Preparation method and application of material for removing organic phosphorus / phosphine in high-salinity wastewater

Abstract

The invention discloses a preparation method and application of a material for removing organic phosphorus / phosphine in high-salinity wastewater, and belongs to the technical field of sewage treatment.The preparation method comprises the following steps that firstly, metal oxide or hydroxide A and metal salt B are mixed, deionized water is added, and turbid liquid C is obtained; 2, preparing an alkali solution for later use; 3, adjusting the pH value of the turbid liquid C by using the alkaline solution obtained in the step 2, and curing by using a magnetic stirrer at room temperature or under a water bath heating condition; and 4, after the reaction is finished, centrifuging the material obtained by curing in the step 3, carrying out suction filtration, cleaning with deionized water, drying at a constant temperature in an air dry oven, and grinding to obtain the chemical for removing organic phosphorus / phosphine. According to the preparation method and application of the material for removing the organic phosphorus / phosphine in the high-salinity wastewater, the prepared agent can efficiently remove organic phosphorus / phosphine pollutants in the wastewater, so that the water quality is improved, and the wastewater treatment efficiency is improved.

Description

Technical Field

[0001] The invention relates to the technical field of sewage treatment, and in particular to a preparation method and application of a material for removing organic phosphorus / phosphine from high-salinity wastewater. Background Art

[0002] Organic phosphorus / phosphine antiscalants contain one or more C-PO(OH) 2 The organic phosphorus / phosphine scale inhibitor has the excellent performance of forming chelate compounds with calcium ions and magnesium ions. This property enables it to effectively inhibit the formation of scale, so it is widely used in reverse osmosis technology, seawater desalination process, boiler water treatment, industrial cooling water system and other fields. With the implementation of the national zero emission policy and the promotion of industrial wastewater recycling schemes, the industry has put forward more stringent requirements on the utilization and regeneration of water resources. Against this background, the application scope of organic phosphorus / phosphine scale inhibitors continues to expand. Market data shows that the global scale inhibitor market is valued at US$3.5 billion in 2022, increasing to US$3.66 billion in 2023, and is expected to reach US$5.05 billion by 2030.

[0003] Although organophosphorus / phosphine scale inhibitors are effective in industrial applications, their residues in wastewater may cause a series of environmental problems, including the reactivation of toxic metals, eutrophication of water bodies due to phosphorus / phosphine enrichment, deterioration of the water ecological environment, and threats to human health. In addition, wastewater usually has complex water quality characteristics and a high-salt environment, which makes traditional removal methods face significant challenges in treating organophosphorus / phosphine. Therefore, there is an urgent need to develop efficient organophosphorus / phosphine removal materials to solve these environmental problems and improve wastewater treatment efficiency, thereby achieving sustainable development and environmental protection. Summary of the invention

[0004] The purpose of the present invention is to provide a method for preparing a material for removing organic phosphorus / phosphine in high-salt wastewater and its application. The prepared agent can efficiently remove organic phosphorus / phosphine pollutants in wastewater, thereby improving water quality and enhancing wastewater treatment efficiency.

[0005] To achieve the above object, the present invention provides a method for preparing a material for removing organic phosphorus / phosphine from high-salinity wastewater, comprising the following steps:

[0006] Step 1: Mix metal oxide or hydroxide A and metal salt B, add deionized water, and obtain suspension C;

[0007] Step 2: prepare alkaline solution for standby use;

[0008] Step 3: adjusting the pH of the suspension C with the alkaline solution obtained in step 2, stirring with a magnetic stirrer, and ripening at room temperature or in a water bath;

[0009] Step 4: After the reaction is completed, the material obtained by ripening in step 3 is centrifuged, filtered, and then washed with deionized water, and then dried and ground in a forced air drying oven at a constant temperature to obtain an agent for removing organic phosphorus / phosphine.

[0010] Preferably, in step 1, when A is a metal oxide, A includes one or more of titanium dioxide, cobalt trioxide, nickel oxide, copper oxide, molybdenum oxide, bismuth oxide, ferric oxide, ferrous oxide, aluminum oxide, and zinc oxide; when A is a hydroxide, A includes one or more of ferric hydroxide, copper hydroxide, zinc hydroxide, aluminum hydroxide, and bismuth hydroxide; and B includes divalent iron Fe 2+ 、Co 2+ 、Zn 2+ Mg 2+ , Ca 2+ , Cu 2+ One or more metal salts.

[0011] Preferably, based on metal, the molar ratio of A to B is A:B=1:50-50:1.

[0012] Preferably, the alkaline solution in step 2 includes one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, and calcium hydroxide.

[0013] Preferably, in step three, the pH is adjusted to 7-12, the water bath heating temperature is 20-100° C., and the aging time is 1-24 h.

[0014] Preferably, in step 4, the temperature of the blast drying oven is 25-80° C., and the drying time is 0.5-24 h.

[0015] The present invention also provides an application of a material for removing organic phosphorus / phosphine in high-salt wastewater. The agent prepared by the above-mentioned method for preparing a material for removing organic phosphorus / phosphine in high-salt wastewater is applied to remove organic phosphorus / phosphine in various wastewaters containing organic phosphorus / phosphine pollutants, and the wastewater containing organic phosphorus / phosphine pollutants includes high-salt wastewater.

[0016] Preferably, the application includes the following steps: adding a reagent to high-salinity wastewater, stirring at room temperature, performing adsorption treatment, and obtaining high-salinity wastewater free of organic phosphorus / phosphine by a solid-liquid separation method.

[0017] Preferably, the dosage of the agent is 50-500 mg / L, the stirring time is 0.5-48 h, and the pH of the high-salt wastewater is 4-11.

[0018] Preferably, the organic phosphorus / phosphine removed by the agent includes: methyl phosphine, hydroxymethyl phosphine, 1-hydroxyphosphonoacetic acid, 2-hydroxyethylphosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, aminotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphoric acid, diethylenetriaminepentamethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, bishydroxytrimethylenephosphonic acid acrylic acid, and the organic phosphorus / phosphine contains one or more C-PO(OH) 2 Group.

[0019] The mechanism of preparing materials for removing organic phosphorus / phosphine from high-salinity wastewater is:

[0020]

[0021] Therefore, the present invention adopts the above-mentioned preparation method and application of a material for removing organic phosphorus / phosphine in high-salt wastewater, which has the following beneficial effects:

[0022] (1) The preparation method is simple, environmentally friendly and low-cost;

[0023] (2) The prepared organic phosphorus / phosphine removal agent shows an ultra-high adsorption removal efficiency for organic phosphorus / phosphine, and can effectively remove organic phosphorus / phosphine in wastewater, thereby improving water quality and enhancing wastewater treatment efficiency.

[0024] The technical solution of the present invention is further described in detail below through the accompanying drawings and embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 This is a scanning electron microscope image of a preparation method of a material for removing organic phosphorus / phosphine from high-salt wastewater and an application example 1 of the present invention;

[0026] Figure 2 This is the XRD diffraction pattern of the agent prepared in the preparation method of the material for removing organic phosphorus / phosphine from high-salt wastewater and the application implementation case 1 of the present invention;

[0027] Figure 3 It is a bar graph showing the removal efficiency of organic phosphorus / phosphine in high-salt wastewater by the agent prepared in implementation cases 1-3 and comparative example 1, according to a method for preparing a material for removing organic phosphorus / phosphine in high-salt wastewater of the present invention and its application. DETAILED DESCRIPTION

[0028] The technical solution of the present invention is further described below through the accompanying drawings and embodiments.

[0029] Unless otherwise defined, technical or scientific terms used in the present invention shall have the common meanings understood by one having ordinary skills in the field to which the present invention belongs.

[0030] Example

[0031] The present invention provides a method for preparing a material for removing organic phosphorus / phosphine from high-salinity wastewater, comprising the following steps:

[0032] Step 1: Mix metal oxide or hydroxide A with metal salt B, add deionized water, and obtain suspension C; when A is a metal oxide, A includes one or more of titanium dioxide, cobalt trioxide, nickel oxide, copper oxide, molybdenum oxide, bismuth oxide, ferric oxide, ferrous oxide, aluminum oxide, zinc oxide, etc.; when A is a hydroxide, A includes one or more of ferric hydroxide, copper hydroxide, zinc hydroxide, aluminum hydroxide, bismuth hydroxide, etc.; B includes divalent iron Fe 2+ 、Co 2+ 、Zn 2+ Mg 2 + , Ca 2+ , Cu 2+ One or more of metal salts, etc. Calculated on the basis of metal, the molar ratio of A to B is A:B=1:50-50:1, preferably A:B=1:5.

[0033] Step 2: prepare an alkaline solution for use, wherein the alkaline solution includes one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, calcium hydroxide, etc.

[0034] Step 3: adjust the pH value of suspension C to 7-12 with the alkaline solution obtained in step 2, stir with a magnetic stirrer, and heat and mature at room temperature or in a water bath. The water bath heating temperature is 20-100° C. and the maturation time is 1-24 h.

[0035] Step 4: After the reaction is completed, the material obtained by ripening in step 3 is centrifuged, filtered, and then washed with deionized water, and then dried and ground in a constant temperature blower drying oven to obtain an organic phosphorus / phosphine removal agent, wherein the temperature of the blower drying oven is 25-80°C and the drying time is 0.5-24h.

[0036] The present invention also provides an application of a material for removing organic phosphorus / phosphine from high-salt wastewater. The agent prepared by the above-mentioned method for preparing a material for removing organic phosphorus / phosphine from high-salt wastewater is applied to remove organic phosphorus / phosphine from various wastewaters containing organic phosphorus / phosphine pollutants. The wastewater containing organic phosphorus / phosphine pollutants includes high-salt wastewater. The application includes the following steps: adding the agent to the high-salt wastewater, stirring at room temperature, performing adsorption treatment, and obtaining high-salt wastewater without organic phosphorus / phosphine by a solid-liquid separation method. The dosage of the agent is 50-500 mg / L, the stirring time is 0.5-48 hours, the pH of the high-salt wastewater is 4-11, and the metal oxide (or hydroxide) A is ensured to be solid and insoluble, and the metal salt B is soluble.

[0037] Organic phosphorus / phosphine that can be removed by the agent includes those containing one or more C-PO(OH) 2 Organic phosphorus / phosphine of groups, such as: methyl phosphine, hydroxymethyl phosphine, 1-hydroxyphosphonoacetic acid, 2-hydroxyethylphosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTCA), aminotrimethylenephosphonic acid (ATMP), 1-hydroxyethylidene-1,1-diphosphoric acid, diethylenetriaminepenta(methylenephosphonic acid) (DTPMP), ethylenediaminetetramethylenephosphonic acid (EDTMP), bis(hydroxytrimethylenephosphonic acid) acrylic acid (BHTPMPA), etc.

[0038] Implementation Case 1

[0039] A method for preparing a material for removing organic phosphorus / phosphine from high-salinity wastewater comprises the following steps:

[0040] (1) mixing bismuth oxide and anhydrous calcium chloride so that the molar ratio of bismuth to calcium is 1:5, and adding deionized water to obtain a solution C;

[0041] (2) mixing sodium hydroxide and sodium bicarbonate to prepare an alkaline solution for use, wherein the ratio of sodium hydroxide to sodium bicarbonate is 2:1;

[0042] (3) Adjusting the pH of solution C to 12 with the alkaline solution prepared in (2), stirring with a magnetic stirrer, and keeping at room temperature for 1 hour to mature;

[0043] (4) After the reaction is completed, the material is centrifuged, filtered, and then washed with deionized water, and then dried in a forced air drying oven at 55° C. for 4 h, and ground to obtain an agent for removing organic phosphorus / phosphine.

[0044] Figure 1 This is a scanning electron microscope image of the drug prepared in Example 1, wherein Figure 1 (a) is the surface morphology of the agent at a certain position. Figure 1 (b) is a surface morphology of the agent at another location. It can be seen from the figure that the surface of the agent is relatively rough and has irregular particles distributed thereon. Figure 2 This is the XRD diffraction pattern of the medicine prepared in Example 1. It can be seen from the figure that multiple sharp diffraction peaks appear in the diffraction pattern, indicating that the medicine has a good crystal structure.

[0045] Implementation Case 2

[0046] A method for preparing a material for removing organic phosphorus / phosphine from high-salinity wastewater comprises the following steps:

[0047] (1) mixing bismuth oxide and anhydrous calcium chloride so that the molar ratio of bismuth to calcium is 1:3, and adding deionized water to obtain a solution C;

[0048] (2) mixing sodium hydroxide and sodium bicarbonate to prepare an alkaline solution for use, wherein the ratio of sodium hydroxide to sodium bicarbonate is 1:1;

[0049] (3) Solution C was adjusted to pH 12 with the mixed alkali solution prepared in (2), stirred with a magnetic stirrer, and heated in a water bath at 70° C. for 1 hour to mature;

[0050] (4) After the reaction is completed, the material is centrifuged, filtered, and then washed with deionized water, and then dried in a forced air drying oven at 55° C. for 4 h, and ground to obtain an agent for removing organic phosphorus / phosphine.

[0051] Implementation Case 3

[0052] A method for preparing a material for removing organic phosphorus / phosphine from high-salinity wastewater comprises the following steps:

[0053] (1) mixing bismuth oxide and anhydrous calcium chloride so that the molar ratio of bismuth to calcium is 1:10, and adding deionized water to obtain a solution C;

[0054] (2) mixing sodium hydroxide and sodium bicarbonate to prepare an alkaline solution for use, wherein the ratio of sodium hydroxide to sodium bicarbonate is 2:1;

[0055] (3) Solution C was adjusted to pH 12 with the mixed alkali solution prepared in (2), stirred with a magnetic stirrer, and heated in a water bath at 70° C. for 1 hour to mature;

[0056] (4) After the reaction is completed, the material is centrifuged, filtered, and then washed with deionized water, and then dried in a forced air drying oven at 75° C. for 6 hours, and ground to obtain an agent for removing organic phosphorus / phosphine.

[0057] Comparative Example 1

[0058] A method for preparing a material for removing organic phosphorus / phosphine from high-salinity wastewater comprises the following steps:

[0059] (1) mixing bismuth oxide and anhydrous calcium chloride so that the molar ratio of bismuth to calcium is 3:8, and adding deionized water to obtain a solution C;

[0060] (2) preparing a mixed solution of sodium hydroxide and sodium bicarbonate for use, wherein the ratio of sodium hydroxide to sodium bicarbonate is 1:1;

[0061] (3) Adjust solution C to pH 9 with the mixed alkali solution prepared in (2), stir with a magnetic stirrer, and heat at room temperature or in a 55°C water bath for 1 hour to mature;

[0062] (4) After the reaction is completed, the material is centrifuged, filtered, and then washed with deionized water, and then dried in a forced air drying oven at 85° C. for 8 h, and ground to obtain an agent for removing organic phosphorus / phosphine.

[0063] Application Testing

[0064] The experiment used actual wastewater containing organic phosphorus / phosphine. The actual water quality was: COD: 220 mg / L, total phosphorus: 11.3 mg P / L, organic phosphorus / phosphine: 9.9 mg P / L, pH: 7.55, TDS: 5.2%, conductivity: 20.5 mS / cm.

[0065] The phosphorus / phosphine removal agents prepared in Implementation Examples 1-3 and Comparative Example 1 were used to treat organic phosphorus / phosphine in actual high-salt wastewater. The specific method was as follows: the phosphorus / phosphine removal agents prepared in Implementation Examples 1-3 and Comparative Example 1 were added to 100 mL of high-salt wastewater at an amount of 200 mg / L, respectively, and stirred and mixed at room temperature for 2 hours, and then solid-liquid separation was performed to obtain effluent after phosphorus / phosphine removal. The organic phosphorus / phosphine content of the treated water was tested and the removal rate and the adsorption amount of the phosphorus / phosphine removal agent were calculated. The measurement results showed that the agents prepared in Implementation Examples 1-3 could efficiently remove organic phosphorus / phosphine from wastewater, and the removal rates of organic phosphorus / phosphine were higher than those in Comparative Example 1, and the removal rate of organic phosphorus / phosphine in high-salt wastewater prepared in Implementation Example 1 was higher, such as Figure 3 shown.

[0066] Therefore, the present invention adopts the above-mentioned preparation method and application of the material for removing organic phosphorus / phosphine in high-salt wastewater, and the prepared agent can effectively remove organic phosphorus / phosphine pollutants in wastewater, thereby improving water quality and enhancing wastewater treatment efficiency.

[0067] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that they can still modify or replace the technical solution of the present invention with equivalents, and these modifications or equivalent replacements cannot cause the modified technical solution to deviate from the spirit and scope of the technical solution of the present invention.

Claims

1. A method for preparing a material for removing organic phosphorus / phosphine from high-salinity wastewater, characterized in that: The following steps are involved: Step 1: Mix metal oxide or hydroxide A and metal salt B, add deionized water, and obtain suspension C; Step 2: prepare alkaline solution for standby use; Step 3: adjusting the pH of the suspension C with the alkaline solution obtained in step 2, stirring with a magnetic stirrer, and ripening at room temperature or in a water bath; Step 4: After the reaction is completed, the material obtained by ripening in step 3 is centrifuged, filtered, and then washed with deionized water, and then dried and ground in a forced air drying oven at a constant temperature to obtain an agent for removing organic phosphorus / phosphine.

2. The method for preparing a material for removing organic phosphorus / phosphine from high-salinity wastewater according to claim 1, characterized in that: In step 1, when A is a metal oxide, A includes one or more of titanium dioxide, cobalt trioxide, nickel oxide, copper oxide, molybdenum oxide, bismuth oxide, ferric oxide, ferrous oxide, aluminum oxide, and zinc oxide; when A is a hydroxide, A includes one or more of ferric hydroxide, copper hydroxide, zinc hydroxide, aluminum hydroxide, and bismuth hydroxide; B includes divalent iron Fe 2+ 、Co 2 + 、Zn 2+ Mg 2+ , Ca 2+ , Cu 2+ One or more metal salts.

3. The method for preparing a material for removing organic phosphorus / phosphine from high-salinity wastewater according to claim 1, characterized in that: Calculated on the basis of metal, the molar ratio of A to B is A:B=1:50-50:

1.

4. The method for preparing a material for removing organic phosphorus / phosphine from high-salinity wastewater according to claim 1, characterized in that: The alkaline solution in step 2 includes one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, and calcium hydroxide.

5. The method for preparing a material for removing organic phosphorus / phosphine from high-salinity wastewater according to claim 1, characterized in that: In step 3, the pH is adjusted to 7-12, the water bath heating temperature is 20-100° C., and the aging time is 1-24 h.

6. The method for preparing a material for removing organic phosphorus / phosphine from high-salinity wastewater according to claim 1, characterized in that: In step 4, the temperature of the blast drying oven is 25-80°C, and the drying time is 0.5-24h.

7. An application of a material for removing organic phosphorus / phosphine from high-salinity wastewater, characterized in that: The agent prepared by the method for preparing a material for removing organic phosphorus / phosphine from high-salinity wastewater as described in any one of claims 1 to 6 is applied to remove organic phosphorus / phosphine from various wastewaters containing organic phosphorus / phosphine pollutants, and wastewater containing organic phosphorus / phosphine pollutants includes high-salinity wastewater.

8. The use of a material for removing organic phosphorus / phosphine from high-salinity wastewater according to claim 7, characterized in that: The application consists of the following steps: A reagent is added to the high-salinity wastewater, stirred at room temperature, subjected to adsorption treatment, and a solid-liquid separation method is used to obtain high-salinity wastewater free of organic phosphorus / phosphine.

9. The use of a material for removing organic phosphorus / phosphine in high-salinity wastewater according to claim 7, characterized in that: The dosage of the agent is 50-500 mg / L, the stirring time is 0.5-48 h, and the pH of the high-salt wastewater is 4-11.

10. The use of a material for removing organic phosphorus / phosphine in high-salinity wastewater according to claim 7, characterized in that: The organic phosphorus / phosphine removed by the agent include: methyl phosphine, hydroxymethyl phosphine, 1-hydroxyphosphonoacetic acid, 2-hydroxyethylphosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, aminotrimethylenephosphonic acid, 1-hydroxyethyl-1,1-diphosphonic acid, diethylenetriamine penta Methylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, bis(hydroxytrimethylenephosphonic acid)acrylic acid, Organic phosphorus / phosphine contains one or more C-PO(OH)2 groups.

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