Method for the preparation of biofilm carrier with biochar fixed by thermoplastic resin

Abstract

The invention, belonging to the field of biological treatment of pollutants and functional materials, presents a method for the preparation of biofilm carrier with biochar fixed by thermoplastic resin. Extrusion grade polyethylene/polypropylene particles are used as the basic material. One or some combination of plant biochar, straw biochar, rice husk biochar, shell biochar, excess sludge and animal waste biochar are used as the functional material. The biofilm carrier with biochar fixed by thermoplastic resin is prepared by the screw extrusion process, which is a simple, flexible and controllable method, and possesses strong adaptability. The reactor with these biofilm carriers has high removal efficiency of refractory organic pollutants.

Claims

1. A method for the preparation of biofilm carrier with biochar fixed by thermoplastic resin, comprising: (1) biochar functional material is ground to powder and dried to a constant weight at ≤80° C.; surface of the biochar functional material comprises oxygen-containing functional groups having a function of redox mediator; (2) biochar functional material powder, which is pretreated according to step (1), is blended into thermoplastic resin particles and stirred evenly; a mass percentage of the biochar functional material powder to the thermoplastic resin particles is 20%-50%; (3) a solid mixture obtained from step (2) is melt extruded into strips by a screw extruder and mechanically cut to obtain a granular blend; a processing temperature of each section of the screw extruder is 130-190° C. to ensure that the thermoplastic resin particles are fully mixed with the biochar functional material powder in a molten state; (4) a granular blend prepared in step (3) and the thermoplastic resin particles are mechanically stirred evenly, and then added to the screw extruder for co-mixing and extrusion, carrier pipes of different shapes are obtained, according to a design of a mould; a ratio of a mass of the biochar functional material powder to a total mass of the thermoplastic resin particles in granular blends is less than 20%; (5) the carrier pipes prepared in step (4) are cut mechanically and biological carriers are obtained according to a required size, the biological carriers are used in a biological treatment of sewage, wherein the biochar functional material is grass biochar, straw biochar, rice husk biochar, nut shell biochar, sludge biomass biochar, animal excrement biochar, or a combination thereof, wherein the thermoplastic resin particles are extruded grade polyethylene particles or extruded grade polypropylene particles.

2. The method for the preparation of biofilm carrier according to claim 1, wherein the screw extruder is heated in four sections, and a temperature range and effects of each section heating are as follows: (1) the temperature is 120-140° C., and the thermoplastic resin reaches a semi-molten state, which is conducive to a continuity of solid transport; (2) the temperature is 130-160° C., which accelerates a transformation of the thermoplastic resin from the semi-molten state to the molten state, and is conducive to a homogeneous mixing of blends in a heating section; (3) the temperature is 140-170° C., which makes the blends in a solid-liquid mixing state, so that the thermoplastic resin in the molten state and the biochar functional material are fully mixed, which is conducive to a uniform distribution of the biochar functional material and the thermoplastic resin in the molten state; (4) the temperature is 115-145° C. to ensure a quantitative and constant pressure outflow of the blends, and to ensure stability and continuity of extrusion and subsequent smooth shaping.

3. The method for the preparation of biofilm carrier according to claim 1, wherein the screw extruder is heated in four sections, and a temperature range and effects of each section heating are as follows: (1) the temperature is 120-140° C., and the thermoplastic resin reaches a semi-molten state, which is conducive to a continuity of solid transport; (2) the temperature is 130-160° C., which accelerates a transformation of the thermoplastic resin from the semi-molten state to the molten state, and is conducive to a homogeneous mixing of blends in a heating section; (3) the temperature is 140-170° C., which makes the blends in a solid-liquid mixing state, so that the thermoplastic resin in the molten state and the biochar functional material are fully mixed, which is conducive to a uniform distribution of the biochar functional material and the thermoplastic resin in the molten state; (4) the temperature is 115-145° C. to ensure a quantitative and constant pressure outflow of the blends, and to ensure stability and continuity of extrusion and subsequent smooth shaping.

Description

DETAIL DESCRIPTION

(1) The specific implementation of the present invention will be described in detail below in conjunction with the technical solution.

Example 1

(2) The preparation of the biofilm carrier with straw biochar fixed by thermoplastic resin: (1) The straw biochar is ground to powder, and dried into constant weight at 60° C.; (2) Biochar powder, which is pretreated according to step (1), is blended into thermoplastic resin particles, and stirred evenly; (3) The solid mixture obtained from step (2) is melt extruded into strips by a screw extruder. The processing temperature of each section of the screw extruder is 175° C. The mass percentage of straw biochar powder to thermoplastic resin particles is 30%; (4) The granular blend prepared in step (3) and the thermoplastic resin particles are mechanically stirred evenly, and then added to the screw extruder for co-mixing and extrusion, the carrier pipes of different shapes are obtained, according to the design of mould. The ratio of biochar functional materials mass to the total mass of thermoplastic resin particles in granular blends is less than 4%; (5) The carrier pipes prepared in step (4) are cut mechanically and the biological carriers are obtained according to the required size.

(3) The biofilm carriers are applied to the aerobic biodegradation experiment of phenol wastewater (the dissolved oxygen was controlled at 2.0-3.0 mg/L), and its effect on the biodegradation performance of microorganisms in water is investigated. In the experiment, the dosage of carriers is 30% of the effective volume of the reactor, and the hydraulic retention time is 8 hours. The experimental results show that: (1) in the absence of microorganisms, the carrier adsorption experiment of phenol in water is carried out, and the results show that the removal rate of phenol through the carrier adsorption is less than 3%. (2) in the presence of microorganisms, compared with the high-density polyethylene carrier without fixed biochar, the removal of phenol in the reactor fixed with high-density polyethylene (HDPE) is nearly 10% higher than that of the high-density polyethylene carrier without fixed biochar.

Example 2

(4) The preparation of the biofilm carrier with straw biochar fixed by thermoplastic resin: (1) The rice husk biochar is ground to powder, and dried into constant weight at 60° C.; (2) Biochar powder, which is pretreated according to step 1, is blended into thermoplastic resin particles, and stirred evenly; (3) The solid mixture obtained from step (2) is melt extruded by a screw extruder. The processing temperature of each section of the screw extruder is 185° C. to ensure that the basic material is fully mixed with biochar functional materials in the molten state, and can be shaped into particles, the mass percentage of rice husk biochar to thermoplastic resin is 50%. (4) The granular blend prepared in step (3) and the thermoplastic resin particles are mechanically stirred evenly, and then added to the screw extruder for co-mixing and extrusion, the carrier pipes of different shapes are obtained, according to the design of mould. The ratio of biochar functional materials mass to the total mass of thermoplastic resin particles in granular blends is less than 8%(5) The carrier pipes prepared in step (4) are cut mechanically and the biological carriers are obtained according to the required size.

(5) The preparation methods of carbonylation modified graphene oxide (GO) as the biofilm carrier of functional materials are as follows: (1) preparation of carbonylation modified GO functional materials: the pH is adjusted to 10 with ammonia. The dispersion hydrothermally reacts at 90° C. for 6 hours, and then is cooled down and dried at 60° C. The solid particles obtained are referred as N-GO. The 0.2 g solid particles N-GO are added to the water (20 mL), and uniformly dispersed by ultrasonication, and then 1.2 g potassium dichromate is added into the dispersion under the condition of the addition of acid (H.sub.2SO.sub.4 5 mL) and ice water bath. After being fully stirred for 3 hours and dried, the solid particles are obtained. They are carbonylation modified graphene oxide, and called as Q-GO. (2) the non-dissolved redox mediator material is ultrasonically dispersed in the water, and mixed with the basic material added with the mass ratio of the mediator material to the basic material being 1:100, and then soaked for 2 hours, stirred every half an hour to make the redox mediator fully contact with the basic material in the water, and the resulting solid mixture is dried at 80° C. The biofilm carriers are prepared by extrusion, cooling, traction, incision and shaping.

(6) The modified (modified by biochar, carbonylation modification of graphene oxide, respectively) and unmodified (HDPE) carriers are used to treat phenol wastewater in the condition of aerobic or anaerobic. The effects of different carriers on the biodegradation performance of microorganisms in water with different phenol concentrations in the influent are investigated. In the experiment, the dosage of carriers is 30% of the effective volume of the reactor.

(7) The experimental results are shown in table 1. It can be seen from the table that under the conditions of aerobic and anaerobic with different phenol concentrations in the influent, the biodegradation performance of phenol in the reactor with modified carrier is better than that of the reactor with unmodified carrier. However, among the reactors with modified carriers, the biochar modified carriers have slightly better biodegradation performance than the reactors with modified carriers modified by carbonylation modification of graphene oxide. In addition, compared with the preparation method of carbonylation modified graphene oxide as functional material, the preparation method of bio-carrier fixed by thermoplastic resin is simpler, easier to operate, more time-saving and conducive to ensuring the continuity of the production process. Furthermore, compared with carbonylation modified graphene oxide as the functional materials, the biochar as the functional materials are more widely sourced, cheaper and more conducive to the realization of large-scale production and application.

(8) TABLE-US-00001 TABLE 1 Effect of modified carriers on biodegradability of phenol Phenol conc. Removal efficiency (%) (mg/L) PE Q-GO Biochar Aerobic 200 94.2 98.9 99.3 HRT 8 h 400 93.9 98.8 99.0 DO 2.0-3.0 600 92.9 98.6 98.7 mg/L 800 89.7 98 98.7 Anaerobic 200 89.3 93.5 96.7 HRT 12 h 400 66.4 90.1 93.6 DO <0.1 600 66.1 89 91.1 mg/L 800 65.4 87.8 89.3 Note: PE represents the reactor with unmodified biological carriers, Q-GO represents the reactor with the biological carriers modified by carbonylation modified graphene oxide, and Biochar represents the reactor with the biological carriers modified by biochar functional materials.