CN112525891A - Method for rapidly evaluating potential release risk of endogenous heavy metals in biomass charcoal - Google Patents
Method for rapidly evaluating potential release risk of endogenous heavy metals in biomass charcoal Download PDFInfo
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- 239000002028 Biomass Substances 0.000 title claims abstract description 135
- 239000003610 charcoal Substances 0.000 title claims abstract description 130
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 35
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 126
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 239000000706 filtrate Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 42
- 239000010949 copper Substances 0.000 claims description 18
- 229910052802 copper Inorganic materials 0.000 claims description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 16
- 239000011701 zinc Substances 0.000 claims description 14
- 229910052725 zinc Inorganic materials 0.000 claims description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 229910052785 arsenic Inorganic materials 0.000 claims description 10
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 9
- 229910052804 chromium Inorganic materials 0.000 claims description 9
- 239000011651 chromium Substances 0.000 claims description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 8
- 238000005374 membrane filtration Methods 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 239000012490 blank solution Substances 0.000 claims description 3
- 238000009616 inductively coupled plasma Methods 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000011156 evaluation Methods 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 19
- 229910052799 carbon Inorganic materials 0.000 description 19
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 210000003608 fece Anatomy 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000010871 livestock manure Substances 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 239000002689 soil Substances 0.000 description 6
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000000227 grinding Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000011437 continuous method Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
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- 206010021143 Hypoxia Diseases 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000003738 black carbon Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000002925 chemical effect Effects 0.000 description 1
- -1 chromium-arsenic hydrogen peroxide Chemical compound 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- OJSIAYFWYKWVKK-UHFFFAOYSA-N copper chromium(3+) Chemical compound [Cr+3].[Cu+2] OJSIAYFWYKWVKK-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
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- 231100000290 environmental risk assessment Toxicity 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000035558 fertility Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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Abstract
The invention relates to a method for rapidly evaluating potential release risk of endogenous heavy metals in biomass charcoal, and belongs to the technical field of environmental protection. The method comprises the following steps: mixing the ground biomass charcoal raw material with aqueous hydrogen peroxide, carrying out water bath and filtration, taking filtrate as a solution to be detected, determining the content of a certain heavy metal element in the solution to be detected, and calculating the potential release amount of a certain endogenous heavy metal of the biomass charcoal. The method disclosed by the invention has the advantages of convenience in operation, short reaction time and the like, and can efficiently realize the evaluation of the potential release risk of the heavy metal in the biomass charcoal.
Description
Technical Field
The invention relates to the technical field of environmental protection, in particular to a method for rapidly evaluating potential release risk of endogenous heavy metals in biomass charcoal.
Background
The biomass charcoal is a refractory, stable, highly aromatic and carbon-rich solid substance formed by slowly pyrolyzing and carbonizing a biomass raw material under the conditions of relatively low temperature and oxygen deficiency. The biomass carbon has larger specific surface area and pore structure, has more negative charges, strong ion exchange capacity and strong basicity, contains a large amount of functional groups such as phenolic hydroxyl, carboxyl, carbonyl and the like on the surface, and has wide application prospect in the aspects of carbon sequestration and emission reduction, soil improvement, fertility maintenance, crop product increase, microbial activity improvement, soil heavy metal remediation, organic pollution remediation and the like.
However, even if there are many advantages to returning biomass char to the field, the environmental risks that it creates need to be addressed. The raw materials for preparing the biomass charcoal are various in sources, and particularly, the raw materials for preparing the biomass charcoal, such as agricultural and forestry wastes, sludge, manure and the like, often contain a large amount of heavy metals. In the process of preparing the biomass charcoal, heavy metals are difficult to volatilize and can be remained in the biomass charcoal, so that the biomass charcoal is rich in heavy metal pollution elements. When the biomass charcoal is used for soil restoration and improvement, the biomass charcoal is subjected to physical, chemical and biological effects in the contact process with soil to generate an aging phenomenon, so that the characteristics of the biomass charcoal are changed, endogenous heavy metal elements can be released, and the soil environment is negatively affected. Therefore, the evaluation of the risk of potential release of endogenous heavy metal elements of biomass charcoal before use is particularly important.
The effectiveness and the release potential of the heavy metal in the biomass charcoal mainly depend on the occurrence form of the heavy metal in the biomass charcoal. The current BCR four-step continuous method and the Tessier five-step continuous method are important means for researching occurrence forms of heavy metals in biomass carbon, and have important significance for environmental risk assessment. However, the two continuous extraction methods have the disadvantages of more complicated operation steps, more intermediate transfer processes, long time consumption and the like. Therefore, a rapid and easy-to-operate method for evaluating the potential release risk of heavy metals in biomass charcoal is needed to be developed.
Disclosure of Invention
The invention aims to provide a method for rapidly evaluating the potential release risk of endogenous heavy metals in biomass charcoal. The method disclosed by the invention has the advantages of convenience in operation, short reaction time and the like, and can efficiently realize the evaluation of the potential release risk of the heavy metal in the biomass charcoal.
The invention provides a method for rapidly evaluating the potential release risk of certain endogenous heavy metal in biomass charcoal, which comprises the following steps:
mixing the ground biomass charcoal raw material with a hydrogen peroxide aqueous solution, carrying out water bath and filtration, taking filtrate as a solution to be detected, determining the content of a certain heavy metal element in the solution to be detected, and calculating the potential release amount of a certain endogenous heavy metal of the biomass charcoal, wherein the calculation formula of the potential release amount of the certain endogenous heavy metal of the biomass charcoal is as follows:
wherein Qx represents the potential release amount of a certain heavy metal element in the biomass charcoal, and the unit is mg/kg;
cx represents the measured content of a certain heavy metal element in the solution to be measured, and the unit is mu g/L;
c0 represents the content of a certain heavy metal element in the hydrogen peroxide blank solution without added biomass charcoal, and the unit is mu g/L;
v represents the dosage of the aqueous hydrogen peroxide solution, and the unit is mL;
m represents the using amount of the biomass charcoal, and the unit is g;
the higher the potential release amount of the endogenous heavy metal in the biomass charcoal, the higher the potential release risk of the endogenous heavy metal in the biomass charcoal.
Preferably, the heavy metals include arsenic, chromium, copper and zinc.
Preferably, the ground biomass charcoal raw material is further sieved before being mixed with the aqueous hydrogen peroxide solution, and the sieving condition is that the biomass charcoal raw material is sieved by 60-200 meshes.
Preferably, the hydrogen peroxide in the aqueous hydrogen peroxide solution is 3-8% by mass.
Preferably, the volume ratio of the biomass charcoal raw material to the aqueous hydrogen peroxide solution is 1 (100-500).
Preferably, the temperature of the water bath is 40-80 ℃.
Preferably, the time of the water bath is 2-24 h.
Preferably, the method further comprises cooling to 10-20 ℃ before filtering.
Preferably, the filtration conditions comprise membrane filtration using a 0.45 μm filter membrane.
Preferably, the content of the certain heavy metal element in the solution to be measured is measured by using an inductively coupled plasma spectrometer.
The invention provides a method for rapidly evaluating potential release risk of endogenous heavy metals in biomass charcoal. The method for rapidly evaluating the potential release risk of the endogenous heavy metal in the biomass charcoal is established, and has a good application prospect in the application of biomass charcoal in agricultural environment. The method has the advantages of convenient operation, short reaction time and the like.
Drawings
FIG. 1 is a graph showing the morphology of biomass charcoal before and after treatment with aqueous hydrogen peroxide solutions of different concentrations according to the present invention;
FIG. 2 is an electron microscope image of biomass charcoal before and after treatment with aqueous hydrogen peroxide solutions of different concentrations provided by the present invention;
FIG. 3 is a graph showing the carbon and nitrogen loss rate of biomass charcoal treated by aqueous hydrogen peroxide solutions of different concentrations according to the present invention;
FIG. 4 shows the potential release amount of heavy metals in biomass charcoal treated by aqueous hydrogen peroxide solution with different concentrations provided by the invention.
Detailed Description
The invention provides a method for rapidly evaluating the potential release risk of certain endogenous heavy metal in biomass charcoal, which comprises the following steps:
mixing the ground biomass charcoal raw material with a hydrogen peroxide aqueous solution, carrying out water bath and filtration, taking filtrate as a solution to be detected, determining the content of a certain heavy metal element in the solution to be detected, and calculating the potential release amount of a certain endogenous heavy metal of the biomass charcoal, wherein the calculation formula of the potential release amount of the certain endogenous heavy metal of the biomass charcoal is as follows:
wherein Qx represents the potential release amount of a certain heavy metal element in the biomass charcoal, and the unit is mg/kg;
cx represents the measured content of a certain heavy metal element in the solution to be measured, and the unit is mu g/L;
c0 represents the content of a certain heavy metal element in the hydrogen peroxide blank solution without added biomass charcoal, and the unit is mu g/L;
v represents the dosage of the aqueous hydrogen peroxide solution, and the unit is mL;
m represents the using amount of the biomass charcoal, and the unit is g;
the higher the potential release amount of the endogenous heavy metal in the biomass charcoal, the higher the potential release risk of the endogenous heavy metal in the biomass charcoal.
Fig. 1 is a morphology graph of biomass charcoal before and after treatment of aqueous hydrogen peroxide solutions with different concentrations, and it can be seen from fig. 1 that, with the increase of the hydrogen peroxide concentration (0-30%), black carbon in the biomass charcoal apparently disappears, carbon in biomass charcoal BC300 and BC500 prepared at low temperature is oxidized more obviously, and the oxidation resistance of BC700 is relatively high. Fig. 2 is an electron microscope image of biomass charcoal before and after the treatment of aqueous hydrogen peroxide solutions with different concentrations, and it can be seen from fig. 2 that the porosity is increased by high-temperature pyrolysis of low-temperature BC300 and high-temperature BC700 raw charcoal, and the surface of the biomass charcoal collapses when treated with 10% hydrogen peroxide.
In the present invention, the heavy metals preferably include arsenic, chromium, copper and zinc. The source of the biomass charcoal is not particularly limited in the present invention, and conventional biomass charcoal commercially available products well known to those skilled in the art may be used.
The method mixes the ground biomass charcoal raw material with aqueous hydrogen peroxide solution and carries out water bath. In the invention, the step of sieving the ground biomass charcoal raw material before mixing with the aqueous hydrogen peroxide solution preferably comprises sieving the raw material under a condition of sieving by a sieve of 60-200 meshes, and more preferably grinding the biomass charcoal by a sieve of 100 meshes. According to the invention, the release amount of the heavy metal can be rapidly evaluated by adopting a simulated oxidation mode, the risk of the heavy metal cannot be accurately reflected even if the hydrogen peroxide concentration is too high or too low, the toxicity of the heavy metal is related to the total amount of the heavy metal and is related to the biological effectiveness to a greater extent, and the operation of measuring the total amount and the form of the proper hydrogen peroxide aqueous solution is simple, convenient and rapid; for example, too high a concentration (> 12%) of aqueous hydrogen peroxide releases very little of the cationic heavy metals copper and zinc; the release amount is close to the maximum value when the concentration of the anionic chromium-arsenic hydrogen peroxide aqueous solution is about 8 percent; the release amount of BC300 copper is the highest at 3% of the hydrogen peroxide water solution, accounting for 84% of the total copper of BC300, and the release amount is very low at 30%, which cannot reflect the potential release capacity of the copper in soil. In the invention, the mass percentage of hydrogen peroxide in the aqueous hydrogen peroxide solution is preferably 3-8%, the setting of the aqueous hydrogen peroxide solution can more accurately reflect the potential maximum release amount of the endogenous heavy metal of the biomass charcoal, the hydrogen peroxide concentration is too low, the oxidation degree is low, and the endogenous heavy metal of the biomass charcoal cannot be completely released; the hydrogen peroxide concentration is too high, and the released heavy metal can generate insoluble metal oxide due to over oxidation, so that the potential release capacity cannot be accurately reflected, particularly cationic heavy metals such as copper and zinc. The method for preparing the aqueous hydrogen peroxide solution is not particularly limited, and the aqueous hydrogen peroxide solution is preferably prepared by diluting an aqueous hydrogen peroxide solution containing 30% by mass. In the invention, the volume ratio of the biomass charcoal raw material to the aqueous hydrogen peroxide solution is preferably 1 (100-500), more preferably 1: 400. the water bath provided by the invention has the function of accelerating the oxidation rate of the biomass charcoal. In the invention, the temperature of the water bath is preferably 40-80 ℃, and more preferably 60 ℃. In the invention, the time of the water bath is preferably 2-24 h, and more preferably 12 h. The limitation of the water bath temperature and time can obtain the relatively proper potential maximum release amount of the heavy metal in the biomass charcoal.
In the invention, cooling is preferably carried out after water bath, namely before filtration, and the cooling is preferably carried out to 10-20 ℃, and more preferably to 15 ℃.
After cooling, the invention performs filtration. In the present invention, the filtration conditions are preferably membrane filtration, and the membrane filtration preferably employs a 0.45 μm filter membrane. The suspended biomass charcoal particles can be removed by the filtering treatment, so that the test result is prevented from being influenced. Filtering to obtain oxidized biomass charcoal solid, and determining the loss rate of carbon and nitrogen in the biomass charcoal; the higher the loss rate of carbon and nitrogen in the biomass charcoal, the biomass charcoal is easily oxidized by the hydrogen peroxide solution, and the endogenous heavy metals in the biomass charcoal can be released into the environment along with the oxidation process.
After filtering, the method takes the filtrate as the solution to be detected, measures the content of certain heavy metal element in the solution to be detected, and calculates the potential release amount of certain endogenous heavy metal of the biomass carbon. In the present invention, the determination of the content of a certain heavy metal element in the solution to be measured is preferably performed by using an inductively coupled plasma spectrometer (ICP-MS).
According to the method, a biomass charcoal sample is ground and sieved, then a certain amount of hydrogen peroxide aqueous solution (1 (100-500)) is added, water bath treatment is carried out for 6-24 hours at the water temperature of 40-100 ℃ to obtain hydrogen peroxide treated biomass charcoal solution, membrane filtration treatment is carried out after the solution is cooled, and then ICP-MS is adopted to carry out heavy metal content detection on the solution to be detected. The method adopts conditions of aqueous hydrogen peroxide solution with specific concentration, solid-to-liquid ratio of biomass charcoal to hydrogen peroxide, water bath temperature, reaction time and the like, has the advantages of convenience in operation, short reaction time and the like, can save time, namely the oxidation time of 12h and 24h has no obvious difference on the release amount of heavy metals, and the potential release capacity of heavy metals in the biomass charcoal can be well evaluated by controlling the heating time to be 12 h.
The method for rapidly evaluating the potential release risk of the endogenous heavy metal in the biomass charcoal according to the present invention is further described in detail with reference to the following specific examples, and the technical solutions of the present invention include, but are not limited to, the following examples.
Example 1
Step a, grinding the pig manure biomass charcoal prepared under the pyrolysis temperature conditions of 300 ℃, 500 ℃ and 700 ℃ and sieving the ground pig manure biomass charcoal with a 100-mesh sieve for later use;
b, adding a certain amount of deionized water into 30 mass percent aqueous hydrogen peroxide solution in proportion to prepare 16 aqueous hydrogen peroxide solutions (0%, 0.5%, 1%, 2%, 3%, 4%, 6%, 8%, 10%, 12%, 15%, 21%, 24%, 27% and 30%) with different concentration gradients for later use;
step c, weighing 0.1000g of biomass charcoal sample (BC300/BC500/BC700) into a 50ml colorimetric tube, respectively adding 40ml of the hydrogen peroxide aqueous solution with different concentration gradients, and heating for 12h under the condition of water bath at 60 ℃ to obtain hydrogen peroxide biomass charcoal solutions with different concentrations;
d, after the hydrogen peroxide-treated biomass charcoal solution is cooled, performing membrane filtration treatment, then cleaning the residual solid for a plurality of times by using deionized water, and drying in an oven to constant weight to obtain different hydrogen peroxide-oxidized biomass charcoal solution to be detected and oxidized biomass charcoal solid;
and e, measuring the content of the heavy metal elements in the solution to be measured by adopting ICP-MS, and calculating the potential release amount of the heavy metal in the biomass charcoal prepared at different temperatures according to the formula (1). And simultaneously, an element analyzer is adopted to determine the loss rate of carbon and nitrogen in the pig manure biomass charcoal before and after oxidation. The test results obtained are shown in fig. 3 and 4.
FIG. 3 is a graph showing the carbon and nitrogen loss rates in biomass charcoal treated with aqueous hydrogen peroxide solutions of different concentrations, wherein A is the carbon loss rate in biomass charcoal treated with aqueous hydrogen peroxide solutions of different concentrations, and B is the nitrogen loss rate in biomass charcoal treated with aqueous hydrogen peroxide solutions of different concentrations. As can be seen from fig. 3, when the mass percentage concentration of the hydrogen peroxide aqueous solution of the carbon in the biomass charcoal prepared at 300 ℃ and 500 ℃ is from 0% to 8%, the loss rate of the carbon in the biomass charcoal rapidly increases to over 90%, then the loss rate of the carbon tends to be smooth along with the increase of the hydrogen peroxide concentration, and finally the loss rate of the carbon in the biomass charcoal prepared at 300 ℃ and 500 ℃ increases from the initial 3.0% and 21.0% to 94.2% and 95.0%; and the loss rate of carbon in the biomass charcoal prepared at 700 ℃ shows a gradually-decreasing trend along with the increase of the concentration of the hydrogen peroxide, and finally the loss rate of the carbon is increased from 31.1% to 87.7%. When the hydrogen peroxide concentration of nitrogen in the biomass charcoal prepared at 300 ℃ and 500 ℃ is from 0% to 8%, the loss rate of carbon in the biomass charcoal is rapidly increased to be more than 91%, then the loss rate of nitrogen tends to be smooth along with the increase of the hydrogen peroxide water solution concentration, and finally the loss rate of nitrogen in the biomass charcoal at 300 ℃ and 500 ℃ is increased to be 95.2% and 95.9% from the initial 3.7% and 10.1%; and the loss rate of nitrogen in the biomass charcoal prepared at 700 ℃ shows a gradually-decreasing trend along with the increase of the concentration of the hydrogen peroxide, and finally the loss rate of the nitrogen is increased from 53.1% to 91.5%.
FIG. 4 shows the potential release amount of heavy metals in biomass charcoal treated with aqueous hydrogen peroxide solutions of different concentrations, where A is the potential release amount of copper in biomass charcoal treated with aqueous hydrogen peroxide solutions of different concentrations, B is the potential release amount of zinc in biomass charcoal treated with aqueous hydrogen peroxide solutions of different concentrations, C is the potential release amount of chromium in biomass charcoal treated with aqueous hydrogen peroxide solutions of different concentrations, and D is the potential release amount of arsenic in biomass charcoal treated with aqueous hydrogen peroxide solutions of different concentrations. As can be seen from fig. 4, the release amounts of copper and zinc in the biomass charcoal are increased and then decreased along with the increase of the hydrogen peroxide concentration, the release rate of copper is higher than that of zinc, and the high-concentration hydrogen peroxide treatment can enable the copper and the zinc in the biomass charcoal to generate stable oxides, so that the concentration of copper and zinc ions in the solution is reduced; the release amount of chromium and arsenic in the biomass charcoal gradually increases and levels with the increase of the concentration of hydrogen peroxide. When the hydrogen peroxide concentration is 3%, 4% and 8%, the copper release amount in the pig manure biomass charcoal BC300, BC500 and BC700 reaches the highest, and respectively reaches 1062mg/kg, 684mg/kg and 259mg/kg, and respectively accounts for 84%, 42% and 13% of the total copper content in the corresponding biomass charcoal; when the hydrogen peroxide concentration is 3%, 2% and 8%, the release amount of zinc in the pig manure biomass charcoal BC300, BC500 and BC700 reaches the highest, and respectively reaches 4261mg/kg, 1825mg/kg and 1325mg/kg, and respectively accounts for 64%, 19% and 12% of the total zinc content in the corresponding biomass charcoal. At a hydrogen peroxide concentration of 8%, the release amounts of chromium in the pig manure biomass char BC300, BC500 and BC700 accounted for 81%, 85% and 66% of the maximum release amounts thereof, while the release amounts of arsenic accounted for 96%, 98% and 92% of the maximum release amounts thereof, respectively, indicating that the release amounts of chromium and arsenic were relatively high even at a lower concentration of 8%.
According to the result, when the mass percentage concentration of the hydrogen peroxide aqueous solution is 3-8%, the potential release capacity of the endogenous heavy metal in the biomass charcoal can be well evaluated.
Example 2
Step a, grinding the pig manure biomass charcoal prepared under the condition of 500 ℃ pyrolysis temperature and sieving the ground pig manure biomass charcoal with a 100-mesh sieve for later use;
b, weighing 0.1000g of biomass charcoal sample BC500 into a 50ml colorimetric tube, adding 40ml of 3% hydrogen peroxide aqueous solution, heating in a water bath at 60 ℃, setting the heating time to be 6h, 12h and 24h, and obtaining hydrogen peroxide oxidized biomass charcoal solutions processed by different water bath heating times;
and c, cooling the biomass charcoal solution to be treated by the hydrogen peroxide, performing membrane filtration treatment, measuring the content of heavy metal elements in the solution to be measured by adopting ICP-MS (inductively coupled plasma-mass spectrometry), and calculating the potential release amount of heavy metals in the biomass charcoal after the biomass charcoal is treated by the water bath heating time according to the formula (1).
TABLE 160 deg.C water bath heating for 6h, 12h and 24h, the release amount (mg/kg) of As, Cr, Cu and Zn in BC500
Time | Arsenic (As) | Chromium (III) | Copper (Cu) | Zinc |
6h | 1.31±0.12 | 3.61±0.03 | 466.43±23.52 | 1489.47±34.76 |
12h | 2.02±0.07 | 4.10±0.16 | 602.21±8.54 | 1641.38±2.48 |
24h | 2.12±0.08 | 4.23±0.08 | 589.78±12.25 | 1556.73±12.73 |
As can be seen from Table 1, the release amount of the endogenous metals arsenic and chromium in the biomass charcoal BC500 increases with the increase of the water bath heating time, and the release amount of the endogenous heavy metals copper and zinc in the BC500 reaches the maximum in the water bath 12 h. Therefore, when the mass percentage concentration of the aqueous hydrogen peroxide solution is 3%, the potential release capacity of the endogenous heavy metal in the biomass charcoal can be well evaluated by controlling the heating time to 12 hours at the water bath temperature of 60 ℃.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A method for rapidly evaluating the potential release risk of certain endogenous heavy metal in biomass charcoal comprises the following steps:
mixing the ground biomass charcoal raw material with a hydrogen peroxide aqueous solution, carrying out water bath and filtration, taking filtrate as a solution to be detected, determining the content of a certain heavy metal element in the solution to be detected, and calculating the potential release amount of a certain endogenous heavy metal of the biomass charcoal, wherein the calculation formula of the potential release amount of the certain endogenous heavy metal of the biomass charcoal is as follows:
wherein Qx represents the potential release amount of a certain heavy metal element in the biomass charcoal, and the unit is mg/kg;
cx represents the measured content of a certain heavy metal element in the solution to be measured, and the unit is mu g/L;
c0 represents the content of a certain heavy metal element in the hydrogen peroxide blank solution without added biomass charcoal, and the unit is mu g/L;
v represents the dosage of the aqueous hydrogen peroxide solution, and the unit is mL;
m represents the using amount of the biomass charcoal, and the unit is g;
the higher the potential release amount of the endogenous heavy metal in the biomass charcoal, the higher the potential release risk of the endogenous heavy metal in the biomass charcoal.
2. The method of claim 1, wherein the heavy metals comprise arsenic, chromium, copper and zinc.
3. The method according to claim 1, wherein the ground biomass charcoal raw material is further sieved before being mixed with the aqueous hydrogen peroxide solution, and the sieving condition is 60-200 meshes.
4. The method according to claim 1, wherein the hydrogen peroxide in the aqueous hydrogen peroxide solution is 3 to 8% by mass.
5. The method according to claim 1, wherein the volume ratio of the biomass charcoal raw material to the aqueous hydrogen peroxide solution is 1 (100-500).
6. The method of claim 1, wherein the temperature of the water bath is 40-80 ℃.
7. The method according to claim 1, wherein the time of the water bath is 2-24 h.
8. The method according to claim 1, further comprising cooling to 10-20 ℃ before the filtering.
9. The method of claim 1, wherein the filtration conditions comprise membrane filtration using a 0.45 μm membrane filter.
10. The method of claim 1, wherein the determination of the content of the heavy metal element in the solution to be tested is performed by using an inductively coupled plasma spectrometer.
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CN105928926A (en) * | 2016-04-19 | 2016-09-07 | 攀钢集团研究院有限公司 | Sample preparation method and detection method for water-soluble heavy metal elements in solid waste |
CN107880892A (en) * | 2017-11-08 | 2018-04-06 | 安徽省宗正农业科技开发有限公司 | A kind of modified biomass charcoal for reducing heavy metal in soil content |
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CN105928926A (en) * | 2016-04-19 | 2016-09-07 | 攀钢集团研究院有限公司 | Sample preparation method and detection method for water-soluble heavy metal elements in solid waste |
CN107880892A (en) * | 2017-11-08 | 2018-04-06 | 安徽省宗正农业科技开发有限公司 | A kind of modified biomass charcoal for reducing heavy metal in soil content |
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