AU2021106086A4 - Preparation method of paper mill coagulation solid waste-based catalyst and products and applications thereof - Google Patents
Preparation method of paper mill coagulation solid waste-based catalyst and products and applications thereof Download PDFInfo
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- solid waste
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- based catalyst
- coagulation solid
- coagulation
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- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 230000015271 coagulation Effects 0.000 title claims abstract description 41
- 238000005345 coagulation Methods 0.000 title claims abstract description 41
- 239000002910 solid waste Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 6
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical class OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 claims description 33
- 239000002957 persistent organic pollutant Substances 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000002351 wastewater Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000000701 coagulant Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229940124530 sulfonamide Drugs 0.000 claims description 4
- 150000003456 sulfonamides Chemical class 0.000 claims description 4
- 238000005336 cracking Methods 0.000 claims description 3
- 230000000593 degrading effect Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 abstract description 25
- 229960004306 sulfadiazine Drugs 0.000 abstract description 25
- 239000000463 material Substances 0.000 abstract description 20
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 9
- 239000003344 environmental pollutant Substances 0.000 abstract description 8
- 229910002804 graphite Inorganic materials 0.000 abstract description 5
- 239000010439 graphite Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 238000000197 pyrolysis Methods 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 25
- 238000006731 degradation reaction Methods 0.000 description 15
- 230000015556 catabolic process Effects 0.000 description 14
- 229910052742 iron Inorganic materials 0.000 description 10
- 230000004913 activation Effects 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 239000002699 waste material Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 231100000719 pollutant Toxicity 0.000 description 6
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000012795 verification Methods 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000003242 anti bacterial agent Substances 0.000 description 3
- 229940088710 antibiotic agent Drugs 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- -1 periodate ions Chemical class 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 241000283891 Kobus Species 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- AAMATCKFMHVIDO-UHFFFAOYSA-N azane;1h-pyrrole Chemical compound N.C=1C=CNC=1 AAMATCKFMHVIDO-UHFFFAOYSA-N 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
- YYXHRUSBEPGBCD-UHFFFAOYSA-N azanylidyneiron Chemical compound [N].[Fe] YYXHRUSBEPGBCD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-M periodate Chemical compound [O-]I(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-M 0.000 description 1
- 231100001239 persistent pollutant Toxicity 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000004062 sedimentation 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
- 239000010802 sludge Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- B01J35/51—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B2101/00—Type of solid waste
- B09B2101/85—Paper; Wood; Fabrics, e.g. cloths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
Abstract
The invention relates to the technical field of catalysts, in particular to a preparation
method of a paper mill coagulation solid waste-based catalyst and products and applications
thereof. The preparation method specifically comprises the following steps: drying paper mill
coagulation solid waste, pyrolyzing under anoxic conditions, and grinding to obtain paper mill
coagulation solid waste-based catalyst. According to the invention, a carbonaceous catalyst
material similar to graphite is prepared by taking coagulation solid waste of a paper mill as a
raw material through anoxic pyrolysis, and it has excellent characteristics of acid and alkali
resistance, adjustable electronic structure, low cost, high conductivity and the like; the catalytic
material of the invention has a very good purification effect on micro-pollutants in water,
especially for sulfadiazine, and the removal rate can reach 99%.
Description
Preparation method of paper mill coagulation solid waste-based catalyst and
products and applications thereof
The invention relates to the technical field of catalysts, in particular to a
preparation method of a paper mill coagulation solid waste-based catalyst and
products and applications thereof.
With the deterioration of environment and the rapid development of civilization,
the discharge of organic refractory wastewater has brought great difficulties to
environmental governance. Sulfonamides are the synthetic antibiotics which are
detected the most and applied the earliest in medical and veterinary practice. However,
most antibiotics ingested in the body are not absorbed, but excreted into the
environment. Even low concentrations of antibiotics may change the microbial
community, induce antibiotic-resistant bacteria, lead to serious human health
problems, and have unpredictable environmental risks. As a broad-spectrum antibiotic,
sulfonamides are difficult to be removed by biological methods, and conventional
chemical processes used in sewage treatment plants can not be completely removed,
and there are still trace residues in aquatic environment. Therefore, efficient removal
of micro-organic pollutants in water has become a technical problem to be solved
urgently by technicians in this field.
Because the traditional biological treatment technology has limited ability to
remove organic refractory pollutants in water, advanced oxidation technology has
become the main means for people to treat this kind of wastewater. Advanced
oxidation processes attack persistent pollutants by using strong oxidants to produce
powerful active substances. Among these oxidants, periodate has attracted more and more attention because of its stability, convenient transportation and storage, and priority in some cases. However, periodate ion is relatively stable when it exists alone in water environment, so it is difficult to directly oxidize and degrade organic pollutants in water, and it usually needs to be activated by catalyst to have rapid reaction effect. There are many ways to activate periodate, including bimetallic activation, metal compound activation, freezing activation, ultrasonic treatment, alkali activation and ultraviolet activation. Among them, transition metal activation is one of the most promising options because it does not need additional energy input, and has mild application conditions and low cost. However, the use of metals is limited by the excessive consumption of chemicals and the generation of metal sludge. Therefore, it is necessary to develop more environmentally friendly and highly active catalytic materials to further improve the ability of catalysts to activate periodate to remove different pollutants.
Paper industry is one of the fastest growing industries, and a large amount of
coagulation waste produced in its production process has also caused potential harm
to the environment. Iron coagulants are widely used because of their wide pH range,
low cost and fast sedimentation. Therefore, paper mill coagulation wastes often
contain a large amount of lignocellulose, iron and nitrogen elements. Therefore, it is
of great significance to provide a catalyst for preparing activated periodate from paper
mill coagulation wastes for efficient removal of micro-organic pollutants in water.
Based on the above, the present invention provides a preparation method of
paper mill coagulation solid waste-based catalyst and its product and application.
The invention relates to a preparation method of paper mill coagulation solid
waste-based catalyst, which comprises the following steps: drying paper mill coagulation solid waste, pyrolyzing under anoxic conditions, and grinding to obtain paper mill coagulation solid-based waste catalyst.
Further, the coagulant of the paper mill coagulation solid waste is polyferric
sulfate.
Further, the drying is specifically: drying at 60-80°C to constant weight, and the
anoxic cracking is specifically: under nitrogen condition, at 500-600°C for 1.5-2 h.
Further, the grinding is specifically ground through a 200-mesh sieve.
The second technical scheme of the invention is the paper mill coagulation solid
waste-based catalyst prepared by the preparation method of the paper mill coagulation
solid waste catalyst.
The third technical scheme of the invention is the application of the paper mill
coagulation solid waste-based catalyst in water containing micro-organic pollutants
treated by activating periodate.
Furthermore, the micro-organic pollutants are sulfonamides, and the pH value of
the water body containing the micro-organic pollutants is less than 8.
The fourth technical scheme of the invention: a method for degrading wastewater
containing micro-organic pollutants takes the paper mill coagulation solid waste
based catalyst as a catalyst, and specifically comprises the following steps:
the catalyst is placed in wastewater containing micro-organic pollutants, stirred
evenly, and periodate is added under stirring condition to react and then filtered.
Furthermore, the concentration of the catalyst in wastewater containing micro
organic pollutants is 0.25-0.75 g/L, the concentration of periodate in wastewater
containing micro-organic pollutants is 1-7.5 mM, the stirring speed is 350-450 rpm,
and the reaction time is 10-90 min.
Compared with the prior art, the invention has the following beneficial effects:
According to the invention, a carbonaceous catalyst material similar to graphite
is prepared by taking coagulation solid waste of a paper mill as a raw material through
anoxic pyrolysis, and has excellent characteristics of acid and alkali resistance,
adjustable electronic structure, low cost, high conductivity and the like; in a further
preferred scheme, paper mill coagulation solid waste with polyferric sulfate as
coagulant is used as raw material, so that iron and nitrogen elements are introduced
into carbon materials to prepare iron-nitrogen co-doped carbon catalyst materials,
which can provide more catalytic activation sites, thereby promoting the electron
transfer mechanism and contributing to the degradation of pollutants; meanwhile, the
introduction of heteroatoms can change the electronic distribution of carbon materials,
destroy the chemical inertia of carbon materials and introduce active sites; and iron
itself can be used as an activator of periodate, thus promoting the degradation of
pollutants; in the degradation process, iron atoms and nitrogen atoms can attract
electrons from adjacent carbon atoms to form electron-rich centers, which are easy to
adsorb periodate ions and further promote the transfer of electrons to periodate. For
sulfadiazine wastewater, the amine of sulfadiazine is easy to lose electrons, which
eventually promotes the transfer of electrons from sulfadiazine to periodate through
the catalyst, forming a closed electronic ring, promoting the role of non-free radical
degradation mechanism dominated by electron transfer, thus improving its catalytic
degradation performance of pollutants and making it available in water purification
and other fields.
The catalytic material of the invention has a very good purification effect on
micro-pollutants in water, especially for sulfadiazine, and the removal rate can reach
99%.
Figure 1 is a scanning electron microscope picture of paper mill coagulation
solid waste-based catalyst in Example 1 of the present invention;
Figure 2 is a high-resolution transmission electron micrograph of paper mill
coagulation solid waste-based catalyst in Example 1 of the present invention;
Figure 3 is an x-ray diffraction spectrum of paper mill coagulation solid waste
based catalyst in Example 1 of the present invention;
Figure 4 is an x-ray photoelectron spectroscopy analysis result of waste catalyst
with coagulation solid in paper mill in Example 1 of the present invention, in which
(a) is Fe 2p spectrum and (b) is N Is spectrum;
Figure 5 is a line chart showing the influence of CWBC/PI on sulfadiazine
degradation rate under different catalyst concentrations in an effect verification
example of the present invention;
Figure 6 is a line chart showing the influence of CWBC catalytic material on
sulfadiazine degradation rate at different pH values in the effect verification example
of the present invention;
Figure 7 is a line chart showing the influence of CWBC catalytic material on
sulfadiazine degradation rate under different PI concentrations in an effect verification
example of the present invention.
Various exemplary embodiments of the present invention will now be described
in detail, which should not be regarded as a limitation of the present invention, but
rather as a more detailed description of certain aspects, characteristics and
embodiments of the present invention.
It should be understood that the terms described in the present invention are only
for describing specific embodiments, and are not intended to limit the present invention. In addition, as for the numerical range in the present invention, it should be understood that every intermediate value between the upper limit and the lower limit of the range is also specifically disclosed. Intermediate values within any stated value or stated range and every smaller range between any other stated value or intermediate values within the stated range are also included in the present invention.
The upper and lower limits of these smaller ranges can be independently included or
excluded from the range.
Unless otherwise stated, all technical and scientific terms used herein have the
same meanings as commonly understood by those skilled in the art to which the
present invention relates. Although the present invention only describes preferred
methods and materials, any methods and materials similar or equivalent to those
described herein may be used in the practice or testing of the present invention. All
documents mentioned in this specification are incorporated by reference to disclose
and describe methods and/or materials related to the documents. In case of conflict
with any incorporated documents, the contents of this specification shall prevail.
Without departing from the scope or spirit of the invention, it is obvious to those
skilled in the art that many modifications and changes can be made to the specific
embodiments of the specification of the invention. Other embodiments derived from
the description of the present invention will be apparent to the skilled person. The
specification and embodiment of that present invention are merely exemplary.
As used herein, "including", "having", "containing", etc. are all open terms,
which means including but not limited to.
Example 1
20 g of paper mill coagulation solid waste (polyferric sulfate as coagulant) with
rice straw as raw material was dried in a vacuum drying oven at 60°C for 12 h to obtain coagulation solid waste dried to constant weight; a certain amount of solid waste was put into a porcelain boat and cracked in a vacuum tube furnace under nitrogen atmosphere at 550°C for 2 h; after the reaction, the composite material was ground in a porcelain boat, and then passed through a 200-mesh sieve to obtain 6 g of catalyst material (CWBC) based on coagulation solid waste of paper mill.
The surface scanning electron microscope analysis (Figure 1), transmission
electron microscope analysis (Figure 2), X-ray diffraction spectrum analysis (Figure 3)
and X-ray photoelectron spectroscopy analysis (Figure 4) were carried out on the
prepared paper mill coagulation solid waste-based catalyst material.
It can be seen from Figure 1 that CWBC has a fluffy structure, and iron and
nitrogen materials are distributed on carbon materials, indicating that iron and
nitrogen are co-doped in CWBC, and Si element comes from paper making process.
It can be seen from Figure 2 that the CWBC catalyst has an irregular multilayer
structure, and many spherical black particles are uniformly dispersed in the carbon
matrix. The lattice spacing of the black particles is 0.221 nm after calculated, which
corresponds to the (113) crystal plane of Fe203, indicating the existence of Fe oxide.
In addition, transmission electron microscope images show that the calculated lattice
spacing of carbon matrix is 0.337 nm, which is consistent with the spacing between
graphite layers (sp 2 hybrid), indicating the existence of graphite phase carbon.
It can be concluded from Figure 3 that CWBC is amorphous structure, and
CWBC has a wide dispersion peak at 20 = 23°, which corresponds to the (002)
diffraction plane of hexagonal graphite structure. The sharp peak of spectrum may be
due to the existence of inorganic phase in papermaking solid waste, such as silicon,
sodium, iron, etc. Due to the small content of iron in the material, the characteristic
peak of iron was not observed in XRD.
It can be seen from Figure 4(a) that the Fe 2p spectra at 711.35 eV, 719.46 eV,
723.19 eV and 732.9 eV correspond to the Fe2p 3/2 and Fe2p/2 of Fe(III) and their
satellite peaks respectively. 714.97 eV and 728.1eV corresponding to Fe(II) 2p/2
spectrum of Fe(II) and its satellite peak. Therefore, XPS Fe spectra shows that iron
exists in CWBC as FeO and Fe203. XPS N Is spectrum (Figure 4(b)) shows four
peaks of 398.29 eV, 400.48 eV, 403.72 eV and 408.02 eV, which correspond to
pyridine nitrogen, pyrrole nitrogen, graphite nitrogen and nitrogen oxide respectively.
Example of effect verification
Taking sulfadiazine (SDZ) as an example, verify the technical effect of removing
pollutants by activating periodate treatment of the products in Example 1. The
specific test method is as follows:
With catalyst concentration (0.25 g/L, 0.50 g/L, 0.75 g/L), sulfadiazine solution
pH value (3, 5, 7, 9, 11) and periodate concentration (1.0 mM, 2.5 mM, 5.0 mM, 7.5
mM) as variables, the catalytic material of Example 1 was uniformly suspended in a
250 mL beaker containing 100 mL SDZ solution (40 M). The mixed suspension was
stirred on a magnetic stirrer at 400 rpm, and then sodium periodate (PI) was added to
make its concentration reach 5 mM. At a specific time interval, 1 mL of solution was
extracted from the reactor, filtered with 0.22 m water filter, immediately quenched
with 20 L of Na2S203(1M), and then the removal effect of SDZ was detected.
Fig. 5 is a line chart showing the influence of CWBC/PI on sulfadiazine
degradation rate under different catalyst concentrations. It can be seen from the figure
that when the catalyst dosage increases from 0.25 g L-1 to 0.50 g L- 1, the degradation
efficiency of SDZ increases, and the corresponding pseudo-first order reaction rate
constants (kobs) are 0.0219 min-' and 0.0586 min-1 , respectively. However, when the
catalyst concentration was further increased to 0.75 g L- 1, the reaction rate constant kob decreased to 0.0319 min-'. This phenomenon may be due to the limitation of PI concentration, which leads to the higher concentration of catalyst can not further improve the reaction rate. Therefore, 0.5 g L-1 was selected as the best dosage of
CWBC catalyst.
Fig. 6 is a line chart showing the influence of CWBC catalytic materials on
sulfadiazine degradation rate at different pH values. It can be seen from the figure that
SDZ can be rapidly degraded under strongly acidic and nearly neutral pH conditions,
and the best removal rate is achieved at pH3.0 (98.94% removal within 90 minutes).
Since the zero point of charge of CWBC is between 3.0 and 5.0, the potential of
CWBC is positive at pH=3.0, which reduces the electrostatic repulsion between
periodate anion and the positively charged catalyst surface, and contributes to the
activation of PI by CWBC. On the contrary, when the pH value increases above 3.12,
the zeta potential of CWBC decreases and the surface of CWBC is negatively charged,
which indicates that the electrostatic repulsion between CWBC and PI is caused by
the increased pH value, which leads to the inhibition of dynamic SDZ degradation. In
addition, the existence forms of heptavalent iodine ions are different at different pH
values. When pH value is lower than 8.0, 104- is dominant, and when pH value
reaches 8.0, its dimeric form (H3106 2-) is the main substance. Compared with the
reduction potential of 104/103 (1.298 V), the reduction potential of H31062-/103
(0.686 V) is lower, which may be the reason why the degradation efficiency of SDZ is
relatively low at higher pH value.
Fig. 7 is a line chart showing the influence of CWBC catalytic materials on
sulfadiazine degradation rate at different PI concentrations; It can be seen from the
figure that with the increase of PI concentration (1 mM, 2.5 mM, 5.0 mM and 7.5
mM), the removal rate of SDZ increases significantly. Higher concentration of PI may produce more active species, which leads to an increase in SDZ degradation rate from
0.0097 min-' to 0.0586 min-' when PI concentration increases from 1.0 mM to 5.0 mm.
However, with the increase of PI concentration from 5.0 mM to 7.5 mM, although the
final removal efficiency has almost no change, the increase rate of reaction rate
constant kobs greatly slows down (from 0.0586 to 0.0601 min-'). This phenomenon can
be explained in the following ways: firstly, excessive PI can compete with SDZ for
reactive radicals; secondly, when the PI concentration is less than 5.0 mM, the dosage
of CWBC is excessive relative to the PI concentration; however, as the PI
concentration further increases to over 5 mM, the higher concentration of PI cannot be
fully activated due to the dose limitation of CWBC, so the removal rate of SDZ is not
greatly improved.
From the above test results, it can be seen that the catalytic material prepared by
this method based on coagulation solid waste of paper mill can activate PI and has
high catalytic oxidation performance for sulfadiazine. The catalytic material can
purify other organic matters in the solution by catalytic oxidation, and has good
application prospect and significance in reducing the pollution of organic pollutants in
wastewater.
The above is only a preferred embodiment of the present invention, and is not
intended to limit the present invention. Any modifications, equivalent substitutions
and improvements made within the spirit and principles of the present invention shall
be included in the scope of protection of the present invention.
Claims (9)
1. A preparation method of paper mill coagulation solid waste-based catalyst is
characterized by comprising the following steps:
drying paper mill coagulation solid waste, cracking under anoxic conditions, and
grinding to obtain paper mill coagulation solid waste catalyst.
2. The preparation method of paper mill coagulation solid waste-based catalyst
according to claim 1 is characterized in that the coagulant of paper mill coagulation
solid waste is polyferric sulfate.
3. The preparation method of paper mill coagulation solid waste-based catalyst
according to claim 1 is characterized in that: drying at 60-80°C to constant weight;
and anoxic cracking at 500-600°C for 1.5-2 h under nitrogen.
4. The preparation method of paper mill coagulation solid waste-based catalyst
according to claim 1 is characterized in that the grinding is specifically grinding
through a 200-mesh sieve.
5. The paper mill coagulation solid waste-based catalyst prepared by the
preparation method of the paper mill coagulation solid waste-based catalyst according
to any one of claims I to 4.
6. The application of the paper mill coagulation solid waste-based catalyst
according to claim 5 in in water containing micro-organic pollutants treated by
activated periodate.
7. The application according to claim 6 is characterized in that the micro-organic
pollutants are sulfonamides, and the pH value of the water containing the micro
organic pollutants is less than 8.
8. A method for degrading wastewater containing micro-organic pollutants,
which is characterized in that the paper mill coagulation solid waste-based catalyst according to claim 5 is used as a catalyst, and specifically comprises the following steps:
The catalyst is placed in wastewater containing micro-organic pollutants, stirred
evenly, and periodate is added under stirring condition to react and then filtered.
9. The method for degrading wastewater containing micro-organic pollutants
according to claim 8 is characterized in that the concentration of the catalyst in
wastewater containing micro-organic pollutants is 0.25-0.75 g/L, the concentration of
periodate in wastewater containing micro-organic pollutants is 1-7.5 mM, the stirring
speed is 350-450 rpm, and the reaction time is 10-90 min.
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