A wastewater organic phosphorus remover and preparation method thereof
The wastewater organic phosphorus remover, prepared by activating and modifying lanthanum-based adsorbents with diatomaceous earth, addresses the inefficiencies of existing methods by enhancing adsorption capacity and stability, achieving high removal efficiency and preventing loss in continuous flow systems.
Patent Information
- Application Number
- CN202311640060.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2023-12-04
- Publication Date
- 2024-12-31
- Estimated Expiration
- 2043-12-04
AI Technical Summary
Existing phosphorus removal methods, such as chemical precipitation, biological treatment, and adsorption, face issues like high operating costs, secondary pollution, poor stability, and low efficiency, particularly with lanthanum-based adsorbents having reduced specific surface area and phosphorus adsorption utilization rate, and are difficult to use in continuous flow systems.
A method involving the preparation of a wastewater organic phosphorus remover by mixing lanthanum salt, sodium dodecylbenzene sulfonate, and diatomaceous earth, followed by activation and modification with triethanolamine dodecylbenzenesulfonate and glyoxal, to enhance adsorption capacity and electrostatic attraction, forming a tighter connection with diatomite to prevent loss in continuous flow systems.
The prepared remover achieves high adsorption speed, large adsorption amount, and high removal rate for organic phosphorus with no secondary pollution, improving the utilization rate and adsorption efficiency through increased active sites and electrostatic effects.
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of sewage treatment, and in particular to a wastewater organic phosphorus remover and a preparation method thereof. Background Art
[0002] Organic phosphorus is a compound containing carbon-phosphorus bonds or a phosphoric acid derivative containing organic groups. Electroplating, printing and dyeing, chemical wastewater and municipal sewage all contain a certain concentration of organic phosphorus. Organic phosphorus wastewater is highly toxic and difficult to degrade. Once discharged into the environment, it will cause great damage to the ecological environment.
[0003] So far, a lot of research work has been carried out in the treatment of organic phosphorus wastewater at home and abroad. The main treatment methods include chemical precipitation, biological method and adsorption method. The application scope and treatment effect of different methods on organic phosphorus wastewater are also quite different. The chemical precipitation method is easy to operate and has a quick effect, but the operating cost is high, and the sludge output is large, which is easy to cause secondary pollution; the biological method has a low operating cost, but the operating conditions and environmental requirements are relatively high, the stability is poor, and it is difficult to meet the emission standards by relying solely on biological treatment; the adsorption method has simple process, easy operation and significant phosphorus removal effect. Among them, the adsorption method has attracted widespread attention due to its low cost, simple operation, high removal efficiency, applicability to both high-concentration and low-concentration phosphorus-containing water bodies, and the ability to recover non-renewable phosphorus resources.
[0004] Lanthanum (La) is a rare earth element with a strong affinity for phosphorus and is an efficient adsorbent for phosphate compounds. However, the specific surface area of common lanthanide compounds is reduced, and the phosphorus adsorption utilization rate is reduced. Secondly, lanthanide compounds used for phosphorus adsorption generally exist in the form of fine particles, which are easily lost with water flow and are difficult to use in continuous flow systems. Summary of the invention
[0005] In view of the above-mentioned defects of the prior art, the technical problem to be solved by the present invention is to provide a wastewater organic phosphorus remover with good adsorption capacity and high utilization rate.
[0006] In order to achieve the above-mentioned object of the invention, the present invention adopts the following technical solutions:
[0007] A method for preparing a wastewater organic phosphorus remover comprises the following steps:
[0008] S1: lanthanum salt, sodium dodecylbenzene sulfonate and water are mixed uniformly to obtain solution 1;
[0009] S2 dissolves sodium carbonate in water to obtain solution 2;
[0010] S3: adding solution 2 to solution 1, heating the solution to react and obtaining an activated lanthanum-based adsorbent;
[0011] S4: dispersing diatomaceous earth in water, adding triethanolamine dodecylbenzenesulfonate, filtering after ultrasonic reaction, collecting solids, washing and drying the solids to obtain modified diatomaceous earth;
[0012] S5: mixing the activated lanthanum-based adsorbent, modified diatomaceous earth, glyoxal and water and heating them for reaction to obtain the wastewater organic phosphorus remover.
[0013] Further preferably, the method for preparing the wastewater organic phosphorus remover comprises the following steps:
[0014] S1: stirring lanthanum salt, sodium dodecyl sulfate and water at 600-800 rpm for 5-10 min to obtain solution 1;
[0015] S2: Mix sodium carbonate and water and stir at 600-800 rpm for 3-5 min to obtain solution 2;
[0016] S3: adding solution 2 to solution 1 at a rate of 2-3 drops / second, heating to 50-80°C for reaction for 2-4 hours, cooling to room temperature after the reaction is completed, filtering, collecting the filter cake, washing the filter cake with water, calcining it in a muffle furnace for 3-5 hours, and grinding it after cooling to obtain an activated lanthanum-based adsorbent;
[0017] S4: dispersing diatomaceous earth in water, adding triethanolamine dodecylbenzenesulfonate, filtering after ultrasonic reaction, collecting solids, washing and drying the solids to obtain modified diatomaceous earth;
[0018] S5: at 20-40°C, the activated lanthanum-based adsorbent, modified diatomaceous earth, glyoxal and water are mixed and placed in a nitrogen atmosphere, heated to 60-80°C for reaction for 2-5h, naturally cooled to 20-30°C, the filter cake is collected, the filter cake is washed with water and then dried at 60-80°C for 6-8h to obtain the wastewater organic phosphorus remover.
[0019] Preferably, the lanthanum salt in step S1 includes at least one of lanthanum nitrate, lanthanum acetate, lanthanum chloride and lanthanum sulfate.
[0020] Preferably, in step S1, the mass ratio of lanthanum salt to sodium dodecylbenzene sulfonate is 1:3-5.
[0021] Preferably, the concentration of solution 2 in step S2 is 10-20 wt %.
[0022] Preferably, in step S3, the mass ratio of solution 1 to solution 2 is 1:3-5.
[0023] Preferably, in step S4, the mass ratio of diatomaceous earth to triethanolamine dodecylbenzenesulfonate is 1:1-2.
[0024] Preferably, the ultrasonic reaction conditions in step S4 are 60-100 Hz and 120-150 W.
[0025] Preferably, in step S5, the mass ratio of the activated lanthanum-based adsorbent, modified diatomaceous earth, glyoxal, and water is 1:10-20:0.5-1:100-200.
[0026] The invention also discloses the application of the wastewater organic phosphorus remover, which is soaked in high-concentration organic phosphorus-containing wastewater at a solid-liquid mass ratio of 1:500-1500, and mechanically stirred for 20-24 hours.
[0027] Lanthanum oxide is a type of rare earth oxide, and rare earth oxide and diatomaceous earth are both commonly used phosphorus removal adsorbents. However, the phosphorus removal adsorbents of rare earth oxide and diatomaceous earth are slow in effect and have a small adsorption capacity, and further improvement is needed.
[0028] The present invention uses diatomite to load the activated lanthanum-based adsorbent. The diatomite has a high content of lanthanum elements, which increases the active sites on the surface of the diatomite. Sodium dodecylbenzene sulfonate can form voids and remain as carbon after calcination of the lanthanum salt, which helps to improve the adsorption effect of the lanthanum-based adsorbent. After the diatomite is ultrasonically modified by triethanolamine dodecylbenzene sulfonate, the interlayer spacing becomes larger, providing more adsorption space for organic phosphorus. Due to the introduction of triethanolamine dodecylbenzene sulfonate, the diatomite interlayer is positively charged, and there is an electrostatic effect of mutual attraction between the diatomite and the negatively charged organic phosphorus. Through the dual combination of adsorption and electrostatic effect, the phosphorus removal effect of the wastewater organic phosphorus remover is higher. By adding ethylenediamine, the connection between the lanthanum-based adsorbent and the diatomite is made tighter, so that the wastewater organic phosphorus remover is not easy to be lost with the water flow in the continuous flow system, and the utilization rate of the material is improved.
[0029] Compared with the prior art, the present invention has the following beneficial effects:
[0030] 1. The wastewater organic phosphorus remover prepared by the present invention is used to treat wastewater containing organic phosphorus, and has a fast adsorption speed, a large adsorption amount and a high removal rate for organic phosphorus in the wastewater, and achieves high efficiency and no secondary pollution in the phosphorus removal of wastewater containing organic phosphorus;
[0031] 2. The present invention increases the active sites on the surface of diatomite by loading activated lanthanum-based adsorbent with diatomite, and improves the adsorption effect of lanthanum-based adsorbent. After ultrasonic modification of diatomite, the interlayer spacing becomes larger, providing more adsorption space for organic phosphorus. Due to the introduction of triethanolamine dodecylbenzenesulfonic acid, the interlayer of diatomite is positively charged, and the phosphorus removal effect of the wastewater organic phosphorus remover is higher through the dual combination of adsorption and electrostatic action. By adding ethylenediamine, the connection between the lanthanum-based adsorbent and diatomite is made tighter, so that the wastewater organic phosphorus remover is not easy to be lost with the water flow in the continuous flow system, and the utilization rate of the material is improved. DETAILED DESCRIPTION
[0032] The following will be combined with the embodiments to clearly and completely describe the concept of the present invention and the technical effects produced, so as to fully understand the purpose, characteristics and effects of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, other embodiments obtained by those skilled in the art without creative work are all within the scope of protection of the present invention.
[0033] To avoid redundancy, the items used in the following examples are all commercially available products unless otherwise specified, and the methods used are all conventional methods unless otherwise specified.
[0034] Example 1
[0035] A method for preparing a wastewater organic phosphorus remover comprises the following steps:
[0036] S1: 10.8 g of lanthanum nitrate, 50 g of sodium dodecyl sulfate and 200 g of water were stirred at 700 rpm for 10 min to obtain solution 1;
[0037] S2: Mix 3.5 g of sodium carbonate and 10 g of water and stir at 700 rpm for 3-5 min to obtain solution 2;
[0038] S3: adding solution 2 to solution 1 at a rate of 2 drops / second, heating to 60°C for reaction for 3 hours, cooling to room temperature after the reaction is completed, filtering, collecting the filter cake, washing the filter cake with water, calcining it in a muffle furnace at 1050°C for 4 hours, and grinding it through a 40-mesh sieve after natural cooling to obtain an activated lanthanum-based adsorbent;
[0039] S4: 150 g of diatomaceous earth was dispersed in 2000 g of water, 220 g of triethanolamine dodecylbenzenesulfonate was added, and the mixture was subjected to ultrasonic reaction at 80 Hz and 140 W for 2 h, and then filtered to collect the solid matter, which was washed with water for 3 times and then dried at 80 ° C for 6 h to obtain modified diatomaceous earth;
[0040] S5: At 30°C, 5g of activated lanthanum-based adsorbent, 70g of modified diatomaceous earth, 3g of glyoxal, and 500g of water are mixed and placed in a nitrogen atmosphere, heated to 70°C for reaction for 4h, naturally cooled to 30°C, and the filter cake is collected. The filter cake is washed with water 3 times and then dried at 80°C for 6h to obtain the wastewater organic phosphorus remover.
[0041] Comparative Example 1
[0042] A method for preparing a wastewater organic phosphorus remover comprises the following steps:
[0043] S1: 10.8 g of lanthanum nitrate, 50 g of sodium dodecyl sulfate and 200 g of water were stirred at 700 rpm for 10 min to obtain solution 1;
[0044] S2: Mix 3.5 g of sodium carbonate and 10 g of water and stir at 700 rpm for 3-5 min to obtain solution 2;
[0045] S3: adding solution 2 to solution 1 at a rate of 2 drops / second, heating to 60°C for reaction for 3 hours, cooling to room temperature after the reaction is completed, filtering, collecting the filter cake, washing the filter cake with water, calcining it in a muffle furnace at 1050°C for 4 hours, and grinding it through a 40-mesh sieve after natural cooling to obtain an activated lanthanum-based adsorbent;
[0046] S4: At 30°C, 5g of activated lanthanum-based adsorbent, 70g of diatomaceous earth, 3g of glyoxal, and 500g of water were mixed and placed in a nitrogen atmosphere, heated to 70°C for reaction for 4h, naturally cooled to 30°C, and the filter cake was collected. The filter cake was washed with water 3 times and then dried at 80°C for 6h to obtain the wastewater organic phosphorus remover.
[0047] Comparative Example 2
[0048] A method for preparing a wastewater organic phosphorus remover comprises the following steps:
[0049] S1: 150 g of diatomaceous earth was dispersed in 2000 g of water, 220 g of triethanolamine dodecylbenzenesulfonate was added, and the mixture was subjected to ultrasonic reaction at 80 Hz and 140 W for 2 h, and then filtered to collect the solid matter, which was washed with water for 3 times and dried at 80 ° C for 6 h to obtain modified diatomaceous earth;
[0050] S2: At 30°C, 5g of lanthanum nitrate, 70g of modified diatomaceous earth, 3g of glyoxal, and 500g of water were mixed and placed in a nitrogen atmosphere, heated to 70°C for reaction for 4h, naturally cooled to 30°C, and the filter cake was collected. The filter cake was washed with water 3 times and then dried at 80°C for 6h to obtain the wastewater organic phosphorus remover.
[0051] Comparative Example 3
[0052] A method for preparing a wastewater organic phosphorus remover comprises the following steps:
[0053] S1: 10.8 g of lanthanum nitrate, 50 g of sodium dodecyl sulfate and 200 g of water were stirred at 700 rpm for 10 min to obtain solution 1;
[0054] S2: Mix 3.5 g of sodium carbonate and 10 g of water and stir at 700 rpm for 3-5 min to obtain solution 2;
[0055] S3: adding solution 2 to solution 1 at a rate of 2 drops / second, heating to 60°C for reaction for 3 hours, cooling to room temperature after the reaction is completed, filtering, collecting the filter cake, washing the filter cake with water, calcining it in a muffle furnace at 1050°C for 4 hours, and grinding it through a 40-mesh sieve after natural cooling to obtain an activated lanthanum-based adsorbent;
[0056] S4: 150 g of diatomaceous earth was dispersed in 2000 g of water, 220 g of triethanolamine dodecylbenzenesulfonate was added, and the mixture was subjected to ultrasonic reaction at 80 Hz and 140 W for 2 h, and then filtered to collect the solid matter, which was washed with water for 3 times and then dried at 80 ° C for 6 h to obtain modified diatomaceous earth;
[0057] S5: At 30°C, 5g of activated lanthanum-based adsorbent, 70g of modified diatomaceous earth and 500g of water are mixed and placed in a nitrogen atmosphere, heated to 70°C for reaction for 4h, naturally cooled to 30°C, and the filter cake is collected. The filter cake is washed with water 3 times and then dried at 80°C for 6h to obtain the wastewater organic phosphorus remover.
[0058] Test Case
[0059] (1) Preparation of simulated phosphorus-containing wastewater
[0060] Add dipotassium hydrogen phosphate into the container to prepare 15 L of phosphorus-containing wastewater with a phosphorus concentration of 5 mg / L. Take 4 500 mL conical flasks and add 500 mL of simulated phosphorus-containing wastewater into each conical flask. Label them A1, A2, A3, and A4 respectively.
[0061] (2) Treatment of simulated phosphorus-containing wastewater
[0062] Take 1g of the wastewater organic phosphorus remover prepared in each embodiment and comparative example and add it to the conical flasks of A1, A2, A3 and A4 respectively, stir it with magnetic force at 25°C, test the concentration of organic phosphorus in the simulated phosphorus-containing wastewater for 10 hours, and refer to the molybdenum antimony anti-spectrophotometric method in the "Water and Wastewater Monitoring and Analysis Methods (Fourth Edition)" to detect the concentration of total phosphorus in the water sample. And calculate the adsorption amount and adsorption rate according to the test results.
[0063] Adsorption rate (η) = (C0-C e )×100% / C0
[0064] Adsorption amount (q e)=(C0-Ce)×V / m;
[0065] Among them, q e is the equilibrium adsorption capacity, mg / g;
[0066] C0 is the initial concentration of the solution, mg / L;
[0067] Ce is the equilibrium concentration of the solution after adsorption, mg / L;
[0068] V is the volume of the solution, L;
[0069] m is the mass of adsorbent added, g.
[0070] The test results are shown in Table 1:
[0071] Table 1 Test results
[0072] 10h adsorption capacity 10h removal rate (%) Example 1 2.663 99.5 Comparative Example 1 2.510 92.3 Comparative Example 2 2.312 90.2 Comparative Example 3 2.221 87.6
[0073] It can be seen from the experimental data in Table 1 that the wastewater organic phosphorus remover of Example 1 has the best effect of removing organic phosphorus, and the difference between Example 1 and other comparative examples is that the wastewater organic phosphorus remover is obtained by reacting an activated lanthanum-based adsorbent, modified diatomaceous earth, and glyoxal. The possible reason for this phenomenon is that the lanthanum content introduced into the diatomaceous earth is relatively high, which increases the active sites on the surface of the diatomaceous earth, and sodium dodecylbenzene sulfonate can form voids and remain as a large amount of carbon after calcination of lanthanum salt, which helps to improve the adsorption effect of the lanthanum-based adsorbent. After the diatomaceous earth is ultrasonically modified by triethanolamine dodecylbenzenesulfonate, the interlayer spacing becomes larger, providing more adsorption space for organic phosphorus. Due to the introduction of triethanolamine dodecylbenzenesulfonate, the diatomaceous earth interlayer is positively charged, and there is an electrostatic effect of mutual attraction between the diatomaceous earth and the negatively charged organic phosphorus. Through the dual combination of adsorption and electrostatic effect, the phosphorus removal effect of the wastewater organic phosphorus remover is higher.
Claims
1. A method for preparing a wastewater organic phosphorus remover, characterized in that: The method comprises the following steps: S1, stirring lanthanum salt, sodium dodecyl sulfate and water at a rotation speed of 600-800 rpm for 5-10 minutes to obtain solution 1; S2: Mix sodium carbonate and water and stir at 600-800 rpm for 3-5 min to obtain solution 2; S3: adding solution 2 to solution 1 at a rate of 1-2 drops / second, heating to 50-80°C for reaction for 2-4 hours, cooling to room temperature after the reaction is completed, filtering, collecting the filter cake, washing the filter cake with water, calcining it in a muffle furnace for 3-5 hours, and grinding it after cooling to obtain an activated lanthanum-based adsorbent; S4: dispersing diatomaceous earth in water, adding triethanolamine dodecylbenzenesulfonate, filtering after ultrasonic reaction, collecting solids, washing and drying the solids to obtain modified diatomaceous earth; S5: at 20-40°C, the activated lanthanum-based adsorbent, modified diatomaceous earth, glyoxal and water are mixed and placed in a nitrogen atmosphere, heated to 60-80°C for reaction for 2-5h, naturally cooled to 20-30°C, the filter cake is collected, the filter cake is washed with water and then dried at 60-80°C for 6-8h to obtain the wastewater organic phosphorus remover. The lanthanum salt in step S1 includes at least one of lanthanum nitrate, lanthanum acetate, lanthanum chloride and lanthanum sulfate; In step S1, the mass ratio of lanthanum salt to sodium dodecylbenzene sulfonate is 1:3-5; The concentration of solution 2 in step S2 is 10-20wt%; The ultrasonic reaction conditions in step S4 are 60-100 Hz, 120-150 W; In the step S4, the mass ratio of diatomaceous earth to triethanolamine dodecylbenzenesulfonate is 1:1-2; In the step S5, the mass ratio of the activated lanthanum-based adsorbent, modified diatomaceous earth, glyoxal, and water is 1:10-20:0.5-1:100-200.
2. A wastewater organic phosphorus remover, characterized in that: The wastewater organic phosphorus remover is prepared by the preparation method of the wastewater organic phosphorus remover according to claim 1.
3. The use of the wastewater organic phosphorus remover as claimed in claim 2, characterized in that: The wastewater organic phosphorus remover is immersed in high-concentration organic phosphorus-containing wastewater at a solid-liquid mass ratio of 1:500-1500, and mechanically stirred for 20-24 hours.