CN112209488B - Improvement of catalytic H by modifying domestic garbage incinerator slag2O2Method for treating organic wastewater - Google Patents
Improvement of catalytic H by modifying domestic garbage incinerator slag2O2Method for treating organic wastewater Download PDFInfo
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- CN112209488B CN112209488B CN202010727463.3A CN202010727463A CN112209488B CN 112209488 B CN112209488 B CN 112209488B CN 202010727463 A CN202010727463 A CN 202010727463A CN 112209488 B CN112209488 B CN 112209488B
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- 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
- C02F1/722—Oxidation by peroxides
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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
- 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
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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
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
Abstract
The invention relates to a method for improving catalytic H by modifying domestic garbage incinerator slag2O2A method of treating organic wastewater, the method comprising: (S1) putting the ball milling beads, the furnace slag and the sodium carbonate into a ball milling tank according to the weight ratio of 15-20: 1: 0.3-0.6, covering a cover, milling for 10-30 min at the speed of 550rpm, and crushing the furnace slag; (S2) putting the ball-milled slag into a muffle furnace, and roasting for 2 hours at 750-900 ℃; (S3) taking out the cooled furnace slag, putting the furnace slag into a weak acid solution at the temperature of 70-80 ℃, stirring the furnace slag for 30-60 min by using a stirrer, and filtering; (S4) adding excessive alkali solution into the filtered supernatant, then centrifugally filtering, and drying the filter residue for 4-6 hours at the temperature of 60-80 ℃; (S5) pumping organic wastewater into the reactor, adjusting the pH of the organic wastewater to 3.0-4.0, and adding H with the molar concentration of 0.1-0.5 mmol/L2O2And then adding the iron-aluminum oxide treated in the step (S4) into a reactor, wherein the adding amount of the slag is 1-10 g/L, reacting for a certain time, and treating the organic wastewater. The method provided by the invention can greatly improve the catalytic activity of H in the slag2O2The effect of treating organic wastewater, and the treatment of waste by waste, has good popularization and application value.
Description
Technical Field
Hair brushBelongs to the field of water pollution control, and relates to a method for improving catalytic H by using modified domestic garbage incinerator slag2O2A method for treating organic wastewater.
Background
Since 2003, the incineration treatment proportion of Chinese municipal solid waste is increased year by year, and in 2020, the incineration power generation proportion in the municipal solid waste treatment accounts for more than 50%. However, the waste incineration inevitably produces a byproduct, namely slag, and the waste incineration slag is greatly different from general slag (mainly refers to slag produced in a metallurgical process) and mainly comprises heterogeneous mixture consisting of slag, metal, ceramic fragments, glass and other non-combustible substances and unburned organic matters. According to the report, about 20% of slag is generated by burning each ton of domestic garbage. With the continuous low-level generation of the waste incineration slag, the development of a resource utilization way of the waste incineration slag is urgently needed.
On the other hand, various biological, chemical and physicochemical treatment methods have been developed to control water pollution. Among them, the Fenton technique has become one of the research hotspots in the field of water pollution control. The reaction mechanism is mainly through Fe2+And H2O2High-reactivity OH is generated, so that a series of chain reactions are initiated to degrade organic matters. In order to solve the problems of narrow pH application range and large mud production amount of the traditional Fenton oxidation technology, a plurality of researches utilize heterogeneous iron-based and aluminum-based Fenton systems to replace ferrous salts, and catalysts used by the heterogeneous catalysts mainly comprise zero-valent iron, zero-valent aluminum and iron oxide (Fe)2O3，γ-FeOOH，Fe3O4Green embroidery, etc.).
The household garbage incineration slag belongs to SiO in terms of chemical composition2-Al2O3-CaO-Fe2O3Systems in which metal oxides such as iron oxides, aluminum oxides, etc. are catalytic H2O2But at present, the domestic garbage slag is not utilized to catalyze H2O2The main reasons for this are reported as follows: firstly, the domestic garbage slag presents a glass state after being burned at high temperature, and metal oxides are difficult to dissolve out; ② its components are too complicatedWherein SiO is more than 40%2And about 20% of CaO pair H2O2Not only is there little catalytic effect, but the formation of hydroxyl reactive oxidizing species (e.g., hydroxyl radicals) is also quenched. Therefore, there is a need to find a method for modifying the slag of a domestic waste incinerator to increase its catalytic H2O2Efficiency.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a modified domestic garbage incinerator slag for improving catalytic H2O2The method for treating the organic wastewater has low cost and good effect of treating the organic wastewater.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for improving catalytic H by modifying domestic garbage incinerator slag2O2A method of treating organic wastewater comprising the steps of:
s1, putting the ball milling beads, the furnace slag and the sodium carbonate into a ball milling tank according to the weight ratio of 15-20: 1: 0.3-0.6, covering a cover, milling for 10-30 min at the speed of 550rpm, and crushing the furnace slag;
s2, placing the ball-milled slag into a muffle furnace, and roasting for 2 hours at 750-900 ℃;
s3, taking out the cooled furnace slag, putting the furnace slag into a weak acid solution at 70-80 ℃, stirring the furnace slag for 30-60 min by using a stirrer, filtering the furnace slag, and dissolving out sodium ferrite and sodium aluminate, namely calcium silicate (2 CaO. SiO)2) Difficult dissolution;
s4, adding excessive alkali solution into the filtered supernatant, then carrying out centrifugal filtration, and drying the filter residue for 4-6 h at the temperature of 60-80 ℃;
s5, pumping organic wastewater into the reactor, adjusting the pH of the organic wastewater to 3.0-4.0, and adding H with the molar concentration of 0.1-0.5 mmol/L2O2And then adding the iron-aluminum oxide treated in the step S4 into a reactor, wherein the adding amount of the slag is 1-10 g/L, reacting for a certain time, and treating the organic wastewater.
In the method of the present invention, in S3, the weakly acidic solution is one of acetic acid and oxalic acid having a pH of 5.0 to 6.0.
The method of the invention, wherein the alkali solution in S4 is a solution of KOH or NaOH.
The invention adopts the technical principle that sodium carbonate and iron and aluminum oxides in the domestic garbage incineration slag are easy to generate soluble sodium ferrite and sodium aluminate at high temperature, so that H is contained in the slag2O2The components with catalytic activity are extracted for subsequent treatment of organic wastewater.
Compared with the prior art, the method has the beneficial effects that:
1. the iron and aluminum oxides with catalytic activity in the domestic garbage incineration slag are extracted to be catalyzed H2O2The waste is treated by the waste and the waste is changed into valuable.
2. Avoids the use of expensive chemical reagents as iron and aluminum precursors in the traditional Fenton-like reaction, and the prepared catalyst has low cost and good catalytic effect.
Drawings
FIG. 1: comparison graph of organic wastewater degraded by original furnace slag
Detailed Description
The present invention will be further described with reference to the following specific examples and drawings, which are not intended to limit the invention in any manner. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
The invention provides a method for improving catalytic H by modifying domestic garbage incinerator slag2O2A method of treating organic wastewater comprising the steps of:
s1, putting the ball milling beads, the furnace slag and the sodium carbonate into a ball milling tank according to the weight ratio of 15-20: 1: 0.3-0.6, covering a cover, milling for 10-30 min at the speed of 550rpm, and crushing the furnace slag.
S2, placing the ball-milled slag into a muffle furnace, roasting for 2 hours at 750-900 ℃, and roasting the slag at the temperature for 2 hours with sodium carbonate and Al in the slag2O3And Fe2O3Reaction of (2)Mainly (reactions 1 and 2), and sodium ferrite (Na) which is easy to hydrolyze is mainly generated2O·Fe2O3) And sodium aluminate (Na)2O·Al2O3)
S3, taking out the cooled furnace slag, putting the furnace slag into a weak acid solution at 70-80 ℃, stirring the furnace slag for 30-60 min by using a stirrer, and filtering the furnace slag, wherein sodium ferrite and sodium aluminate are dissolved out, and calcium silicate (2 CaO. SiO)2) It is difficult to dissolve.
S4, adding excessive alkali solution into the filtered supernatant, then carrying out centrifugal filtration, and drying the filter residue for 4-6 h at the temperature of 60-80 ℃.
S5, pumping organic wastewater into the reactor, adjusting the pH of the organic wastewater to 3.0-4.0, and adding H with the molar concentration of 0.1-0.5 mmol/L2O2And then adding the iron-aluminum oxide treated in the step (S4) into a reactor, wherein the adding amount of the slag is 1-10 g/L, reacting for a certain time, and treating the organic wastewater.
Preferably, in S3, the acid solution is one of acetic acid and oxalic acid having a pH of 5.0 to 6.0.
Preferably, the alkali solution in S4 is a solution of KOH or NaOH.
Example 1
The invention is carried out according to the following method:
s1, putting the ball milling beads, the slag and the sodium carbonate into a ball milling tank according to the weight ratio of 15: 1: 0.4, covering the ball milling tank with a cover, milling for 30min at the rotating speed of 550rpm, and crushing the slag.
S2, putting the ball-milled slag into a muffle furnace, and roasting for 2 hours at 800 ℃.
S3, taking out the cooled slag, putting the cooled slag into oxalic acid solution with the pH value of 5.0 at 80 ℃, stirring the solution for 60min by a stirrer, and filtering the solution, wherein sodium ferrite and sodium aluminate are dissolved out, and calcium silicate (2 CaO. SiO)2) It is difficult to dissolve.
And S4, adding excessive alkali solution into the filtered supernatant, then centrifugally filtering, and drying the filter residue for 6 hours at the temperature of 60 ℃.
S5, pumping 1L of 50ppm paracetamol into the reactorAdjusting pH of the organic wastewater to 4.0, adding H with molar concentration of 0.2mmol/L2O2Then, the iron-aluminum oxide treated in step (S4) is added into the reactor, the adding amount of the slag is 5g/L, and the treatment effect after 2 hours of reaction is shown in the following table:
TABLE 1 efficiency of Paracetamol removal
| Time/ |
0 | 10 | 30 | 60 | 120 |
| Removal Rate (%) | 0 | 13.4 | 57.5 | 95.6 | 97.7 |
Comparative example 1
The difference from the example 1 is that after the slag is ball-milled for 30min and crushed, the original domestic garbage incinerator slag is directly used (S5) as a catalyst, the wastewater degradation condition is the same as that of the comparative example 1, the comparative effect is shown in figure 1, and the method provided by the invention can greatly improve the catalytic effect of the slag.
According to the inventionThe technical principle is that sodium carbonate and iron and aluminum oxides in the domestic garbage incineration slag are easily generated into soluble sodium ferrite and sodium aluminate at high temperature, so that H is contained in the slag2O2The components with catalytic activity are extracted for subsequent treatment of organic wastewater.
Compared with the prior art, the method has the beneficial effects that:
1. the iron and aluminum oxides with catalytic activity in the domestic garbage incineration slag are extracted to be catalyzed H2O2The waste is treated by the waste and the waste is changed into valuable.
2. Avoids the use of expensive chemical reagents as iron and aluminum precursors in the traditional Fenton-like reaction, and the prepared catalyst has low cost and good catalytic effect.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (2)
1. Modified domestic waste incinerator slag for improving catalytic H2O2A method of treating organic wastewater comprising the steps of:
s1, putting the ball milling beads, the furnace slag and the sodium carbonate into a ball milling tank according to the weight ratio of 15-20: 1: 0.3-0.6, covering a cover, milling for 10-30 min at the speed of 550rpm, and crushing the furnace slag;
s2, placing the ball-milled slag into a muffle furnace, and roasting for 2 hours at 750-900 ℃;
s3, taking out the cooled furnace slag, putting the furnace slag into a weakly acidic solution at 70-80 ℃, stirring the furnace slag for 30-60 min by using a stirrer, and filtering the furnace slag, wherein the weakly acidic solution is one of acetic acid and oxalic acid with the pH value of 5.0-6.0;
s4, adding excessive alkali solution into the filtered supernatant, then carrying out centrifugal filtration, and drying the filter residue for 4-6 h at the temperature of 60-80 ℃;
s5, pumping organic wastewater into the reactor, adjusting the pH of the organic wastewater to 3.0-4.0, and adding H with the molar concentration of 0.1-0.5 mmol/L2O2And then adding the iron-aluminum oxide treated in the step S4 into a reactor, wherein the adding amount of the slag is 1-10 g/L, reacting for a certain time, and treating the organic wastewater.
2. The method of claim 1, wherein the alkali solution in S4 is a solution of KOH or NaOH.
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