CN108083415B - Sewage treatment filler and manufacturing method thereof - Google Patents

Abstract

The invention relates to a novel sewage treatment filler and a preparation method thereof, wherein the sewage treatment filler comprises the following components: a base material,A protective film and a carbon film, characterized in that: the protective film is attached to the surface of the substrate to prevent the substrate from being corroded by sewage, the carbon film is attached to the surface of the protective film, and the metal oxide or the functional group is attached to the surface of the carbon film. The invention can effectively treat different waste water by changing the metal oxide or the functional group attached to the surface of the filler substrate. For removing TDS in water and converting H₂O₂Becomes OH, and produces organic substances in the wastewater with excellent effect.

Description

Sewage treatment filler and manufacturing method thereof

Technical Field

The invention relates to a sewage treatment filler and a manufacturing method thereof, belonging to the technical field of sewage treatment.

Background

At present, the filler for sewage treatment in the market is single, and except the filler which can carry out simple physical adsorption and filtration and generate chemical reaction, no other filler which can carry out deeper treatment on sewage exists. In order to solve the problem, the invention develops a novel sewage filler and a production process on the basis of the original simple sewage treatment filler.

Disclosure of Invention

The invention aims to overcome the problems in the prior art and provides a novel sewage treatment filler and a preparation method thereof. For removal of Total Dissolved Solids (TDS) in water, conversion of H₂O₂Changed to OH, and has excellent effect of removing organic substances and the like in sewage.

A wastewater treatment packing comprising: base material, protection film, carbon film, its characterized in that: the protective film is attached to the surface of the substrate to prevent the substrate from being corroded by sewage, the carbon film is attached to the surface of the protective film, and the metal oxide or the functional group is attached to the surface of the carbon film.

The base material is as follows: steel wire balls, structural fillers or porous ceramic filter plates. The preferred substrate is a steel wire ball having a three-dimensional structure.

The protective film is as follows: silica, alumina, aluminophosphates, molecular sieves or zeolites. A preferred protective film is zeolite.

The carbon film is activated carbon, graphite, a carbon nanotube or graphene.

The metal oxide is as follows: scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, technetium, molybdenum,

ruthenium, silver, cadmium, tungsten or cerium oxide. Among them, manganese, zirconium and tungsten are preferable.

The source compound of the functional group is linear aliphatic (aliphatic) quaternary amine and phosphoric acid H₃PO₄With sodium dihydrogen phosphate NaH₂PO₄Sodium hydrogen phosphate Na₂HPO₄Or a zeolite. Among them, linear aliphatic (aliphatic) quaternary amines are preferable.

The manufacturing method of the sewage treatment filler is characterized by comprising the following steps:

step 1: firstly, etching a steel wire ball (SB) by using ferric chloride (FeCl3) or hydrochloric acid to remove oil stains on the steel wire and coarsen the surface of the steel wire, thereby increasing the adhesive force of a covering object on the steel wire;

step 2: cleaning and drying the etched steel wire ball (SB), soaking the steel wire ball (SB) in a solution containing silicon dioxide, aluminum oxide, aluminum phosphate, molecular sieve or zeolite for 2-5 hours to ensure that the medicament and the steel wire fully react, and then sintering at the constant temperature of 800 ℃ for 3 hours at 700-;

and step 3: the steel wire ball (SB) plated with the protective film is then fixed with activated carbon, graphite, carbon nanotubes or graphene on the protective film of the steel wire ball (SB) by using a ceramic adhesive at the temperature of 700 plus 800 ℃ and in an oxygen-free state to form a coated steel wire ball (CSB) coated with a carbon film.

And 4, step 4: the coated steel wire ball (CSB) is dipped in the solution of metal oxide or the source compound of functional group for 2 to 5 hours, the liquid medicine fully wets the surface and the holes of the carbon material, and the liquid medicine is bonded with the metal oxide attached to the surface of the carbon material or reacts with the functional group to generate bonding, thus obtaining the sewage treatment filler.

The invention is realized by changing the metal oxide or the function attached to the surface of the filler substrateThe ball can effectively treat different waste water. For removal of Total Dissolved Solids (TDS) in water, conversion of H₂O₂Changed to OH, and has excellent effect of removing organic substances and the like in sewage.

Drawings

FIG. 1 is a schematic structural diagram of a steel wire ball substrate according to the present invention.

FIG. 2 is a diagram of the manufacturing process of the coated steel wire covered by the adsorbent and the catalyst according to the present invention;

FIG. 3 shows WO of the present invention₃-ZrO₂Catalyst for removing H from water₂Schematic representation of conversion to. OH free radical.

Detailed Description

The invention is further described with reference to the accompanying drawings.

The sewage treatment filler of the present invention utilizes a filter carrier having a three-dimensional (3D) structure, such as: steel wire balls, structural fillers or porous ceramic filter plates. Preferably, the steel wire ball is prepared by using the steel wire ball (SB) shown in FIG. 1 as a substrate, gradually adding the carbon material and the metal oxide or functional group on the steel wire ball (SB) by the Pech iin i method through the process shown in FIG. 2, and finally preparing the catalyst or functional group covered coated steel wire ball (CSB). The steps of the flow of fig. 2 are: the steel wire ball (SB) is etched by hydrochloric acid, aiming at removing oil stains on the steel wire, roughening the surface of the steel wire and increasing the adhesive force of a covering on the steel wire. The etched steel wire ball (SB) was cleaned and dried, and immersed in a zeolite solution for 3 hours to allow the agent to react sufficiently with the steel wire, and then sintered at a constant temperature of 800 ℃ for 3 hours to form a protective film on the surface of the steel wire. The protective film has three functions: to prevent corrosion of the steel wool, to support the catalyst or adsorbent particles, and to zeolite itself.

The steel wire ball (SB) coated with the protective film is then fixed with activated carbon on the protective film of the steel wire ball (SB) by a ceramic adhesive under the conditions of 700-. The surface of the carbon material has a plurality of functional groups, so that the carbon material is easy to be connected with a specific metal oxide or a specific functional group required by water treatment to reach the standard by a chemical method. The plasticity of the carbon material is far larger than that of the ceramic protective film, so that the carbon material has an infinite space in the application of water treatment. The coated steel wire ball (CSB) is immersed in the solution of metal oxide or functional group source compound for 2 hours, the liquid medicine fully wets the surface and pores (pores) of the carbon material, and the liquid medicine is attached with the metal oxide on the surface of the carbon material or reacts with the functional group to generate bonding, and the sewage treatment filler is obtained. The following table shows specific functional groups or transition metals on the periodic table, their derived adsorbents (adsorbents), or oxide catalysts, each having a specific fouling-removal function.

The working principle and the characteristics of the invention are as follows:

according to the invention, different functional groups can be prepared to be attached to the surface of the filler material according to the characteristics of sewage, and different waste water can be treated on line in a targeted manner.

Table a functional group of an on-line adsorbent and a metal element of an on-line catalyst

CSB 1-4 in the table are described as follows:

the CSB 1-4 is operated in an overflow mode, and wastewater is pumped through a packed column of CSB, and the functions of the adsorbent and the catalyst are exerted. Through the 3D structure of the CSB, the wastewater flowing through can be completely contacted with the CSB and processed.

CSB-1: the source compounds of the functional groups are tetraethylammonium hydroxide, H3PO4 phosphate and sodium dihydrogen phosphate NaH₂PO₄Sodium hydrogen phosphate Na₂HPO₄And a zeolite. Basically, the seawater flows through CSB-1, and the TDS of the outlet water is lower than that of the inlet water. The difference is only the adsorption capacity of the adsorption functional group, and the unit is: mg TDS/g adsorbent. Experiments have shown that linear aliphatic (aliphatic) quaternary amines have higher adsorption capacities than other functional groups and are therefore preferred. CSB-1 has the feasibility of being developed as a "sludge free" desalination process.

CSB-2: iron has many oxidation valences, and iron oxides and hydroxides have 16 or more. For example: hematite (α -Fe2O3), maghemite (γ -Fe2O3), magnetite (Fe2O4), wustite (FeO), goethite (α -FeOOH), and patina [ Fougerite, Fe2+4Fe3+2(OH-)12, also including Fe (OH)2 and Fe (OH)3 ]. Each iron compound has its catalytic action, so that CSB-2 can derive multiple catalysts for treating various COD and non-COD pollutants.

CSB-3 designed to function as an on-line H₂Conversion to H₂O₂Zirconium oxide (ZrO) is produced using zirconium and tungsten as preferred metal elements₂) With tungsten oxide (WO)₃) Two catalysts. Although FIG. 3 shows WO₃-ZrO₂Catalyst to remove H₂And O₂First oxidized into hydrogen peroxide (H)₂O₂)，H₂O₂Then converted into OH free radical; however, in the "over-flow" mode of operation, H₂O₂The reaction radicals → OH are not nearly complete and require the assistance of other catalysts.

CSB-4: designed to function as an on-line H₂O₂Converted to OH, and made into iron oxide (Fe) with iron, cobalt, nickel and copper as preferred metal elements₂O₃) Cobalt oxide (CoO/Co)₃O₄) Nickel oxide (NiO) and copper oxide (CuO). Taking CSB-4 made of four metals of iron, cobalt, nickel and copper, except converting H₂O₂It can decompose various COD waste water for OH. The 20 transition metals listed in the table, together with the anion of the source compound, the sintering temperature, the sintering atmosphere (atmosphere) and the sintering time, all influence the catalytic behavior of the catalysts produced. The foregoing factors can yield tens of millions of combinations. In other words, the development of CSB is a continuous task that can lead to more efficient and environmentally friendly water treatment.

2 coated steel wire balls (CSB) with only zeolite carrier, code number CSB-Z (each CSB-Z weighs 50g), were placed in a plastic container with an inner diameter of 5cm and a length of 24 cm. 2L of untreated seawater stock was passed through the vessel with a pump at a flow rate of 2L/min. One cup of effluent is collected every 200mL, the TDS difference value of each cup of effluent and stock solution is calculated, the TDS of each cup is reduced, and the result is shown in a second table:

table II CSB-Z desalinated seawater

The amount of salt removed was ppm (mg/L) x0.2L

Adsorption capacity of CSB-Z-total salt removal/adsorbent weight

＝2180mg/100g＝21.8mg/g

In fact, the weight of each steel wire ball is 50g (measured to be 48.5g), and the weight of the zeolite carrier covered on the steel wire ball is far less than 100 g. In other words, the adsorption capacity of CSB-Z is much larger than that of Modified Active Carbon (MAC).

Claims (3)

1. A wastewater treatment packing comprising: base material, protection film, carbon film, its characterized in that: the protective film is attached to the surface of the base material to prevent sewage from corroding the base material, the carbon film is attached to the surface of the protective film, and metal oxide or functional groups are attached to the surface of the carbon film;

the base material is a steel wire ball with a three-dimensional structure; the carbon film is activated carbon, graphite, a carbon nanotube or graphene; the source compound of the functional group is linear aliphatic quaternary amine and phosphoric acid H₃PO₄With sodium dihydrogen phosphate NaH₂PO₄Sodium hydrogen phosphate Na₂HPO₄Or a zeolite;

the manufacturing method of the sewage treatment filler comprises the following steps: step 1: firstly, ferric chloride FeCl is used₃Or the steel wire ball is etched by hydrochloric acid, oil stains on the steel wire are removed, the surface of the steel wire is roughened, and the adhesive force of a covering on the steel wire is increased; step 2: cleaning and drying the etched steel wire ball, soaking the steel wire ball in a solution containing silicon dioxide, aluminum oxide, aluminum phosphate, molecular sieve or zeolite for 2-5 hours to ensure that the medicament and the steel wire fully react, and then sintering at the constant temperature of 800 ℃ for 3 hours at 700-; and step 3: plating the steel wire ball with the protective film, and then using a ceramic adhesive to mix the activated carbon, the graphite and the nano carbon at the temperature of 700 plus materials and 800 ℃ in an oxygen-free stateThe pipe or the graphene is fixed on the protective film of the steel wire ball to form a coated steel wire ball coated with a carbon film; and 4, step 4: and soaking the coated steel wire ball in a solution of a metal oxide or a source compound of a functional group for 2-5 hours, wherein the liquid medicine fully wets the surface and the holes of the carbon material, and the liquid medicine is bonded with the metal oxide attached to the surface of the carbon material or reacts with the functional group to generate bonding, so that the sewage treatment filler is obtained.

2. The sewage treatment packing of claim 1, wherein: the protective film is as follows: silica, alumina, aluminophosphates, molecular sieves or zeolites.

3. The sewage treatment packing of claim 1, wherein: the metal oxide is as follows: scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, silver, cadmium, tungsten or cerium oxide.

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