BIOFILM COMPOSITE CARRIER AND PREPARATION METHOD AND USE THEREOF
20220340461 · 2022-10-27
Inventors
Cpc classification
C02F3/2806
CHEMISTRY; METALLURGY
Y02W10/10
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
International classification
Abstract
A biofilm composite carrier and a preparation method and use thereof are provided. The biofilm composite carrier includes a polyurethane framework, an adhesive and a functional material, wherein the functional material is adhered to the surface and pores of the polyurethane framework through the adhesive, and the functional material is a mixture of zeolite and tourmaline. The biofilm composite carrier is beneficial to the quick start-up and stable operation of the municipal sewage deammonification system under conditions of low temperature and low ammonium.
Claims
1. A biofilm composite carrier, comprising a polyurethane framework, an adhesive and a functional material, wherein the polyurethane framework has a volume, a surface, and pores, the functional material is adhered to the surface and pores of the polyurethane framework through the adhesive, and the functional material is a mixture of zeolite and tourmaline.
2. The biofilm composite carrier of claim 1, wherein a ratio of the volume of the polyurethane framework to the mass of the adhesive to the mass of the functional material is in a range of 1 cm.sup.3:(0.015-0.025) g:(0.1-0.2) g.
3. The biofilm composite carrier of claim 1, wherein the zeolite in the mixture of zeolite and tourmaline is Na-pretreated zeolite, and the adhesive is waterborne polyurethane.
4. The biofilm composite carrier of claim 1, wherein a mass ratio of zeolite to tourmaline in the mixture of zeolite and tourmaline is in a range of (1-3):1.
5. A method for preparing the biofilm composite carrier of claim 1, comprising steps of: mixing a zeolite powder and a tourmaline powder to obtain a zeolite-tourmaline mixed powder; mixing the zeolite-tourmaline mixed powder with an adhesive solution to obtain a functional carrier adhesive; and placing the polyurethane framework in the functional carrier adhesive and impregnating, removing residual liquid, then placing the polyurethane framework obtained after removing residual liquid in the zeolite-tourmaline mixed powder, and adhering the zeolite-tourmaline mixed powder to obtain the biofilm composite carrier.
6. The method of claim 5, wherein the method further comprises subjecting the zeolite powder to a pretreatment before mixing the zeolite powder and the tourmaline powder, and the pretreatment comprises soaking the zeolite powder in a sodium chloride solution for an activation.
7. The method of claim 6, wherein the zeolite powder has a particle size of 200 to 800 meshes, the sodium chloride solution has a temperature of 70-100° C., and the sodium chloride solution has a concentration of 1-1.5 mol/L, and a ratio of the mass of the zeolite powder to the volume of the sodium chloride solution is in a range of (15-25) g:100 mL.
8. The method of claim 5, wherein a mass ratio of the zeolite powder to the tourmaline powder is in a range of (1-3):1.
9. The method of claim 5, wherein the adhesive solution is a waterborne polyurethane solution, the waterborne polyurethane solution has a concentration of 30±2% by mass, and a mass ratio of the zeolite-tourmaline mixed powder to the waterborne polyurethane solution is in a range of 1:(5-10).
10. A method for using the biofilm composite carrier of claim 1 in the field of enhancing a municipal sewage deammonification system, comprising using the biofilm composite carrier as a filler for enhancing the municipal sewage deammonification system.
11. The biofilm composite carrier of claim 2, wherein the zeolite in the mixture of zeolite and tourmaline is Na-pretreated zeolite, and the adhesive is waterborne polyurethane.
12. The biofilm composite carrier of claim 2, wherein a mass ratio of zeolite to tourmaline in the mixture of zeolite and tourmaline is in a range of (1-3):1.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0030]
[0031]
[0032]
[0033]
DETAILED DESCRIPTION OF THE EMBODIMENTS
[0034] The present disclosure provides a biofilm composite carrier, comprising a polyurethane framework, an adhesive and a functional material, wherein the functional material is adhered to the surface and pores of the polyurethane skeleton through the adhesive, as shown in
[0036] In the present disclosure, there is no special limitation on the pore structure of the polyurethane framework. In some embodiments, the polyurethane framework is polyurethane sponge.
[0037] In some embodiments, the adhesive is waterborne polyurethane. In the present disclosure, there is no special limitation on the type of the waterborne polyurethane, and any waterborne polyurethane that could play a role of adhesion well known to those skilled in the art may be used.
[0038] In the present disclosure, the functional material is a mixture of zeolite and tourmaline. In some embodiments, the zeolite in the mixture of the zeolite and the tourmaline has a particle size not larger than 200 meshes, preferably 200-800 meshes. In some embodiments, the zeolite is Na-pretreated zeolite. In some embodiments, the tourmaline in the mixture of zeolite and tourmaline has a particle size of 200-800 meshes, preferably 400-600 meshes; in some embodiments, the tourmaline is iron tourmaline.
[0039] In some embodiments, a mass ratio of the zeolite to the tourmaline is in a range of (1-3):1, preferably (1.5-2.5):1, and more preferably (1.8-2.2):1.
[0040] In some embodiments, a ratio of the volume of the polyurethane framework to the mass of the adhesive to the mass of the functional material is in a range of 1 cm.sup.3:(0.015-0.025) g:(0.1-0.2) g, preferably 1 cm.sup.3:(0.016-0.023) g:(0.13-0.19) g, and more preferably 1 cm.sup.3:(0.018-0.02) g:(0.15-0.16) g.
[0041] The present disclosure also provides a method for preparing the biofilm composite carrier described in the above technical solutions, which comprises the following steps: [0042] mixing a zeolite powder and a tourmaline powder to obtain a zeolite-tourmaline mixed powder; [0043] mixing the zeolite-tourmaline mixed powder with an adhesive solution to obtain a functional carrier adhesive; and [0044] placing the polyurethane framework in the functional carrier adhesive and impregnating, removing residual liquid, placing the polyurethane framework obtained after removing residual liquid in the zeolite-tourmaline mixed powder, and adhering the zeolite-tourmaline mixed powder to obtain the biofilm composite carrier.
[0045] In the present disclosure, all the raw materials are commercially available products well known to those skilled in the art, unless otherwise specified.
[0046] In the present disclosure, the zeolite powder and the tourmaline powder are mixed to obtain the zeolite-tourmaline mixed powder.
[0047] In some embodiments, the method further comprises subjecting the zeolite powder to a pretreatment before mixing the zeolite powder and the tourmaline powder; in some embodiments, the pretreatment comprises soaking the zeolite powder in a sodium chloride solution for an activation.
[0048] In some embodiments, the zeolite powder has a particle size of 200-800 meshes, preferably 400-600 meshes. In some embodiments, the sodium chloride solution has a temperature of 70-100° C., preferably 70-90° C., and more preferably 70-80° C. In some embodiments, the sodium chloride solution has a concentration of 1-1.5 mol/L, preferably 1-1.3 mol/L.
[0049] In some embodiments, a ratio of the mass of the zeolite powder to the volume of the sodium chloride solution is in a range of (15-25) g:100 mL, preferably (15-23) g:100 mL, and more preferably (17-20) g:100 mL.
[0050] In some embodiments, the activation is conducted for 0.5-2 h, preferably 1-1.5 h.
[0051] In some embodiments, the zeolite powder is a porous aluminate crystal with a skeleton structure, which has a plurality of pore passages and channels inside, and exhibits strong ion exchange capacity, especially ammonia ion exchange capacity which is sequenced in front, so that the zeolite powder has high selective adsorption capacity on ammonium. However, impurities such as water and organic matters often exist in pores and channels of natural zeolite, which will reduce the pore space. The above pretreatment could effectively remove the impurities in the pores and the channels of the natural zeolite. Meanwhile, ion exchange volume could be improved by replacing the impurities in the pores and the channels of the zeolite with sodium ions which have a smaller ionic radius in the soaking of a sodium chloride solution, thus improving the selective adsorption capacity on ammonium.
[0052] In some embodiments, the method further comprises after the activation, subjecting the activated zeolite to a washing, a drying, a grinding and a sieving in sequence. In some embodiments, the washing is conducted by washing the activated zeolite with distilled water to neutral. In some embodiments, the drying is conducted at 105° C. for 24 h. In some embodiments, the drying is conducted by baking; the baking is conducted in an oven. In the present disclosure, there is no special limitation on the process of grinding, and any process well known to those skilled in the art may be used. In some embodiments, the sieving is conducted with a screen with a mesh number of 200 meshes.
[0053] In some embodiments, the tourmaline powder has a particle size of 200-800 meshes, preferably 300-800 meshes, and more preferably 500-600 meshes. In some embodiments, the tourmaline powder is iron tourmaline powder.
[0054] In some embodiments, a mass ratio of the zeolite powder to the tourmaline powder is in a range of (1-3):1, preferably (1.5-3):1, and more preferably (2.2-2.7):1.
[0055] In some embodiments, the mixing of the zeolite powder and the tourmaline powder is conducted by oscillation; the oscillation is conducted at an oscillation speed of 3200 rpm/min, and the oscillation is conducted for 20 min; the oscillation is conducted in a high-speed oscillator.
[0056] After the zeolite-tourmaline mixed powder is obtained, the zeolite-tourmaline mixed powder is mixed with an adhesive solution to obtain a functional carrier adhesive.
[0057] In some embodiments, the adhesive solution is a waterborne polyurethane solution; the waterborne polyurethane solution has a concentration of 30±2% by mass; a mass ratio of the zeolite-tourmaline mixed powder to the waterborne polyurethane solution is in a range of 1:(5-10), preferably 1:(6-10), and more preferably 1:(7-9).
[0058] In some embodiments, the mixing of the zeolite-tourmaline mixed powder and adhesive solution is conducted by stirring; the stirring is conducted at a rotating speed of 120 rpm/min, and the stirring is conducted for 2 min; the stirring is conducted in a magnetic stirrer.
[0059] After the functional carrier adhesive is obtained, the polyurethane framework is placed in the functional carrier adhesive and impregnated; after residual liquid is removed, the resulting polyurethane framework is placed in the zeolite-tourmaline mixed powder, and the zeolite-tourmaline mixed powder is adhered to said polyurethane framework to obtain the biofilm composite carrier.
[0060] In some embodiments, the polyurethane framework is polyurethane sponge, and the polyurethane sponge is a cube with the a side length of 1-3 cm.
[0061] In some embodiments, before the polyurethane framework is placed in the functional carrier adhesive and impregnated, the polyurethane framework is subjected to a pretreatment. In some embodiments, the pretreatment comprises washing and drying in sequence; the washing is conducted by washing with distilled water for three times; the drying is conducted at 75° C. for 24 h; in some embodiments, the drying is conducted by baking, and the baking is conducted in a drying oven.
[0062] In some embodiments, a ratio of the volume of the polyurethane framework to the mass of the functional carrier adhesive is in a range of (1-27) cm.sup.3:(0.015-0.675) g, preferably (1-27) cm.sup.3:(0.02-0.54) g.
[0063] In some embodiments, the residual liquid is removed by absorbing the residual liquid inside the polyurethane framework and on the surface of the polyurethane framework using a filter paper.
[0064] In some embodiments, the process of placing the polyurethane framework in the zeolite-tourmaline mixed powder and adhering the zeolite-tourmaline mixed powder to the polyurethane framework is conducted by means of pressing and/or kneading to sufficiently contact and uniformly adhere the interior and surface of the polyurethane framework with the powder.
[0065] In some embodiments, the zeolite-tourmaline mixed powder is loaded in two steps, which could adhere more mixed powder.
[0066] In some embodiments, the method further includes after the adhesion is completed, subjecting the resulting polyurethane framework to a post-treatment; subjecting the resulting polyurethane framework to the post-treatment comprises: subjecting the resulting polyurethane framework to an oscillating, a blowing off, a first drying, a washing and a second drying in sequence. In some embodiments, the oscillating is conducted at an oscillation speed of 200 rpm/min, and the oscillating is conducted for 2 h; the oscillating is conducted in an oscillator. In some embodiments, the blowing off is conducted by means of air stripping at ambient temperature; the blowing off is to remove the excessive zeolite-tourmaline mixed powder in the pores of the polyurethane framework. In some embodiments, the first drying and the second drying are conducted at 75° C. for 24 h; the first drying and the second drying are conducted by baking, and the baking is conducted in an oven. In some embodiments, the washing is conducted by soaking in distilled water.
[0067] The present disclosure also provides use of the biofilm composite carrier described in the above technical solution or prepared by the method described in the above technical solution in the field of enhancing municipal sewage deammonificaiton. In some embodiments, the biofilm composite carrier is used as a filler for enhancement of municipal sewage deammonification system.
[0068] In some embodiments, a method for enhancing municipal sewage deammonificaiton comprises the following steps: [0069] introducing municipal sewage into a packed bed reactor with a filler for nitrogen removal, wherein the filler is the biofilm composite carrier described in the above technical solution or prepared by the method described in the above technical solution.
[0070] In some embodiments, the biofilm composite carrier filled in the packed bed reactor accounts for 15-45%, preferably 20-40% of the volume of the packed bed reactor.
[0071] In some embodiments, the municipal sewage has an ammonium concentration of less than 50 mg N.Math.L.sup.−1.
[0072] In some embodiments, a hydraulic retention time of the municipal sewage is in a range of 6.6-11.3 h, preferably 7-10 h. The municipal sewage has a total nitrogen load of 0.1-0.2 kg N (m.Math.d).sup.−1, preferably 0.13-0.16 kg N (m.Math.d).sup.−1.
[0073] In some embodiments, the nitrogen removal is conducted under conditions of: a temperature of 33±3° C.; a pH of 8.0±0.3; a dissolved oxygen concentration of 0.1 mg O.sub.2.Math.L.sup.−1; a reflux ratio of (1-10):1, preferably (3-7):1, and more preferably (5-6):1; an aeration rate of 0-6 mL/min, an aeration time of 4-15 min, an aeration stopping time of 15-26 min, and aeration and no-aeration are alternately conducted; the nitrogen removal is conducted in dark.
[0074] In the present disclosure, there is no special limitation on the packed bed reactor, and any packed bed reactor well known to those skilled in the art may be used. In a specific embodiment of the present disclosure, the packed bed reactor is an upflow packed bed reactor with a height of 39 cm, an inner diameter of 7 cm, a total volume of 1.5 L, and an effective capacity of 1.3 L.
[0075] The biofilm composite carrier and preparation method and use thereof provided by the present disclosure will be described in detail with reference to examples below, but they should not be construed as limiting the protection scope of the present disclosure.
EXAMPLE 1
[0076] 15 g of 200-mesh zeolite powder was added into 100 mL of a NaCl solution with a temperature of 70° C. and a concentration of 1 mol/L, and soaked for 2 h for an activation. The resulting zeolite powder after the activation was elutriated to be neutral with distilled water, baked in an oven at a temperature of 105° C. for 24 h, ground by a grinder, and then sieved through a 200-mesh screen, obtaining a Na-pretreated zeolite powder.
[0077] 22.5 g of the Na-pretreated zeolite powder and 7.5 g of 800-mesh tourmaline powder were mixed in a high-speed oscillator at an oscillation rate of 3200 rpm/min for 20 min, obtaining a zeolite-tourmaline mixed powder.
[0078] A polyurethane sponge with a side length of 1 cm was washed with distilled water for three times, and baked in an oven at 75° C. for 24 h, obtaining a pretreated polyurethane sponge; [0079] 3 g of the zeolite-tourmaline mixed powder and 30 g of a waterborne polyurethane solution with a concentration of 30±2% by mass were mixed in a magnetic stirrer at a rotating speed of 120 rpm/min for 2 min, obtaining a functional carrier adhesive.
[0080] The pretreated polyurethane sponge with a volume of 200 cm.sup.3 is placed in 33 g of the functional carrier adhesive, fully impregnated, and taken out. Residual liquid inside and on the surface of the polyurethane sponge was sucked by a filter paper, and the resulting polyurethane sponge was then placed in the zeolite-tourmaline mixed powder, squeezed and/or kneaded to fully contact the inside and surface thereof with the zeolite-tourmaline mixed powder and uniformly adhere the zeolite-tourmaline mixed powder to the polyurethane sponge, and then taken out. The resulting material was oscillated by using a shaker at the oscillation speed of 200 rpm/min for 2 h, then blowed off by means of air stripping at ambient temperature to take out residual powder in pores, dried in an oven at 75° C. for 24 h, washed with distilled water to clean floating powder, and then dried in an oven at 75° C. for 24 h, obtaining a biofilm composite carrier (which had a loading of the zeolite-tourmaline mixed powder of 0.15 g/cm.sup.3, a mass ratio of the Na-pretreated zeolite to the tourmaline of 3:1, and a loading of the waterborne polyurethane of 0.015 g/cm.sup.3).
EXAMPLE 2
[0081] This example was conducted in procedures similar to those of Example 1, and the obtained biofilm composite carrier had a loading of the zeolite-tourmaline mixed powder of 0.17 g/cm.sup.3, a mass ratio of the Na-pretreated zeolite to the tourmaline of 2:1, and a loading of the waterborne polyurethane of 0.019 g/cm.sup.3.
EXAMPLE 3
[0082] This example was conducted in procedures similar to those of Example 1, and the obtained biofilm composite carrier had a loading of the zeolite-tourmaline mixed powder of 0.16 g/cm.sup.3, a mass ratio of the Na-pretreated zeolite to the tourmaline of 2:1, and a loading of the waterborne polyurethane of 0.018 g/cm.sup.3.
EXAMPLE 4
[0083] This example was conducted in procedures similar to those of Example 1, and the obtained biofilm composite carrier had a loading of the zeolite-tourmaline mixed powder of 0.16 g/cm.sup.3, a mass ratio of the Na-pretreated zeolite to the tourmaline of 1:1, and a loading of the waterborne polyurethane of 0.018 g/cm.sup.3.
EXAMPLE 5
[0084] This example was conducted in procedures similar to those of Example 1, and the obtained biofilm composite carrier had a loading of the zeolite-tourmaline mixed powder of 0.17 g/cm.sup.3, a mass ratio of the Na-pretreated zeolite to the tourmaline of 1:1, and a loading of the waterborne polyurethane of 0.019 g/cm.sup.3.
EXAMPLE 6
[0085] This example was conducted in procedures similar to those of Example 1, and the obtained biofilm composite carrier had a loading of the zeolite-tourmaline mixed powder of 0.18 g/cm.sup.3, a mass ratio of the Na-pretreated zeolite to the tourmaline of 1:1, and a loading of the waterborne polyurethane of 0.020 g/cm.sup.3.
Comparative Example 1
[0086] A polyurethane sponge with a side length of 1 cm was washed with distilled water for three times, and dried in an oven at 75° C. for 24 h, obtaining a treated polyurethane sponge.
Comparative Example 2
[0087] This comparative example was conducted as described in Example 1, except that no tourmaline powder was added, and the obtained zeolite-polyurethane biofilm carrier had a loading of the zeolite of 0.15 g/cm.sup.3, and a loading of the waterborne polyurethane of 0.015 g/cm.sup.3; the specific structural schematic diagram is shown in
Use Example
[0088] A deammonification system was constructed in an upflow packed bed reactor using the biofilm composite carriers prepared in the Examples 1-6, the treated polyurethane sponge obtained in the Comparative Example 1 and the biofilm composite carrier obtained in the Comparative Example 2 as fillers, which was specifically as follows:
[0089] Three identical upflow packed bed reactors were taken, wherein the reactor had a height of 39 cm, an inner diameter of 7 cm, a total capacity of 1.5 L and an effective capacity of 1.3 L. The biofilm composite carrier prepared in Example 1, the treated polyurethane sponge obtained in Comparative Example 1 and the zeolite-polyurethane biofilm obtained in Comparative Example 2 were placed in the three reactors respectively, and a reflux ratio was controlled at 5:1. The specific nitrogen removal conditions were as follows: an aeration was conducted for 4 min, and an aeration stopping was conducted for 26 min; an aeration rate was 6 mL/min; the outside of the reactor was wrapped up with black shading cloth, and further wrapped up with an electric blanket to maintain the temperature at 33±3° C.; a dissolved oxygen concentration was 0.1 mg O.sub.2.Math.L.sup.−1, a pH was 8.0±0.3, an ammonium concentration of artificial municipal sewage was set to 50 mg N.Math.L.sup.−1, a hydraulic retention time was 6.6 h, a total nitrogen loading rate of the influent was 0.2 kg N.Math.(m.sup.3.Math.d).sup.−1. The test results are shown in
[0090]
[0091] The effects of the novel biofilm composite carrier systems constructed by the biofilm composite carriers prepared in Examples 2-6 are similar to that of the novel biofilm composite carrier system constructed by the biofilm composite carrier prepared in Example 1.
[0092] The foregoing is only a preferred embodiment of the present disclosure, and it should be noted that, for those skilled in the art, various improvements and modifications could be made without departing from the principle of the present disclosure, and these improvements and modifications should also be considered as the protection scope of the present disclosure.