CN113698058A - Sludge pretreatment method based on sulfoporphyrin iron catalyst Fenton system - Google Patents
Sludge pretreatment method based on sulfoporphyrin iron catalyst Fenton system Download PDFInfo
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Abstract
The invention discloses a sludge pretreatment method based on a sulfonatoporphyrin iron catalyst Fenton-like system, which comprises the following steps of: mixing the sulfonic group porphyrin iron catalyst, methanol and hydrogen peroxide solution, stirring, mixing the obtained mixed solution with sludge, and performing hydrolysis treatment to complete the pretreatment of the sludge. According to the sludge pretreatment method based on the sulfoporphyrin iron catalyst Fenton system, the sulfoporphyrin iron catalyst, methanol and hydrogen peroxide solution are mixed and stirred to generate mixed liquid containing high-valence iron species, and then the mixed liquid is mixed with sludge, and the sludge is effectively treated by using the high-valence iron species.
Description
Technical Field
The invention belongs to the technical field of sludge treatment, and relates to a sludge pretreatment method based on a sulfono porphyrin iron catalyst Fenton-like system.
Background
The fenton system is one of typical advanced oxidation technologies widely proven to promote sludge hydrolysis, and is a system in which ferrous ions activate hydrogen peroxide to generate hydroxyl radicals, and the radicals with strong oxidizing property are exchanged with electrons of extracellular polymers, so that the extracellular polymers are rapidly decomposed. The oxidation potential of the hydroxyl free radical is 2.7-2.8V, which is much higher than that of hydrogen peroxide (1.76V), and the hydroxyl free radical is a core substance for promoting the hydrolysis of sludge in a Fenton system. The fenton system is mainly divided into the following processes: 1) reacting ferrous ions with hydrogen peroxide to generate hydroxyl radicals and ferric ions; 2) reacting the iron ions with hydrogen peroxide to generate ferrous ions and peroxy radicals; 3) the newly generated ferrous ions further react with hydrogen peroxide to generate more hydroxyl radicals, and the generation of the hydroxyl radicals is accompanied with the circulation process of the ferric ions and the ferrous ions. However, the conventional fenton system for sludge pretreatment has the following disadvantages: 1) the pH of the sludge is usually about 7, and the iron ions and the ferrous ions in the fenton system need to maintain the ionic form in a strong acid environment, so in order to rapidly separate the iron ions and the ferrous ions from the solution in the form of hydroxide, a large amount of acidic reagent needs to be added to control the pH of the fenton reaction to be between 2 and 3, which greatly limits the application of the fenton system in the sludge. 2) The TS and VS of the sludge are high, and the hydrolysis of extracellular polymers and microbial cell walls is difficult, so that the input hydrogen peroxide is consumed by the sludge before contacting ferrous ions, so that the hydrolysis capacity of the existing Fenton system for the sludge is very limited, and the sludge pretreatment by using the Fenton system needs high hydrogen peroxide dosage. 3) The circulation of ferric ions and ferrous ions can be affected by the concentration of the two ions, and the accumulation of the ferric ions makes insufficient ferrous ions to activate hydrogen peroxide, so that the generation of hydroxyl radicals is slow, and the oxidation capacity of a Fenton system is reduced.
In the improved technical scheme provided by researchers, the Fenton-like system is a coupled Fenton system which combines variable valence metal ions such as iron ions, copper ions, chromium ions, manganese ions and the like with oxidants such as hydrogen peroxide and the like to generate hydroxyl radicals, the reaction process is similar to that of the Fenton system, and the coupled Fenton system is derived on the basis of the hydroxyl radicals by using auxiliary modes such as electricity, light, microwaves, ultrasound and the like to improve the degradation capability of the Fenton system. In addition, tetraphenylporphyrin ferric chloride (hereinafter referred to as ferriporphyrin) is a biomimetic enzyme taking cytochrome P450 as a prototype, is a unique structure formed by wrapping central iron ions with a porphin skeleton, and has high specific catalytic activity, so that various oxidants can be catalyzed to generate different free radicals and active species. Unlike the traditional fenton system, ferriporphyrin catalyzes the formation of higher valence ferrite species from hydrogen peroxide with a higher oxidation potential than hydroxyl radicals. At present, a fenton-like system formed by metalloporphyrin is used for catalyzing and degrading a homogeneous and single system such as trichlorophenol, lignin, printing and dyeing wastewater and the like, but the research on complex objects such as sludge is rarely carried out.
The production of high valence ferrite species from hydrogen peroxide catalyzed by ferriporphyrin requires three processes: hydroxyl replaces chloride ions, hydrogen peroxide coordinates, and oxygen-oxygen bond heterolysis, then high-valence ferrite acts on a sludge substrate, and the rapid hydrolysis of extracellular polymers is realized through electron transfer. However, in the course of practical research by the present inventors, it was found that the sludge pretreated by the ferriporphyrin-hydrogen peroxide fenton system still has several disadvantages: 1) the high solid property of the sludge has negative effects on the reagent diffusion and mass transfer efficiency of a metalloporphyrin Fenton system, so that the coordination of hydroxyl substituted chloride ions and hydrogen peroxide is hindered, and the oxygen-oxygen bond heterolysis process is not facilitated to occur; 2) the sludge system has the characteristics of complexity and variability, and is not beneficial to the generation of an oxygen-oxygen bond heterolysis process, so that sufficient high-valence ferrite species are difficult to stably generate, and the existing metalloporphyrin Fenton system is difficult to realize effective hydrolysis of the sludge and the subsequent resource utilization of the sludge is difficult to realize. Therefore, aiming at the defects and difficulties in the existing ferriporphyrin-hydrogen peroxide Fenton system, the invention aims to obtain the sludge pretreatment method which has the advantages of low catalyst and oxidant dosage, mild reaction conditions, high treatment efficiency, good treatment effect and good adaptability, and has very important significance for realizing efficient hydrolysis of sludge.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a sludge pretreatment method based on a sulfonatoporphyrin iron catalyst Fenton system, which has the advantages of low catalyst and oxidant consumption, mild reaction conditions, high treatment efficiency, good treatment effect and good adaptability.
In order to solve the technical problems, the invention adopts the technical scheme that:
a sludge pretreatment method based on a sulfonatoporphyrin iron catalyst Fenton system comprises the following steps:
s1, mixing the sulfonated iron porphyrin catalyst, methanol and a hydrogen peroxide solution, and stirring to obtain a mixed solution;
and S2, mixing the mixed liquid obtained in the step S1 with sludge for hydrolysis treatment, and finishing the pretreatment of the sludge.
The sludge pretreatment method based on the sulfoporphyrin iron catalyst Fenton system is further improved, wherein the dosage of the sulfoporphyrin iron catalyst is 5-80 mg of sulfoporphyrin iron catalyst added in each liter of sludge.
In the sludge pretreatment method based on the sulfoporphyrin iron catalyst Fenton system, the sulfoporphyrin iron catalyst is tetra (4-sulfophenyl) porphyrin iron chloride.
In the method for pretreating sludge based on the sulfoporphyrin iron catalyst fenton-like system, the tetra (4-sulfophenyl) porphyrin iron chloride is prepared from tetra (4-sulfophenyl) porphyrin and ferrous chloride; the preparation method of the tetra (4-sulfophenyl) porphyrin iron chloride comprises the following steps: mixing tetra (4-sulfophenyl) porphyrin, ferrous chloride and N, N-dimethylformamide, heating and refluxing at 153-200 ℃, adding acetone, separating out a solid, and filtering to obtain a crude tetra (4-sulfophenyl) porphyrin ferric chloride product; performing column chromatography on the crude tetra (4-sulfophenyl) porphyrin iron chloride product by adopting dichloromethane, collecting a color band corresponding to the tetra (4-sulfophenyl) porphyrin iron chloride, and removing the dichloromethane to obtain the tetra (4-sulfophenyl) porphyrin iron chloride.
The sludge pretreatment method based on the sulfoporphyrin iron catalyst Fenton system is further improved, wherein the molar ratio of the tetra (4-sulfophenyl) porphyrin to the ferrous chloride is 0.2-1: 1; the ratio of the tetra (4-sulfophenyl) porphyrin to the N, N-dimethylformamide is 0.1 mmol: 10 mL; the refluxing time is 2.5-3.5 h.
In the method for pretreating sludge based on the sulfoporphyrin iron catalyst Fenton system, the tetra (4-sulfophenyl) porphyrin is prepared from tetraphenylporphyrin and concentrated sulfuric acid; the preparation method of the tetra (4-sulfophenyl) porphyrin comprises the following steps: adding tetraphenylporphyrin into concentrated sulfuric acid, heating to 100-120 ℃, reacting for 2.5-4 h, cooling, adjusting the pH value to 8-9, heating and concentrating, placing in ice water for cooling, and filtering to obtain filtrate and filter cake; removing sodium sulfate in the filtrate and the filter cake, collecting the concentrated solution, and drying to obtain a crude product; dissolving the crude product in methanol, adding acetone, stirring to separate out a precipitate, filtering to obtain a purple solid, repeating the operation for three times, collecting the solid, and drying to obtain tetra (4-sulfophenyl) porphyrin; the ratio of the tetraphenylporphyrin to the concentrated sulfuric acid is 500 mg: 10 mL; the volume ratio of the methanol to the acetone is 1-10: 1-20.
The sludge pretreatment method based on the sulfoporphyrin iron catalyst Fenton system is further improved, wherein the using amount of the methanol is 3.6-20 mL of methanol added in each liter of sludge; the dosage of the hydrogen peroxide solution is 10 mL-50 mL of hydrogen peroxide solution added into each liter of sludge; the mass concentration of the hydrogen peroxide solution is 30%.
The sludge pretreatment method based on the sulfoporphyrin iron catalyst Fenton-like system is further improved, wherein the sludge is activated sludge generated in a sewage treatment plant; the TSS in the sludge is 25 g/L-45 g/L.
In the above method for pretreating sludge based on the sulfoporphyrin iron catalyst fenton-like system, in step S1, the stirring is performed at 25-35 ℃; the stirring time is 0.5-3 h.
In the above method for pretreating sludge based on the sulfoporphyrin iron catalyst fenton-like system, the hydrolysis treatment is performed at a rotation speed of 100 rpm to 200 rpm in step S2; the hydrolysis treatment is carried out at the temperature of 25-35 ℃; the time of the hydrolysis treatment is 1-5 h; after the hydrolysis treatment is finished, centrifuging and filtering a product obtained after the hydrolysis treatment; the rotating speed of the centrifugation is 8000 rpm; the filtration adopts a filter membrane with the pore diameter of 0.45 mu m.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides a sludge pretreatment method based on a sulfoporphyrin iron catalyst Fenton-like system. The sulfonic group porphyrin iron catalyst adopted in the invention is a water-soluble catalyst which can be dissolved in water solution, and meanwhile, the sulfonic group porphyrin iron catalyst dissolved in the water solution can be ionized, in particular to H which is ionized into free state by hydrogen connected with sulfonic group+Therefore, the addition of the sulfonic group porphyrin iron catalyst can reduce the pH value of an aqueous solution system, and further, hydrogen peroxide is used in the system with lower pH valueThe solution is an oxidant, methanol is a cocatalyst, the sulfonic acid group porphyrin iron catalyst is activated, the sulfonic acid group porphyrin iron catalyst is heterolytic in the activation process to generate a high-valence iron species (Fe IV = O) with double-bond oxygen, the high-valence iron species is an active intermediate with strong oxidizing property, meanwhile, the high-valence iron species (Fe IV = O) with double-bond oxygen generated in the activation process can also obviously increase the oxidation-reduction potential of the system, and the two advantages are both beneficial to realizing effective hydrolysis of sludge; on the basis, the mixed liquid containing the high-valence iron species (Fe IV = O) is mixed with the sludge, so that the high-valence iron species (Fe IV = O) can be rapidly contacted with a sludge substrate and react, the substrate in the sludge can be rapidly converted into soluble organic matters (such as protein and carbohydrate), the effective hydrolysis of the sludge is realized, and the subsequent resource utilization effect of the sludge is favorably improved; more importantly, in the hydrolysis system, the product of high-valence iron species (Fe IV = O) acting on the sludge substrate and losing electrons and double bond oxygen can be recombined with negatively charged chloride ions in the system and regenerated into the sulfoporphyrin iron catalyst, so that the sulfoporphyrin iron catalyst fenton system can be continuously utilized to carry out circulating hydrolysis on the sludge, the efficient sludge hydrolysis can be ensured, and the consumption of raw materials (such as catalyst and oxidant) can be further reduced, so that the treatment cost is lower. Compared with the traditional Fenton and Fenton-like systems, when the Fenton-like system based on the sulfoporphyrin iron catalyst is used for treating sludge, the dosage of the sulfoporphyrin iron catalyst and hydrogen peroxide is greatly reduced, wherein the dosage of the sulfoporphyrin iron catalyst and the hydrogen peroxide is 0.25 mg/g TSS and 0.19 mL/g TSS in sequence according to the TSS in the sludge; in conventional Fenton and Fenton-like systems, hydrogen peroxide and metal cations are generally used in amounts greater than 50 mg/g TSS. In addition, compared with the traditional Fenton and Fenton-like systems, when the Fenton-like system based on the iron sulfoporphyrin catalyst is used for treating sludge, the iron sulfoporphyrin catalyst is a water-soluble catalyst and has a pH adjusting function, and meanwhile, the iron sulfoporphyrin catalyst is a bionic enzyme and can be used for treating sludge at the optimal temperature of the enzymeThe catalyst shows higher catalytic activity in a temperature range (such as 30-40 ℃), so that the sludge is hydrolyzed at the temperature of 30-40 ℃ (the reaction condition is mild), which is beneficial to greatly reducing the treatment energy consumption, and the pH of the sludge does not need to be adjusted in the treatment process because the sulfoporphyrin iron catalyst can be converted into active species with strong oxidizing property and the reaction condition is mild. The pH of the sludge needs to be adjusted in the conventional process, but for bulky sludge substrates, pH adjustment is difficult and the amount of acid and base required is high. The invention relates to a sludge pretreatment method based on a sulfoporphyrin iron catalyst Fenton system, which comprises the steps of mixing and stirring a sulfoporphyrin iron catalyst, methanol and a hydrogen peroxide solution to generate a mixed solution containing high-valence iron species (Fe IV = O), and further mixing the mixed solution with sludge, wherein the sludge is effectively treated by utilizing the high-valence iron species (Fe IV = O).
(2) In the invention, 5-80 mg of the sulfonic group porphyrin iron catalyst is added into each liter of sludge by optimizing the dosage of the sulfonic group porphyrin iron catalyst, so that the hydrolysis performance of the sludge is effectively improved, and the ammonia nitrogen content can be controlled at a proper concentration, because: under the dosage, the sulfoporphyrin iron Fenton system obviously improves soluble protein and carbohydrate (total sugar) in the sludge, and because the protein and the carbohydrate account for more than 70 percent of total organic matters in the sludge and are main components of the sludge, the improvement of the two organic matters can fully indicate that the hydrolysis efficiency of the sludge is effectively improved. However, if the usage amount of the sulfonated iron porphyrin catalyst is too large, the content of anaerobic digestion inhibitors such as ammonia nitrogen and the like is increased, which is not favorable for subsequent resource utilization, and the examples show that: after the hydrolysis is completed, the active species with strong oxidizing property can also continuously decompose the dissolved small molecular organic matters into an ionic form with smaller molecular weight, such as ammonia nitrogen. In the invention, the effective effect can be ensured by optimizing the dosage of the methanol to be 3.6 mL-20 mL of methanol added in each liter of sludgeThe dissolved catalyst can avoid secondary pollution to the maximum extent, because: in the fenton-like system, the main function of methanol as a promoter is to help hydrogen peroxide coordinate on the catalyst, and the function is indispensable. On one hand, the solubility of methanol to water-soluble tetra (4-sulfophenyl) porphyrin iron chloride is limited, and the catalyst cannot be completely dissolved due to the excessively low methanol dosage, so that the catalyst diffusion is influenced, and the process of substituting hydroxyl for chloride ions is hindered. On the other hand, methanol is an organic substance, which may cause secondary pollution, so the dosage should not be too high, and waste can be avoided. In the invention, by optimizing the dosage of the hydrogen peroxide solution to 10-50 mL of the hydrogen peroxide solution added in each liter of sludge, the excessive hydrogen peroxide and the sufficient coordination can be ensured, and no waste is caused because: theoretically, the mass ratio of catalyst to oxidant (hydrogen peroxide) in the hydrogen peroxide complexation reaction is about 10:1, and if a density of 1.11g/cm is used3The theoretical amount of the hydrogen peroxide solution corresponding to 5-80 mg of the catalyst is 1.5-24 mL calculated by the hydrogen peroxide solution with the mass concentration of 30%, namely the hydrogen peroxide solution is not lower than the dosage under an ideal condition, but the hydrogen peroxide must be excessive in actual operation to ensure sufficient coordination, and in addition, the limiting factors in the actual operation also require the increase of the amount of the hydrogen peroxide, such as factors of natural decomposition of the hydrogen peroxide, uneven coordination opportunities, interference of other reagents and the like existing in the reaction, the hydrogen peroxide in the system is consumed, so that the content of an oxidant in the system is low, and sufficient oxidation active substances cannot be provided.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
Fig. 1 is a flow chart of a sludge pretreatment process based on a sulfonatoporphyrin iron catalyst fenton-like system in example 1 of the present invention.
FIG. 2 is a diagram showing the action mechanism of the sulfoporphyrin iron catalyst Fenton-like system of the present invention.
FIG. 3 is a graph showing the effect of the concentration change of soluble organic substances after the sulfonated iron porphyrin catalyst is used for treating sludge under different conditions in example 1 of the present invention.
FIG. 4 is a graph showing the effect of the change in the protein concentration after the sludge treatment with different types of catalysts (FeTSPPCl, FeTAPPCl, FeTPPCl, TSPP, MnTSPPCl) in example 1 of the present invention.
FIG. 5 is a graph showing the effect of the change in the concentration of the carbonized compound after the sludge treatment with different types of catalysts (FeTSPPCl, FeTAPPCl, FeTPPCl, TSPP, MnTSPPCl) in example 1 of the present invention.
FIG. 6 is a graph showing the effect of the change in the ammonia nitrogen concentration after the sludge treatment by the different types of catalysts (FeTSPPCl, FeTAPPCl, FeTPPCl, TSPP, MnTSPPCl) in example 1 of the present invention.
FIG. 7 is a graph showing the effect of the concentration change of soluble organics after the iron sulfoporphyrin catalyst (FeTSPPCl) is used for treating sludge under different types of promoters in example 1 of the present invention.
FIG. 8 is a graph showing the effect of the concentration change of soluble organic substances after the sulfonated iron porphyrin catalyst is used for treating sludge under different adding modes in example 1 of the invention.
FIG. 9 is a graph showing the effect of pH change after sludge treatment with iron sulfoporphyrin (FeTSPPCl) catalyst under different dosages in example 2 of the present invention.
FIG. 10 is a graph showing the effect of conductivity change of sludge treated with iron sulfoporphyrin (FeTSPPCl) catalyst under different dosages in example 2 of the present invention.
FIG. 11 is a graph showing the effect of the change in the concentration of proteins after the sludge is treated with iron sulfoporphyrin (FeTSPPCl) catalyst under different dosage conditions in example 2 of the present invention.
FIG. 12 is a graph showing the effect of the change in the concentration of carbonized compounds after sludge treatment with iron sulfoporphyrin (FeTSPPCl) catalyst under different dosages in example 2 of the present invention.
FIG. 13 is a graph showing the effect of changes in the ammonia nitrogen concentration after sludge treatment with iron sulfoporphyrin (FeTSPPCl) catalyst under different dosages in example 2 of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
The materials and equipment used in the following examples are commercially available; unless otherwise specified, the data used in the present invention are the average of three or more parallel tests.
Example 1
A sludge pretreatment method based on a sulfoporphyrin iron catalyst Fenton system is shown in a process flow diagram of figure 1 and comprises the following steps:
s1, preparing a 1 g/L aqueous solution of a sulfoporphyrin iron catalyst (tetra (4-sulfophenyl) porphyrin iron chloride, FeTSPPCl), placing 1mL into a reactor, sequentially adding 0.36 mL of anhydrous methanol and 2.5 mL of a 30% hydrogen peroxide solution into the reactor, stirring, and specifically placing the reactor into a 30 ℃ oscillator for full oscillation reaction for 3 hours to obtain a mixed solution.
S2, adding 100mL of activated sludge (TSS =40.39 g/L, pH = 6.98) into the reactor filled with the mixed liquid in the step S1 for hydrolysis treatment, specifically, using a sealing film to bind the mouth of the reactor, simultaneously placing the reactor in a constant-temperature shaking incubator at 30 ℃ and 150 rpm for culturing for 5h, after that, centrifuging the obtained product at 8000 rpm, filtering the obtained filtrate by using a filter membrane with the pore diameter of 0.45 μm, and finishing the pretreatment of the sludge. In the invention, the sealing film is a breathable film, so that on one hand, the overflow of a sample in the processes of violent oxidation reaction and vibration stirring can be prevented, and on the other hand, the good breathability can control the anaerobic bacteria not to generate a methanogenesis process, so that carbon is separated from a system, and the detection of the hydrolysis effect is influenced.
In this example, the sulfonic acid group porphyrin iron catalyst (tetra (4-sulfophenyl) porphyrin iron chloride, FeTSPPCl) prepared by DMF method includes the following steps:
(1) preparation of tetra (4-sulfophenyl) porphyrin
(1.1) sulfonation: in a 50mL single-neck flat-bottomed flask, 500 mg (0.814 mmol) of Tetraphenylporphyrin (TPP) was dissolved in 10mL of concentrated sulfuric acid, and the solution was put in an oil bathThe reaction mixture was heated to 120 ℃ with stirring, and the reaction mixture was allowed to react continuously at a constant temperature for 4 hours, cooled to room temperature, and then carefully poured into 50mL of ice-water. In the step, one-SO is respectively introduced into four meso-position benzene rings of TPP3H, the reaction is greatly influenced by time and temperature, and the target molecule can be obtained only by strictly controlling the reaction conditions. Due to TSPPS-H4Is very soluble in water, and can be used for preparing TSPP-H by adding water4The ice water is used for preventing concentrated sulfuric acid from releasing heat when meeting water. In summary, TSPP-H generated at this time4Dissolved in 50mL of water, the impurities are mainly SO which is not completely reacted4 2-And TPP (non-dissolved state). The structural formula of the TSPP prepared in the step is as follows:
(1.2) removal of SO4 2-: after the step (1.1) is finished, adjusting the pH value to 8-9 by using a sodium hydroxide concentrated solution and a sodium bicarbonate diluted solution, removing part of the solvent by rotary evaporation until the solution is concentrated to about 20mL, continuously cooling by using ice water, and filtering by using a Buchner funnel with qualitative filter paper to remove sodium sulfate. In this step, Na is introduced+Can be reacted with SO4 2-React to Na2SO4The pH is adjusted to be alkaline so that Na is present+Overdose, and prevention of H2SO4Reaction with methanol in the subsequent step to form (CH)3)2SO4、CH3OSO2OH and other organic impurities. Concentrating to saturate the solution, adding Na at low temperature2SO4Na is more easily separated out from the solution2SO4·10H2O crystal, filtering to remove part of Na2SO4·10H2O and water-insoluble TPP. The TSPP is still dissolved in water, and the impurity is dissolved Na2SO4. After this step, TSPP-H4Has been converted into TSPP-Na4。
(1.3) removal of sodium sulfate: after completion of step (1.2), the filter cake was washed with 50mL of methanol ("cake" designation filter paper for sodium carbonate accumulation upon filtrationThe substance on the filter paper (the main components are sodium sulfate solid (light yellow) to be filtered and residual porphyrin compound (purple) which have solubility relations that the sodium sulfate is not dissolved in the methanol, the porphyrin compound is easily dissolved in the methanol, the process that the filter cake is changed from purple to light yellow, namely the process that the porphyrin is transferred to the filter paper, and the sodium sulfate is remained on the filter paper) is changed to light yellow. To the filtrate (the "filtrate" was a methanol solution containing a porphyrin compound as a main component and a small amount of sodium sulfate as an impurity) was added 100mL of methanol, and sodium sulfate was precipitated and removed by filtration. The filtrate was dried (rotary evaporation, as above, which was used to remove the solvent methanol) and dissolved in 200mL of methanol, and the solution was filtered again to remove a small amount of sodium sulfate. Concentrating the filtrate (the concentrated filtrate refers to the filtrate after rotary evaporation, wherein a large amount of solvent is lost, the porphyrin compound is viscous liquid, but methanol still remains), and drying the filtrate at 120 ℃ for 12 hours by using an oven to obtain a crude product. In this step, the TSPP remaining on the filter residue after washing with methanol is transferred as far as possible to the filtrate and the procedure is repeated until Na has been reached2SO4Completely separated out. At this point the TSPP is dissolved in methanol and the impurity level is low (e.g. partially incompletely reacted organic compounds).
(1.4) purification: after the step (1.3) is finished, the crude product is dissolved in 20mL hot methanol, then 200mL acetone is added, stirring is carried out to separate out a precipitate, a Buchner funnel with qualitative filter paper is used for filtering to obtain a purple solid, the operation is repeated for three times, and the obtained solid is dried in an oven at 120 ℃ for 12 hours to obtain tetra (4-sulfophenyl) porphyrin (hereinafter referred to as TSPP)4"S" means a sulfonic acid group, "4" means the number of sulfonic acid groups, and the subscript "4" may not be labeled) as a pure product. In this step, the TSPP and a small amount of organic impurities are all dissolved by a plurality of operations and then the TSPP is extracted by acetone, and if the operations are not performed, the purification effect is not good, because most of the organic impurities are o-, m-, and p-sodium sulfonate-based porphyrins which do not react completely, and the solubility is similar to that of the target product, so that the purification is difficult.
(2) TSPP (TSPP)4(0.2 mmol) and FeCl2·4H2O（1mmol）Adding into 20mL of N, N-Dimethylformamide (DMF), refluxing at 200 ℃ for 3.5h, cooling to room temperature, directly adding 50mL of acetone, separating out a solid, and filtering to obtain a crude product of tetra (4-sulfophenyl) metalloporphyrin. And finally, performing column chromatography by using dichloromethane, collecting a specific color band, and evaporating dichloromethane to obtain FeTSPPCl solid.
The structural formula of FeTSPPCl is as follows:
control group: FeTSPPCl was not added, and other conditions were the same.
Initial group: the "FeTSPPCl, hydrogen peroxide solution and anhydrous methanol" were replaced with 2.86mL of water, and the other conditions were the same.
The content of soluble organic matter in the filtrate obtained from each group was measured, and TSS and VSS of the solid sample obtained after centrifugation were measured, and the results are shown in tables 1 and 2.
TABLE 1 content variation of soluble protein, carbohydrate, ammonia nitrogen in sludge under different treatment conditions
TABLE 2 change in the removal rate of organic substances from sludge under different treatment conditions
Note: in Table 1, example 1 was 1mL of FeTSPPCl +0.36 mL of methanol +2.5 mL of 30% hydrogen peroxide +100 mL of sludge control group was 0.36 mL of methanol +2.5 mL of 30% hydrogen peroxide +100 mL of sludge; initial group 2.86mL water +100 mL sludge storage 4oC。
As can be seen from tables 1 and 2, compared with the control group, the content of soluble organic matters (protein, carbohydrate, ammonia nitrogen) in the activated sludge treated by the FeTSPPCl fenton system is respectively increased by 239%, 118% and 39%, and the improvement effect is very obvious. Meanwhile, after the treatment of a FeTSPPCl Fenton system, the removal rate of organic matters in the sludge is higher, and the organic matters in the sludge can be more effectively removed.
FIG. 2 is a diagram showing the action mechanism of the sulfoporphyrin iron catalyst Fenton-like system of the present invention. As can be seen from fig. 2, in the process of the first step, chlorine bonded to the central trivalent iron is replaced by hydroxyl in the alcohol solution, and the removed chlorine is dissociated in the form of ions in the solution. In the second process, the oxidant represented by hydrogen peroxide replaces the hydroxyl in the first process, the central ferric iron of the iron porphyrin is combined with one oxygen atom in the hydrogen peroxide, and the removed hydroxyl returns to the alcohol solution. The processes (c) and (c) are carried out selectively, the course of which depends on the pH, the type of metalloporphyrin and the concentration of alcohol (solvent polarity): the homolytic process, the O-O bond of the hydrogen peroxide is directly broken, and the product is 1 mol of hydroxyl radical and 1 mol of porphyrin group with positive charge; thirdly, the process is the core of the Fenton-like system, hydrogen peroxide firstly removes one hydrogen atom and then generates O-O bond fracture, and the fracture mode is called as heterolysis. The removed hydroxyl group is combined with hydrogen atom to generate a molecule of water, and the porphyrin group is converted into a high-valence iron species with double-bond oxygen, which is an active intermediate with strong oxidizing property. H of heterolytic cracking removal+The pH of the solution was lowered, yielding "Fe iv = O" with a significant rise in the redox potential. However, in the process (iv), after the hydrogen peroxide is coordinated on the catalyst, the oxygen-oxygen bond of the hydrogen peroxide is directly broken, and the obtained products are hydroxyl radicals (i.e. the traditional fenton oxidation species, because the sludge contains valence-variable metal ions, the radical can be generated by directly adding the hydrogen peroxide into the sludge) and porphin radicals (also called porphyrin radicals, and has little meaning to the sludge hydrolysis) with weak oxidizability and positive charges, so that the effect of generating the homolysis (the process (iv)) is similar to the effect of the hydroxyl radicals (directly adding the hydrogen peroxide). Therefore, the improvement of the treatment effect of the Fenton-like system is to make the reaction tend to heterolysis (process c), and meanwhile, under the condition that the porphyrin type is not changed, the pH is mainly influenced by the pH and the polarity of the solvent, and on the premise that the methanol dosage is reduced as much as possible, the pH is a key factorLowering the pH may make the heterolytic process more likely to occur. In the process, high-valence ferrite species acts on a sludge substrate and loses electrons and double bond oxygen, and the product is combined with chloride ions with negative electricity to regenerate iron porphyrin so as to complete catalytic reaction ring closure. Therefore, in order to enable the Fenton system to act on sludge, an alcohol solution is needed as a cocatalyst to induce the process II, and the reaction is beneficial to heterolysis by controlling conditions.
In order to verify the necessity of various reagents in the system, a group of experiments are designed in the invention, the sludge is treated under different conditions by taking FeTSPPCl as a catalyst (the difference is shown in figure 3, and other conditions are the same as those in example 1), and the experimental results are shown in figure 3.
FIG. 3 is a graph showing the effect of the concentration change of soluble organic substances after the sulfonated iron porphyrin catalyst is used for treating sludge under different conditions in example 1 of the present invention. As can be seen from FIG. 3, methanol alone had no effect on sludge hydrolysis. On the other hand, since the sludge itself contains a plurality of valence-variable metal ions, the sludge can generate a fenton reaction to generate hydroxyl radicals only after the addition of hydrogen peroxide, and a certain hydrolysis effect is exhibited. The result of adding only one of metalloporphyrin and methanol to hydrogen peroxide is similar to that of hydrogen peroxide alone, and is also the same as that of hydroxyl radical. Only when metalloporphyrin, methanol and hydrogen peroxide coexist, Fe IV = O can be generated, and the sludge hydrolysis effect is greatly improved, because the oxidizing property of the Fe IV = O is higher than that of hydroxyl radicals, the sludge hydrolysis degree is higher.
On the basis of the fenton-like system, different kinds of porphyrin compounds are tested, the influence of the central metal type of the metalloporphyrin skeleton and the hydrophilic group on the axial ligand on the homolytic and heterolytic selectivity is mainly considered, specifically, amino ferriporphyrin (fetapp hcl), fat-soluble ferriporphyrin (fettpcl) without hydrophilic group, porphyrin compound (TSPP) without central metal and sulfonated manganoporphyrin (MnTSPPCl) are respectively adopted to replace tetra (4-sulfophenyl) porphyrin iron chloride (FeTPPCl) prepared in example 1 and are used as catalysts to treat sludge (except that the catalysts are different, other conditions are the same as those in example 1), meanwhile, three representative organic matters (protein, carbonized compound and ammonia nitrogen) are selected to represent the hydrolysis effect, and the experimental results are shown in the following fig. 4-6.
FIG. 4 is a graph showing the effect of the change in the protein concentration after the sludge treatment with different types of catalysts (FeTSPPCl, FeTAPPCl, FeTPPCl, TSPP, MnTSPPCl) in example 1 of the present invention. FIG. 5 is a graph showing the effect of the change in the concentration of the carbonized compound after the sludge treatment with different types of catalysts (FeTSPPCl, FeTAPPCl, FeTPPCl, TSPP, MnTSPPCl) in example 1 of the present invention. FIG. 6 is a graph showing the effect of the change in the ammonia nitrogen concentration after the sludge treatment by the different types of catalysts (FeTSPPCl, FeTAPPCl, FeTPPCl, TSPP, MnTSPPCl) in example 1 of the present invention. As can be seen from FIGS. 4-6, only FeTSPPCl as a catalyst can effectively hydrolyze the organic substances in the sludge without the aid of other acid-base reagents, and the fundamental reason is that FeTSPPCl makes the reaction more prone to heterolytic reaction in an acidic environment, while the hydrophilic group "HSO" of FeTSPPCl3"capable of ionizing a portion" of H+", to favor heterolysis, to produce a greater amount of" feiv = O ", so as to enable efficient oxidation of organic matter (proteins, carbohydrates, etc.) in the sludge. However, fetapp pcl (amino iron porphyrin) does not have this advantage, and only a very small fraction of "feiv = O" is produced, but the hydrolysis effect is still slightly higher than that of the control group. Fat-soluble iron porphyrin (FeTPPCl) without a hydrophilic group has poor solubility in a solvent of a few methanol and a majority of water, and is difficult to combine with hydrogen peroxide, and "FeIV = O" is difficult to generate. While porphyrin compounds (TSPP) without central metal could not coordinate with hydrogen peroxide and could not produce "Fe iv = O", their hydrolytic effect was substantially identical to that of the control group. While MnTSPPCl (sulfomanganic porphyrin) can coordinate with hydrogen peroxide to complete the processes of (i) and (ii), but Mn cannot generate high-valence manganese oxide similar to 'Fe IV = O', namely: MnTSPPCl consumed a portion of the hydrogen peroxide but did not produce new oxidized species, which were less effective in hydrolysis than the control.
According to the Fenton-like formation mechanism, an alcohol solution is needed as a cocatalyst, several groups of different solvents are designed to observe the hydrolysis effect of the solvents on the sludge, specifically, ethanol, N-dimethylformamide and water are used to replace methanol in example 1 to treat the sludge (except for the cocatalyst, other conditions are the same as those in example 1), and the result is shown in FIG. 7:
FIG. 7 is a graph showing the effect of the concentration change of soluble organics after the iron sulfoporphyrin catalyst (FeTSPPCl) is used for treating sludge under different types of promoters in example 1 of the present invention. As can be seen from FIG. 7, the hydrolysis effect is best when methanol is used as a promoter with reference to water, and the hydrolysis effect is better when ethanol with hydroxyl is used as a promoter, and the experimental results of the two hydroxyl-containing substances are higher than that of N, N-dimethylformamide (DMF, a universal solvent) with the best solubility, so that the methanol and ethanol not only dissolve the metalloporphyrin, but also participate in the catalytic reaction process, but the hydrolysis effect of ethanol is lower than that of methanol. The invention analyzes and experiments the experimental results of N, N-dimethylformamide, designs a group of experimental groups which are added with the same amount of N, N-dimethylformamide but do not contain metalloporphyrin (FeTSPPCl), and discovers that: the addition of N, N-dimethylformamide alone also enables an increase in the content of soluble organics, which is attributed to the excellent solubility of this solvent, but N, N-dimethylformamide still has no effect on the concentration of sludge-soluble organics as it does not promote the catalyst to produce the active species "Fe iv = O" to decompose the poorly soluble organics.
Due to the complexity of the sludge environment, the processes of the first step and the second step in the Fenton-like reaction can be inhibited, so that a step-by-step feeding strategy is adopted to protect the hydrogen peroxide coordination process from being smoothly carried out. Therefore, the invention verifies the influence of different adding modes on the sludge pretreatment effect, and specifically comprises the following steps: the materials are added in the following three ways, wherein the adding way 1 is to mix FeTSPPCl, methanol and hydrogen peroxide and add activated sludge, namely the corresponding treatment method in the embodiment 1; the adding mode 2 is that FeTSPPCl solid, methanol and hydrogen peroxide are directly added into the sludge in sequence; the adding mode 3 is that FeTSPPCl-methanol solution and hydrogen peroxide are directly added into the sludge in sequence. The control group was the same as example 1 except that no catalyst was added; the blank set was water instead of "FeTSPPCl solids, methanol, hydrogen peroxide" and the results are shown in figure 8. FIG. 8 is a graph showing the effect of the concentration change of soluble organic substances after the sulfonated iron porphyrin catalyst is used for treating sludge under different adding modes in example 1 of the invention. As can be seen from fig. 8, when sludge is treated according to the addition strategy corresponding to the addition mode 1 (processes of (i), (ii) and (iii) involved in the mechanism diagram), insoluble organic matters in the sludge can be effectively hydrolyzed and converted into soluble organic matters, and the obtained hydrolysis effect is obviously superior to that of other addition modes.
Example 2
A sludge pretreatment method based on a sulfonatoporphyrin iron catalyst Fenton system comprises the following steps:
s1, preparing the iron sulfoporphyrin catalyst (ferric tetra (4-sulfophenyl) porphyrin chloride, FeTSPPCl) prepared in example 1 into 1 g/L aqueous solution, respectively placing 0mL, 1mL, 2mL, 4mL and 8mL into different reactors, sequentially adding 0.36 mL of anhydrous methanol and 2.5 mL of 30% hydrogen peroxide solution into the reactors, stirring, and specifically placing the reactors into a 30 ℃ oscillator for full oscillation reaction for 3 hours to obtain a mixed solution.
S2, adding 100mL of activated sludge (TSS =40.39 g/L, pH = 6.98) into different reactors filled with mixed liquor in the step S1 (the concentration of corresponding FeTSPPCl in the reactors is 0mg/L, 10mg/L, 20mg/L, 40mg/L and 80mg/L in sequence), carrying out hydrolysis treatment, specifically, bundling the mouth of the reactor by using a sealing film, meanwhile, placing the reactor in a constant-temperature shaking incubator at 30 ℃ and 150 rpm for culturing for 5h, after finishing, centrifuging the obtained product at 8000 rpm, filtering the obtained filtrate by using a filter membrane with the pore diameter of 0.45 mu m, and finishing the pretreatment of the sludge.
Blank: the "FeTSPPCl, hydrogen peroxide solution and anhydrous methanol" were replaced with 2.86mL of water, and the other conditions were the same.
The pH and conductivity of each group of sludge obtained after hydrolysis were measured, and the content change of soluble organic matter in each group of filtrate was measured, and the results are shown in fig. 9 to 13.
FIG. 9 is a graph showing the effect of pH change after sludge treatment with iron sulfoporphyrin (FeTSPPCl) catalyst under different dosages in example 2 of the present invention. FIG. 10 is a graph showing the effect of conductivity change of sludge treated with iron sulfoporphyrin (FeTSPPCl) catalyst under different dosages in example 2 of the present invention. As can be seen from fig. 9 and 10, the acidic substances in the sludge are increased by the pretreatment of the FeTSPPCl fenton system, the soluble organic substances are partially acidified, and the number of ions in the solution is increased, so that the addition of the FeTSPPCl can effectively promote the hydrolysis of the sludge.
FIG. 11 is a graph showing the effect of the change in the concentration of proteins after the sludge is treated with iron sulfoporphyrin (FeTSPPCl) catalyst under different dosage conditions in example 2 of the present invention. FIG. 12 is a graph showing the effect of the change in the concentration of carbonized compounds after sludge treatment with iron sulfoporphyrin (FeTSPPCl) catalyst under different dosages in example 2 of the present invention. FIG. 13 is a graph showing the effect of changes in the ammonia nitrogen concentration after sludge treatment with iron sulfoporphyrin (FeTSPPCl) catalyst under different dosages in example 2 of the present invention. From fig. 12 to 13, the addition of the FeTSPPCl can significantly improve the hydrolysis effect of the sludge, wherein when the addition concentration of the FeTSPPCl is greater than 10 mol/L, the soluble protein is regularly decreased, and this trend is opposite to the concentration of the soluble ammonia nitrogen, which indicates that "Fe iv = O" generated by the FeTSPPCl can not only hydrolyze the macromolecular organic substances in the sludge into soluble small molecular proteins, but can also continue to further decompose the proteins into free ammonia nitrogen, which is an inhibitor for gas production in subsequent anaerobic digestion, so the usage amount of the FeTSPPCl should be controlled within 80mg/L, and particularly, when the usage amount of the FeTSPPCl is within 20mg/L, the generation of anaerobic digestion inhibitors such as ammonia nitrogen and the like can be effectively inhibited on the premise of ensuring a higher acid yield.
From the results, on the basis of a FeTSPPCl catalytic mechanism, a Fenton-like system formed by searching a proper reagent proportion, adopting a sectional type feeding strategy and adding a proper cocatalyst is successfully applied to sludge pretreatment, and positive effects on the aspects of the dissolution level of organic matters, the removal rate of organic matter solids, the hydrolysis degree of sludge and the like are achieved.
In conclusion, compared with the existing traditional Fenton and Fenton-like systems, when the Fenton-like system based on the sulfoporphyrin iron catalyst is used for treating sludge, the dosage of the sulfoporphyrin iron catalyst and the hydrogen peroxide is greatly reduced, wherein the dosage of the sulfoporphyrin iron catalyst and the hydrogen peroxide is 0.25 mg/g TSS and 0.19 mL/g TSS in sequence according to the TSS in the sludge; in conventional Fenton and Fenton-like systems, hydrogen peroxide and metal cations are generally used in amounts greater than 50 mg/g TSS. In addition, compared with the traditional Fenton and Fenton-like systems, when the Fenton-like system based on the sulfoporphyrin iron catalyst is used for treating sludge, the sulfoporphyrin iron catalyst is a water-soluble catalyst and has a pH adjusting function, and meanwhile, the sulfoporphyrin iron catalyst is a bionic enzyme and can show higher catalytic activity in the optimal temperature range (such as 30-40 ℃) of the enzyme, so that the sludge is hydrolyzed at the temperature of 30-40 ℃ (the reaction condition is mild), the treatment energy consumption is greatly reduced, and the sulfoporphyrin iron catalyst can be converted into active species with strong oxidizing property and the reaction condition is mild, so that the pH of the sludge is not required to be adjusted in the treatment process. The pH of the sludge needs to be adjusted in the conventional process, but for bulky sludge substrates, pH adjustment is difficult and the amount of acid and base required is high. The invention relates to a sludge pretreatment method based on a sulfoporphyrin iron catalyst Fenton system, which comprises the steps of mixing and stirring a sulfoporphyrin iron catalyst, methanol and a hydrogen peroxide solution to generate a mixed solution containing high-valence iron species (Fe IV = O), mixing the mixed solution with sludge and effectively treating the sludge by using the high-valence iron species (Fe IV = O).
The above examples are merely preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (9)
1. A sludge pretreatment method based on a sulfonatoporphyrin iron catalyst Fenton system is characterized by comprising the following steps:
s1, mixing the sulfonated iron porphyrin catalyst, methanol and a hydrogen peroxide solution, and stirring to obtain a mixed solution; the dosage of the sulfonic group porphyrin iron catalyst is 5 mg-80 mg of sulfonic group porphyrin iron catalyst added in each liter of sludge; the dosage of the methanol is 3.6 mL-20 mL of methanol added in each liter of sludge; the dosage of the hydrogen peroxide solution is 10 mL-50 mL of hydrogen peroxide solution added into each liter of sludge;
and S2, mixing the mixed liquid obtained in the step S1 with sludge for hydrolysis treatment, and finishing the pretreatment of the sludge.
2. The method for pretreating sludge based on a sulfoporphyrin iron catalyst fenton-like system according to claim 1, wherein the sulfoporphyrin iron catalyst is tetra (4-sulfophenyl) porphyrin iron chloride.
3. The method for pretreating sludge based on a sulfoporphyrin iron catalyst fenton-like system according to claim 2, wherein the tetra (4-sulfophenyl) porphyrin iron chloride is prepared from tetra (4-sulfophenyl) porphyrin and ferrous chloride; the preparation method of the tetra (4-sulfophenyl) porphyrin iron chloride comprises the following steps: mixing tetra (4-sulfophenyl) porphyrin, ferrous chloride and N, N-dimethylformamide, heating and refluxing at 153-200 ℃, adding acetone, separating out a solid, and filtering to obtain a crude tetra (4-sulfophenyl) porphyrin ferric chloride product; performing column chromatography on the crude tetra (4-sulfophenyl) porphyrin iron chloride product by adopting dichloromethane, collecting a color band corresponding to the tetra (4-sulfophenyl) porphyrin iron chloride, and removing the dichloromethane to obtain the tetra (4-sulfophenyl) porphyrin iron chloride.
4. The method for pretreating sludge based on a sulfonatoporphyrin iron catalyst fenton-like system according to claim 3, wherein the molar ratio of the tetra (4-sulfophenyl) porphyrin to the ferrous chloride is 0.2-1: 1; the ratio of the tetra (4-sulfophenyl) porphyrin to the N, N-dimethylformamide is 0.1 mmol: 10 mL; the refluxing time is 2.5-3.5 h.
5. The method for pretreating sludge based on a sulfoporphyrin iron catalyst fenton-like system according to claim 4, wherein the tetra (4-sulfophenyl) porphyrin is prepared from tetraphenylporphyrin and concentrated sulfuric acid; the preparation method of the tetra (4-sulfophenyl) porphyrin comprises the following steps: adding tetraphenylporphyrin into concentrated sulfuric acid, heating to 100-120 ℃, reacting for 2.5-4 h, cooling, adjusting the pH value to 8-9, heating and concentrating, placing in ice water for cooling, and filtering to obtain filtrate and filter cake; removing sodium sulfate in the filtrate and the filter cake, collecting the concentrated solution, and drying to obtain a crude product; dissolving the crude product in methanol, adding acetone, stirring to separate out a precipitate, filtering to obtain a purple solid, repeating the operation for three times, collecting the solid, and drying to obtain tetra (4-sulfophenyl) porphyrin; the ratio of the tetraphenylporphyrin to the concentrated sulfuric acid is 500 mg: 10 mL; the volume ratio of the methanol to the acetone is 1-10: 1-20.
6. The method for pretreating sludge based on a sulfoporphyrin iron catalyst fenton-like system according to any one of claims 1 to 5, wherein the mass concentration of the hydrogen peroxide solution is 30%.
7. The method for pretreating sludge based on a sulfonatoporphyrin iron catalyst fenton-like system according to claim 6, wherein the sludge is activated sludge generated in a sewage treatment plant; the TSS in the sludge is 25 g/L-45 g/L.
8. The method for pretreating sludge based on a sulfoporphyrin iron catalyst fenton-like system according to any one of claims 1 to 5, wherein in step S1, the stirring is performed at 25 to 35 ℃; the stirring time is 0.5-3 h.
9. The method for pretreating sludge based on a sulfoporphyrin iron catalyst fenton-like system according to any one of claims 1 to 5, wherein in step S2, the hydrolysis treatment is performed at a rotation speed of 100 rpm to 200 rpm; the hydrolysis treatment is carried out at the temperature of 25-35 ℃; the time of the hydrolysis treatment is 1-5 h; after the hydrolysis treatment is finished, centrifuging and filtering a product obtained after the hydrolysis treatment; the rotating speed of the centrifugation is 8000 rpm; the filtration adopts a filter membrane with the pore diameter of 0.45 mu m.
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