CN115301236A - Method for preparing iron mud-based catalytic active granular biochar through in-situ iron modification - Google Patents
Method for preparing iron mud-based catalytic active granular biochar through in-situ iron modification Download PDFInfo
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Abstract
The invention discloses a method for preparing iron mud-based catalytic active granular biochar by in-situ iron modification, and belongs to the fields of hazardous waste recycling treatment and functional material synthesis. The method comprises three stages of conditioning and granulating excess sludge, preparing biochar by high-temperature pyrolysis and activation, cleaning, purifying and drying to prepare finished granular carbon, and the like. The organisms prepared by the inventionCarbon having a surface area of 432.41 +/-33.54 square meters per gram (R) 2 Specific surface area of = 0.991) and rich micro-mesoporous structure, contains a large amount of iron catalytic active sites, has surface activation energy of 157 square meters per gram per K, can efficiently catalyze and activate sodium persulfate to degrade sulfonamide antibiotics, and realizes resource utilization of hazardous wastes. The result shows that 500ppm of biological carbon can absorb 19.22mg/L of sulfanilamide antibiotic, 100ppm of sodium persulfate is activated, and 29.31mg/L of sulfanilamide antibiotic (63.44%) can be catalytically degraded in 30min, which indicates that the iron mud based catalytic particle biological carbon prepared by the invention has obvious catalytic activity and can bring remarkable economic and environmental benefits.
Description
The technical field is as follows:
the invention belongs to the field of hazardous waste recycling treatment and functional material synthesis, and particularly belongs to the field of preparation of a functional catalytic material, namely preparation of catalytic active granular biochar from sludge with high iron content, by recycling biomass hazardous solid wastes.
Background art:
the treatment and recycling of excess sludge, especially the safe treatment and high-value treatment of sludge in metal-containing industry, are key targets of scientific research and technical attack. At present, there are four main technical routes for sludge treatment at home and abroad, which are as follows: the method comprises the following steps of deep sludge dewatering, landfill route, aerobic fermentation, land utilization route, anaerobic fermentation-land utilization route, sludge drying-incineration-ash landfill or building material utilization route. In the four routes, the sludge landfill and the sludge fermentation land utilization are simple treatment modes with low economic cost, and are important selection schemes in sludge treatment in China. However, due to the limitation of space and land utilization, new standards that prohibit the use of sludge as an organic fertilizer raw material are issued particularly in the ministry of agriculture, and industrial sewage sludge is listed after the national records of hazardous waste. The former three sludge treatment methods are greatly limited. The mode of burning the sludge and then burying the sludge saves land, but increases cost and has limited resource utilization degree of the sludge. Therefore, the search for a new sludge treatment and resource path scheme is of great significance to our current situation, especially under the era goal background of "carbon peak and carbon neutralization".
The biochar is a carbon-rich solid substance obtained by pyrolyzing biomass at high temperature under an anoxic condition, has a large specific surface area and a developed pore structure, and can be used for pollution remediation, soil improvement, carbon sequestration, climate change alleviation and the like. The sludge is used as biomass with rich carbon content and is a good raw material for preparing the biochar. In the prior art, there has been a related search. However, most of the sludge-based biochar preparation technologies take sludge generated by conventional municipal sewage treatment as a basic raw material, and the application effect and the preparation cost of modification by artificially adding iron salt are short. The invention CN112410047A discloses an iron-carrying sludge biochar and a preparation method and application thereof [1] The method is specially used for doping iron powder into the sludge, so that the manufacturing cost is increased, and the method is researched for producing the iron-containing biochar. More negative iron sludge biochar adopts a post-loading method, namely, the biochar is prepared and then is soaked in an iron salt solvent, and transition state iron salt is loaded through the action of chemical combination and an adhesive, so that the process is complex and the cost is high.
At present, fenton process is often used for treating pollutants difficult to degrade, and ferric salt flocculants such as polyferric sulfate are often used for dehydration conditioning in a plurality of municipal sewage treatment plants, so that the dehydrated sludge contains a large amount of high-valence iron, and the sludge generated in an industrial wastewater treatment system is classified as dangerous waste. Therefore, the dewatered sludge with high iron content is selected as a resource treatment object, on one hand, the harmless treatment of the sludge with iron content can be realized, on the other hand, the property of the transition metal of the dewatered sludge can be utilized to carry out in-situ modification to prepare a catalytic functional material, and then a novel pollutant removal method which changes waste into valuable and treats waste with waste is constructed.
The invention content is as follows:
the invention aims to provide a method for preparing iron-sludge-based catalytically active granular biochar by in-situ iron modification, and provides a scheme with high feasibility and high application value by aiming at the problem that the dewatered sludge with high iron content generated as hazardous waste in a sewage treatment plant which uses a ferric salt flocculating agent and contains a Fenton oxidation process in a large amount in sludge dewatering is difficult to treat and simultaneously has the practical contradiction that biomass and transition metal have the recycling potential.
In order to achieve the aim, the invention provides a method for preparing iron-sludge-based catalytically active granular biochar by in-situ iron modification, which mainly comprises three stages:
(1) The dewatered sludge tempering and granulation process includes: removing water, doping an activating agent and a modifying agent, mixing and granulating;
(2) The preparation of the biochar by high-temperature pyrolysis activation comprises the following steps: controlling the heating rate, the pyrolysis temperature and the pyrolysis time while taking ammonia as a reducing atmosphere;
(3) Cleaning, purifying and drying to prepare finished granular carbon, comprising the following steps: washing the carbon by hydrochloric acid and water at a specific temperature, and drying at a specific temperature.
Preferably, before the high-iron content dewatered sludge is subjected to tempering and granulation, the water content of the high-iron content dewatered sludge with the water content of about 80 percent is reduced to 60 to 70 percent. Wherein, the range of high iron content is 10% -27%, and the selection basis of controlling the water content at 60% -70% mainly includes two: firstly, the granulation is easy to form, the water discharged after the compression is less, and the granularity is higher; and secondly, the solubility of the doped particle activator is low, the form of the particle activator is easy to maintain, and certain help is provided for pore forming in the pyrolysis process. The selection of this parameter is experimentally compared.
Preferably, granular urea with the grain diameter of 20-200 microns is used as an activating agent and a modifying agent at the same time, and the doping ratio is 20-50mg/gTSS. The selection of urea is mainly based on three criteria: the urea is taken as nitrogenous organic matter and is easy to decompose into reducing gases such as ammonia gas and the like at high temperature in the pyrolysis temperature range, and can reduce high-valence iron contained in the urea at high temperature and play a role in nitrogen doping of the biochar; secondly, the granular urea has a certain pore-forming effect on the interior of the granular sludge in the early stage of pyrolysis, and in the process of decomposing and generating gas, gas overflows to further generate more microporous structures; thirdly, the doping amount of the urea is selected according to the electronic measurement of the chemical reaction of the content of the ferric iron in the ironCalculated (Fe) 3+ →Fe 0 ；N 3- →N 0 )。
Preferably, the diameter of the sludge is controlled to be 0.8-1.0cm during granulation. The selection basis of the sludge is as follows: firstly, the particles are contracted and reduced in volume by releasing moisture and volatile organic matters in the sludge carbonization process in the pyrolysis process, and the diameter range of the final finished product particles is 0.4-0.8cm; secondly, the particle volume control of the finished product carbon is mainly taken into consideration when the finished product carbon is used as an adsorptive particle-state heterogeneous catalyst and a bed adsorption material, and the granularity range of the biochar of the general heterogeneous catalyst is wide and is generally 50-5 multiplied by 10 3 Micron size; as a bed material, the granular material is convenient for layering and preventing loss, and the granularity is generally 0.5-5cm.
Preferably, when the biochar is prepared by high-temperature pyrolysis, ammonia gas is used as reducing atmosphere gas, nitrogen gas is used for removing air, and then the quartz tube is filled with the ammonia gas and is maintained for 30-60min.
Preferably, the parameters of the high-temperature pyrolysis are as follows: the heating rate is 3-5 ℃/min, the pyrolysis temperature is 900 ℃, the pyrolysis time is 60min, and after the pyrolysis is finished, the ammonia gas residue is discharged by adopting nitrogen before the crude biochar is taken out.
The temperature rise rate, the pyrolysis temperature and the pyrolysis time range in the pyrolysis process in the test process are respectively 1/3/5/10 ℃/min;400/600/900 ℃;30/60/120min. The parameters selected in the invention are obtained by optimizing a uniform design test taking the specific surface area of the biochar as a target. Compared with the conventional methane-hydrogen mixed gas, the ammonia generated by the urea has the properties of reducibility and nitrogen doping, and the nitrogen evacuation is mainly used for preventing the ammonia from causing a large amount of leakage to pollute the environment and causing health damage to operators.
Preferably, the washing temperature and the drying temperature are both maintained at 70 +/-5 ℃ during the purification to prepare the finished catalytic granular biochar.
Preferably, hydrochloric acid pickling refers to pickling with 2.5-3.5mol/L hydrochloric acid for 20-30min; the water washing means repeatedly washing with deionized water until the deionized water is neutral. The cleaning conditions are also selected according to two main criteria: firstly, the hydrochloric acid washing under the concentration has higher chemical dissolution effect on ash and other metal oxides in the biochar; secondly, the loss of iron element content in the biochar caused by washing with 3mol of hydrochloric acid for 30min is 17-25% at most, and too low concentration is not beneficial to washing out ash and too long pickling time causes efficiency reduction and more iron element loss. Therefore, the washing time is controlled to be 2.5-3.5mol/L and is not more than 30min, and the washing time has the best effect on maintaining the quality of the product.
The invention provides an iron mud-based catalytic active granular biochar prepared by in-situ iron modification, which is prepared by the preparation method.
The invention also provides a method for degrading sulfamethoxazole, which adopts the in-situ iron modification to prepare the mixture of the iron mud-based catalytic active particle biochar and sodium persulfate, and takes the mixture as a degradation reagent, preferably, the mass ratio of the sodium persulfate to the biochar is 1:5.
the scientific principle of the invention is that multistage pore forming is carried out on the sludge carbonization process by utilizing the process of producing ammonia gas by high-temperature decomposition and gasification of granular urea and the process of gasifying water, high-valence ferric salt existing in sludge is subjected to reduction reaction at high temperature by utilizing the reducibility of ammonia gas to generate low-valence ferric compounds, and chemical groups with catalytic functions such as nitrogen-iron bonds, carbon-nitrogen bonds and the like are formed by the reaction of ammonia gas, ferric salt, nitrogen and carbon at high temperature, so that in-situ iron modification in the preparation process of biochar is realized, and the granular biochar material with high-efficiency catalytic activity is prepared.
Compared with the prior art, the invention has the following beneficial effects:
1. the preparation method designed by the invention adopts an innovative in-situ iron modification method, adopts granular urea as an activating agent and a modifying agent at the same time, reduces high-valence iron in the biochar to be bivalent, univalent or even zero-valence by taking ammonia gas as a reducing atmosphere during preparation, and endows the biochar prepared by the invention with extremely high catalytic activity by combining rich pore structures.
2. The granular catalytic biochar designed by the invention has a certain stable structure, and can still maintain a higher granular state after being stirred and washed, so that the granular catalytic biochar has higher heterogeneous catalysis and potential of becoming a catalytic bed material.
3. The in-situ iron modified catalytic granular biochar prepared by the design method has higher specific surface area and higher catalytic activity than those in reported literatures [2,3] 。
4. The invention recycles the hazardous waste and endows the hazardous waste with higher added value to process other hazardous wastes, realizes the effects of changing waste into valuable, treating the waste with waste and treating the hazardous waste with danger, and has obvious economic benefit and environmental benefit.
5. The biochar prepared by the invention has the advantages of 432.41 +/-33.54 square meters per gram (R) 2 The specific surface area of = 0.991) and the abundant micro-mesoporous structures, contains a large number of iron catalytic active sites, has surface activation energy of 157 square meters per gram per K, can efficiently catalyze and activate sodium persulfate to degrade sulfonamides, resist organisms, and realize the resource utilization of hazardous wastes. The result shows that 500ppm of biological carbon can absorb 19.22mg/L of sulfonamide antibiotic, activate 100ppm of sodium persulfate, and catalyze and degrade 29.31mg/L (63.44%) of sulfonamide antibiotic within 30min, which indicates that the iron mud-based catalytic particle biological carbon prepared by the invention has obvious catalytic activity and can bring remarkable economic and environmental benefits.
Description of the drawings:
FIG. 1 is a process diagram of a system for preparing biochar according to the present invention.
FIG. 2 is a flowchart of the operation of the design method of the present invention.
FIG. 3 is a graph of samples of an iron-mud-based catalytic hierarchical porous granular biochar finished product and a control group prepared by the method.
FIG. 4 is an in-situ iron-modified hierarchical porous catalytic biochar apparent morphology (FSEM) diagram prepared by the method
FIG. 5 is an adsorption-desorption curve of biochar prepared in the present invention, wherein A is in-situ iron-modified FN-SBC biochar; b is blank group nitrogen atmosphere biochar CK-SBC.
FIG. 6 shows the pore size distribution and surface activation energy distribution of less than 100nm for catalytic multistage Kong Tieni biochar prepared by the method. Wherein a and a' are the pore size distribution and the surface activation energy of the FN-SBC prepared by doping urea and ammonia gas atmosphere; b and b' are the pore size distribution and the surface activation energy of the F-SBC activated by not doping urea in the ammonia atmosphere; and c' are the pore size distribution and the surface activation energy of the CK-SBC activated by not doping urea in the nitrogen atmosphere.
FIG. 7 is an XRD spectrum of in situ modified catalytic biochar FN-SBC (FSBC-urea) and a blank CK-SBC (FSBC-ori), wherein the crystal of iron compounds with low valence state is obviously increased.
FIG. 8 shows the effect of the in-situ iron modified catalytic particle prepared by the invention on catalyzing the degradation of Sulfamethoxazole (SMX) by activating sodium persulfate through FN-SBC.
The specific implementation mode is as follows:
the invention is further illustrated with reference to the following figures and examples. It should be understood that the specific embodiments described herein are for the purpose of illustrating the invention better and are not to be construed as limiting the invention.
< example 1>
The method for preparing the biochar with catalytic activity by pyrolyzing the dewatered iron-containing excess sludge comprises the following steps:
(1) The method comprises the steps of drying residual sludge (with iron content of 17.4%) with water content of 80% in a sewage treatment plant containing a Fenton process and an iron salt flocculant treatment process until the water content is 65%, doping urea particles (50 mg/gTSS), fully mixing uniformly, and preparing sludge particles of 0.8-1.0 cm.
(2) And carrying out pyrolysis activation in an ammonia atmosphere to prepare the biochar. And (3) beginning to remove air by using nitrogen, filling the quartz tube with ammonia gas, maintaining for 30min, heating to 900 ℃ at a heating rate of 5 ℃/min in an ammonia gas atmosphere in a program-controlled tube furnace, and maintaining pyrolysis for 60min. And cooling and taking out to obtain the pyrolytic biochar.
(3) Washing the purified biochar with acid, and drying to obtain the finished granular carbon. 3mol/L hydrochloric acid is used for leaching for 30min; repeatedly washing with deionized water at 70 deg.C to neutrality; drying in a 70 ℃ oven to prepare the in-situ iron modified catalytic activity iron mud based granular biochar.
Fig. 1 and fig. 2 show the process and operation flow chart of the preparation system for preparing the in-situ iron modified catalytic carbon.
The specific surface area, porosity and pore size of the biochar material prepared by the method are measured by adopting BET (BET). The BET specific surface area of the obtained biochar material is 432.41 +/-33.54 square meters per gram (R) 2 ＝0991), and the surface activation energy is 157 square meters per gram K.
Wherein, figure 5 is a nitrogen adsorption and desorption curve of the biochar at 300 ℃.
Fig. 3,4,6,7 shows the practical effects of the present invention from the aspects of the finished product state, the appearance (pore and iron element distribution), the promotion of the surface activation energy after iron modification, and the most obvious abundant crystal form of low valence state iron compounds in biochar prepared by in situ iron modification.
< example 2>
The method for degrading sulfamethoxazole by using the catalytic biochar activated sodium persulfate prepared by the invention comprises the following steps:
(1) Preparing 50mg/L sulfamethoxazole solution. Because sulfamethoxazole is extremely insoluble in water, when the sulfamethoxazole is prepared, the sulfamethoxazole can be subjected to ultrasonic treatment in a small amount of deionized water for 5min, and then the sulfamethoxazole is transferred into a volumetric flask and then stirred for ten hours by using a magnetic stirrer at the rotating speed of 800rpm/min, so that the sulfamethoxazole is ensured to be fully dissolved.
(2) The degradation experiments were performed in 150ml Erlenmeyer flasks. Firstly, 100ml of prepared sulfamethoxazole solution with the concentration of 50mg/L is taken and put into an erlenmeyer flask, and then 10mg of sodium persulfate (namely, the concentration of the sodium persulfate is 100 mg/L) and 50mg of biochar (namely, the concentration of the biochar is 500 mg/L) are simultaneously added into the erlenmeyer flask.
(3) The reaction was stirred with a magnetic stirrer at 200rpm/min, and 1 mL was sampled every ten minutes, filtered through a 0.22 micron filter head and applied to a brown vial. The content of SMX was quantitatively analyzed by HPLC within 24 h.
The result of high performance liquid chromatography sample measurement shows that the biochar material prepared by the method can activate sodium persulfate to degrade sulfamethoxazole, the degradation effect is 63.44% in 30min, the degradation content is 29.31mg/L, and the specific degradation efficiency is 117.24mg/g/h.
Comparative example 1
The comparative example is that the catalytic active charcoal prepared by the invention can be used for removing sulfamethoxazole by single adsorption, and the specific steps are as follows:
(1) The degradation experiments were carried out in 150ml Erlenmeyer flasks. Firstly, 100ml of prepared sulfamethoxazole solution with the concentration of 50mg/L is taken and put into an erlenmeyer flask, and then 50mg of biochar (namely the biochar concentration is 500 mg/L) is added into the erlenmeyer flask.
(2) The reaction was stirred with a magnetic stirrer at 200rpm/min, and 1 mL was sampled every ten minutes, filtered through a 0.22 micron filter tip, and applied to a brown sample vial. The content of SMX was quantitatively analyzed by HPLC within 24 h.
The result of high performance liquid chromatography sample detection shows that the sulfamethoxazole is degraded by using the biochar only, the effect is that the sulfamethoxazole is degraded by 39.49% in 30min, the adsorption capacity is 19.22mg/L, the specific adsorption rate is 76.88mg/g/h, although the adsorption is strong, the removal effect of the biochar is far away from the catalytic activation of sodium persulfate.
Comparative example 2
Comparative example 2 is a method for degrading sulfamethoxazole solution by adopting sodium persulfate alone, which comprises the following specific steps:
(1) The degradation experiments were carried out in 150ml Erlenmeyer flasks. 100ml of sulfamethoxazole solution with the concentration of 50mg/L is taken out and put into an erlenmeyer flask, and 10mg of sodium persulfate (namely the concentration of the sodium persulfate is 100 mg/L) is added into the erlenmeyer flask.
(2) The reaction was stirred with a magnetic stirrer at 200rpm/min, and 1 mL was sampled every ten minutes, filtered through a 0.22 micron filter tip, and applied to a brown sample vial. The content of SMX was quantitatively analyzed by HPLC within 24 h.
The result of the high performance liquid chromatography sample testing is that the sulfamethoxazole is degraded by sodium persulfate, and the effect is only 8.37% in 30 min. The degradation effect is much less than that of example 1.
FIG. 8 is a degradation curve of sulfamethoxazole degraded by sodium persulfate activated by biochar material in example 2 and its comparative example.
According to example 2, comparative examples 1 and 2, it is demonstrated that the invention relates to the synergistic effect of the biochar material activating sodium persulfate to degrade sulfamethoxazole.
The foregoing is a further detailed description of the invention in connection with specific preferred embodiments and it is not intended to limit the invention to the specific embodiments described. For those skilled in the art to which the invention pertains, numerous simple deductions or substitutions may be made without departing from the spirit of the invention, which shall be deemed to belong to the scope of the invention.
Reference documents:
[1] shao Yingying, li Zhaoyi, licong, xu Bin, zhang Weiyi, shao Yanqiu, zhu Ying, an iron-carrying sludge biochar and a preparation method and application thereof [ P ]. Shandong province: CN112410047A,2021-02-26.
[2] Shen Min research on red mud modified sludge biochar activated peroxymonosulfate degraded sulfamethoxazole [ D ] Huazhong university of science and technology, 2020.
[3] Sang Rui, meng Xianrong, xu Wei, schweilin, research on the degradation of naphthalene in water by activated sodium persulfate with sludge-based biochar [ J ] modern chemical engineering: 1-14[2022-06-05].
Claims (9)
1. A method for preparing iron mud base catalytic active particle biochar by in-situ iron modification mainly comprises three stages:
(1) High-iron content dewatered sludge tempering and granulation, comprising: removing water, doping an activating agent and a modifying agent, mixing and granulating;
(2) Preparing biochar by high-temperature pyrolysis activation, comprising the following steps: controlling the heating rate, the pyrolysis temperature and the pyrolysis time while taking ammonia as a reduction atmosphere;
(3) Cleaning, purifying and drying to prepare finished granular carbon, comprising the following steps: washing the carbon by hydrochloric acid and water at a specific temperature, and drying at a specific temperature.
2. The method for preparing the iron sludge-based catalytically active granular biochar by in-situ iron modification according to claim 1, wherein the method comprises the following steps: the range of the iron content of the high iron content is 10-27%, and the water content of the high iron content dewatered sludge with the water content of about 80% is reduced to 60-70%.
3. The method for preparing the iron sludge-based catalytically active granular biochar by in-situ iron modification according to claim 1, wherein the method comprises the following steps: granular urea with the grain diameter of 20-200 microns is used as an activating agent and a modifying agent at the same time, and the doping ratio is 20-50mg/gTSS.
4. The method for preparing the iron sludge-based catalytically active granular biochar by in-situ iron modification according to claim 1, wherein the method comprises the following steps: the diameter of the sludge grain is controlled to be 0.8-1.0cm during granulation.
5. The method for preparing the iron sludge-based catalytically active granular biochar by in-situ iron modification according to claim 1, wherein the method comprises the following steps: when the biochar is prepared by high-temperature pyrolysis, ammonia gas is used as reducing atmosphere gas, nitrogen gas is used for removing air, then the quartz tube is filled with the ammonia gas, and the ammonia gas is maintained for 30-60min.
6. The method for preparing the iron-sludge-based catalytically active granular biochar by in-situ iron modification according to claim 1, wherein the method comprises the following steps: the parameters of the high-temperature pyrolysis are as follows: the heating rate is 3-5 ℃/min, the pyrolysis temperature is 900 ℃, the pyrolysis time is 60min, and after pyrolysis is finished, nitrogen is adopted to evacuate residual ammonia before the crude biochar is taken out.
7. The method for preparing the iron sludge-based catalytically active granular biochar by in-situ iron modification according to claim 1, wherein the method comprises the following steps: the temperature of water washing and the temperature of drying are both maintained at 70 +/-5 ℃.
8. The method for preparing the iron sludge-based catalytically active granular biochar by in-situ iron modification according to claim 1, wherein the method comprises the following steps: hydrochloric acid pickling refers to slowly mixing and pickling 2.5-3.5mol/L hydrochloric acid for 20-30min; the water washing means repeatedly washing with deionized water until the deionized water is neutral.
9. An in-situ iron modification method for preparing iron mud-based catalytic active granular biochar is characterized by comprising the following steps: prepared by the preparation method of any one of claims 1 to 9.
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