weight is constant (the weight difference is not more than 0.02g after 2 hours), and preparing the deashed vinegar residue biochar-5.
The biochar described in examples 4 to 8 adsorbed cr (vi) in the aqueous solution under the same conditions, respectively, and the results are shown in table 3.
TABLE 3 comparison of the capacity of the biochar for removing Cr (VI) from the vinegar residue in different ways of deashing
It can be seen from table 3 that the deashing washing helps to improve the capacity of the vinegar residue biochar to remove cr (vi), wherein the deashing effect is best with dilute hydrochloric acid or dilute sulfuric acid.
Example 9:
the embodiment provides a preparation method of alkali modified vinegar residue biochar, which comprises the following steps:
(1) modifying the vinegar residue biochar before carbonization: 1 part of vinegar residue and 2.5 parts of KOH solution (the concentration of the KOH solution is 1.6g/L) are soaked for 12 hours, so that the pH value of the vinegar residue after soaking is neutral (6.5).
(2) Drying and dehydrating: hot air drying the vinegar residue at 60 deg.C to constant weight (weight difference of 2 hr is not more than 0.5% of the weight of the vinegar residue), to obtain dried vinegar residue (water content of dried vinegar residue is less than 5%);
(3) crushing the dried raw materials: crushing the dried vinegar residue, and sieving the crushed vinegar residue with a 80-mesh sieve to obtain vinegar residue powder with the particle size of less than 0.18 mm;
(4) carbonizing treatment: pulverizing the vinegar residue under nitrogen atmosphere at 10 deg.C/min-1Heating to 700 deg.C, maintaining for 2 hr, and keeping at 10 deg.C/min-1Cooling to 300 ℃, and then naturally cooling to room temperature;
(5) and (3) deashing treatment: 1 part by mass of the vinegar residue biochar is placed in 40 parts by volume of dilute hydrochloric acid solution (1 part of hydrochloric acid is added into 3 parts of deionized water) at 30 ℃ for 180 r.min-1After shaking for 4 hours, performing solid-liquid separation, and reserving a solid component, namely the deashed vinegar residue biochar; wherein the mass volume ratio of the vinegar residue biochar to the dilute hydrochloric acid solution is as follows in g: the mL is 1: 40.
(6) Washing treatment: and washing the deashed vinegar residue biochar with deionized water to remove redundant acid until the difference between the pH value of the washing water and the pH value of the deionized water is not more than 0.5.
(7) And (3) drying treatment: and (3) drying the washed deashed biochar in a hot air drying box at 60 ℃ until the weight is constant (the weight difference is not more than 0.02g in 2 h), and modifying the biochar-1 with alkali.
Example 10:
the embodiment provides a preparation method of alkali modified vinegar residue biochar, which comprises the following steps:
(1) modifying the vinegar residue biochar before carbonization: 1 part of vinegar residue and 2.5 parts of KOH solution are soaked for 12 hours, so that the pH value of the soaked vinegar residue is 8.95.
(2) Drying and dehydrating: hot air drying the vinegar residue at 60 deg.C to constant weight (weight difference of 2 hr is not more than 0.5% of the weight of the vinegar residue) to obtain dried vinegar residue;
(3) crushing the dried raw materials: crushing the dried vinegar residue, and sieving the crushed vinegar residue with a 80-mesh sieve to obtain vinegar residue powder with the particle size of less than 0.18 mm;
(4) carbonizing treatment: pulverizing the vinegar residue under nitrogen atmosphere at 10 deg.C/min-1Heating to 700 deg.C, maintaining for 2 hr, and keeping at 10 deg.C/min-1Cooling to 300 ℃, and then naturally cooling to room temperature.
(5) And (3) deashing treatment: 1 part by mass of the vinegar residue biochar is placed in 40 parts by volume of dilute hydrochloric acid solution (1 part of hydrochloric acid is added into 3 parts of deionized water) at 30 ℃ for 180 r.min-1After shaking for 4 hours, performing solid-liquid separation, and reserving a solid component, namely the deashed vinegar residue biochar; wherein the mass volume ratio of the vinegar residue biochar to the dilute hydrochloric acid solution is as follows in g: the mL is 1: 40.
(6) Washing treatment: and washing the deashed vinegar residue biochar with deionized water to remove redundant acid until the difference between the pH value of the washing water and the pH value of the deionized water is not more than 0.5.
(7) And (3) drying treatment: and (3) drying the washed deashed biochar in a hot air drying box at 60 ℃ until the weight is constant (the weight difference is not more than 0.02g in 2 h), and modifying the biochar-2 with alkali.
Example 11:
the embodiment provides a preparation method of alkali modified vinegar residue biochar, which comprises the following steps:
(1) modifying the vinegar residue biochar before carbonization: 1 part of vinegar residue and 2.5 parts of KOH solution are soaked for 12 hours, so that the pH value of the soaked vinegar residue is 11.63.
(2) Drying and dehydrating: hot air drying the vinegar residue at 60 deg.C to constant weight (weight difference of 2 hr is not more than 0.5% of the weight of the vinegar residue) to obtain dried vinegar residue;
(3) crushing the dried raw materials: crushing the dried vinegar residue, and sieving the crushed vinegar residue with a 80-mesh sieve to obtain vinegar residue powder with the particle size of less than 0.18 mm;
(4) carbonizing treatment: pulverizing the vinegar residue under nitrogen atmosphere at 10 deg.C/min-1Heating to 700 deg.C, and maintaining 2After h, at 10 ℃ for min-1Cooling to 300 ℃, and then naturally cooling to room temperature.
(5) And (3) deashing treatment: 1 part by mass of the vinegar residue biochar is placed in 40 parts by volume of dilute hydrochloric acid solution (1 part of hydrochloric acid is added into 3 parts of deionized water) at 30 ℃ for 180 r.min-1After shaking for 4 hours, performing solid-liquid separation, and reserving a solid component, namely the deashed vinegar residue biochar; wherein the mass volume ratio of the vinegar residue biochar to the dilute hydrochloric acid solution is as follows in g: the mL is 1: 40.
(6) Washing treatment: and washing the deashed vinegar residue biochar with deionized water to remove redundant acid until the difference between the pH value of the washing water and the pH value of the deionized water is not more than 0.5.
(7) And (3) drying treatment: and (3) drying the washed deashed biochar in a hot air drying box at 60 ℃ until the weight is constant (the weight difference is not more than 0.02g in 2 h), and modifying the biochar with alkali to be 3.
Example 12:
the embodiment provides a preparation method of alkali modified vinegar residue biochar, which comprises the following steps:
(1) modifying the vinegar residue biochar before carbonization: 1 part of vinegar residue and 2.5 parts of KOH solution are soaked for 12 hours, so that the pH value of the soaked vinegar residue is 11.63.
(2) Drying and dehydrating: hot air drying the vinegar residue at 60 deg.C to constant weight (weight difference of 2 hr is not more than 0.5% of the weight of the vinegar residue) to obtain dried vinegar residue;
(3) crushing the dried raw materials: crushing the dried vinegar residue, and sieving the crushed vinegar residue with a 80-mesh sieve to obtain vinegar residue powder with the particle size of less than 0.18 mm;
(4) carbonizing treatment: pulverizing the vinegar residue under nitrogen atmosphere at 10 deg.C/min-1Heating to 700 deg.C, maintaining for 2 hr, and keeping at 10 deg.C/min-1Cooling to 300 ℃, and then naturally cooling to room temperature.
(5) And (3) deashing treatment: 1 part by mass of the vinegar residue biochar is placed in 40 parts by volume of dilute hydrochloric acid solution (1 part of hydrochloric acid is added into 3 parts of deionized water) at 30 ℃ for 180 r.min-1After shaking for 4 hours, performing solid-liquid separation, and reserving a solid component, namely the deashed vinegar residue biochar; wherein the mass volume ratio of the vinegar residue biochar to the dilute hydrochloric acid solution is as follows in g: the mL is 1: 40.
(6) Washing treatment: and washing the deashed vinegar residue biochar with deionized water to remove redundant acid until the difference between the pH value of the washing water and the pH value of the deionized water is not more than 0.5.
(7) And (3) drying treatment: and (3) drying the washed deashed biochar in a hot air drying box at 60 ℃ until the weight is constant (the weight difference is not more than 0.02g in 2 h), and modifying the biochar with alkali to be 3.
Example 13:
the embodiment provides a preparation method of salt modified vinegar residue biochar, which comprises the following steps:
(1) modifying the vinegar residue biochar before carbonization: taking 1 part of vinegar residue and 2.5 parts of ZnCl2Solution (ZnCl)2Soaking vinegar residue (m: m) ═ 0.5:1) for 12 h.
(2) Drying and dehydrating: hot air drying the vinegar residue at 60 deg.C to constant weight (weight difference of 2 hr is not more than 0.5% of the weight of the vinegar residue) to obtain dried vinegar residue;
(3) crushing the dried raw materials: crushing the dried vinegar residue, and sieving the crushed vinegar residue with a 80-mesh sieve to obtain vinegar residue powder with the particle size of less than 0.18 mm;
(4) carbonizing treatment: pulverizing the vinegar residue under nitrogen atmosphere at 10 deg.C/min-1Heating to 700 deg.C, maintaining for 2 hr, and keeping at 10 deg.C/min-1Cooling to 300 ℃, then naturally cooling to room temperature, washing with deionized water until the pH value of washing water is stable, and preparing the modified vinegar residue biochar before carbonization;
(5) and (3) deashing treatment: 1 part by mass of the vinegar residue biochar is placed in 40 parts by volume of dilute hydrochloric acid solution (1 part of hydrochloric acid is added into 3 parts of deionized water) at 30 ℃ for 180 r.min-1After shaking for 4 hours, performing solid-liquid separation, and reserving a solid component, namely the deashed vinegar residue biochar; wherein the mass volume ratio of the vinegar residue biochar to the dilute hydrochloric acid solution is as follows in g: the mL is 1: 40.
(6) Washing treatment: and washing the deashed vinegar residue biochar with deionized water to remove redundant acid until the difference between the pH value of the washing water and the pH value of the deionized water is not more than 0.5.
(7) And (3) drying treatment: and (3) drying the washed deashed biochar in a hot air drying box at 60 ℃ until the weight is constant (the weight difference is not more than 0.02g in 2 h), and modifying the biochar-1 with salt.
Example 14:
the embodiment provides a preparation method of salt modified vinegar residue biochar, which comprises the following steps:
(1) modifying the vinegar residue biochar before carbonization: taking 1 part of vinegar residue and 2.5 parts of ZnCl2Solution (ZnCl)2Soaking vinegar residue (m: m) at a ratio of 1:1) for 12 h.
(2) Drying and dehydrating: hot air drying the vinegar residue at 60 deg.C to constant weight (weight difference of 2 hr is not more than 0.5% of the weight of the vinegar residue) to obtain dried vinegar residue;
(3) crushing the dried raw materials: crushing the dried vinegar residue, and sieving the crushed vinegar residue with a 80-mesh sieve to obtain vinegar residue powder with the particle size of less than 0.18 mm;
(4) carbonizing treatment: pulverizing the vinegar residue under nitrogen atmosphere at 10 deg.C/min-1Heating to 700 deg.C, maintaining for 2 hr, and keeping at 10 deg.C/min-1Cooling to 300 ℃, then naturally cooling to room temperature, washing with deionized water until the pH value of washing water is stable, and preparing the modified vinegar residue biochar before carbonization;
(5) and (3) deashing treatment: 1 part by mass of the vinegar residue biochar is placed in 40 parts by volume of dilute hydrochloric acid solution (1 part of hydrochloric acid is added into 3 parts of deionized water) at 30 ℃ for 180 r.min-1After shaking for 4 hours, performing solid-liquid separation, and reserving a solid component, namely the deashed vinegar residue biochar; wherein the mass volume ratio of the vinegar residue biochar to the dilute hydrochloric acid solution is as follows in g: the mL is 1: 40.
(6) Washing treatment: and washing the deashed vinegar residue biochar with deionized water to remove redundant acid until the difference between the pH value of the washing water and the pH value of the deionized water is not more than 0.5.
(7) And (3) drying treatment: and (3) drying the washed deashed biochar in a hot air drying box at 60 ℃ until the weight is constant (the weight difference is not more than 0.02g in 2 h), and modifying the biochar-2 with salt.
Example 15:
the embodiment provides a preparation method of salt modified vinegar residue biochar, which comprises the following steps:
(1) modifying the vinegar residue biochar before carbonization: taking 1 part of vinegar residue and 2.5 parts of ZnCl2Solution (ZnCl)2Vinegar residue (m: m) ═2:1) soaking for 12 h.
(2) Drying and dehydrating: hot air drying the vinegar residue at 60 deg.C to constant weight (weight difference of 2 hr is not more than 0.5% of the weight of the vinegar residue) to obtain dried vinegar residue;
(3) crushing the dried raw materials: crushing the dried vinegar residue, and sieving the crushed vinegar residue with a 80-mesh sieve to obtain vinegar residue powder with the particle size of less than 0.18 mm;
(4) carbonizing treatment: pulverizing the vinegar residue under nitrogen atmosphere at 10 deg.C/min-1Heating to 700 deg.C, maintaining for 2 hr, and keeping at 10 deg.C/min-1Cooling to 300 ℃, then naturally cooling to room temperature, washing with deionized water until the pH value of washing water is stable, and preparing the modified vinegar residue biochar before carbonization;
(5) and (3) deashing treatment: 1 part by mass of the vinegar residue biochar is placed in 40 parts by volume of dilute hydrochloric acid solution (1 part of hydrochloric acid is added into 3 parts of deionized water) at 30 ℃ for 180 r.min-1After shaking for 4 hours, performing solid-liquid separation, and reserving a solid component, namely the deashed vinegar residue biochar; wherein the mass volume ratio of the vinegar residue biochar to the dilute hydrochloric acid solution is as follows in g: the mL is 1: 40.
(6) Washing treatment: and washing the deashed vinegar residue biochar with deionized water to remove redundant acid until the difference between the pH value of the washing water and the pH value of the deionized water is not more than 0.5.
(7) And (3) drying treatment: and (3) drying the washed deashed biochar in a hot air drying box at 60 ℃ until the weight is constant (the weight difference is not more than 0.02g in 2 h), and modifying the biochar with salt to be 3.
Example 16:
the embodiment provides a preparation method of salt modified vinegar residue biochar, which comprises the following steps:
(1) modifying the vinegar residue biochar before carbonization: taking 1 part of vinegar residue and 2.5 parts of ZnCl2Solution (ZnCl)2Soaking vinegar residue (m: m) in a ratio of 3:1 for 12 h.
(2) Drying and dehydrating: hot air drying the vinegar residue at 60 deg.C to constant weight (weight difference of 2 hr is not more than 0.5% of the weight of the vinegar residue) to obtain dried vinegar residue;
(3) crushing the dried raw materials: crushing the dried vinegar residue, and sieving the crushed vinegar residue with a 80-mesh sieve to obtain vinegar residue powder with the particle size of less than 0.18 mm;
(4) carbonizing treatment: pulverizing the vinegar residue under nitrogen atmosphere at 10 deg.C/min-1Heating to 700 deg.C, maintaining for 2 hr, and keeping at 10 deg.C/min-1Cooling to 300 ℃, then naturally cooling to room temperature, washing with deionized water until the pH value of washing water is stable, and preparing the modified vinegar residue biochar before carbonization;
(5) and (3) deashing treatment: 1 part by mass of the vinegar residue biochar is placed in 40 parts by volume of dilute hydrochloric acid solution (1 part of hydrochloric acid is added into 3 parts of deionized water) at 30 ℃ for 180 r.min-1After shaking for 4 hours, performing solid-liquid separation, and reserving a solid component, namely the deashed vinegar residue biochar; wherein the mass volume ratio of the vinegar residue biochar to the dilute hydrochloric acid solution is as follows in g: the mL is 1: 40.
(6) Washing treatment: and washing the deashed vinegar residue biochar with deionized water to remove redundant acid until the difference between the pH value of the washing water and the pH value of the deionized water is not more than 0.5.
(7) And (3) drying treatment: and (3) drying the washed deashed biochar in a hot air drying box at 60 ℃ until the weight is constant (the weight difference is not more than 0.02g in 2 h), and modifying the biochar with salt to be 4.
The biochar described in examples 9 to 16 adsorbed cr (vi) in the aqueous solution under the same conditions, respectively, and the results are shown in table 4.
TABLE 4 comparison of the Cr (VI) removing ability of the vinegar residue biochar in different modification modes (original Cr (VI) concentration is 100 mg. L)-1)
As can be seen from Table 4, the removal capacity of the modified vinegar residue biochar to Cr (VI) is higher than that of the control group, and the removal capacity of the alkali modified vinegar residue biochar-1 in the alkali modification is the highest and is 30.61 mg.L-1. However, the effect of the salt modified biochar is far higher than that of the optimal group of alkali modified biochar, and the removal capacity of the salt modified biochar is close to 100 percent, which is sufficient for ZnCl2The advantage of (c) is.
In order to further clearly distinguish the Cr (VI) removing capability of the salt modified biochar, the strip is not changed under other conditionsThe Cr (VI) concentration was adjusted to 500 mg.L-1The biochar described in examples 13 to 16 adsorbed cr (vi) in the aqueous solution under the same conditions, respectively, and the results are shown in table 5.
TABLE 5 comparison of Cr (VI) removal Capacity of different salt-modified Vinegar residue biochar (original Cr (VI) concentration is 500 mg. L)-1)
As can be seen from Table 5, the ability of the salt-modified vinegar residue biochar-2 and the salt-modified vinegar residue biochar-3 to remove Cr (VI) is obviously superior to that of other groups, and the effect of the salt-modified vinegar residue biochar-2 is the best, 190.78 mg.L-1Is 19.14 times of the unmodified vinegar residue biochar, and is sufficient to show the high efficiency of the modified biochar disclosed by the invention.
Example 17:
the embodiment provides a preparation method of vinegar residue biochar by sulfuric acid carbonization, which comprises the following steps:
(1) drying and dehydrating the raw materials: hot air drying the vinegar residue at 60 deg.C to constant weight (weight difference of 2 hr is not more than 0.5% of the weight of the vinegar residue) to obtain dried vinegar residue;
(2) crushing the dried raw materials: crushing the dried vinegar residue, and sieving the crushed vinegar residue with a 80-mesh sieve to obtain vinegar residue powder with the particle size of less than 0.18 mm;
(3) carbonizing treatment: uniformly mixing the vinegar residue and concentrated sulfuric acid according to a ratio of 1:2(m: v), and standing for 8 hours to finish the dehydration and carbonization process;
(4) washing treatment: and washing the carbonized vinegar residue biochar with deionized water to remove redundant acid until the difference between the pH value of the washing water and the pH value of the deionized water is not more than 0.5.
(5) And (3) drying treatment: and (3) drying the washed deashed biochar in a hot air drying box at 60 ℃ until the weight is constant (the weight difference is not more than 0.02g after 2 hours), thus obtaining the sulfuric acid carbonized biochar.
Example 18:
the embodiment provides a preparation method of vinegar residue biochar acidified by hydrochloric acid, which comprises the following steps:
(1) drying and dehydrating the raw materials: hot air drying the vinegar residue at 60 deg.C to constant weight (weight difference of 2 hr is not more than 0.5% of the weight of the vinegar residue) to obtain dried vinegar residue;
(2) crushing the dried raw materials: crushing the dried vinegar residue, and sieving the crushed vinegar residue with a 80-mesh sieve to obtain vinegar residue powder with the particle size of less than 0.18 mm;
(3) carbonizing treatment: uniformly mixing the vinegar residue and concentrated hydrochloric acid according to the ratio of 1:2(m: v), and standing for 8 hours to finish the dehydration and carbonization process;
(4) washing treatment: and washing the carbonized vinegar residue biochar with deionized water to remove redundant acid until the difference between the pH value of the washing water and the pH value of the deionized water is not more than 0.5.
(5) And (3) drying treatment: and (3) drying the washed deashed biochar in a hot air drying box at 60 ℃ until the weight is constant (the weight difference is not more than 0.02g after 2 hours), thus obtaining the hydrochloric acid acidified biochar.
Example 19:
the embodiment provides a preparation method of nitric acid acidified vinegar residue biochar, which comprises the following steps:
(1) drying and dehydrating the raw materials: hot air drying the vinegar residue at 60 deg.C to constant weight (weight difference of 2 hr is not more than 0.5% of the weight of the vinegar residue) to obtain dried vinegar residue;
(2) crushing the dried raw materials: crushing the dried vinegar residue, and sieving the crushed vinegar residue with a 80-mesh sieve to obtain vinegar residue powder with the particle size of less than 0.18 mm;
(3) carbonizing treatment: uniformly mixing the vinegar residue and concentrated nitric acid according to a ratio of 1:2(m: v), and standing for 8 hours to finish the dehydration and carbonization process;
(4) washing treatment: and washing the carbonized vinegar residue biochar with deionized water to remove redundant acid until the difference between the pH value of the washing water and the pH value of the deionized water is not more than 0.5.
(5) And (3) drying treatment: and (3) drying the washed deashed biochar in a hot air drying box at 60 ℃ until the weight is constant (the weight difference is not more than 0.02g after 2 h), thus obtaining the nitric acid-acidified biochar.
Example 20:
the embodiment provides a preparation method of modified sulfuric acid carbonized vinegar residue biochar, which comprises the following steps:
(1) vinegarModifying the slag biochar before carbonization: taking 1 part of vinegar residue and 2.5 parts of ZnCl2Solution (ZnCl)2Soaking vinegar residue (m: m) at a ratio of 1:1) for 12 h.
(2) Drying and dehydrating: hot air drying the vinegar residue at 60 deg.C to constant weight (weight difference of 2 hr is not more than 0.5% of the weight of the vinegar residue) to obtain dried vinegar residue;
(3) crushing the dried raw materials: crushing the dried vinegar residue, and sieving the crushed vinegar residue with a 80-mesh sieve to obtain vinegar residue powder with the particle size of less than 0.18 mm;
(4) carbonizing treatment: uniformly mixing the vinegar residue and concentrated sulfuric acid according to a ratio of 1:2(m: v), and standing for 8 hours to finish the dehydration and carbonization process;
(5) washing treatment: and washing the carbonized vinegar residue biochar with deionized water to remove redundant acid until the difference between the pH value of the washing water and the pH value of the deionized water is not more than 0.5.
(6) And (3) drying treatment: and (3) drying the washed deashed biochar in a hot air drying box at 60 ℃ until the weight is constant (the weight difference is not more than 0.02g after 2 hours), thus obtaining the modified sulfuric acid carbonized biochar.
The biochar described in example 4, example 14, and examples 17 to 20 adsorbed cr (vi) in the aqueous solution under the same conditions, and the results are shown in table 6.
TABLE 6 comparison of Cr (VI) removal Capacity of different salt-modified Vinegar residue biochar (original Cr (VI) concentration is 500 mg. L)-1)
As can be seen from Table 6, the effect of nitric acid-acidified vinegar residue on Cr (VI) removal is lower than that of vinegar residue biochar under physical carbonization, while the effect of sulfuric acid-acidified vinegar residue and hydrochloric acid-acidified vinegar residue on Cr (VI) removal is much higher than that of physical heating carbonization, probably because the sulfonation reaction of sulfuric acid during carbonization increases the number of functional groups on the surface of biochar, and the functional groups can effectively complex Cr (VI) and ZnCl2The modified vinegar residue is carbonized by sulfuric acid dehydration instead of a physical heating carbonization mode, the adsorption effect is further improved, and the results show that the sulfuric acid dehydration and carbonization and ZnCl are obtained2The modification has a synergistic improvement effect on Cr (VI) removal, can simplify the processing flow of the biochar and reduce the energy consumption in the production process, and is a high-efficiency, green and promising heavy metal adsorbent.
Example 21:
the modified vinegar residue biochar prepared by the invention is used for removing Cr (VI) in a water body, and the modified vinegar residue biochar does not have the risk of causing secondary pollution to the water body:
the deashed vinegar residue biochar-1, the salt-modified vinegar residue biochar-2 and the modified sulfuric acid-carbonized biochar of example 4, example 14 and example 20 were subjected to thermal cracking gas analysis, and the products thereof are shown in Table 7.
TABLE 7 pyrolysis products of different vinegar residue biochar
Pyrolysis products of the deashed vinegar residue biochar-1 (example 4), the salt-modified vinegar residue biochar-2 (example 14) and the modified sulfuric acid carbonized vinegar residue biochar (example 20) are shown in table 7. A total of 22 pyrolysis products including ketones, hydrocarbons, nitriles, alcohols, esters and the like were detected in the deashed vinegar residue biochar-1, revealing the degradation of carbohydrates such as lignin and hemicellulose. 4 kinds of nitrile compounds (n-butyronitrile, cyanoacetic acid, acetonitrile and n-butane isonitrile) were detected in the deashed vinegar residue biochar-1, and these lower nitriles were highly toxic. The biochar containing toxic compounds is used for sewage treatment, and secondary pollution can be caused. While nitrile substances are not detected in the salt modified vinegar residue biochar-2 and the modified sulfuric acid carbonized vinegar residue biochar, nitrogen-containing substances mainly exist in the form of amino compounds probably because ZnCl2The carbonization can be promoted to break carbon-nitrogen triple bonds in the biochar under the same condition, so that the formation of toxic compounds in the biochar is inhibited through modification. Therefore, the modified sulfuric acid carbonized vinegar residue biochar has double factors of effectiveness and safety.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (10)
1. A preparation method of modified vinegar residue biochar for removing Cr (VI) in a water body is characterized by comprising the following steps: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
mixing the vinegar residue raw material with a modifier, soaking for 12h to obtain pretreated vinegar residue, and drying by hot air at the temperature of 60-65 ℃ to constant weight to obtain dried vinegar residue;
crushing the dried vinegar residue, sieving with a 80-mesh sieve to obtain vinegar residue powder with the particle size of less than 0.18mm, carbonizing, cooling to obtain vinegar residue biochar, soaking in dilute acid solution for deashing to obtain deashed vinegar residue biochar;
washing the ash-removed vinegar residue biochar with deionized water, removing redundant acid, and placing the vinegar residue biochar in a hot air drying box to be dried to constant weight to obtain the modified vinegar residue biochar; wherein,
the modifier is ZnCl2The mass ratio of the modifier to the vinegar residue raw material is 1: 1-2: 1.
2. The method for preparing the modified vinegar residue biochar for removing Cr (VI) in the water body as claimed in claim 1, wherein the modified vinegar residue biochar comprises the following steps: and drying the mixture by hot air at the temperature of 60-65 ℃ to constant weight, wherein the weight difference of 2 hours in the drying process is not more than 0.5 percent of the weight of the vinegar residue according to the standard of drying to constant weight.
3. The method for preparing the modified vinegar residue biochar for removing the Cr (VI) in the water body as claimed in claim 1 or 2, wherein the modified vinegar residue biochar comprises the following steps: the carbonization treatment comprises physical heating carbonization and concentrated acid dehydration carbonization.
4. The method for preparing the modified vinegar residue biochar for removing Cr (VI) in the water body as claimed in claim 3, wherein the modified vinegar residue biochar comprises the following steps: the physical heating carbonization comprises the following steps of,
carbonizing the vinegar residue powder at 700 ℃ for 2-2.5 h, wherein the temperature rise rate during carbonization is 10-15 ℃ min-1。
5. The method for preparing the modified vinegar residue biochar for removing Cr (VI) in the water body as claimed in claim 1, wherein the modified vinegar residue biochar comprises the following steps: cooling to obtain the vinegar residue biochar, wherein the cooling is carried out at 10 ℃ per minute-1Cooling to 200-300 ℃, and naturally cooling to room temperature.
6. The method for preparing the modified vinegar residue biochar for removing Cr (VI) in the water body as claimed in claim 3, wherein the modified vinegar residue biochar comprises the following steps: the soaking and deashing of the dilute acid solution comprises,
1 part by mass of the vinegar residue biochar is put into 40 parts by volume of dilute acid solution at the temperature of 30 ℃ for 180 r.min-1After shaking for 4 hours, carrying out solid-liquid separation, and reserving a solid component, namely the ash-removed vinegar residue biochar; wherein,
the dilute acid solution is dilute hydrochloric acid or dilute sulfuric acid, and is prepared by adding 1 volume part of hydrochloric acid or sulfuric acid into 3 volume parts of water, uniformly mixing and cooling.
7. The method for preparing the modified vinegar residue biochar for removing Cr (VI) in the water body as claimed in claim 3, wherein the modified vinegar residue biochar comprises the following steps: the concentrated acid is dehydrated and carbonized, including,
mixing the vinegar residue and concentrated acid according to the mass volume ratio g: uniformly mixing the materials in a ratio of 1: 2-4 by mL, standing for 8-9 h, and finishing the dehydration and carbonization process; wherein the concentrated acid is concentrated sulfuric acid.
8. The product prepared by the preparation method of the modified vinegar residue biochar for removing Cr (VI) in the water body as claimed in any one of claims 1 to 7 is characterized in that: the product Py-GC-MS detects no toxic nitrile substances.
9. Use of the product of claim 8 for removing Cr (vi) from a body of water.
10. The use of claim 9, wherein: the use of a composition according to any one of the preceding claims,
when the product input amount is 2 g.L-1In this case, the concentration of Cr (VI) is preferably 200 to 500 mg.L-1The removing time is 1-5 h.
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