Polyurethane foam loaded schwertmannite material as well as preparation method and application thereof

Abstract

The invention discloses a polyurethane foam loaded schwertmannite material as well as a preparation method and application thereof, and belongs to the technical field of environmental governance materials. According to the material, polyurethane foam is added in the synthesis process of the Schwertmannite to complete loading of the Schwertmannite, the material has the advantages of efficient arsenic removal of the Schwertmannite and good adsorption performance of the polyurethane foam, and when the material is applied to treatment of arsenic-polluted water, efficient removal of arsenic can be achieved, and the material is greener and more environmentally friendly. The polyurethane foam loaded Schwertmannite material is simple in preparation process and has a good regeneration effect, regeneration and reutilization are achieved through elution of an alkaline solution, it is verified that the arsenic removal effect of the polyurethane foam loaded Schwertmannite material is not obviously affected, the utilization rate of the Schwertmannite material is greatly increased, and the treatment cost of arsenic-polluted water is reduced. The material provided by the invention can be suitable for in-situ treatment of different arsenic-polluted water bodies, is simple in use process and low in cost, and has a good application prospect.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of environmental governance materials, and particularly relates to a polyurethane foam loaded schulte mineral material and a preparation method and application thereof. BACKGROUND

[0002] Metallurgy, mining, fossil fuel combustion, agricultural chemicals, food additives, etc. are important reasons for arsenic pollution in the environment. When arsenic-containing minerals or slag are washed by rainwater, a large amount of arsenic elements will enter the surface water environment, causing the arsenic content in the water body to exceed the standard. Drinking water with excessive arsenic content may cause acute arsenic poisoning, damage to the skin, nervous system, immune system, etc., and greatly increase the risk of cancer. Therefore, strengthening the treatment of arsenic-containing wastewater and arsenic-containing groundwater is of great significance to human health and the ecological environment.

[0003] Schulte mineral is a kind of hydroxyl iron sulfate mineral with porous tunnel structure and large specific surface area. The functional groups (SO4 2- , OH - ) contained in the tunnel and surface of the schulte mineral can replace arsenate ions through adsorption to remove arsenic. At present, schulte mineral shows good effect in the treatment and remediation of arsenic-containing water bodies or arsenic-contaminated soil. However, direct use of schulte mineral in water bodies may cause certain color or turbidity, which may potentially affect water quality. At the same time, when schulte mineral is used for a certain number of times, its adsorption performance will be greatly reduced, and the arsenic removal effect will be significantly reduced. At present, it is difficult to recycle and regenerate the schulte mineral adsorbed with a large amount of arsenic substances, resulting in low reuse rate.

[0004] In summary, it is necessary to provide an arsenic removal material for removing arsenic from water bodies, and the material itself is easy to recycle and regenerate, which is very necessary for efficient, green and low-cost governance of arsenic-contaminated water bodies. SUMMARY

[0005] 1. Problem to be solved

[0006] The present application provides a polyurethane foam loaded schulte mineral material to solve the problem that direct addition of schulte mineral material in existing water body arsenic removal may affect water quality, and the schulte mineral itself is difficult to recycle and regenerate. The schulte mineral is loaded on a hydrophilic polyurethane foam with high porosity and high specific surface area during in-situ synthesis, and the obtained material has the advantages of high-efficiency arsenic removal of schulte mineral and good adsorption performance of polyurethane foam itself. As a water body arsenic removal material, it is easy to recycle and regenerate and can be regenerated and reused by elution with an alkaline solution, which is more green and environmentally friendly.

[0007] 2. Technical solution

[0008] To solve the above problems, the technical scheme adopted by the present application is as follows:

[0009] The present application provides a kind of polyurethane foam load schmitt mineral material, and the load of schmitt mineral in the material is 0.3%~35% (w / w).

[0010] Further, the load of schmitt mineral in the above-mentioned material is 0.3%~1% (w / w) or 25%~35% (w / w). The material with 0.3%~1% schmitt mineral load in the present application is obtained by adding polyurethane foam in the reaction system for synthesizing schmitt mineral by chemical method; the material with 25%~35% schmitt mineral load is obtained by adding polyurethane foam in the reaction system for synthesizing schmitt mineral by biological method, and different schmitt mineral load materials provide more selectivity for the treatment of water bodies with different degrees of arsenic pollution.

[0011] Further, the load of schmitt mineral in the above-mentioned material is 25%~35% (w / w).

[0012] Further, the load of schmitt mineral in the above-mentioned material is 30%~35% (w / w).

[0013] Further, the load of schmitt mineral in the above-mentioned material is 32.05% (w / w).

[0014] Further, the specific surface area of the above-mentioned polyurethane foam is 0.3~0.5m 2 / g, and the porosity is 90%~98%. In the present application, polyurethane foam with high specific surface area and high porosity is selected as the carrier material, which has good adsorption performance on one hand, so that schmitt mineral can fully contact and react with pollutants; on the other hand, high porosity has no significant effect on the volume of water body during preparation or use; in addition, its good elastic characteristics have a certain buffering effect when loading schmitt mineral, which can protect the loaded schmitt mineral from damage in practical application and ensure the stability of the performance of schmitt mineral.

[0015] Further, the specific surface area of the above-mentioned polyurethane foam is 0.35m 2 / g, and the porosity is 97.2%.

[0016] The present application also provides a preparation method of the above-mentioned polyurethane foam load schmitt mineral material, which comprises: adding polyurethane foam in the reaction system for synthesizing schmitt mineral by chemical method or biological method, so that schmitt mineral is synthesized on the surface of polyurethane foam or the synthesized schmitt mineral is attached to the surface of polyurethane foam, especially the inner surface of the pore of polyurethane foam, to obtain polyurethane foam load schmitt mineral material.

[0017] Further, the above preparation method comprises adding polyurethane foam into a reaction system for synthesizing schultesite by chemical method.

[0018] Further, the above preparation method comprising adding polyurethane foam into a reaction system for synthesizing schultesite by chemical method comprises the following steps:

[0019] S1: Synthesis and loading of schultesite

[0020] Preparation of Fe 2+ solution, adding polyurethane foam into the solution, adding an oxidant under stirring at room temperature, adjusting pH of the reaction system, and performing the reaction in an aerobic environment.

[0021] S2: Washing and drying treatment

[0022] After the above S1 reaction is completed, the polyurethane foam in the system is collected, washed with dilute sulfuric acid solution and deionized water, and dried to obtain a schultesite material loaded on the polyurethane foam.

[0023] Further, in the above S1, the oxidant is 30% H2O2.

[0024] Further, in the above S1, the oxidant is added in an amount with a final concentration of 2.0-6.0 g / L.

[0025] Further, in the above S1, H2O2 is added in an amount with a final concentration of 5.0 g / L.

[0026] Further, in the above S2, the pH of the dilute sulfuric acid solution is 2.0-2.5.

[0027] Further, the above preparation method comprises adding polyurethane foam into a reaction system for synthesizing schultesite by biological method.

[0028] Further, the above preparation method comprising adding polyurethane foam into a reaction system for synthesizing schultesite by biological method comprises the following steps:

[0029] M1: Synthesis and loading of schultesite

[0030] Preparation of Fe 2+ solution, adding polyurethane foam into the solution, adding an oxidant under stirring at room temperature, adjusting pH of the reaction system, and performing the reaction in an aerobic environment.

[0031] M2: Washing and drying treatment

[0032] After the above M1 reaction is completed, the polyurethane foam in the system is collected, washed with deionized water and ethanol, and dried to obtain a schultesite material loaded on the polyurethane foam.

[0033] Further, in the above M1, the strain density after inoculation is 107 ~10 8 cells / mL of inoculum.

[0034] Further, the above-mentioned A. ferrooxidans is A. ferrooxidans LX5 (CGMCC NO. 0727, deposited on March 13, 2002), classified as Thiobacillus ferrooxidans, deposited at the China General Microbiological Culture Collection Center, and located at the Institute of Microbiology, Chinese Academy of Sciences, Datun Road, Chaoyang District, Beijing, China, as described in CN1375553A.

[0035] Further, in the above-mentioned S1 or M1, the polyurethane foam is added at a ratio of 15% to 30% (v / v) of the Fe 2+ The solution is FeSO4·7H2O solution.

[0036] Further, the concentration of the above-mentioned FeSO4·7H2O is 20 to 50 g / L.

[0037] Further, the concentration of the above-mentioned FeSO4·7H2O is 22.4 g / L.

[0038] Further, in the above-mentioned S1 or M1, the polyurethane foam is added at a ratio of 15% to 30% (v / v) of the Fe 2+ solution.

[0039] Further, in the above-mentioned S1 or M1, the polyurethane foam is added at a ratio of 15% to 30% (v / v) of the Fe 2+ solution.

[0040] Further, in the above-mentioned S1 or M1, the pH of the reaction system is adjusted to 2 to 3.

[0041] Further, in the above-mentioned S1 or M1, the pH of the reaction system is adjusted to 2.5.

[0042] Further, in the above-mentioned S1 or M1, the reaction in the aerobic environment is carried out at 25 to 35 °C, 160 to 200 rpm for 24 to 48 h.

[0043] Further, in the above-mentioned S1 or M1, the reaction in the aerobic environment is carried out at 28 °C, 180 rpm for 24 h.

[0044] The present application also provides the use of the above-mentioned polyurethane foam loaded with schneiderite in the treatment of arsenic-contaminated water bodies.

[0045] Further, the treatment of arsenic-contaminated water bodies includes in-situ treatment and ex-situ treatment.

[0046] Further, the above-mentioned arsenic-contaminated water treatment is in-situ treatment. The polyurethane foam loaded schulte mineral material in the application is simple to use, light and easy to transport, and is suitable for in-situ treatment of arsenic-contaminated water, which is better than ex-situ treatment, does not need to re-construct a treatment unit, and saves sewage transportation cost.

[0047] Further, the above-mentioned arsenic-contaminated water includes arsenic-contaminated surface water.

[0048] Further, the above-mentioned application includes directly adding the polyurethane foam loaded schulte mineral material in the arsenic-contaminated water, and / or assembling the polyurethane foam loaded schulte mineral material in series to form a combined material addition, and / or pre-filling the polyurethane foam loaded schulte mineral material into a suspended ball filler, and then assembling the suspended ball filler in series to form a combined material addition.

[0049] Further, the above-mentioned application is to directly use the polyurethane foam loaded schulte mineral material in the arsenic-contaminated water.

[0050] Further, the above-mentioned application includes the following steps:

[0051] N1: According to the effective arsenic concentration in the surface water to be treated and the water quality execution standard after the treatment and repair, and combining the runoff of the water to be treated, the absolute amount of effective arsenic to be removed is calculated, and then according to the schulte mineral loading amount and the iron content in the polyurethane foam loaded schulte mineral material, the amount of polyurethane foam loaded schulte mineral material to be added is determined by the iron-arsenic ratio;

[0052] N2: The above-mentioned polyurethane foam loaded schulte mineral material is preferably arranged in the cross section of the surface water to be treated, and when the absolute amount of effective arsenic to be treated is large or the treatment and repair time requirement is high, it can be arranged in multiple water flow cross sections; and according to the average flow rate of the surface water and the effective arsenic concentration in the water, the unit cross filling rate of the polyurethane foam loaded schulte mineral material in the surface water to be treated is adjusted.

[0053] N3: According to the adsorption kinetics of the polyurethane foam loaded schulte mineral material to arsenic and the initial concentration of effective arsenic in the water, the recovery and regeneration time of the composite material is calculated to avoid desorption after the composite material is saturated with arsenic, so as to realize rapid removal of arsenic by the composite material and repeated use.

[0054] Further, the suitable range of the iron-arsenic ratio in N1 is between 1:(50-150).

[0055] 3. Beneficial effects

[0056] Compared with the prior art, the application has the beneficial effects that:

[0057] (1) The polyurethane foam loaded schmidtite material and its preparation method and application provided by the application are used by loading schmidtite on a carrier material, polyurethane foam, avoiding the potential impact of directly adding powdered schmidtite on water quality, and being more green and low-carbon; the treated surface water meets the discharge standard, and the polyurethane foam loaded schmidtite material after use can be regenerated and reused by elution with an alkaline solution, and the arsenic removal effect is not significantly affected after verification, greatly improving the utilization rate of schmidtite and reducing the cost of treating arsenic-polluted water bodies.

[0058] (2) The polyurethane foam loaded schmidtite material and its preparation method and application provided by the application are suitable for treating occasional arsenic-polluted surface water, are convenient to use, and can realize in-situ arsenic removal of water bodies by direct addition or simple assembly of the material, avoiding the high cost of constructing a treatment unit and transporting water bodies that the traditional ex-situ arsenic removal needs to face.

[0059] (3) The polyurethane foam loaded schmidtite material and its preparation method and application provided by the application, polyurethane foam has the characteristics of high specific surface area and high porosity, and its high porosity is beneficial to the flow of water and almost does not hinder the circulation of surface water. Therefore, the polyurethane foam loaded schmidtite material is suitable for the treatment of different arsenic-polluted water bodies, including surface water bodies with strong flowability.

[0060] (4) The preparation method of the polyurethane foam loaded schmidtite material provided by the application is to add polyurethane foam in the reaction system for synthesizing schmidtite by a chemical method or a biological method, so that schmidtite is synthesized on the surface of the polyurethane foam or the synthesized schmidtite is attached to the surface of the polyurethane foam, especially the inner surface of the pore of the polyurethane foam, and the loading on the polyurethane foam is completed during the synthesis of schmidtite, the preparation process is simple, and the operation requirement is low. At the same time, the loading amount of schmidtite in the polyurethane foam loaded schmidtite material obtained by chemical means and biological means shows certain difference, providing more possibilities for material selection for treating different arsenic-polluted water bodies. BRIEF DESCRIPTION OF DRAWINGS

[0061] Figure 1 It is a sample comparison chart of polyurethane foam before and after loading schmidtite, in which (a) is a polyurethane foam sample before loading schmidtite; and (b) is a polyurethane foam sample after loading schmidtite.

[0062] Figure 2 It is the removal result of As(V) in simulated surface water by the polyurethane foam loaded schmidtite material.

[0063] Figure 3The removal results of As(V) in simulated surface water by schlenkite and schlenkite material loaded on polyurethane foam, wherein (a) is the schlenkite material loaded on polyurethane foam treatment group; (b) is the schlenkite treatment group.

[0064] Figure 4 The influence of water quality appearance of simulated surface water by schlenkite and schlenkite material loaded on polyurethane foam.

[0065] Figure 5 The removal results of As(V) in surface water by schlenkite material loaded on polyurethane foam under different water quality factors.

[0066] Figure 6 The removal results of As(V) in surface water by schlenkite material loaded on polyurethane foam and the removal results of As(V) after regeneration. DETAILED DESCRIPTION

[0067] The present application will be further described below in conjunction with specific examples.

[0068] It should be noted that unless otherwise defined, all technical and scientific terms used herein have the same meanings as commonly understood by one of ordinary skill in the art to which this application belongs. The examples herein are not intended to be limiting. Unless otherwise indicated, conventional methods and techniques of the chemical arts can be used. Unless otherwise indicated, the reagents and instruments used are conventional products available commercially.

[0069] As used herein, the terms "about" and "approximately" are used to provide flexibility to a given term, measurement, or value. The degree of flexibility of a particular variable can be readily determined by one of skill in the art.

[0070] As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items. The term "at least one of' is intended to be synonymous with "one or more of." For example, "at least one of A, B, and C" explicitly includes just A, just B, just C, and various combinations thereof.

[0071] Concentrations, amounts, and other numerical data can be presented herein in a range format. It is to be understood that such range format is used merely for convenience and brevity and should be construed as having been followed to the right of the recited range to indicate that every number, or sub-range, within the given range, is disclosed, unless otherwise indicated. For example, a range of about 1 to about 4.5 should be interpreted to include not only the explicitly recited limits of about 1 to about 4.5, but also the individual numbers such as 2, 3, and 4, and the sub-ranges such as 1-3, 2-4, etc. The same applies to ranges that only recite one numerical value, such as "less than about 4.5," which should be interpreted to include all of the above-referenced values and ranges. Furthermore, such an interpretation should apply regardless of the breadth of the range or the characteristics being described.

[0072] As used herein, polyurethane foam (PUF) is a synthetic material with a wide range of applications, made from polyether and isocyanate through a polymerization reaction, and a large number of bubbles are formed during the reaction, thus producing a foam structure. In this application, the polyurethane foam is a hydrophilic polyurethane purchased from Zhangzhou Shanggushui Environmental Protection Technology Co., Ltd., with a specific surface area of 0.35 m2 / g and a porosity of 97.2%. 2

[0073] As used herein, the loading of the Schlenk mineral in the polyurethane foam is the percentage of the mass of the loaded Schlenk mineral to the mass of the polyurethane foam, calculated by the following formula (1):

[0074] The loading of the Schlenk mineral = (m2-m1) / m1x100% …… formula (1);

[0075] Wherein: m1 is the mass of the original polyurethane foam added to the reaction system, i.e. the mass of the polyurethane foam after drying before loading the Schlenk mineral; m2 is the mass of the polyurethane foam loaded with the Schlenk mineral after drying after the reaction.

[0076] In the examples, the acidophilic iron-oxidizing Thiobacillus is Thiobacillus ferrooxidans LX5 (A. ferrooxidans LX5), with the preservation number of CGMCC NO. 0727, the preservation time of March 13, 2002, the classification name of Thiobacillus ferrooxidans, the preservation unit of China General Microbiological Culture Collection Center, and the preservation address of Institute of Microbiology, Chinese Academy of Sciences, Datun Road, Chaoyang District, Beijing, as described in Chinese Invention Patent CN1375553A.

[0077] Example 1

[0078] ​This embodiment provides a method for preparing polyurethane foam-supported Sch@PUF mineral material and the prepared polyurethane foam-supported Sch@PUF mineral material.

[0079] In this embodiment, the preparation method involves adding polyurethane foam to the reaction system for chemically synthesizing Scheringer minerals, so that the Scheringer minerals are synthesized on the surface of the polyurethane foam or the synthesized Scheringer minerals are attached to the surface of the polyurethane foam, especially the inner surface of the pores of the polyurethane foam, thereby obtaining a polyurethane foam-loaded Scheringer mineral material.

[0080] Specifically, the preparation method includes the following steps:

[0081] S1, prepare 500 mL of a 22.4 g / L FeSO4·7H2O solution, and add 1 cm³ of washed and dried liquid at 15% (v / v) solution concentration. 3 PUF (total mass of PUF m1 = 2.665 g) was weighed; 30% H2O2 with a final concentration of 5 g / L was added under magnetic stirring at room temperature (25°C); the pH of the reaction system was adjusted to 2.5 with 1 M NaOH and 0.1 M H2SO4; the reaction was carried out in a shaker for 24 h at 28°C and 180 rpm, and the pH was kept stable at 2.5 during the reaction.

[0082] S2. After the reaction is complete, the PUF is taken out and washed with dilute sulfuric acid solution (pH 2-2.5) and deionized water in sequence. It is then dried at a low temperature of 40°C (the total mass of the PUF loaded with Schiele mineral is m2 = 2.679 g) to obtain polyurethane foam loaded with Schiele mineral material, which is stored for later use.

[0083] Macroscopic photographs of polyurethane foam before and after loading with Schiele minerals, as shown below. Figure 1 As shown, (a) is a polyurethane foam sample before loading Scheringer minerals, and (b) is a polyurethane foam sample after loading Scheringer minerals. It can be seen that the appearance changed from white to yellow, and Scheringer minerals were loaded on the surface of the polyurethane foam (including the surface of the pores).

[0084] Calculations show that the polyurethane foam loaded with Schiele mineral material prepared in this embodiment has a Schiele mineral loading of 0.52%.

[0085] Example 2

[0086] This embodiment provides a method for preparing polyurethane foam-supported Sch@PUF mineral material and the prepared polyurethane foam-supported Sch@PUF mineral material.

[0087] In this embodiment, the preparation method involves adding polyurethane foam to the reaction system for the biological synthesis of Scheringer minerals, so that the Scheringer minerals are synthesized on the surface of the polyurethane foam or the synthesized Scheringer minerals are attached to the surface of the polyurethane foam, especially the inner surface of the pores of the polyurethane foam, thereby obtaining a polyurethane foam-loaded Scheringer mineral material.

[0088] Specifically, the preparation method includes the following steps:

[0089] S1, prepare 500 mL of a 22.4 g / L FeSO4·7H2O solution, and add 1 cm³ of washed and dried liquid at 15% (v / v) solution concentration. 3 PUF (total mass of PUF m1 = 2.665 g); inoculated with 10% (v / v) of *Acidithiobacillus ferrooxidans* resting cells (final bacterial density in the reaction system after inoculation was approximately 10). 7 ~10 8 The initial pH was adjusted to 2.7 with 10 mol / L NaOH and 0.1 mol / L H2SO4; the mixture was placed in a shaker and reacted for 72 h at 28 °C and 180 rpm.

[0090] S2. After the reaction is complete, the PUF is taken out and washed with deionized water and ethanol in sequence, and dried at a low temperature of 40°C (the total mass of the PUF loaded with Schiele minerals is m2 = 3.5191g) to obtain polyurethane foam loaded with Schiele minerals material, which is stored for later use.

[0091] Calculations show that the polyurethane foam loaded with Schiele mineral material prepared in this embodiment has a Schiele mineral loading of 32.05%.

[0092] In this embodiment, after the PUF is removed, the remaining suspension is centrifuged at 8000 rpm, 4°C, and 5 min. The precipitate is washed with deionized water at pH 2.5 and the process is repeated three times to separate Scheider minerals. After freeze-drying for 24 h, unloaded Scheider minerals are obtained and stored in a desiccator for later use.

[0093] Example 3

[0094] This embodiment provides the application of polyurethane foam-loaded Schiele mineral material in arsenic removal (As(V)).

[0095] In this embodiment, the polyurethane foam-loaded Sch@PUF material used is the polyurethane foam-loaded Sch@PUF material prepared in Example 1.

[0096] In this embodiment, the application includes the following steps:

[0097] To the As(V) solution (simulated surface water) with a concentration of 100 μg / L, a certain amount of Sch@PUF (the amount is 0.025% (w / w) of the absolute amount of Sch added to the As(V) solution) was added, the reaction system was 200 mL, the reaction condition was 180 rpm, 28°C, and the pH of the system was maintained at about 7 (using 2-morpholinoethanesulfonic acid buffer to regulate), and three repeated treatment groups were set. At 0, 10, 30, 60, 120, 240, 480 and 720 min of the reaction stage, the water sample was filtered with a 0.45 μm filter membrane, and the concentration of As(V) therein was determined by atomic fluorescence method (the specific conditions refer to "Water and Wastewater Monitoring and Analysis Methods" (4th edition), China Environmental Science Press) and the removal rate was calculated.

[0098] Result analysis:

[0099] The results are shown in Figure 2 As shown, with the increase of the treatment time, the concentration of As(V) gradually decreased, and after 12 h of adsorption, the removal rate of Sch@PUF to As(V) in water reached 73.14%; the adsorption capacity of Sch@PUF to As(V) in water was 8.58 mg / g, and the concentration of As(V) in the solution decreased from 100 μg / L to 26.86 μg / L, which was obviously lower than the surface water discharge standard (within 50 μg / L), and the results showed that the polyurethane foam loaded with 0.52% of Sch mineral material had high efficiency in adsorption and treatment of As(V) in surface water.

[0100] Example 4

[0101] The present embodiment provides the application of polyurethane foam loaded with Sch mineral material in arsenic removal (As(V)).

[0102] In the present embodiment, the polyurethane foam loaded with Sch mineral material used is the polyurethane foam loaded with Sch mineral material (Sch@PUF) prepared in Example 2.

[0103] In the present embodiment, the application comprises the following steps:

[0104] Sch@PUF and Sch were added into two groups of As(V) solution with a concentration of 100 μg / L, respectively, and were recorded as the polyurethane foam loaded Schafferite material treatment group and the Schafferite material treatment group. The absolute amount of Sch added in the two treatment groups was consistent (all in terms of the absolute amount of Sch accounting for 0.025% (w / w) of the As(V) solution). The reaction system was 200 mL, the reaction condition was 180 rpm and 28°C, and the pH of the system was maintained at about 7 (using 2-morpholinoethanesulfonic acid buffer to regulate). Three sets of repeats were set for each of the two treatment groups. Sampling was performed at 0, 10, 30, 60, 120, 240 and 480 min in the reaction stage. The water sample was filtered with a 0.45 μm filter membrane, and the concentration of As(V) therein was determined by atomic fluorescence method (for specific conditions, refer to “Water and Wastewater Monitoring and Analysis Methods” (4th edition), China Environmental Science Press) and the removal rate was calculated.

[0105] Result analysis:

[0106] The results are shown in Figure 3 Compared with the Sch treatment group, the removal rate of As(V) in the Sch@PUF treatment group was slower, but the As(V) removal rate had reached more than 97% at 60 min. The adsorption of As reached equilibrium after 60 min in both treatment groups, and As(V) in the final solution was basically completely removed after 480 min of treatment. The effluent met the surface water discharge standard (≤50 μg / L). The results showed that the high-efficiency arsenic removal performance of the Schafferite loaded on the polyurethane foam material was almost not affected. However, compared with Sch, Sch@PUF was more convenient to recover. At the same time, the effects of the Sch treatment group and the Sch@PUF treatment group on the water quality of the water body were compared, and the results are shown in Figure 4 It can be seen that the turbidity of the water body in the Sch treatment group was higher, and the water body in the Sch@PUF treatment group was almost not affected.

[0107] Example 5

[0108] This example provides a study on the influence of different water quality factors of surface water on the arsenic removal effect of Sch@PUF.

[0109] Since As(V) and P are in the same main group, competitive adsorption will occur. In addition, common organic matters in water may also be adsorbed on the surface of Sch@PUF, interfering with arsenic removal. Therefore, this example investigates the influence of a certain concentration of phosphate and organic matter (in terms of COD) on the arsenic removal effect of Sch@PUF.

[0110] In this example, the polyurethane foam loaded Schafferite material used is the polyurethane foam loaded Schafferite material (Sch@PUF) prepared in Example 2.

[0111] Specifically, As(V) and P (in the form of PO43-) were prepared into a solution with a concentration of 100 μg / L.3- A solution containing both As(V) and P at a concentration of 100 μg / L was prepared. Sch@PUF was added (the amount added was calculated as 0.025% (w / w) of the total As(V) and P concentration). The reaction system was 200 mL, and the reaction conditions were 180 rpm, 28°C, and pH maintained at approximately 7 (using 2-morpholine ethanesulfonic acid buffer). After 6 hours of reaction, samples were taken to determine the As(V) concentration and calculate the removal rate. Similarly, in the same As(V) and P concentration system, a COD concentration of 100 mg / L (prepared using glucose reagent) was set, and the pH was neutral to investigate the effect of COD on arsenic removal under As(V) and P coexistence conditions. The treatment and detection of water samples in both treatment groups were the same as in Example 3.

[0112] Results analysis:

[0113] The results are as follows Figure 5 As shown, under neutral conditions, whether As(V) and P coexist, or As(V), P, and COD coexist, Sch@PUF exhibits high removal rates for As(V), with average removal rates of 99.85±0.07% and 99.45±0.13%, respectively. This indicates that the presence of phosphate and organic matter has almost no impact on the As(V) removal efficiency of Sch@PUF. This further demonstrates that the Sch@PUF of this invention can guarantee the removal efficiency of As(V) when different pollutants coexist in surface water, and it shows good application prospects for arsenic treatment under different pollution conditions in surface water.

[0114] Example 6

[0115] This embodiment provides a test of the regeneration and cyclic adsorption performance of polyurethane foam-loaded Schiele mineral material.

[0116] In this embodiment, the polyurethane foam-loaded Sch@PUF material used is the polyurethane foam-loaded Sch@PUF material prepared in Example 1.

[0117] Specifically, the following steps are included:

[0118] (1) Washing

[0119] The Sch@PUF adsorbed with As(V) in Example 3 was washed with deionized water, and 0.01 mol / L NaOH was added at a solid-liquid ratio of 1:200 for elution and regeneration. The elution reaction conditions were 180 rpm, 25°C, and 30 min. After elution, the Sch@PUF was taken out, washed again with deionized water, and dried at a low temperature of 40°C.

[0120] (2) Reloading (Re-adsorption)

[0121] The Sch@PUF dried in step (1) was put into 100 μg / L As(V) solution again, the system was 200 mL, the reaction condition was 180 rpm, 28℃, and the sample was taken after 6h reaction, filtered by 0.45 μm filter membrane, and the concentration of As(V) was determined by atomic fluorescence method (same as actual example 3) and the removal rate was calculated.

[0122] (3) repeating step (1) and step (2) for 2 times of regeneration cycle test.

[0123] Result analysis:

[0124] The results are shown in Figure 6 As can be seen from the results, the concentration of As(V) in the solution treated by initial Sch@PUF adsorption before elution and regeneration was 26.86 μg / L, the concentration of As(V) in the solution treated by 1 time of elution and re-adsorption was 31.75 μg / L, which increased slightly, the concentration of As(V) in the solution treated by 2 times of elution and re-adsorption was 31.71 μg / L, which was almost the same as the treatment group of 1 time of elution and re-adsorption; the removal rate of Sch@PUF for As(V) was calculated to be 73.14%, 68.25% and 68.29% before and after elution, respectively, which showed that NaOH in the above example had no significant effect on the re-adsorption performance of Sch@PUF while eluting the As(V) adsorbed by Sch@PUF, which indicated that the Sch@PUF material had good regeneration and recycling effect.

[0125] In summary, two kinds of polyurethane foam loaded with Sch@PUF were prepared by chemical method and biological method respectively, in which the loading amount of Sch@PUF prepared by chemical method was 0.52%, and the loading amount of Sch@PUF prepared by biological method was 32.05%; the above two kinds of Sch@PUF were used as surface water arsenic removal materials, and both showed excellent arsenic removal performance, and the effluent reached the surface water discharge standard. Through elution and re-adsorption experiment test, the arsenic removal material had good regeneration and recycling effect, and the regeneration process was realized only by elution of deionized water and NaOH, which was very convenient. The Sch@PUF provided by the application has important significance for in-situ efficient, green and low-cost arsenic removal.

Claims

1. A polyurethane foam loaded skutterudite material, characterized in that, The loading amount of the schottkyite in the material is 0.3%-35% (w / w).

2. The polyurethane foam supported skutterudite material of claim 1, wherein, The loading amount of the schottkyite is 0.3%-1% (w / w) or 25%-35% (w / w).

3. The polyurethane foam supported skutterudite material of claim 1 or 2, wherein, The specific surface area of the polyurethane foam is 0.3 to 0.5 m 2 / g, and the porosity is 90 to 98%.

4. The method of producing a polyurethane foam supported skleromer material according to any of claims 1 to 3, characterized in that The method comprises adding polyurethane foam into a reaction system for synthesizing schottkyite by a chemical method or a biological method, and obtaining the polyurethane foam loaded schottkyite material after the synthesis of the schottkyite.

5. The preparation method according to claim 4, wherein, The preparation method comprises adding polyurethane foam into a reaction system for synthesizing schottkyite by a chemical method, and specifically comprises the following steps: S1: synthesis and loading of schottkyite Formulating Fe 2+ The solution, polyurethane foam is added to the solution, the oxidant is added under stirring at room temperature, the pH of the reaction system is adjusted, and the reaction is carried out in an aerobic environment. S2: washing and drying treatment After the end of the S1 reaction, the polyurethane foam in the system is collected, washed with a dilute sulfuric acid solution and deionized water, and dried to obtain the polyurethane foam loaded schottkyite material; or The preparation method comprises adding polyurethane foam into a reaction system for synthesizing schottkyite by a biological method, and specifically comprises the following steps: M1: synthesis and loading of schottkyite Formulating Fe 2+ A solution is prepared, polyurethane foam is added to the solution, and Thiobacillus ferroxidans is inoculated. The pH of the reaction system is adjusted, and the reaction is carried out in an aerobic environment. M2: washing and drying treatment After the end of the M1 reaction, the polyurethane foam in the system is collected, washed with deionized water and ethanol, and dried to obtain the polyurethane foam loaded schottkyite material.

6. The preparation method according to claim 5, characterized in that, In the S1, the oxidant is H2O2, and the oxidant is added in an amount of 2.0-6.0 g / L according to the final concentration.

7. The preparation method according to claim 5, characterized in that, The Acidithiobacillus ferrooxidans in the M1 is inoculated at a ratio of 10 7 ~ 10 8 cells / mL of strain density after inoculation.

8. The method according to claim 6 or 7, characterized in that ， According to claim 5, in the S1 or M1, Fe 2+ The solution is a FeS04-7H20 solution, and the concentration of FeS04-7H20 is 20-50 g / L; and / or Polyurethane foams according to Fe 2+ 15% to 30% (v / v) addition of solution; and / or The pH of the reaction system is adjusted to 2-3.

9. The polyurethane foam loaded schottkyite material according to any one of claims 1-3, for use in the treatment of arsenic contaminated water.

10. Use according to claim 9, characterized in that, The use comprises adding the polyurethane foam loaded schottkyite material into the arsenic contaminated water, and / or assembling the polyurethane foam loaded schottkyite material into a combined material in series, and / or pre-filling the polyurethane foam loaded schottkyite material into a suspended ball filler, and then assembling the suspended ball filler into a combined material in series.

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