CN117138749B - Method for preparing nitrogen-rich biochar by using melamine impregnated paper waste and application of nitrogen-rich biochar in adsorbing Cr (VI) in water - Google Patents
Method for preparing nitrogen-rich biochar by using melamine impregnated paper waste and application of nitrogen-rich biochar in adsorbing Cr (VI) in water Download PDFInfo
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 239000010893 paper waste Substances 0.000 title claims abstract description 59
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 58
- 229920000877 Melamine resin Polymers 0.000 title claims abstract description 33
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 title claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 32
- 238000000034 method Methods 0.000 title abstract description 25
- 238000000197 pyrolysis Methods 0.000 claims abstract description 22
- 239000002699 waste material Substances 0.000 claims abstract description 19
- 239000002028 Biomass Substances 0.000 claims abstract description 16
- 230000004913 activation Effects 0.000 claims abstract description 10
- 238000001179 sorption measurement Methods 0.000 claims description 28
- 239000002994 raw material Substances 0.000 claims description 10
- 238000001994 activation Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 238000003763 carbonization Methods 0.000 claims description 4
- 229910001385 heavy metal Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000004380 ashing Methods 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 8
- 238000004064 recycling Methods 0.000 abstract description 7
- 239000003575 carbonaceous material Substances 0.000 abstract description 3
- 238000010668 complexation reaction Methods 0.000 abstract description 3
- 230000009881 electrostatic interaction Effects 0.000 abstract description 3
- 238000005342 ion exchange Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 2
- 239000011651 chromium Substances 0.000 description 37
- 230000000694 effects Effects 0.000 description 15
- 239000000843 powder Substances 0.000 description 11
- 241001070941 Castanea Species 0.000 description 9
- 235000014036 Castanea Nutrition 0.000 description 9
- 239000000123 paper Substances 0.000 description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 7
- 229910052804 chromium Inorganic materials 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 239000012190 activator Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 238000007605 air drying Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 239000010902 straw Substances 0.000 description 3
- 241001093951 Ailanthus altissima Species 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 241001093963 Ailanthus Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000425037 Toona sinensis Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical group C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000011093 chipboard Substances 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- -1 nitrogen-containing compound Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 231100001234 toxic pollutant Toxicity 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3014—Kneading
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
-
- 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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
- C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
- B01J2220/4893—Residues derived from used synthetic products, e.g. rubber from used tyres
-
- 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
Abstract
The invention discloses a recycling treatment method of impregnated paper waste containing melamine, which belongs to the technical field of impregnated paper waste recovery, and adopts industrial nitrogen-rich waste impregnated paper waste as a pyrolyzed nitrogen source to reutilize waste, thereby solving the problem of waste pollution; the porous structure of the prepared biochar can be effectively improved by chemical activation and pyrolysis of the mixture of the impregnated paper waste and the biomass, the specific surface area is increased, the carbon material with rich N content is prepared, the electronic structure of the biochar is changed, the surface physical form of the biochar is further improved, and the treatment of Cr (VI) pollution is realized by complexation, cation-pi ion exchange, electrostatic interaction and precipitation.
Description
Technical Field
The invention belongs to the technical field of gumming paper waste recovery, and particularly relates to a method for preparing nitrogen-rich biochar by using melamine gumming paper waste and application of the nitrogen-rich biochar in adsorbed water Cr (VI).
Background
Biomass contains agricultural waste, forestry waste and the like, and is a renewable green energy source with large reserves. The high-value utilization of the abandoned biomass accords with the new aim of developing renewable new energy sources in China. With the continuous and deep research, high-value utilization means such as biogas technology, fuel ethanol technology, biomass gasification technology, biomass liquefaction technology and biomass carbonization technology are widely developed. The biomass pyrolysis carbonization technology has the advantages of high energy conversion efficiency, low energy consumption and the like, but compared with the traditional activated carbon, the biochar has the problems of underdeveloped pore structure, thin types and numbers of surface functional groups and the like, and the adsorption and removal effects of the biochar on chromium pollution in water and soil can be reduced.
The melamine gumming paper waste is about 5% generated during gumming and hot pressing in the manufacturing process of the artificial board in the market, and the estimated annual production of the gumming paper waste is about 100 ten thousand tons. The waste contains about 24-30% of N element because of a large amount of resin substances. If the waste is buried, formaldehyde, urea and the like can be released to pollute soil, atmosphere and water to different degrees; when burned, secondary pollution such as NOx is generated. However, there is little attention paid to the disposal of melamine impregnated paper waste at home and abroad, and only attempts have been made to press chipboards by using waste impregnated paper powder instead of part of urea-formaldehyde resin adhesive. Therefore, there is a need for a clean and efficient disposal/reuse approach.
Chromium contamination is generally classified as Cr (III) and Cr (VI) contamination. Among them, cr (VI) is a toxic pollutant which is carcinogenic and harmful to a greater extent than Cr (III), and is usually treated by adsorption and desorption and reduction to Cr (III) under anaerobic conditions. In life, the sources of chromium pollution are mainly concentrated in the wastewater discharged from factories, and the lands and wastewater polluted by chromium show orange colors. Cr (III) in the water body is mainly adsorbed on solid substances and exists in sediment, and Cr (VI) is mostly dissolved in water. Chromium after entering the soil is easily oxidized into soluble complex anions, and then is transferred into surface water or underground water through leaching. When the chromium content in the soil is too high, nitrification of organic substances is inhibited, and chromium is accumulated in the plant body.
Disclosure of Invention
This section is intended to outline some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description summary and in the title of the application, to avoid obscuring the purpose of this section, the description summary and the title of the invention, which should not be used to limit the scope of the invention.
The present invention has been made in view of the above and/or problems occurring in the prior art.
Therefore, the invention aims to overcome the defects in the prior art and provide a method for preparing nitrogen-enriched biochar by using melamine gummed paper waste.
In order to solve the technical problems, the invention provides the following technical scheme that melamine-containing gummed paper waste and biomass raw materials are subjected to blending, activation, pyrolysis and ash removal to prepare nitrogen-rich biochar, and the nitrogen-rich biochar is used for adsorbing heavy metal Cr (VI) in water.
As a preferable scheme of the method for preparing the nitrogen-enriched biochar by using the melamine gummed paper waste, the invention comprises the following steps: the content of N in the melamine-containing gummed paper waste is 24-30%.
As a preferable scheme of the method for preparing the nitrogen-enriched biochar by using the melamine gummed paper waste, the invention comprises the following steps: the activation is via ZnCl 2 Activating, wherein the activator is impregnated with the blended gumThe mass ratio of the paper waste to the biomass raw material is 1:12-18, and the activation time is 5-12 h.
As a preferable scheme of the method for preparing the nitrogen-enriched biochar by using the melamine gummed paper waste, the invention comprises the following steps: the pyrolysis is pyrolysis carbonization in a constant temperature zone of a tube furnace, wherein the pyrolysis temperature is 600-800 ℃, and the pyrolysis time is 30-90 min.
As a preferable scheme of the method for preparing the nitrogen-enriched biochar by using the melamine gummed paper waste, the invention comprises the following steps: the heating rate of the pyrolysis is 5-20 ℃/min.
As a preferable scheme of the method for preparing the nitrogen-enriched biochar by using the melamine gummed paper waste, the invention comprises the following steps: the de-ashing is carried out by immersing for 12 hours after ultrasonic treatment in dilute hydrochloric acid for 0.5 hours, filtering, washing to neutrality by de-ionized water, and drying in an oven at 105 ℃.
The invention also aims to provide the nitrogen-enriched biochar obtained by the melamine-containing gummed paper waste recycling treatment method.
It is another object of the present invention to provide the use of nitrogen-enriched biochar for adsorbing Cr (vi) in water.
As a preferable scheme for the application of the nitrogen-enriched biochar in adsorbing Cr (VI) in water, the invention comprises the following steps: the adsorption rate of the nitrogen-enriched biochar with the addition amount of 1g/L to the Cr (VI) in the 20mg/L chromium-polluted waste liquid is 100 percent.
The invention has the beneficial effects that:
according to the invention, industrial nitrogen-rich waste gummed paper waste is used as a pyrolytic nitrogen source, so that the waste is secondarily utilized, and the problem of waste pollution is solved; the porous structure of the prepared biochar can be effectively improved by chemical activation and pyrolysis of the mixture of the impregnated paper waste and the biomass, the specific surface area is increased, the carbon material with rich N content is prepared, the electronic structure of the biochar is changed, the surface physical form of the biochar is further improved, and the treatment of Cr (VI) pollution is realized by complexation, cation-pi ion exchange, electrostatic interaction and precipitation.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. Wherein:
FIG. 1 is a pore structure diagram of the nitrogen-enriched biochar prepared by the method.
FIG. 2 is a graph showing the morphology of the nitrogen-enriched biochar obtained by co-pyrolysis of pure ailanthus wood of the present invention and 30% gummed paper containing waste of example 5.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
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 other than those described herein, and persons skilled in the art will readily appreciate that the present invention is not limited to the specific embodiments disclosed below.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be 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.
The nitrogen content of the gummed paper waste used in the invention is 26%, and the other raw materials are commonly sold or conventionally available in the field without special description.
The N element content of the prepared nitrogen-enriched biochar is characterized by elemental analysis, and the concentration of Cr (VI) after adsorption is determined by a spectrophotometer.
And (3) determining the Cr (VI) content in the filtrate by referring to the national standard "determination of hexavalent chromium in water quality" and the dibenzoyl dihydrazide spectrophotometry (GB 7467-87).
Example 1
The embodiment provides a recycling treatment method for co-pyrolysis of melamine-containing gummed paper waste and chestnut shells, which specifically comprises the following steps:
1) Washing chestnut shells and gumming paper waste with clear water, air-drying, crushing, and sieving with a 50-mesh sieve to obtain chestnut shell powder and gumming paper powder;
2) Mixing pretreated chestnut shell powder and gummed paper waste in a mass ratio of 1:1, and carrying out 30% ZnCl treatment 2 The solution is dried in an oven at 80 ℃ after being activated for 12 hours, the dried sample is placed in a sample boat, transferred to a constant temperature area of a tube furnace, heated to 600 ℃ at a heating rate of 10 ℃/min and kept for 30 minutes, and then naturally cooled to room temperature;
3) Adding 100mL of dilute hydrochloric acid (1 mol/L) into the cooled biochar, standing for 12h after ultrasonic treatment for 0.5h, filtering by using a suction filtration device, washing to be neutral by using pure water at 80 ℃, collecting, drying and preserving.
Example 2
The embodiment provides a recycling treatment method for co-pyrolysis of melamine-containing gummed paper waste and rice straw, which comprises the following steps:
1) Washing rice straw and gumming paper raw materials with clear water, air-drying, crushing and sieving with a 50-mesh sieve to obtain chestnut shell powder and gumming paper powder;
2) Mixing the pretreated rice straw powder and the impregnated paper powder according to the mass ratio of 7:3, and ZnCl treating 2 Drying in an oven at 80 ℃ after activation, placing the dried sample in a sample boat, transferring to a tubular furnace constant temperature area, heating to 700 ℃ at a heating rate of 10 ℃/min, maintaining for 30min, and naturally cooling to room temperature;
3) Adding 100mL of dilute hydrochloric acid (1 mol/L) into the cooled biochar, standing for 12h after ultrasonic treatment for 0.5h, filtering by using a suction filtration device, washing to be neutral by using pure water at 80 ℃, collecting, drying and preserving.
Example 3
The embodiment provides a recycling treatment method for co-pyrolysis of melamine-containing gummed paper waste and ailanthus altissima, which specifically comprises the following steps:
1) Washing the Chinese toon wood and gumming paper waste with clear water, air-drying, crushing and sieving with a 50-mesh sieve to obtain chestnut shell powder and gumming paper powder;
2) Mixing pretreated chestnut shell powder and gummed paper waste in a mass ratio of 1:1, and carrying out 30% ZnCl treatment 2 The solution is dried in an oven at 80 ℃ after being activated for 12 hours, the dried sample is placed in a sample boat, transferred to a constant temperature area of a tube furnace, heated to 600 ℃ at a heating rate of 10 ℃/min and kept for 30 minutes, and then naturally cooled to room temperature;
3) Adding 100mL of dilute hydrochloric acid (1 mol/L) into the cooled biochar, standing for 12h after ultrasonic treatment for 0.5h, filtering by using a suction filtration device, washing to be neutral by using pure water at 80 ℃, collecting, drying and preserving.
Example 4
The embodiment is used for verifying the application effect of the nitrogen-enriched biochar obtained by the melamine-containing gummed paper waste recycling treatment method in adsorbing Cr (VI) in water, and specifically comprises the following steps of
Accurately weighing 0.2829g of potassium dichromate, drying in a drying oven at 105 ℃ for 2 hours, dissolving in pure water, and then fixing the volume to 1L to obtain mother liquor with the Cr (VI) content of 100mg/L, diluting a proper amount of mother liquor with pure water for 5 times, and regulating the pH value to 2 to obtain chromium-polluted waste liquor with the Cr (VI) content of 20 mg/L;
adding the prepared nitrogen-enriched biochar into the diluted chromium-polluted waste liquid according to the adding amount of 1mg/L, carrying out vibration adsorption for 1h at the rotating speed of 200rpm, and then carrying out suction filtration by using a filter membrane of 0.45 micrometers, and collecting filtrate.
The N content, the adsorption amount to Cr (VI) and the removal rate of the biochar obtained in examples 1 to 3 were measured, and the results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the nitrogen-enriched biochar prepared by blending and pyrolyzing different biomass raw materials and gummed paper waste in the scheme of the invention has excellent effect of adsorbing Cr (VI) in water, and can reach 100% removal rate, which shows that the recycling treatment method of the melamine-containing gummed paper waste effectively realizes the secondary utilization of industrial waste, solves the problem of waste pollution, and simultaneously reduces the heavy metal Cr (VI) pollution in water.
Comparative example 1
The difference between this example and example 1 is that the raw material in step 2) is pure chestnut shell, and the other process parameters are the same as those in example 1, so as to obtain the biochar of this example.
Comparative example 2
This example differs from example 1 in that the activator in step 2) is modified to be NaHCO 3 The remaining process parameters were the same as in example 1 to prepare biochar of this example.
The N content, the adsorption amount and the removal rate of Cr (VI) of the biochar obtained in comparative example 1 and comparative example 2 were compared with those of example 1 by the method of example 4, and the results are shown in Table 2.
TABLE 2
As can be seen from table 2, compared with pure chestnut shells, the method introduces the gumming paper waste for co-pyrolysis, so that the adsorption capacity of the prepared biochar to Cr (VI) is greatly improved, and the nitrogen element of the gumming paper waste in the pyrolysis process can be transferred to the biochar and react with biomass raw materials, so that the number of active sites and the surface area of the biochar are improved, a pore structure is formed, the void property of the biochar is increased, and the adsorption effect is further improved;
meanwhile, the kind of the activator has obvious influence on the technical effect of the invention, the activator initiates chemical reaction in the pyrolysis process to generate active substances, the number of active sites of the biochar is increased to improve the adsorption capacity of the biochar, more active sites can be generated by adopting zinc chloride activation, the adsorption effect of the biochar is improved, and the sodium bicarbonate activation mainly forms mesopores to prepare the nitrogen-rich biochar with higher nitrogen content, but as can be seen from the data of the table 2, the adsorption effect of the biochar cannot be effectively improved due to the excessively high nitrogen content, and compared with the example 1, the nitrogen content is improved by 3.22 percent, but the Cr (VI) removal rate is reduced by 43.83%!
Example 5
This example was used to determine the effect of the relative content of melamine-containing gummed paper waste on the adsorption performance of the resulting biochar when the treatment was carried out, and was different from example 3 in that the gummed paper waste was adjusted to a ratio of 10%, 20%, 30% and 50% (example 3), and the remaining process parameters were the same as in example 1, and the results are shown in table 3.
TABLE 3 Table 3
Fig. 1 is a schematic diagram of a pore structure of the nitrogen-enriched biochar prepared by the method, fig. 2 is a comparison of the morphology of nitrogen contained in the pure biochar (pure ailanthus altissima) and the nitrogen-enriched biochar (the proportion of gum dipping paper waste is 30%) (the peak of the N1s spectrogram in XPS analysis), and fig. 2 shows that the intensity of the nitrogen peak in the nitrogen-enriched biochar is higher than that of the pure biochar, and the existence morphology of the nitrogen is increased from 2 types to 4 types, which indicates that the number and the types of the nitrogen-containing functional groups are increased, thereby being beneficial to the increase of surface active sites and the improvement of the subsequent adsorption effect.
As can be seen from table 3, the ratio of the impregnated paper has a significant effect on the effect of preparing the biochar to adsorb Cr (vi), the melamine in the impregnated paper waste is a nitrogen-containing compound, and the melamine reacts with the biomass material to provide nitrogen-rich active sites, so that the surface area and pore structure of the biochar are increased, and the adsorption capacity is improved, and meanwhile, other organic substances in the impregnated paper waste can also provide more adsorption sites, so that the adsorption capacity of the nitrogen-rich biochar to Cr (vi) is improved, other components in the impregnated paper waste can also have a certain reducibility, and can undergo a reduction reaction with Cr (vi), so that the adsorption effect is further improved.
However, when the content of the impregnated paper waste is too high, it may cause a decrease in adsorption effect, and too high of the impregnated paper waste content may cause the pore structure of the nitrogen-rich biochar to become uneven, impeding diffusion of Cr (vi) into adsorption sites, and decreasing adsorption effect. The specific surface area of the biochar is possibly reduced, the number of adsorption sites is reduced, and the adsorption capacity is reduced; meanwhile, too high a content of the impregnated paper waste may cause an increase in organic substances in the nitrogen-rich biochar, which may compete with Cr (vi) for adsorption sites, thereby reducing adsorption effects, and thus, in practical applications, it is necessary to find a suitable content of the impregnated paper waste to obtain optimal adsorption performance.
In conclusion, the industrial nitrogen-rich waste gummed paper waste is adopted as a pyrolytic nitrogen source, so that the waste is secondarily utilized, and the problem of waste pollution is solved; the porous structure of the prepared biochar can be effectively improved by chemical activation and pyrolysis of the mixture of the impregnated paper waste and the biomass, the specific surface area is increased, the carbon material with rich N content is prepared, the electronic structure of the biochar is changed, the surface physical form of the biochar is further improved, and the treatment of Cr (VI) pollution is realized by complexation, cation-pi ion exchange, electrostatic interaction and precipitation.
It should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, 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 the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered in the scope of the claims of the present invention.
Claims (8)
1. The application of nitrogen-rich biochar prepared from melamine impregnated paper waste in adsorbing Cr (VI) in water is characterized in that: comprises the steps of blending, activating, pyrolyzing and deashing melamine-containing gumming paper waste and biomass raw materials to prepare nitrogen-rich biochar, and the nitrogen-rich biochar is used for adsorbing heavy metal Cr (VI) in water.
2. Use of the nitrogen-enriched biochar prepared from melamine impregnated paper waste as claimed in claim 1 for adsorbing Cr (vi) in water, characterized in that: in the raw materials of the nitrogen-rich biochar, the proportion of the melamine-containing gummed paper waste is 30-40%.
3. Use of the nitrogen-enriched biochar prepared from melamine impregnated paper waste as claimed in claim 1 or 2 for adsorbing Cr (vi) in water, characterized in that: the content of N in the melamine-containing gummed paper waste is 24-30%.
4. Use of the nitrogen-enriched biochar prepared from melamine impregnated paper waste as claimed in claim 1 for adsorbing Cr (vi) in water, characterized in that: the activation is via ZnCl 2 And (3) activating, wherein the mass ratio of the activating agent to the blended gummed paper waste to the biomass raw material is 1:12-18, and the activating time is 5-12 hours.
5. Use of the nitrogen-enriched biochar prepared from melamine impregnated paper waste as claimed in claim 1 for adsorbing Cr (vi) in water, characterized in that: the pyrolysis is pyrolysis carbonization in a constant temperature zone of a tube furnace, wherein the pyrolysis temperature is 600-800 ℃, and the pyrolysis time is 30-90 min.
6. Use of the nitrogen-enriched biochar prepared from melamine impregnated paper waste as claimed in claim 1 or 5 for adsorbing Cr (vi) in water, characterized in that: the heating rate of pyrolysis is 5-20 ℃/min.
7. Use of the nitrogen-enriched biochar prepared from melamine impregnated paper waste as claimed in claim 1 for adsorbing Cr (vi) in water, characterized in that: the de-ashing is carried out by immersing for 12 hours after ultrasonic treatment in dilute hydrochloric acid for 0.5 hours, filtering, washing to neutrality by de-ionized water, and drying in an oven at 105 ℃.
8. Use of the nitrogen-enriched biochar according to claim 1 for the adsorption of Cr (vi) in water, characterized in that: the adsorption rate of the nitrogen-enriched biochar with the addition amount of 1g/L to Cr (VI) in 20mg/L chromium-polluted waste liquid is 100 percent.
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| CN108905979A (en) * | 2018-07-02 | 2018-11-30 | 安徽宇瑞环保建设有限公司 | A kind of preparation method of the composite reactive charcoal of adsorbable heavy metal ions in sewage |
| CN113603087A (en) * | 2021-09-03 | 2021-11-05 | 四川大学 | Nitrogen-rich biomass-based activated carbon with hierarchical pore microchannel structure and application thereof |
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| CN108905979A (en) * | 2018-07-02 | 2018-11-30 | 安徽宇瑞环保建设有限公司 | A kind of preparation method of the composite reactive charcoal of adsorbable heavy metal ions in sewage |
| CN113603087A (en) * | 2021-09-03 | 2021-11-05 | 四川大学 | Nitrogen-rich biomass-based activated carbon with hierarchical pore microchannel structure and application thereof |
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| Kenny Vanreppelen，et al.Activated carbon by co-pyrolysis and steam activation from particle board and melamine formaldehyde resin: production, adsorption properties and techno economic evaluation.Journal of Sustainable Development of Energy,Water and Environment Systems.2013,第41-57页. * |
| 宁平，等.《生物质活性炭催化剂的制备及脱硫应用》.冶金工业出版社,2019,第29-30页. * |
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