CN106881349B - Preparation and use methods of PCBs contaminated soil in-situ remediation agent based on waste biomass - Google Patents
Preparation and use methods of PCBs contaminated soil in-situ remediation agent based on waste biomass Download PDFInfo
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- CN106881349B CN106881349B CN201710182821.5A CN201710182821A CN106881349B CN 106881349 B CN106881349 B CN 106881349B CN 201710182821 A CN201710182821 A CN 201710182821A CN 106881349 B CN106881349 B CN 106881349B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
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- B09C1/00—Reclamation of contaminated soil
- B09C1/10—Reclamation of contaminated soil microbiologically, biologically or by using enzymes
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
The invention combines the current situation that soil PCBs is seriously polluted and the quantity of waste biomass in China is huge, establishes a new process suitable for preparing an environment-friendly PCBs polluted soil in-situ remediation agent by taking the waste biomass as a raw material, and comprises the following steps: 1) mixing biomass, water and ferric salt, and then carrying out hydrothermal co-treatment to prepare iron-loaded hydrothermal carbon; 2) carrying out high-temperature heat treatment on the iron-loaded hydrothermal carbon to obtain the iron-loaded hydrothermal carbon. The method for preparing the PCBs polluted soil in-situ remediation agent by using the waste biomass as the carbon source has the advantages of simple preparation process, capability of quickly and efficiently dechlorinating and degrading PCBs in the soil, greenness, environmental friendliness, low price and the like.
Description
Technical Field
The invention relates to waste biomass treatment and disposal, belongs to a novel solid waste resource utilization technology in the field of environmental protection and comprehensive resource utilization, and is particularly suitable for high-added-value resource utilization of waste biomass such as huge straws.
Background
PCBs are typical Persistent Organic Pollutants (POPs), can enter animals and human bodies through accumulation, concentration and amplification of biological chains, and have induction effects on pathological changes and even canceration of skin, liver, gastrointestinal system, nervous system, reproductive system and immune system. Acute toxicity of PCBs is low, but human exposure to low dose environments for extended periods of time may lead to proliferative responses, endocrine disorders, hepatotoxicity, reproductive toxicity, and carcinogenesis. Social public hazards have developed in industrially developed countries and regions, such as: rice bran oil events occurred in kyushu county and taiwan of china, north japan. PCBs entering the environment are affected by weather, biological, hydrological, geological and other factors, and soil is one of the ultimate major storage sites. Due to the great potential hazard of PCBs, the repair technology of soil polluted by PCBs is more and more highly regarded worldwide. The existing repair method for soil polluted by PCBs mainly comprises biological in-situ repair and chemical pyrolysis repair. The bioremediation method has the problems that the biodegradation efficiency is not high due to the strong hydrophobicity of PCBs; in addition, biodegradation of high Cl substituted PCBs presents significant difficulties. The pyrolysis method, i.e., the high-temperature destruction method, mainly includes an incineration pyrolysis method, an arc pyrolysis method, an ultrasonic radiation method, a plasma arc method, a molten lead method, a molten aluminum method, and the like. The degradation destruction rate of the PCBs treated by the pyrolysis method can basically reach more than 99 percent, wherein the incineration method has wide treatment range and is particularly suitable for high-concentration polluted soil. However, the pyrolysis treatment cost is generally high, and the pyrolysis treatment method is basically not suitable for the treatment of low-concentration polluted soil. So far, a cheap and green in-situ remediation agent for soil polluted by PCBs is lacked. The method has important practical significance for converting the waste biomass into the carbonized functional material to repair and improve the polluted soil. The renewable waste biomass is used as the raw material to prepare the green and cheap PCBs polluted soil in-situ remediation agent, so that an effective high-added-value utilization technology is found for a large amount of waste biomass while the soil remediation efficiency is improved and the production cost of the soil remediation agent is reduced.
Disclosure of Invention
The invention aims at the current situations that the soil PCBs in China is seriously polluted, the existing soil PCBs polluted is low in remediation efficiency and expensive in cost, and the like, and combines the advantage of abundant waste biomass resources in China to establish a new process for preparing the in-situ remediation agent for the soil PCBs polluted by taking the waste biomass as a raw material. The specific process comprises the following steps: mixing the waste biomass with ferric acetate, carrying out hydrothermal treatment under certain conditions, and then carrying out high-temperature heat treatment on the carbonized solid product in an inert atmosphere.
A preparation method of an in-situ remediation agent for contaminated soil based on waste biomass PCBs is characterized by comprising the following steps: mixing the waste biomass, iron acetate and water, carrying out hydrothermal carbonization on the mixture to convert the mixture into iron-loaded hydrothermal carbon, and then carrying out high-temperature heat treatment on the iron-loaded hydrothermal carbon in an inert atmosphere to prepare the PCBs contaminated soil in-situ restoration agent.
The hydrothermal carbonization step comprises the steps of firstly mixing the waste biomass with ferric acetate, and carrying out hydrothermal carbonization treatment to prepare iron-loaded hydrothermal carbon, wherein the mass ratio of the dry basis mass of the waste biomass to the ferric acetate is 1:1-10: 1; the mass ratio of the waste biomass (dry basis) to the water is 1:5-1: 10.
In the step of hydrothermal carbonization treatment, the hydrothermal temperature is 180-230 ℃, and the hydrothermal treatment time is 30-90 min.
The iron-loaded hydrothermal carbon is generated to 500-800 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere, and the treatment time is 30-90 min.
The waste biomass is biomass waste such as straw, livestock and poultry manure and the like.
The in-situ remediation agent for the polluted soil based on the waste biomass PCBs is prepared by the method.
The obtained soil remediation agent can rapidly and efficiently degrade and dechlorinate PCBs in soil in situ. The preparation effect of the process is influenced by factors such as hydrothermal treatment temperature, hydrothermal treatment time, addition of iron acetate, high-temperature heat treatment conditions and the like.
The invention has the following advantages:
1) the biomass and the ferric acetate are creatively used for hydrothermal co-treatment, and the purposes of uniform loading of iron ions and high yield of hydrothermal carbon are achieved. The iron ions as the biomass expanding agent can effectively destroy the crystal structure in the cellulose in the biomass, so the carbonization process of the biomass can be accelerated by adding the iron ions. Meanwhile, abundant polar functional groups (such as phenolic hydroxyl, carboxyl, aldehyde group, lactone group and the like) are introduced on the surface of the hydrothermal carbon by hydrothermal treatment, and the polar functional groups are uniformly distributed on the surface of the hydrothermal carbon in an inner sphere coordination mode through iron ions under self-generated pressure, so that further condensation (alcoholic hydroxyl and aldehyde group), dehydration (such as hydroxyl, carboxyl and the like) and other reactions between the functional groups on the surface of the hydrothermal carbon are prevented, and the yield of the hydrothermal carbon is improved. In addition, the uniformly distributed iron ions also provide conditions for preparing uniformly-loaded zero-valent iron through the next heat treatment. Although there have been reports of preparing biochar-loaded zero-valent iron from waste biomass by pyrolysis carbonization with iron salt, polar functional groups on the surface of the pyrolyzed biochar are very rare due to the complete dehydration and decarbonylation reactions during pyrolysis. Therefore, the distribution of the zero-valent iron generated by reduction in the pyrolysis process on the surface of the pyrolytic carbon is very uneven, the size distribution range of the zero-valent iron is wide and mostly in the micrometer scale, and the degradation efficiency of PCBs is greatly reduced.
2) The mass mixing ratio of the waste biomass (dry basis) and the ferric acetate in the hydrothermal process is preferably 10:1-1:1, and the mass ratio of the waste biomass (dry basis) and the water is preferably 1:5-1: 10. The iron salt is preferably ferric acetate rather than ferric chloride, ferric sulfate and ferric nitrate to avoid environmental pollution. Too low water addition can cause incomplete biomass carbonization due to too low autogenous pressure of a hydrothermal reaction system, and too high water addition can cause great energy consumption in the hydrothermal treatment process and reduce the loading efficiency of iron ions on the surface of the hydrothermal carbon. The low addition amount of the iron acetate can cause limited zero-valent iron to be generated due to insufficient iron source, and the excessive addition amount of the iron source can cause physical adsorption of iron ions on the surface of the hydrothermal carbon to cause agglomeration of the zero-valent iron generated in the subsequent heat treatment process.
3) The temperature of the hydrothermal treatment is preferably between 180 and 230 degrees, and the treatment time is 30-90 min. Too low temperature and too short time can lead to undeveloped hydrothermal carbon pore structure and insufficient surface functional groups due to incomplete biomass carbonization reaction; too high a reaction temperature and too long a reaction time may result in too low a hydrothermal char yield, collapse of pore structure and exfoliation of surface functional groups due to excessive carbonization of the biomass, and aggravate hydrolysis of iron ions.
4) And (4) high-temperature heat treatment. The hydrothermal carbon heat treatment process generates reducing atmosphere (mainly H)2CO and amorphous high-activity carbon), and iron ions loaded on the surface of the hydrothermal carbon are reduced to zero-valent iron in situ in a reducing atmosphere (the generated zero-valent iron is between 6 and 8nm due to in-situ reduction, and the particle size distribution is very uniform); in addition, under the heat treatment condition, iron ions not only activate hydrothermal carbon but also catalyze the conversion of amorphous carbon to graphitic carbon in the reduction process, so that a high-graphitization porous carbon material uniformly loaded with zero-valent iron is prepared, and conditions are provided for improving the adsorption capacity of PCBs through the pi-pi bond effect of a benzene ring structure and a graphitization carbon structure in PCBs and further improving the dechlorination degradation efficiency.
5) The heat treatment temperature is preferably 500-800 ℃, and the treatment time is preferably 30-60 min. If the temperature is too low, the reduction of iron ions is not thorough due to insufficient reducing atmosphere generated by hydrothermal carbon heat treatment, and the graphitization degree of the prepared repairing agent is not high due to the unobvious iron catalysis; the excessive temperature and the excessive treatment time not only increase the energy consumption of the treatment process, but also cause the agglomeration of the zero-valent iron to reduce the activity of the zero-valent iron.
6) The prepared repairing agent is simple to use, and can realize efficient degradation of PCBs in soil after being physically mixed with the polluted soil.
The waste biomass in the invention is straw, livestock and poultry manure and the like, so that waste is changed into valuable, the production cost is saved, and the environmental pollution is reduced.
The invention is further described in the following with reference to the drawings and embodiments of the specification.
Drawings
FIG. 1 shows the micro-morphology of the PCBs contaminated soil in-situ remediation agent prepared from straw.
FIG. 2 is a schematic diagram of a production process flow of the in-situ remediation agent for soil polluted by waste biomass PCBs.
Detailed Description
The in-situ repair agent for the soil polluted by PCBs is prepared by using waste biomass such as plant branches, straws, livestock and poultry manure and the like. The main raw materials of the straw biomass utilized by the invention comprise corn stalks, corncobs, wheat straws, cotton stalks, branches, leaves, soybean stalks, straws, waste wood, sawdust and the like; the livestock and poultry manure mainly refers to pig manure, chicken manure, cow manure and the like.
Example 1
1. Preparation of the raw materials
Pulverizing corn stalk to less than 5 mm; PCBs contaminated soil is taken from a storage point of a waste capacitor, a soil sample is dried in a fume hood for 24 hours, leaves, plant roots, stones and the like in the soil sample are removed, and the soil sample is crushed and sieved by a 120-mesh sieve. The samples were stored in aluminum foil sample bags protected from light (chlorine content in soil 8.26% and all present as organochlorine).
2. Preparation of restorative
1) Mixing the crushed straws with ferric acetate, adding water, and uniformly stirring to prepare a mixed material, wherein the straw (dry basis) is prepared by mixing the crushed straws with the ferric acetate in a ratio of 5:1, mixing in a mass ratio; the mass ratio of the straw (dry basis) to the water is 1: 5.
2) Adding the mixed material into a hydrothermal reaction kettle, heating the reaction kettle to 200 ℃, and carrying out hydrothermal treatment for 60 minutes.
3) After cooling to room temperature, solid-liquid separation was carried out, and the obtained solid product was dried at 105 ℃ for 24 hours.
4) And carrying out high-temperature heat treatment on the dried solid product in the atmosphere of nitrogen. Heating to 600 deg.C at a rate of 5 deg.C/min and maintaining for 30 min;
5) and cooling to room temperature in the nitrogen atmosphere to obtain the PCBs contaminated soil in-situ restoration agent. The microstructure of the prepared repairing agent is shown in figure 1, and the repairing agent has a highly developed pore structure, and zero-valent iron with the size of about 7.5nm is uniformly loaded on the surface of a carbon material.
3. Degradation of PCBs in contaminated soil
1) PCBs contaminated soil samples are added with a certain amount of repairing agent (2% and 5%) and then are mechanically stirred for 1 hour to be fully mixed.
2) The well mixed soil was incubated in a biochemical incubator at 25 ℃ and 1g of soil samples were taken for analysis after fixed time intervals (10 days, 20 days, 30 days, 40 days and 50 days).
3) The soil samples were freeze-dried and Soxhlet extracted with 100mL of dichloromethane for 48 h. The extract was rotary evaporated, the extract was concentrated to 10mL on a rotary evaporator (0.02MPa), transferred to a 50mL pear-shaped flask, rotary evaporated again to about 1mL, and then 10mL n-hexane was added for solvent substitution to concentrate to about 1 mL.
4) Purifying the concentrated solution by a Florida silica gel chromatographic column, respectively eluting with 15mL of n-hexane and 70mL of dichloromethane/n-hexane (3:7, V/V) mixed solution, concentrating the second component eluent to about 1mL, transferring to a sample bottle, drying under a soft high-purity nitrogen flow, and carrying out GC-MS analysis with the constant volume of 1mL of chromatographically pure hexane.
The concentration of PCBs in the soil was determined by gas chromatography-mass spectrometry (Agilent 7890A/5975C equipped with HP-5 chromatography columns). The measurement conditions were analysis conditions: the initial temperature was 100 deg.C, ramped up to 210 deg.C at a ramp rate of 2 deg.C/min and held for 1 min.
The dechlorination rate of PCBs is calculated according to the following formula
Wherein T isClChloride ions generated after degradation of PCBs; nn is the number of monochloro to decachloro PCBs in the soil sample.
The dechlorination effect of PCBs in the contaminated soil is shown in Table 1.
Example 2
Except that straw is used as the raw material;
except for the step 1), mixing the straw (dry basis) and the ferric acetate in a mass ratio of 5:1 and the straw (dry basis) and the water in a mass ratio of 1:5 in the preparation process of the repairing agent; step 2), heating the reaction kettle to 200 ℃ and treating for 80 minutes; step 4) the same procedure as in example 1 was repeated, except that the thermochemical treatment was carried out at 700 ℃ for 60 minutes. The dechlorination effect of PCBs in the soil is shown in table 1.
Example 3
Except that the pig manure is used as the raw material;
in the preparation process of the repairing agent, except for the step 1), the mass ratio of the pig manure (dry basis) to the iron acetate is 5:2, and the mass ratio of the pig manure (dry basis) to the water is 1: 5; step 2), heating the reaction kettle to 220 ℃ and treating for 60 minutes; step 4) the same as in example 1 was repeated except that the heat treatment was carried out at 600 ℃ for 60 minutes.
The dechlorination effect of PCBs in the soil is shown in table 1.
Table 1 dechlorination of PCBs in contaminated soils.
As can be seen from the table 1, the repairing agent prepared by the invention can realize the rapid and efficient in-situ degradation and dechlorination of PCBs after being added into the soil polluted by PCBs, the dechlorination rate of PCBs is over 57 percent after 60 days, and the repairing agent is prepared by taking waste biomass as a raw material, so the repairing agent has the characteristics of environmental protection, low price and the like.
Claims (3)
1. A preparation method of a PCBs contaminated soil in-situ remediation agent based on waste biomass is characterized by comprising the following steps: mixing the waste biomass and ferric acetate, carrying out hydrothermal carbonization treatment to prepare iron-loaded hydrothermal carbon, and then carrying out heat treatment on the iron-loaded hydrothermal carbon in an inert atmosphere to prepare the PCBs contaminated soil in-situ remediation agent; the preparation method of the iron-loaded hydrothermal carbon comprises the steps of mixing waste biomass, ferric acetate and water, and carrying out hydrothermal carbonization treatment, wherein the mass ratio of the dry basis mass of the waste biomass to the ferric acetate is 1:1-10: 1; the mass ratio of the dry basis mass of the waste biomass to the water is 1:5-1: 10; in the hydrothermal carbonization treatment, the hydrothermal temperature is 180-230 ℃, and the hydrothermal treatment time is 30-90 min; carrying out heat treatment on the solid product after the hydrothermal carbonization in an inert atmosphere at the treatment temperature of 500-800 ℃ for 30-90 min; the waste biomass is straw or livestock and poultry manure.
2. The method for preparing the waste biomass-based PCBs contaminated soil in-situ remediation agent according to claim 1, wherein the PCBs contaminated soil in-situ remediation agent comprises: the prepared repairing agent is mixed with the polluted soil to achieve the aim of repairing the soil.
3. The PCBs contaminated soil in-situ remediation agent obtained by the preparation method of the waste biomass-based PCBs contaminated soil in-situ remediation agent of claim 1 or 2.
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| CN108752133A (en) * | 2018-06-26 | 2018-11-06 | 中国科学院生态环境研究中心 | A kind of preparation and its application of multifunction soil improver |
| CN109013693A (en) * | 2018-08-28 | 2018-12-18 | 上海大学 | The green restorative procedure of organic polluted soil |
| CN113842881B (en) * | 2021-09-28 | 2023-09-05 | 厦门大学嘉庚学院 | Oyster shell powder enhanced biochar for removing seawater culture water body micro-plastics and preparation method and application thereof |
| CN114871268A (en) * | 2022-05-17 | 2022-08-09 | 上海大学 | Method for restoring soil polluted by tetracycline antibiotics |
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