CN113000025B - Phosphorus removal adsorbent and preparation method and application thereof - Google Patents
Phosphorus removal adsorbent and preparation method and application thereof Download PDFInfo
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- CN113000025B CN113000025B CN202110251682.3A CN202110251682A CN113000025B CN 113000025 B CN113000025 B CN 113000025B CN 202110251682 A CN202110251682 A CN 202110251682A CN 113000025 B CN113000025 B CN 113000025B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/043—Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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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
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
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- Hydrology & Water Resources (AREA)
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- Treatment Of Sludge (AREA)
Abstract
The invention relates to a phosphorus removal adsorbent and a preparation method and application thereof. The raw materials of the phosphorus removal adsorbent are waste limestone and sludge, the waste limestone is building stones and waste stones generated in the mining production process of mines, and the sludge is a material generated in the sewage treatment process. The preparation method comprises the following steps: waste limestone and sludge are mixed and then heated in a tubular furnace. The aim of effectively removing phosphate in water is achieved by using the waste limestone modified biochar. The material after adsorbing the phosphate can be used as a soil conditioner, can be used as a slow-release phosphate fertilizer to promote plant growth, and can also be used as a passivator to restore the heavy metal polluted soil such as Cd and the like.
Description
Technical Field
The invention belongs to the technical field of sewage dephosphorization, and particularly relates to a dephosphorization adsorbent and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Biological methods, chemical methods and adsorption methods are widely applied to dephosphorization of water bodies, however, methods such as chemical precipitation and the like require high investment cost and expensive maintenance cost, and biological treatment is greatly influenced by external factors such as carbon sources, water quality and the like and is not easy to control. Adsorption has attracted attention from many researchers because of its advantages such as low cost, easy control, and eco-friendliness. The biochar prepared by taking sludge as a raw material has economic and environment-friendly double benefits as an adsorbing material, but the removal effect of the biochar on phosphate is poor due to the characteristics of negative charges on the surface and the like. It is necessary to improve the adsorption capacity of the biochar raw material on phosphate by modifying the biochar raw material.
At present, la 3+ 、Al 3+ 、Fe 3+ 、Mg 2+ 、Ca 2+ Isometallic cationThe sub-modified biochar has been proved to significantly improve the adsorption performance on phosphate. And Al 3+ 、Fe 3+ And La 3+ Can be released in aqueous solution under redox or acidic conditions, and has toxic effect on water environment and aquatic organisms. While chemical reagents (La) are currently used 3+ 、Al 3+ 、Fe 3+ 、Mg 2+ 、Ca 2+ ) The modified and synthesized material has complex operation and high cost, and limits the wide application of the modified material in practice.
Disclosure of Invention
In view of the problems in the prior art, the present invention aims to provide a phosphorus removal adsorbent, and a preparation method and an application thereof. The waste limestone modified sludge biochar is utilized to achieve the aim of effectively removing phosphate in water. Limestone is a compound of CaCO 3 The hexagonal crystal is a main component and has the advantages of low cost, wide distribution, environmental friendliness, no toxicity and the like; and the material after adsorbing the phosphate can be used as a soil conditioner, can be used as a slow-release phosphate fertilizer to promote plant growth, can also be used as a passivator to restore the heavy metal polluted soil such as Cd and the like, and has higher development and utilization values.
In order to solve the technical problems, the technical scheme of the invention is as follows:
in a first aspect, a phosphorus removal adsorbent is prepared from waste limestone and sludge, wherein the waste limestone is a waste material generated in the processes of building stone production and limestone ore mining, and the sludge is a material generated in the process of sewage treatment.
The calcium-rich waste limestone is used for modifying the biochar and can replace CaCl 2 、Ca(OH) 2 And the chemical reagent modifier can achieve a better treatment effect and save the cost.
In some embodiments of the invention, the dry weight to mass ratio of waste limestone to sludge is from 2 to 6; preferably 3 to 6.
In a second aspect, the preparation method of the above phosphorus removal adsorbent comprises: and mixing the waste limestone and the sludge, and heating in a tubular furnace to obtain the phosphorus removal adsorbent.
The sludge is heated to obtain the biochar, and the biochar is modified by using the natural mineral of the waste limestone, so that the problem of poor phosphate adsorption effect of the biochar is solved. Compared with the existing method for modifying the biochar by using a chemical reagent, the method has the advantage of low cost.
In some embodiments of the invention, the heat treatment is carried out at a temperature of 600 to 900 ℃ for 1 to 3 hours; preferably 800 ℃ and 2h. The modification effect on the biochar is better in a high-temperature environment of 800 ℃.
In some embodiments of the invention, the ramp rate is 5-15 ℃/min; preferably 10 deg.C/min.
In some embodiments of the present invention, the waste limestone powder is pulverized to obtain a waste limestone powder having a particle size of 0.1mm or less before mixing with the sludge.
In some embodiments of the invention, the sludge is dried before being mixed with the waste limestone, wherein the drying temperature is 90-110 ℃ and the drying time is 16-30h. Before mixing, the sludge is dried, mainly to reduce the water content in the sludge, which is more beneficial to obtaining the biochar with stable structure and better pore structure.
In a third aspect, the phosphorus removal adsorbent is applied to the field of phosphorus removal of water bodies.
In a fourth aspect, the method for removing phosphorus from water body by using the phosphorus removal adsorbent is that the phosphorus removal adsorbent is put into wastewater, and a phosphate-loaded material and the treated wastewater are obtained after adsorption.
In a fifth aspect, the phosphate-loaded material obtained by the above method.
And in a sixth aspect, the phosphate-loaded material is applied to a passivating agent for phosphate fertilizer or Cd-contaminated soil.
The phosphorus-removing adsorbent after adsorption can produce mineral such as calcium hydrogen phosphate dihydrate, is rich in phosphorus ore, can be used as phosphorus fertilizer, and contains main component CaCO in waste limestone 3 Is hexagonal crystal, and is environment friendly and non-toxic.
One or more technical schemes of the invention have the following beneficial effects:
(1) The method is simple, and the raw materials are easily obtained
The annual sludge yield of China exceeds 4000 million, a large amount of cost is spent on treating the sludge, and the sludge used in the method can realize the recycling of the sludge, reduce the treatment cost and create economic benefits; the used waste limestone is easy to obtain, and the comprehensive utilization of waste is realized.
(2) High phosphorus removal efficiency
The removal rate can reach more than 90 percent by adding 0.05g of material into 25mL of 200mg/L phosphate (pH is 2.0-10.0); the maximum theoretical adsorption capacity calculated by a Langmuir adsorption isothermal model is 231.3mg/g, which is superior to the traditional dephosphorizing adsorbent material at present.
(3) The material after adsorbing the phosphate is used as a phosphate fertilizer to promote the growth of plants (leaf lettuce)
The absorbed material is added into soil according to 1% of the dry weight of the soil, the germination rate and the plant height of the plant are promoted by 21.7% and 45% respectively, and the dry weight and the fresh weight of the plant are increased by 50.4% and 52% respectively.
(4) Repairing Cd-polluted soil by using material with adsorbed phosphate as passivator
The adsorbed material is added into soil according to 1% of the dry weight of the soil, and for the leaf lettuce planted in the soil with the Cd content of 10mg/kg, the germination rate and the plant height of the plant are respectively promoted by 8.9% and 5.8%, the dry weight and the fresh weight of the plant are respectively increased by 19.7% and 14.3%, and the exchangeable state Cd in the soil is reduced by 9.5%.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description, serve to explain the invention and not to limit the invention.
FIG. 1 is a flow chart of the preparation and reuse of the phosphorus removal adsorbent.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. 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.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise. The invention will be further illustrated by reference to the following examples
Example 1
(1) Drying the residual sludge of the sewage treatment plant at 105 ℃ for 24 hours, and crushing the dried sludge by a crusher through a 0.1mm sieve; the limestone is washed by deionized water for three times, and is crushed by a crusher and sieved by a sieve with 0.1mm after being dried.
(2) Screening waste limestone and sludge according to the dry weight ratio of limestone to sludge of 3:1, placing the mixture into a quartz boat, heating the quartz boat from room temperature to 800 ℃ in a programmable tube furnace OTF-1200X at the speed of 10 ℃/min, and heating the quartz boat at 800 ℃ N 2 Keeping the powder in the atmosphere for 2h, cooling the powder to room temperature, cleaning the obtained powder with deionized water to remove residues on the surface, then placing the powder in an oven for drying at 95 ℃, grinding the powder after drying, sieving the powder with a 0.1mm sieve, and storing for later use.
Example 2
The heating temperature in the tube furnace was 700 ℃ as compared with example 1.
Example 3
The heating temperature in the tube furnace was 600 ℃ compared to example 1.
Comparative example 1
Compared to example 1, the dry weight to mass ratio of waste limestone to sludge is 1.
Example 4
Compared to example 1, the dry weight to mass ratio of waste limestone and sludge is 2.
Example 5
Compared to example 1, the dry weight mass ratio of the waste limestone to the sludge is 4.
Example 6
Compared to example 1, the dry weight mass ratio of the waste limestone to the sludge is 6.
Comparative example 2
Compared to example 1, the dry weight to mass ratio of waste limestone to sludge is 1.
Comparative example 3
Compared with the embodiment 2, the dry weight mass ratio of the waste limestone to the sludge is 1.
Example 7
Compared with the example 2, the dry weight mass ratio of the waste limestone to the sludge is 2.
Comparative example 4
Compared with the example 3, the dry weight mass ratio of the waste limestone to the sludge is 1.
Example 8
Compared with the example 3, the dry weight mass ratio of the waste limestone to the sludge is 2.
Comparative example 5
Sludge biochar was obtained by following the individual sludge in the same manner as in step (2) of example 1.
Experimental example 1
0.05g of the phosphorus removal adsorbent obtained in different examples and the sludge biochar and the waste limestone obtained in comparative example 1 and comparative example 2 are respectively taken and put into 25ml of 200mg/L phosphate (pH 2.0) to obtain a phosphate loaded material and treated wastewater. The adsorption removal rates of the different examples are shown in table 1.
TABLE 1 adsorption removal rates at different mass ratios and different calcination temperatures
As can be seen from Table 1, the adsorption removal rate of 3-6 is the best, and the adsorption removal rate of the phosphorus removal adsorbent at the calcination temperature of 800 ℃ is the highest. The adsorption effect of the pure sludge biochar and limestone is lower than that of the phosphorus removal adsorbent. The phosphorus removal adsorbent with the proportion of 1.
Experimental example 2
The results of experiments performed on different examples compared to experimental example 1 at pH 1.5, 4, 5, 7, 10, 11 of phosphate, respectively, are shown in table 2.
TABLE 2 removal rates at different pH
As can be seen from Table 2, the phosphorus removal adsorbents of the invention have certain differences in adsorption removal effects on phosphorus-containing solutions with different pH values, but the adsorption removal rates of the phosphorus removal adsorbents of the invention are more than 70%, and the adsorption removal rates of the phosphorus removal adsorbents of the invention are basically stable under different pH conditions when the mass ratio of limestone to sludge is in the range of 3-6. The phosphorus removal adsorbent obtained by calcining at 600 ℃ and 700 ℃ has poor adsorption removal effect, and the phosphorus removal adsorbent with the proportion of 1.
Example 9
The phosphate-loaded material obtained in example 1 was added to the soil for lettuce planting at 1% of the dry weight of the soil, so that the germination rate and plant height of lettuce were increased by 21.7% and 45%, respectively, and the dry weight and fresh weight of plants were increased by 50.4% and 52%, respectively, for lettuce growth.
Example 10
The phosphate-loaded material obtained in the example 1 is added into the soil for planting the leaf lettuce polluted by Cd according to 1% of the dry weight of the soil, the content of Cd in the Cd-polluted soil is 10mg/kg, the germination rate and the plant height of the leaf lettuce are respectively promoted by 8.9% and 5.8%, the dry weight and the fresh weight of the leaf lettuce are respectively increased by 19.7% and 14.3%, and the exchangeable Cd in the soil is reduced by 9.5%.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. The phosphorus removal adsorbent is characterized in that: the raw materials are waste limestone and sludge, the waste limestone is waste materials generated in the processes of building stone production and limestone ore mining, and the sludge is a material generated in the process of sewage treatment;
the preparation method of the phosphorus removal adsorbent comprises the following steps:
mixing waste limestone and sludge, and then heating in a tubular furnace to obtain a phosphorus removal adsorbent;
the temperature of the heating treatment is 800 ℃ for 2h;
the heating rate is 5-15 ℃/min;
the dry weight mass ratio of the waste limestone to the sludge is 3-6;
before mixing the waste limestone with the sludge, firstly carrying out crushing treatment to obtain waste limestone powder with the particle size of less than or equal to 0.1 mm;
the sludge is dried before being mixed with the waste limestone, the drying temperature is 90-110 ℃, and the drying time is 16-30h.
2. The phosphorus removal adsorbent of claim 1, wherein: the heating rate was 10 ℃/min.
3. The phosphorus removal adsorbent of any one of claims 1-2, wherein the phosphorus removal adsorbent is used in the field of phosphorus removal of water bodies.
4. The method for removing phosphorus from water body by using the phosphorus removal adsorbent of any one of claims 1-2, is characterized in that: the method comprises the steps of putting the phosphorus removal adsorbent into the wastewater, and obtaining the phosphate-loaded material and the treated wastewater after adsorption.
5. A phosphate loaded material obtainable by the process of claim 4.
6. Use of the phosphate-loaded material of claim 5 as a passivating agent for phosphate fertilizers or Cd contaminated soil.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20160052800A1 (en) * | 2013-07-12 | 2016-02-25 | Suzhou Micro Ceramics Heavy Metal Filter Technology Co., Ltd. | A filter material having a function of adsorbing and fixing arsenic and heavy metals |
| CN105688805A (en) * | 2016-01-08 | 2016-06-22 | 中国环境科学研究院 | Method for synthesizing mesoporous carbon material by catalyzing sludge of urban sewage treatment plant through alkaline-earth metal method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20160052800A1 (en) * | 2013-07-12 | 2016-02-25 | Suzhou Micro Ceramics Heavy Metal Filter Technology Co., Ltd. | A filter material having a function of adsorbing and fixing arsenic and heavy metals |
| CN105688805A (en) * | 2016-01-08 | 2016-06-22 | 中国环境科学研究院 | Method for synthesizing mesoporous carbon material by catalyzing sludge of urban sewage treatment plant through alkaline-earth metal method |
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