CN113772906A - Method for enhancing biological recycling of sludge by utilizing pretreatment of acidic ion exchange resin - Google Patents
Method for enhancing biological recycling of sludge by utilizing pretreatment of acidic ion exchange resin Download PDFInfo
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- CN113772906A CN113772906A CN202111107369.9A CN202111107369A CN113772906A CN 113772906 A CN113772906 A CN 113772906A CN 202111107369 A CN202111107369 A CN 202111107369A CN 113772906 A CN113772906 A CN 113772906A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/02—Biological treatment
- C02F11/04—Anaerobic treatment; Production of methane by such processes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
Abstract
The invention relates to a method for strengthening biological resource of sludge by utilizing pretreatment of acidic ion exchange resin, which comprises the following steps: (1) isoelectric point pretreatment: adding acidic ion exchange resin to adjust the isoelectric point of the sludge; (2) resin regeneration: separating the pretreated sludge from the resin by using a screen, and regenerating the resin by using acid; (3) anaerobic digestion: carrying out anaerobic fermentation on the pretreated sludge obtained in the step (2) to produce acid or anaerobic digestion to produce methane; (4) resource recovery: and (4) carrying out solid-liquid separation, collecting filtrate, adjusting the pH value to form struvite precipitate and recovering phosphorus. Compared with the prior art, the invention realizes the aims of high-efficiency release of phosphorus and high value-added recovery of sludge in the biological treatment process; the acidic ion exchange resin acidizes the sludge to carry out isoelectric point pretreatment, strengthens the hydrolysis of organic matters, and promotes the release of anaerobic acid production or methane production and organic phosphorus; the acidic ion exchange resin adsorbs metal, so that the precipitation of the metal and phosphorus is hindered, and the release of phosphorus in the sludge is further enhanced.
Description
Technical Field
The invention relates to the technical field of sludge recycling, in particular to a method for strengthening sludge biological recycling by utilizing pretreatment of acidic ion exchange resin.
Background
Due to the necessity and non-regenerability of phosphorus resources, the long-term stable supply of phosphate rock is of great concern to all mankind. China is a large population country, and the annual extraction amount of phosphorite accounts for 40-50% of the total world exploitation amount due to intensive cultivation. Although the phosphorite reserves in China are ranked second globally, the total amount is less than 5% of the global reserves. The uneven resource distribution and the huge exploitation demand make the shortage of phosphorus resources in China urgent and the phosphorus resource recovery become the strategic demand of sustainable development.
The sludge yield of China is high, and the latest data in 2021 of housing and urban and rural construction department of the people's republic of China shows that the sludge yield of China in 2019 reaches 6500 million tons (calculated by 80% of water content). According to the treatment requirement of sewage treatment, the phosphorus content in the inlet water of China is generally 4-5mg/L, and the outlet water requirement is less than 0.5 mg/L. Thus, 90% of the phosphorus in the wastewater is transferred to the sludge. Research shows that the phosphorus content in sludge in China is 2-5% of the dry weight of the sludge. Sludge is therefore an important source of phosphorus recovery.
Because of the existence of toxic substances such as heavy metal, pathogenic bacteria and the like, the method for recovering phosphorus from sludge after releasing phosphorus from sludge becomes the main mode for recovering phosphorus from sludge at present. Based on the occurrence form of phosphorus in the sludge, intracellular polyphosphate, extracellular organophosphorus, Fe-P and the like in the sludge can be effectively released in the anaerobic conversion process of the sludge, so that the realization of phosphorus release and recycling in the anaerobic recycling process becomes a sustainable development direction.
Disclosure of Invention
Practical studies show that the phosphorus release efficiency in the anaerobic digestion process is very low, and phosphorus (<100mg/L) in the biogas slurry does not meet the minimum economic requirement of struvite recovery. In order to improve the release of phosphorus in the anaerobic recycling process, a pretreatment-anaerobic digestion combined technology is developed, but the prior technologies have the problems of low efficiency of improving the release of phosphorus, high energy consumption, reduction of methane yield while improving the release of phosphorus, and the like.
The invention aims to overcome the defects of the prior art and provide a method for enhancing sludge biological recycling by utilizing acidic ion exchange resin pretreatment, aiming at realizing high-efficiency phosphorus release and high-added-value recovery in the biological treatment process of sludge.
The inventors have appreciated that isoelectric pretreatment can effectively enhance hydrolysis of sludge organics to promote anaerobic acidogenesis and methanogenesis. The limiting step combined with anaerobic phosphorus release is the adsorption interception of EPS on the one hand and the precipitation of metal on the other hand. The adsorption and interception of EPS, namely the hydrolysis of organic matters, namely the hydrolysis of EPS, effectively promote the release of phosphorus in EPS; the precipitation of the metal may be achieved by removal of the metal. The acidic ion exchange resin can adjust the isoelectric point of the sludge and adsorb metals at the same time, so that the purposes of promoting EPS hydrolysis and removing metals are achieved, and comprehensive efficient release of phosphorus and high-added-value recovery in the biological treatment process are synchronously realized.
The purpose of the invention can be realized by the following technical scheme:
the technical scheme aims to protect a method for strengthening sludge biological recycling by utilizing acidic ion exchange resin pretreatment, which comprises the following steps:
(1) isoelectric point pretreatment: adding acidic ion exchange resin into the sludge until the isoelectric point of the sludge is adjusted;
(2) resin regeneration: separating the sludge pretreated in the step (1) from the resin by using a screen to obtain pretreated sludge, regenerating the separated resin by using acid, and recycling the regenerated resin in the step (1);
(3) anaerobic recycling: adjusting the pH of the pretreated sludge obtained in the step (2) to be neutral, and then carrying out anaerobic fermentation to produce acid or anaerobic digestion to produce methane to obtain anaerobic fermentation sludge;
(4) resource recovery: and (4) carrying out solid-liquid separation on the anaerobic fermentation sludge obtained in the step (3), collecting filtrate, adding magnesium salt and adjusting pH to form struvite precipitate and collecting the struvite precipitate so as to recover phosphorus, and refluxing the residual filtrate to a sewage treatment plant to realize carbon recovery.
Further, the sludge in the step (1) is excess sludge generated by a sewage plant, and comprises one or more mixed sludge of activated sludge for biological phosphorus removal and sludge for chemically enhanced phosphorus removal, the solid content of the sludge is 1-4 wt%, and the isoelectric point of the sludge is pH 2.5-4.
Furthermore, the dosage of the acidic ion exchange resin in the step (1) is 1-1.5g/g TS, and the reaction time is 3-4 h.
Further, the screen mesh used in the step (2) is 55 meshes, and the acid regeneration solution used is hydrochloric acid or sulfuric acid solution.
Further, the anaerobic resource condition in the step (3) is as follows: mixing the sludge subjected to isoelectric point pretreatment and the inoculation sludge according to the mass ratio TS of 1 (0.5-1), and then adjusting the pH to 6.8-7.3, the temperature is 37 ℃, and the anaerobic fermentation time is 10-30 days.
Further, the inoculation sludge is anaerobic digestion sludge cultured in a laboratory or sludge rich in acid-producing bacteria obtained by water bath at 100 ℃ for 30 min.
Further, in the step (3), the pH value of the pretreated sludge is adjusted to 6.8-7.3 by using a sodium hydroxide solution, and the concentration of the sodium hydroxide solution is 1-2M.
Further, the solid-liquid separation in the step (4) adopts a filter pressing or centrifugal mode.
Further, in the step (4), the magnesium salt is MgCl2·6H2O, adding magnesium salt to ensure that the molar ratio of Mg/P in the filtrate is (1-1.4) to 1.
Further, in the step (4), the pH of the filtrate is adjusted to 8 to 10 using a sodium hydroxide solution having a concentration of 1 to 2M.
Compared with the prior art, the invention has the following technical advantages:
(1) according to the invention, isoelectric point pretreatment is carried out through acidic ion exchange resin, so that on one hand, metal is adsorbed, phosphorus precipitated by the metal in sludge and phosphorus adsorbed by EPS are effectively released, on the other hand, organic matter hydrolysis is enhanced, further release of organic phosphorus in an anaerobic process is promoted, and finally, the release efficiency of phosphorus in sludge is improved by more than 3 times;
(2) according to the invention, the acidic ion exchange resin is used for isoelectric point pretreatment to promote organic hydrolysis, so that the acid production efficiency and the methane production efficiency are improved by more than 3 times;
(3) the acidic ion exchange resin used in the invention can be regenerated and recycled, and meets the requirement of sustainable development.
Drawings
FIG. 1 is a flow chart of a method for enhancing sludge bio-recycling by acidic ion exchange resin pretreatment in the technical scheme.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
According to the method for enhancing biological recycling of sludge by pretreatment of the acidic ion exchange resin in the technical scheme, the acidic ion exchange resin is added into the sludge for isoelectric point pretreatment, so that the hydrolysis of sludge organic matters is enhanced, metals are removed, and the efficient release of phosphorus and the recovery of high added values (acid and methane) are synchronously realized in the anaerobic recycling process, and the method specifically comprises the following steps:
(1) adding a proper amount of acidic ion exchange resin into the excess sludge to adjust the pH value of the sludge to an isoelectric point, and fully stirring; wherein the excess sludge is one or more of activated sludge for biologically enhanced phosphorus removal or sludge for chemically enhanced phosphorus removal; the isoelectric point of the sludge is 2.5-4, preferably 2.8-3.8, the adding amount of the acidic cation exchange resin is 1-1.5g/g TS, preferably 1.3-1.5g/g TS, and the stirring time is 4 h;
(2) separating the pretreated sludge in the step (1) from the resin by screening, acidifying and regenerating the resin, and recycling the resin in the step (1);
(3) carrying out anaerobic fermentation on the pretreated sludge obtained in the step (2) to produce acid or anaerobic digestion to produce methane; wherein the mass ratio of the pretreated sludge to the inoculation sludge is 1: (0.5-1), the temperature is 37 ℃, and the time is 6-12 days;
(4) performing solid-liquid separation on the sludge obtained in the step (3) in a centrifugal or filter pressing mode, and adding magnesium salt MgCl into the biogas slurry2·6H2O, adjusting the molar ratio of Mg/P in the filtrate to be (1.2-1.4):1, adjusting the pH value of the preoxidized residual sludge to be 8-10 by adopting a sodium hydroxide solution with the concentration of 1-2M, and filtering to obtain the birdAnd (4) recovering phosphorus from the precipitate of the crystals of the fecalite, and taking the residual filtrate as a carbon source to flow back to a sewage treatment plant.
Example 1
The sludge used in the embodiment is biological phosphorus removal activated sludge of a certain sewage treatment plant in the Shanghai, the Total Solid (TS) and the Volatile Solid (VS) of the sludge are respectively 2.87% and 1.67%, the VS/TS is 58.36%, and the isoelectric point is pH 2.8; the inoculated sludge is the sludge which is obtained by carrying out water bath at 100 ℃ for 30min on anaerobic digestion sludge domesticated in a laboratory and is enriched with acid-producing bacteria, wherein TS is 3.55%, and VS/TS is 42.41%.
And adding 1.3g/g TS acidic ion exchange resin into the sludge until the pH value of the isoelectric point is 2.8, and stirring for 4 hours. Separating resin from the mixed sludge by using a sieve, mixing the pretreated sludge and the inoculation sludge according to the mass ratio of 2:1, and adjusting the pH of the sludge to 7.0 by using 1M sodium hydroxide. The batch experiment was carried out in a 37 ℃ water bath with 100r/min stirring for 12 days.
The Volatile Fatty Acid (VFAs) and soluble phosphorus contents were measured daily during the experiment.
Comparative example 1
The difference from the embodiment 1 is that the pretreatment of acidic ion exchange resin is not added, and the anaerobic fermentation is carried out by adopting the sludge and the inoculation sludge with the same amount under the same condition.
The Volatile Fatty Acid (VFAs) and soluble phosphorus contents were measured daily during the experiment.
Compared with the comparative example 1, the content of phosphorus in the biogas slurry is improved by 4 times and the yield of VFAs is improved by 4 times after 10 days of anaerobic fermentation in example 1, wherein more than 90 percent of phosphorus is recovered in the form of struvite crystals, and the residual filtrate rich in VFAs is returned to a sewage treatment plant to supplement carbon sources required by denitrification and dephosphorization, and the concrete table is as follows:
for anaerobic acid production, the hydrolysis of organic matters is the rate-limiting step of anaerobic digestion of sludge; isoelectric point pretreatment, organic hydrolysis strengthening and anaerobic acid production promoting. For phosphorus release, on one hand, the acidic ion exchange resin is pretreated at an isoelectric point to strengthen organic hydrolysis and promote the hydrolysis release of organic phosphorus; on the other hand, the acidic ion exchange resin can remove metals, prevent the combination of the metals and phosphorus and further promote the release of the metal mineral phosphorus.
Example 2
The sludge used in the experiment is the mixed sludge of activated sludge and chemical sludge of a certain sewage treatment plant, wherein TS is 3.39%, VS is 1.97%, and VS/TS is 58.25%; the inoculation sludge is anaerobic digestion sludge domesticated in a laboratory, wherein TS is 3.20 percent, and VS/TS is 45.34 percent.
Adding 1.5g/g TS acidic ion exchange resin into the sludge to adjust the pH value of the sludge to 3.8 at the isoelectric point, stirring for 4 hours, and then screening and separating the resin. The mass ratio of the pretreated sludge to the inoculated sludge is 1: 1, and adjusting the pH of the mixed sludge to 6.8 by using 1M sodium hydroxide. The batch anaerobic digestion experiment is carried out in water bath at 37 ℃ and stirring at 100r/min, and the reaction time is 30 days.
The methane production and soluble phosphorus content were measured daily during the experiment.
Comparative example 2
The difference from the example 2 is that no acidic ion exchange resin is added for pretreatment, and the sludge and the inoculation sludge with the same amount are subjected to anaerobic digestion under the same conditions.
The methane production and soluble phosphorus content were measured daily during the experiment.
The reason for this is that for anaerobic digestion, hydrolysis of organic matter is the rate-limiting step for anaerobic digestion of sludge; isoelectric point pretreatment, organic hydrolysis strengthening, anaerobic digestion promotion and methane production. For phosphorus release, on one hand, the acidic ion exchange resin is pretreated at an isoelectric point to strengthen organic hydrolysis and promote the hydrolysis release of organic phosphorus; on the other hand, the acidic ion exchange resin can remove metals, prevent the combination of the metals and phosphorus and further promote the release of the metal mineral phosphorus.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A method for strengthening sludge biological recycling by utilizing acidic ion exchange resin pretreatment is characterized by comprising the following steps:
(1) isoelectric point pretreatment: adding acidic ion exchange resin into the sludge until the isoelectric point of the sludge is adjusted;
(2) resin regeneration: separating the sludge pretreated in the step (1) from the resin by using a screen to obtain pretreated sludge, regenerating the separated resin by using acid, and recycling the regenerated resin in the step (1);
(3) anaerobic recycling: adjusting the pH of the pretreated sludge obtained in the step (2) to be neutral, and then carrying out anaerobic fermentation to produce acid or anaerobic digestion to produce methane to obtain anaerobic fermentation sludge;
(4) resource recovery: and (4) carrying out solid-liquid separation on the anaerobic fermentation sludge obtained in the step (3), collecting filtrate, adding magnesium salt and adjusting pH to form struvite precipitate and collecting the struvite precipitate so as to recover phosphorus, and refluxing the residual filtrate to a sewage treatment plant to realize carbon recovery.
2. The method for enhancing the biological resource utilization of the sludge by utilizing the pretreatment of the acidic ion exchange resin as claimed in claim 1, wherein the sludge in the step (1) is excess sludge produced by sewage plants, the excess sludge comprises one or more mixed sludge of activated sludge for biological phosphorus removal and sludge for chemically enhanced phosphorus removal, the solid content of the sludge is 1-4 wt%, and the isoelectric point of the sludge is pH 2.5-4.
3. The method for enhancing sludge biological recycling through acidic ion exchange resin pretreatment as claimed in claim 1, wherein the dosage of the acidic ion exchange resin in step (1) is 1-1.5g/g TS, and the reaction time is 3-4 h.
4. The method for enhancing sludge biological resource by utilizing acidic ion exchange resin pretreatment as claimed in claim 1, wherein the screen used in step (2) is 55 mesh, and the acid regeneration solution used is hydrochloric acid or sulfuric acid solution.
5. The method for enhancing sludge biological resource utilization by utilizing acidic ion exchange resin pretreatment as claimed in claim 1, wherein the anaerobic resource utilization conditions in step (3) are as follows: mixing the sludge subjected to isoelectric point pretreatment and the inoculation sludge according to the mass ratio TS of 1 (0.5-1), and then adjusting the pH to 6.8-7.3, the temperature is 37 ℃, and the anaerobic fermentation time is 10-30 days.
6. The method for enhancing sludge biological resource utilization by utilizing acidic ion exchange resin pretreatment as claimed in claim 5, wherein the inoculation sludge is laboratory-cultured anaerobic digestion sludge or sludge rich in acid-producing bacteria obtained by water bath at 100 ℃ for 30 min.
7. The method for enhancing sludge biological resource utilization by utilizing acidic ion exchange resin pretreatment as claimed in claim 1, wherein in step (3), the pH of the pretreated sludge is adjusted to 6.8-7.3 by using sodium hydroxide solution, and the concentration of the sodium hydroxide solution is 1-2M.
8. The method for enhancing sludge biological recycling by utilizing acidic ion exchange resin pretreatment as claimed in claim 1, wherein the solid-liquid separation in step (4) is performed by means of filter pressing or centrifugation.
9. The method of claim 1, wherein the ionic exchange is carried out by acidThe method for strengthening sludge biological recycling through resin exchange pretreatment is characterized in that the magnesium salt in the step (4) is MgCl2·6H2O, adding magnesium salt to ensure that the molar ratio of Mg/P in the filtrate is (1-1.4) to 1.
10. The method for enhancing sludge biological resource utilization by utilizing acidic ion exchange resin pretreatment as claimed in claim 1, wherein in step (4), the pH of the filtrate is adjusted to 8-10 by using sodium hydroxide solution, and the concentration of the sodium hydroxide solution is 1-2M.
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- 2021-09-22 CN CN202111107369.9A patent/CN113772906B/en active Active
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|---|---|---|---|---|
| US3772191A (en) * | 1970-04-25 | 1973-11-13 | W Thorn | Method of digesting and further processing fresh sewage sludge or sopropel |
| WO2017061117A1 (en) * | 2015-10-09 | 2017-04-13 | 高橋金属株式会社 | Adsorbent dispersion and adsorption method |
| CN110240375A (en) * | 2019-05-20 | 2019-09-17 | 同济大学 | A kind of processing method suitable for excess sludge anaerobic digestion |
| CN111517606A (en) * | 2020-05-15 | 2020-08-11 | 同济大学 | Method for strengthening anaerobic digestion of sludge by utilizing acid fermentation of kitchen waste based on isoelectric point |
| CN113087325A (en) * | 2021-03-27 | 2021-07-09 | 同济大学 | Targeted clean extraction method for sludge phosphorus recovery |
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| 甄广印等著: "《城市污泥强化深度脱水资源化利用及卫生填埋末端处置关键技术研究》", 31 August 2017, 上海：同济大学出版社 * |
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