CN112741979B - Dearsenic adsorbent in pyrolysis treatment process of urban garbage - Google Patents
Dearsenic adsorbent in pyrolysis treatment process of urban garbage Download PDFInfo
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- 238000000197 pyrolysis Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims abstract description 10
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- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 51
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 50
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- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 31
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- 238000001354 calcination Methods 0.000 claims description 9
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- 231100000111 LD50 Toxicity 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 1
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/33—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by chemical fixing the harmful substance, e.g. by chelation or complexation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/40—Inorganic substances
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2203/00—Aspects of processes for making harmful chemical substances harmless, or less harmful, by effecting chemical change in the substances
- A62D2203/02—Combined processes involving two or more distinct steps covered by groups A62D3/10 - A62D3/40
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Business, Economics & Management (AREA)
- Emergency Management (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a dearsenic adsorbent in the pyrolysis treatment process of urban garbage. The main components of the additive are nano copper oxide, kaolin and the like, wherein the nano copper oxide is used as a main active ingredient and can obviously enhance the chemical adsorption effect of the kaolin on arsenic. The prepared composite additive has the advantages of good thermal stability and high treatment efficiency, and experiments show that compared with other composite additives, the additive has higher adsorption capacity and integrates the traditional advantages of low price and easy obtainment of kaolin.
Description
Technical Field
The invention mainly reduces the content of arsenic waste gas in toxic waste gas generated by pyrolysis and gasification of municipal solid waste to achieve the aim of harmless treatment, and belongs to the field of solid waste treatment.
Background
The garbage has wide sources, most of the garbage is generated in daily life of people, and also comprises a part of dangerous waste which is polluted greatly and is difficult to degrade, and the dangerous waste both contain various heavy metals, such As lead Pb, cadmium Cd, chromium Cr, arsenic As, copper Cu, zinc Zn and the like. Wherein arsenic is a highly toxic substance, which can cause different degrees of damage to the heart and lung, respiration, immunity and other systems of people, and the semi-lethal dose of arsenite is 14 mg/kg. The pyrolysis of the garbage can inevitably cause the release of the heavy metals to harm human health.
At present, the treatment of arsenic pollution is divided into the removal of soil, water and gaseous arsenic. The gaseous arsenic is generally removed by adsorption or a combination of oxidation and adsorption. A great deal of research focuses on the trapping of arsenic and compounds thereof in coal-fired flue gas or oxidizing atmosphere, the solid adsorbent has wide application in removing heavy metals in the flue gas, and the raw materials of the adsorbent are cheap and easy to obtain, and have excellent adsorption effect and low secondary pollution. It is mainly used for trapping heavy metals with low toxicity and high relative content. The existence and conversion form of arsenic in a reducing atmosphere such as a garbage pyrolysis atmosphere and the effect of removing arsenic by using a solid adsorbent are relatively few, and the reaction principle is a blank in the field.
Pollutant control technologies generated by the garbage pyrolysis technology are also divided into three types, namely: before heat treatment, during heat treatment and tail gas treatment. The garbage components with high metal content are sorted out before heat treatment so as to reduce the sources of the garbage components, and the method can effectively recover some useful metals such as precious metals and the like, but needs manual sorting, consumes time and money, and has high treatment cost; the pyrolysis and gasification gas mostly adopts the mode of burning to retrieve its energy in the form of heat, and the tail gas processing apparatus that needs is similar with burning, and occupation of land is wide, the investment is high.
Kaolin is used as a natural adsorbent, has wide sources and low economic cost, but the pure kaolin has low capability of removing reduced arsenic and cannot meet the harmless requirement of removing arsenic poisons. In order to improve the adsorption effect, it is common to modify a solid adsorbent by physical and chemical means to obtain a high-efficiency solid adsorbent, but such methods are simpler and have limited improved removal effects.
Disclosure of Invention
The technical problem is as follows:
the technical scheme is as follows: in order to solve the technical problems, the invention provides a copper-based kaolin composite dearsenization adsorbent which can obviously enhance the retention of arsenic.
The preparation method of the dearsenic adsorbent in the pyrolysis treatment process of the town garbage comprises the following steps:
weighing copper acetate, sodium hydroxide and kaolin, wherein the copper acetate is fully dissolved in deionized water, and the sodium hydroxide is dissolved in 5% isopropanol solution. And (3) continuously stirring the copper solution in a magnetic stirrer, slowly adding an isopropanol solution of sodium hydroxide into the solution, fully stirring, and performing water bath aging. Centrifugally filtering the obtained copper hydroxide precipitate, washing with deionized water, washing with ethanol, drying in an oven, calcining in a muffle furnace, and grinding to obtain nano CuO powder; adding nano CuO powder into a 3% hexadecyl trimethyl ammonium bromide aqueous solution, and ultrasonically dispersing in an ultrasonic cell crusher to form CuO sol;
and step two, drying the kaolin in an oven, taking out the dried kaolin powder from the oven, and adding the kaolin powder into the nano CuO sol. And (4) carrying out ultrasonic treatment on the mixed solution on an ultrasonic cell crusher, taking out the mixed solution and stirring. After three times of filtration and washing, the mixture was dried in an oven. The obtained product is the nano CuO-kaolin nano composite additive.
Wherein:
the concentration of the isopropanol solution described in step one was 5%.
The temperature of the water bath in the first step is 55-80 ℃, and the aging time is 2-4 h.
The calcining temperature in the step one is 350-500 ℃, and the drying time is 1-2 h.
In the second step, the ratio of kaolin to copper ions is 50-100.
In the second step, the ultrasonic time is 12-20 min, and the ultrasonic frequency is 15-40 kHz.
In the second step, the stirring time is 10-25 min, the washing times are 3-5 times, and the drying temperature is 110-130 ℃.
The key steps of the invention are as follows:
the water bath temperature is 55-80 ℃, and the aging time is 2-4 h. The mass ratio of kaolin to copper ions is 50-100: 1. In the first step, the ultrasonic time is 5-10 min, and the ultrasonic frequency is 10-20 kHz. The stirring time is 10-25 min. The ultrasonic time is 12-20 min, and the ultrasonic frequency is 15-40 kHz. The stirring time is 10-25 min.
The action principle is as follows: CuO has strong reactivity to arsenic pollutants under the reducing condition, and can oxidize arsenic in the reducing state such as arsenic simple substance and the like into trivalent arsenic and pentavalent arsenic. The nano copper oxide is uniformly distributed on the surface of the kaolin, so that active sites for reaction with arsenic pollutants are increased. The nano CuO enters the pore canal on the surface of the kaolin, so that the physical adsorption of the kaolin to arsenic is converted into chemical adsorption, and the adsorption effect is enhanced.
The main purpose of using the isopropanol solution of NaOH is to increase the dissolution of copper acetate by utilizing the strong solubility of isopropanol to lipophilic substances so as to enable the copper acetate to fully react with NaOH. The CuO nano powder is added into a 3% hexadecyl trimethyl ammonium bromide aqueous solution to be ultrasonically dispersed to form CuO sol, and the hexadecyl trimethyl ammonium bromide is used as a cationic surfactant, so that the CuO sol has excellent properties of penetration, static resistance and the like and is uniformly covered on the surface of kaolin or enters pores of the kaolin. An organic solvent having the same effect as cetyltrimethyl ammonium bromide is also acceptable.
Has the advantages that:
1. the main raw material kaolin adopted by the invention is natural mineral, has wide sources, is produced in many areas of China, is cheap and easy to obtain, and has low economic cost. A small amount of nano copper oxide is organically combined with kaolin by means of ultrasound and the like, the prepared additive has obvious treatment advantages compared with a single-component additive, the adsorption capacity of the single-component additive can be achieved within a short time, the effect improved by the nano copper oxide modified kaolin is 2-3 times that of the original kaolin, and the limit value of the single-component additive is far exceeded. In addition, the content ratio of the nano copper oxide in the modified additive is low, and the advantages of high quality, low price and low cost are not lost.
2. The proportion of the nano copper oxide and the kaolin is adjusted to be proper, the nano copper oxide and the kaolin are not only uniformly distributed on the surface of the kaolin and increase the active adsorption sites of the composite additive, but also the increase of the nano particles causes partial particles to enter between the structural layers of the kaolin and enlarge the interlayer spacing, thereby increasing the physical adsorption.
3. Under the reducing condition, the kaolin loaded with the nano copper oxide has better thermal stability within the temperature range of 400-800 ℃. The increase of the temperature can improve the adsorption capacity of the composite additive to the reduction-state arsenic.
Drawings
FIG. 1 is a flow chart of the preparation of the dearsenic adsorbent of the present invention.
FIG. 2 is a scanning electron micrograph of the nano-copper oxide.
FIG. 3 shows the adsorption amounts of A, CuO, B, Fe in the composite additive and the comparison with several single-component additives2O3; C, CuO/Fe2O3; D, Kaolin; E, CuO/Kaolin。
FIG. 4 is a graph of the removal rate of the additive package and the pyrolysis of garbage.
Detailed Description
In the invention, the percentage of the isopropanol is volume percentage, and the percentage of the hexadecyl trimethyl ammonium bromide aqueous solution is mass volume percentage.
Example 1
(1) Preparing 0.2M copper acetate solution and 1M sodium hydroxide solution, adding 5% isopropanol, reacting fully, carrying out water bath at 65 ℃, aging for 2h, carrying out centrifugal filtration, washing with deionized water, precipitating in a muffle furnace, calcining for 2h at 400 ℃, and grinding to obtain the nano copper oxide powder. Pouring 0.1g of nano CuO (ultrasonic frequency 15 kHz) into a 3% hexadecyl trimethyl ammonium bromide aqueous solution, and ultrasonically dispersing the mixture in an ultrasonic cell crusher for 6min at the ultrasonic frequency 15kHz to form CuO sol;
(2) drying kaolin in an oven at 105 ℃, taking out 7g of dried kaolin powder from the oven, adding the kaolin powder into the nano CuO sol, performing ultrasonic treatment, taking out the mixed solution, stirring, filtering, washing and drying to obtain the de-arsenic adsorbent, wherein the mass ratio of the kaolin to the nano copper oxide is 70: 1; the ultrasonic time is 12min, and the ultrasonic frequency is 25 kHz; stirring for 15min, washing for 5 times, drying at 120 deg.C, and electron microscope detection results are shown in FIG. 2.
Embodiment 2 a dearsenic adsorbent in town refuse pyrolysis treatment process, which is characterized in that: the preparation method comprises the following steps:
(1) weighing copper acetate, sodium hydroxide and kaolin, wherein the copper acetate is fully dissolved in deionized water, and the sodium hydroxide is dissolved in 5% isopropanol solution; continuously stirring the copper solution, slowly adding an isopropanol solution of sodium hydroxide into the solution, fully stirring, and then aging in a water bath; centrifugally filtering the obtained copper hydroxide precipitate, washing with water, washing with ethanol, drying in an oven at 80 ℃, calcining, and grinding to obtain nano CuO powder; adding nano CuO powder into a 3% hexadecyl trimethyl ammonium bromide aqueous solution, and performing ultrasonic dispersion to form CuO sol; the temperature of the water bath is 55 ℃, and the aging time is 2 h; the drying time is 1 h; the calcining temperature is 350 ℃, the ultrasonic time is 5min, and the ultrasonic frequency is 10 kHz.
(2) Drying kaolin in an oven at 105 ℃, taking out the dried kaolin powder from the oven, adding the kaolin powder into the nano CuO sol, performing ultrasonic treatment, taking out the mixed solution, stirring, filtering, washing and drying to obtain the de-arsenic adsorbent. The mass ratio of the kaolin to the nano copper oxide is 50: 1; the ultrasonic time is 12min, and the ultrasonic frequency is 15 kHz; stirring for 10min, washing for 3 times, and drying at 110 deg.C.
Embodiment 3 a dearsenic adsorbent in town refuse pyrolysis treatment process, which is characterized in that: the preparation method comprises the following steps:
(1) weighing copper acetate, sodium hydroxide and kaolin, wherein the copper acetate is fully dissolved in deionized water, and the sodium hydroxide is dissolved in 5% isopropanol solution; continuously stirring the copper solution, slowly adding an isopropanol solution of sodium hydroxide into the solution, fully stirring, and then aging in a water bath; centrifugally filtering the obtained copper hydroxide precipitate, washing with water, washing with ethanol, drying in an oven at 80 ℃, calcining, and grinding to obtain nano CuO powder; adding nano CuO powder into a 3% hexadecyl trimethyl ammonium bromide aqueous solution, and performing ultrasonic dispersion to form CuO sol; the water bath temperature is 80 ℃, and the aging time is 4 hours; the drying time is 2 h; the calcining temperature is 500 ℃, the ultrasonic time is 10min, and the ultrasonic frequency is 20 kHz.
(2) Drying kaolin in an oven at 105 ℃, taking out the dried kaolin powder from the oven, adding the kaolin powder into the nano CuO sol, performing ultrasonic treatment, taking out the mixed solution, stirring, filtering, washing and drying to obtain the de-arsenic adsorbent. The mass ratio of the kaolin to the nano copper oxide is 100: 1; the ultrasonic time is 20min, and the ultrasonic frequency is 40 kHz; stirring for 25min, washing for 5 times, and drying at 130 deg.C.
Example 4
Comparison of the composite additive prepared in example 1 with several other single-component and multi-component additives for adsorption experiments (A, CuO; B, Fe)2O3; C, CuO/Fe2O3; D, Kaolin; E, CuO/Kaolin）。
In the experiment, arsenic is derived from arsine gas generated by a hydride generator, and the adsorption experiment is carried out on a fixed bed. The additives after the experiment are carried out on a graphite digestion furnace by adopting HCl-HNO3-HF-HClO4And (4) digesting the four strong acids, and performing an on-machine experiment of ICP-OES on the obtained clear liquid after digestion is completed.
The electric heating furnace heats the quartz tube with the adsorbent to the required temperature, and the carrier gas keeps the inertia in the tube in the processAnd (3) in the atmosphere, after the specified temperature is reached, opening the hydride generator, introducing arsenic-containing gas with fixed concentration, closing the hydride generator after the corresponding adsorption time, waiting for the instrument to be stably cooled, and taking out the adsorbed product to be tested. The carrier gas system mainly has N2Gas supply system composition for bearing CO required by experiment2CO and HCl, etc. The tail gas treatment device is formed by connecting scrubbing cylinders filled with 10% nitric acid in series.
The experimental conditions were pure nitrogen atmosphere, adsorption experiment was carried out at 500 deg.C, and the adsorption time of each additive was 30 min. The experimental result is shown in fig. 3, compared with the single-component additive, the multi-component composite additive has higher adsorption amount under the same condition, and the removal effect is obviously enhanced. The adsorption amounts of the kaolin (D) and the copper oxide (A) which are the individual components are respectively 3.55mg g-1And 3.84mg g-1And the adsorption amount of the additive (E) after the compounding is increased to 11.65mg g-1Therefore, the removal effect of the composite additive on the reduced arsenic is obviously enhanced compared with the single action of kaolin and nano copper oxide.
Example 5
The composite additive prepared in example 1, garbage powder and a fluidized bed are subjected to co-pyrolysis, and the carrier gas is N2The flow rate is 90L/min, the temperature range is 450-650 ℃, the adding ratio is 2% and 4%, and the experimental effect of the additive is obtained by measuring arsenic in the bottom slag by adopting the method in the embodiment 4; the result is shown in figure 4, and the adsorption effect is obviously enhanced at the temperature of 600-650 ℃. As the addition ratio increases, the retention rate also increases accordingly.
Claims (2)
1. A de-arsenic adsorbent in the pyrolysis treatment process of urban garbage is characterized in that: the preparation method comprises the following steps:
(1) weighing copper acetate, sodium hydroxide and kaolin, wherein the copper acetate is fully dissolved in water, and the sodium hydroxide is dissolved in 5% isopropanol solution; continuously stirring the copper solution, slowly adding an isopropanol solution of sodium hydroxide into the solution, fully stirring, and then aging in a water bath; centrifugally filtering the obtained copper hydroxide precipitate, washing with water, washing with ethanol, drying in an oven at 80 ℃, calcining, and grinding to obtain nano CuO powder; adding nano CuO powder into a 3% hexadecyl trimethyl ammonium bromide aqueous solution, and performing ultrasonic dispersion to form CuO sol;
(2) drying kaolin in an oven at 105 ℃, taking out the dried kaolin powder from the oven, adding the kaolin powder into the nano CuO sol, performing ultrasonic treatment, taking out the mixed solution, stirring, filtering, washing and drying to obtain the de-arsenic adsorbent;
wherein: the mass ratio of the kaolin to the nano copper oxide in the step (2) is 50-100: 1; the ultrasonic time is 12-20 min, and the ultrasonic frequency is 15-40 kHz; the stirring time is 10-25 min, the washing times are 3-5 times, and the drying temperature is 110-130 ℃.
2. The de-arsenic adsorbent of claim 1, wherein: the temperature of the water bath in the step (1) is 55-80 ℃, and the aging time is 2-4 h; the drying time is 1-2 h; the calcining temperature is 350-500 ℃, the ultrasonic time is 5-10 min, and the ultrasonic frequency is 10-20 kHz.
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