CN113786807B - Adsorbent for removing total phosphorus and organic pollutants in sewage and preparation method and application thereof - Google Patents
Adsorbent for removing total phosphorus and organic pollutants in sewage and preparation method and application thereof Download PDFInfo
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- CN113786807B CN113786807B CN202111307442.7A CN202111307442A CN113786807B CN 113786807 B CN113786807 B CN 113786807B CN 202111307442 A CN202111307442 A CN 202111307442A CN 113786807 B CN113786807 B CN 113786807B
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- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising 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
- C02F1/00—Treatment of water, waste water, or sewage
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Abstract
The invention relates to an adsorbent for removing total phosphorus and organic pollutants in sewage, and a preparation method and application thereof. The preparation method comprises the following steps: carrying out polymerization reaction on the biochar, the alumite and water to obtain an alumite biochar adsorbent; then reacting the iron-aluminum alum biochar adsorbent with an inorganic metal salt solution at 50-90 ℃ for 4-6h, and then carrying out hydrothermal reaction to obtain an adsorbent for removing total phosphorus and organic pollutants in the sewage; the inorganic metal salt solution at least comprises an inorganic aluminum salt and an inorganic iron salt.
Description
Technical Field
The invention relates to the field of adsorption purification, in particular to an adsorbent for removing total phosphorus and organic pollutants in sewage, and a preparation method and application thereof.
Background
With the rapid development of national economy, industrial production and life are developed at a high speed, and the amount of generated sewage is increased year by year while the industrial production and life level is improved. According to the national institute of statistics of China annual book of statistics in 2020, the usage amount of industrial and domestic sewage in 2020 years in China is 1714 billion cubic meters, the total discharge amount is 660.6 billion cubic meters, wherein the annual discharge amount of the industrial sewage is 305.6 billion cubic meters, and accounts for 46.26%; the discharge amount of domestic sewage is 355 hundred million tons, the proportion is 53.74 percent, and the discharge amount is continuously increased.
Industrial sewage and domestic sewage are treated mainly by urban industrial sewage treatment plants and municipal sewage treatment plants, and are discharged into the external environment after reaching the national sewage discharge standard. Industrial sewage has the characteristics of high organic pollutants (CODcr), high TDS and toxic substances, while municipal sewage has the characteristics of high nitrogen and high phosphorus. At present, a core treatment process for industrial sewage and municipal sewage is a biochemical process and a rear-end advanced treatment process thereof, the two processes mainly aim at Total Phosphorus (TP) and organic pollutant (CODcr) indexes in the sewage, and because a biochemical system is influenced by factors such as inlet water pollutant concentration, water temperature and aeration amount in the sewage treatment process, the requirement that the total phosphorus and CODcr short-term outlet water cannot reach the technical indexes may exist, most of products for removing phosphorus and CODcr are general chemicals or medicaments with oxidability, a large amount of sludge can be generated in actual application or harmful effects can be generated on microorganisms in the biochemical system due to the oxidability of the chemicals, and therefore, the standard discharge of the sewage cannot be safely and stably ensured.
Therefore, an adsorbing material which has small sludge production and mild performance and can be used in cooperation with a biochemical system is urgently needed, and can be used for removing total phosphorus and organic pollutants (CODcr) in sewage in cooperation with microorganisms in the biochemical system or be independently used for a product with less sludge production in an advanced treatment process to ensure the stable operation of a sewage treatment plant.
Disclosure of Invention
The invention provides an adsorbent for removing total phosphorus and organic matters in sewage and a preparation method thereof, which can be used in cooperation with aerobic microorganisms in a biochemical system or independently used in an advanced treatment process in the sewage treatment process of the industrial and municipal fields to ensure that the treated sewage meets the index requirements of primary discharge standard of total phosphorus less than or equal to 0.5mg/L and CODcr less than or equal to 50mg/L in GB8978 integrated discharge Standard of Sewage.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of an adsorbent for removing total phosphorus and organic pollutants in sewage comprises the following steps:
carrying out polymerization reaction on the biochar, the alumite and water to obtain an alumite biochar adsorbent;
then reacting the iron-aluminum alum charcoal adsorbent with an inorganic metal salt solution at 50-90 ℃ for 4-6h, and then carrying out hydrothermal reaction to obtain the adsorbent for removing total phosphorus and organic pollutants in the sewage;
the inorganic metal salt solution at least comprises an inorganic aluminum salt and an inorganic iron salt.
In one embodiment, the mass ratio of the biochar to the alumite to the water is (0.1-0.3): (0.2-0.4): (0.3-0.7).
In one embodiment, the mass ratio of aluminum ions in the inorganic aluminum salt to iron ions in the inorganic iron salt is (0.16-0.7): (0.3-0.84).
In one embodiment, the inorganic aluminum salt comprises aluminum sulfate, aluminum hydroxide, aluminum trichloride; the inorganic iron salts include ferrous sulfate, ferric sulfate and polymeric ferric sulfate.
In one embodiment, the conditions under which the polymerization occurs are: reacting for 1-4h at 150-210 ℃.
In one embodiment, the hydrothermal reaction is carried out under the following conditions: the reaction time is 2-3h at 140-180 ℃.
The invention also provides an adsorbent for removing total phosphorus and organic pollutants in sewage, which is prepared by the preparation method.
The invention also provides application of the adsorbent for removing total phosphorus and organic pollutants in sewage in removing total phosphorus and organic pollutants in sewage.
Compared with the prior art, the invention has the following beneficial effects:
the adsorbent for removing the total phosphorus and the organic pollutants in the sewage provided by the invention has the function of adsorbing the total phosphorus and the organic pollutants in the sewage; the adsorbent can form 'granular-like sludge' in an aerobic section, so that the particles of the generated 'granular-like sludge' have aerobic, anoxic and anaerobic functions, and the pollutant removal efficiency is improved; the device is applied to an aerobic section of a sewage biochemical unit and can be used for a coagulation sedimentation section; the adsorbent provided by the invention has the characteristics of less sludge generation amount and high sludge-water separation speed.
The action mechanism of the adsorbent for removing the total phosphorus and the organic pollutants in the sewage provided by the invention is that the biological iron-aluminum-alum carbon is taken as a carrier core, and an aluminum salt and iron salt inorganic molecular structure is inserted into a pore channel of the biological iron-aluminum-alum carbon to obtain the biological iron-aluminum-alum carbon adsorbent, the total phosphorus, the organic pollutants and part of Fe & lt 2+ & gt are adsorbed on the surface of the activated carbon and in the pore channel of the activated carbon simultaneously through the physical adsorption capacity of the biological iron-aluminum-alum carbon, and the Fe & lt 2+ & gt provides necessary trace elements for microorganisms, so that the biological activity of the microorganisms can be improved. Meanwhile, trivalent aluminum salt and ferric salt polymerized on the pore and the surface of the ferroalumite biochar are used as a 'tentacle' of the biochar to capture the activated sludge zoogloea and partial pollutants at the periphery through the charge action. The adsorbent provided by the invention can finally form 'granular-like sludge' which takes biochar as an inner core and has a compact structure in sewage, the 'granular-like sludge' can realize anaerobic, anoxic and aerobic functions, and the 'granular-like sludge' has the advantages of compact structure, good settling property and the like. Municipal and industrial sewage treated by the adsorbent can reach the primary discharge standard of GB8978 Integrated wastewater discharge Standard, total phosphorus is less than or equal to 0.5mg/L and CODcr is less than or equal to 50mg/L.
Drawings
FIG. 1 is a schematic diagram of an industrial application of a biochemical unit of an adsorbent for removing total phosphorus and organic pollutants from sewage;
FIG. 2 is a schematic diagram of an industrial application of an adsorbent air-flotation unit for removing total phosphorus and organic pollutants from sewage;
FIG. 3 is a schematic diagram of an industrial application of an adsorbent coagulating sedimentation unit for removing total phosphorus and organic pollutants from sewage;
FIG. 4 is a graph showing the effect of the adsorbent addition on the total phosphorus content in the wastewater in example 1;
FIG. 5 is a graph showing the effect of CODcr content in sewage after addition of the adsorbent in example 1;
FIG. 6 is a graph showing the effect of the adsorbent addition on the total phosphorus content in the wastewater in example 2;
FIG. 7 is a graph showing the effect of CODcr content in sewage after addition of the adsorbent in example 2;
FIG. 8 is a graph showing the effect of the adsorbent addition on the total phosphorus content in the wastewater in example 3;
FIG. 9 is a graph showing the effect of CODcr content in sewage after addition of the adsorbent in example 3.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings, which illustrate embodiments of the present invention. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, as those skilled in the art will recognize without departing from the spirit and scope of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The following are specific examples
The invention is further illustrated by the following examples:
as shown in fig. 1-3, which are schematic diagrams of the adding positions of a biochemical unit and a deep treatment unit in a sewage treatment process in industrial application of adsorbents of total phosphorus and organic pollutants in sewage, it can be seen from fig. 1 that the adsorbents of the total phosphorus and the organic pollutants in the sewage are added in an aerobic tank or a secondary sedimentation tank of the biochemical unit; or to the water inlet pipeline of the advanced treatment unit in figures 2 and 3. The adsorbent for removing the total phosphorus and the organic pollutants in the sewage is suitable for processes with internal and external backflow or filling materials, such as AO, AAO, CAST, MBBR and the like in a biochemical process, and a coagulation sedimentation tank and an air flotation process in an advanced treatment unit.
Several more typical embodiments are now described:
example 1
Step 1, adding biochar, alumite and deionized water into a hydrothermal reactor, wherein the mass of the biochar, the alumite and the deionized water is 300kg, 200kg and 500kg respectively, reacting for 3 hours at the temperature of 200 ℃, and filtering and drying to obtain the alumite biochar adsorbent.
And 2, adding 100kg of iron-aluminum-vanadium biochar adsorbent and 900kg of metal salt solution into a normal-pressure stirring reactor, wherein the metal salt solution is prepared by mixing polymeric ferric sulfate, aluminum sulfate and deionized water, the mass of the polymeric ferric sulfate, the aluminum sulfate and the deionized water is 360kg, 180kg and 360kg respectively, and stirring and reacting for 5 hours at the temperature of 60 ℃.
And 3, adding 600kg of the solution obtained in the step 2 into a hydrothermal reactor, reacting for 3h at 180 ℃, filtering and drying to obtain the adsorbent for removing total phosphorus and organic matters in the sewage.
The prepared adsorbent for removing the total phosphorus and the organic pollutants in the sewage is developed for industrial application research in an industrial sewage plant in the Panjin market, the sewage plant adopts an anoxic plus AAO process flow, the CODcr of inlet water is 200-340mg/L, TP is 2.0-4.0mg/L, the daily treated sewage is 5000m3, the pH is 6.0-7.5, and the DO is 1.0-2.0mg/L during the industrial application. After the field application for 1 month, biochemical effluent figures 1 and 2 are respectively the effect graphs of CODcr and TP after adding the adsorbent, and the total phosphorus and the CODcr which meet the requirements of the first-level discharge standard in GB8978 Integrated wastewater discharge Standard are less than or equal to 0.5mg/L and less than or equal to 50mg/L. The sedimentation performance of the 'granular-like sludge' formed in the application period is excellent, and the sedimentation time of the sludge is reduced to 5min from 15min before the adsorbent is added.
Example 2
Step 1, adding biochar, alumite and deionized water into a hydrothermal reactor, reacting for 3 hours at 180 ℃, filtering and drying to obtain the alumite biochar adsorbent, wherein the mass of the biochar, the alumite and the deionized water is 100kg, 300kg and 600kg respectively.
And 2, adding 200kg of iron-aluminum alum biochar adsorbent and 800kg of metal salt solution into a normal-pressure stirring reactor, wherein the metal salt solution is prepared by mixing ferrous sulfate, aluminum sulfate and deionized water, the mass of the ferrous sulfate, the aluminum sulfate and the deionized water is 250kg, 150kg and 600kg respectively, and stirring and reacting for 6 hours at the temperature of 80 ℃.
And 3, adding 400kg of the solution obtained in the step 2 into a hydrothermal reactor, reacting for 2h at 160 ℃, filtering and drying to obtain the adsorbent for removing the total phosphorus and organic pollutants in the sewage.
The prepared adsorbent for removing the total phosphorus and the organic pollutants in the sewage is developed for industrial application research in municipal sewage plants in Panjin city, the sewage plants adopt an AAO process flow, during the industrial application, the CODcr of inlet water is 200-330mg/L, TP is 2.1-3.6mg/L, the daily treated sewage is 10000m3, the pH is 6.5-7.5, and the DO is 1.0-1.5mg/L. After the field application for 1 month, the biochemical effluent graphs 3 and 4 respectively show the effect graphs of CODcr and TP after adding the adsorbent, and the total phosphorus and the CODcr are less than or equal to 0.5mg/L and less than or equal to 50mg/L which meet the requirements of the first-level discharge standard in GB8978 Integrated wastewater discharge Standard.
Example 3
Step 1, adding biochar, alumite and deionized water into a hydrothermal reactor, wherein the mass of the biochar, the alumite and the deionized water is 100kg, 200kg and 700kg respectively, reacting for 4 hours at 150 ℃, and filtering and drying to obtain the alumite biochar adsorbent.
And 2, adding 300kg of iron-aluminum alum biochar adsorbent and 700kg of metal salt solution into a normal-pressure stirring reactor, wherein the metal salt solution is prepared by mixing ferrous sulfate, ferric sulfate, aluminum sulfate and deionized water, the mass of the four is 250kg, 100kg, 200kg and 450kg respectively, and stirring and reacting for 5 hours at the temperature of 70 ℃.
And 3, adding 500kg of the solution obtained in the step 2 into a hydrothermal reactor, reacting for 3h at 180 ℃, filtering and drying to obtain the adsorbent for removing the total phosphorus and organic pollutants in the sewage.
The prepared adsorbent for removing the total phosphorus and the organic pollutants in the sewage is developed for industrial application research in a sewage plant in villages and towns in Panjin city, the sewage plant adopts an AO process flow, during the industrial application, the CODcr of inlet water is 220-340mg/L, TP is 2.1-3.9mg/L, the daily treated sewage is 300m3, the pH is 6.0-8.0, and the DO is 0.8-1.2mg/L. After the field application for 1 month, the biochemical effluent graphs 5 and 6 respectively show the effect graphs of CODcr and TP after adding the adsorbent, which both meet the requirements of primary discharge standard in GB8978 Integrated wastewater discharge Standard that the total phosphorus is less than or equal to 0.5mg/L and the CODcr is less than or equal to 50mg/L.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is specific and detailed, but not to be understood as limiting the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (3)
1. A preparation method of an adsorbent for removing total phosphorus and organic pollutants in sewage is characterized by comprising the following steps:
carrying out polymerization reaction on the biochar, the alumite and water to obtain an alumite biochar adsorbent;
then reacting the iron-aluminum alum charcoal adsorbent with an inorganic metal salt solution at 50-90 ℃ for 4-6h, and then carrying out hydrothermal reaction to obtain the adsorbent for removing the total phosphorus and organic pollutants in the sewage;
the inorganic metal salt solution at least comprises an inorganic aluminum salt and an inorganic iron salt;
the mass ratio of the biochar to the iron aluminite to the water is (0.1-0.3) to (0.2-0.4) to (0.3-0.7), and the mass ratio of aluminum ions in the inorganic aluminum salt to iron ions in the inorganic iron salt is (0.16-0.7) to (0.3-0.84);
the inorganic aluminum salt comprises aluminum sulfate, aluminum hydroxide and aluminum trichloride; the inorganic ferric salt comprises ferrous sulfate, ferric sulfate and polymeric ferric sulfate;
the conditions under which the polymerization reaction occurs are as follows: reacting for 1-4h at 150-210 ℃;
the conditions for carrying out the hydrothermal reaction are as follows: the reaction time is 2-3h at 140-180 ℃.
2. An adsorbent for removing total phosphorus and organic pollutants in sewage, which is prepared by the preparation method of claim 1.
3. The use of the adsorbent for removing total phosphorus and organic pollutants in sewage according to claim 2 in removing total phosphorus and organic pollutants in sewage.
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| CN103127907A (en) * | 2011-12-05 | 2013-06-05 | 中国科学技术大学 | Nanometer adsorption material and preparation method thereof |
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| JP2006346548A (en) * | 2005-06-15 | 2006-12-28 | Unitika Ltd | Chemical filter for removal of organic matter |
| CN103721677B (en) * | 2014-01-13 | 2016-09-14 | 农业部沼气科学研究所 | A kind of preparation method of the biomass carbon composite for waste water dephosphorization |
| CN104084126B (en) * | 2014-07-09 | 2016-05-18 | 福建工程学院 | The preparation method of biomass-based iron aluminium complex spherical charcoal |
| CN104291420B (en) * | 2014-09-11 | 2016-01-20 | 陕西省石油化工研究设计院 | A kind of dephosphorization agent containing inorganic mineral and using method thereof |
| JP6958805B2 (en) * | 2017-07-21 | 2021-11-02 | 国立大学法人山梨大学 | Method for Producing Iron Particle-Porous Carbon Complex |
| CN107335408A (en) * | 2017-07-31 | 2017-11-10 | 河海大学 | A kind of preparation method and application for the cyclodextrin for coating iron aluminium hydroxide |
| CN109647337A (en) * | 2019-01-21 | 2019-04-19 | 河南永泽环境科技有限公司 | A kind of composite adsorbing material of denitrogenation dephosphorizing and preparation method thereof |
| GB201913290D0 (en) * | 2019-09-13 | 2019-10-30 | Carbogenics Ltd | Adsorbent for municipal wastewater treatment |
| CN111807453A (en) * | 2020-07-17 | 2020-10-23 | 长沙理工大学 | Modified biochar for adsorbing phosphorus in water body and preparation method and application thereof |
| CN113117643A (en) * | 2021-01-07 | 2021-07-16 | 河南省高新技术实业有限公司 | Modified biomass charcoal adsorption material, preparation method and application thereof, and method for regenerating modified biomass charcoal adsorption material |
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| WO2011038459A1 (en) * | 2009-10-01 | 2011-04-07 | Commonwealth Scientific And Industrial Research Organisation | Remediation composition comprising alum sludge |
| CN103127907A (en) * | 2011-12-05 | 2013-06-05 | 中国科学技术大学 | Nanometer adsorption material and preparation method thereof |
| CN103495384A (en) * | 2013-08-30 | 2014-01-08 | 蚌埠德美过滤技术有限公司 | Modified activated carbon air purification adsorbent and its preparation method |
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