2. Heating and Thermal Treatment
MW has become increasingly common as a thermal method for treating wastewater and sediments in recent years, owing to its rapid and selective heating
[9,10,11,12,13,14,15][9][10][11][12][13][14][15]. The thermal effect of MW
[16] describes how ultrahigh-frequency energy can be consumed by microwave absorbers and dissipated as thermal energy. For many environments, including water solutions, microwave heating with dielectric losses is typical
[13].
Water is a positive-charged molecule (or dipole) with a negative-charged opposite end. Dipolar polarization occurs due to intermolecular inertia, responsible for most of the microwave heating observed in liquids. The rapid change in the electric field of microwave radiation causes a rotation of dipoles. At the same time, the rate at which the dipole rotates (reverses) cannot accurately correlate to the rate at which the electric field shifts direction. It induces “internal friction” between water molecules, which leads to direct and very uniform heating of the reaction mixture. However, reflections and refractions at local boundaries between phases lead to the appearance of so-called “hot spots” and the effect of “overheating”, which has been extensively discussed by researchers
[15,17,18,19,20,21][15][17][18][19][20][21].
Figure 1 presents the schematic diagram of microwave action
[3[3][17],
17], illustrating the advantages and scope of application of microwave processing. Microwave heating penetrates the liquid and creates the rapidly changing field: dipoles (water molecules) continuously react attempting to align in the field, which generates heat; heat is uniformly distributed throughout the water.
Figure 1. The scheme of mechanism of the MW water heating.
Under the influence of MW, several parameters such as strength, frequency, duration, treatment temperature, and sample volumes
[9,14,22,23,24,25,26,27][9][14][22][23][24][25][26][27] can influence the efficiency of pollutant decomposition and mineralisation of wastewater and sediments. It is confirmed in the materials
[25,26,27][25][26][27], which use the Netherlands, Kenya, China, and other countries as examples of MW-heating of faecal sludge (
Figure 2).
Figure 2. Dependence of temperature on the time of MW-heating of: (
a) faecal sludge in Kenya, 100 g sample
[27]; (
b) faecal sludge in Kenya, 200 g sample
[27]; and (
c) active sludge in China Reprinted with permission from ref.
[25].
As a rule, the efficiency of the MW system tends to rise with the increase of power and time of microwave irradiation
[22]. It is due to the release of extra heat, contributing to the rapid movement of water molecules. In addition, increased time and power of irradiation amplify the decomposition of various contaminants in the water environment
[9].
In some cases, the efficiency of the MW system is reduced at very high temperatures by evaporating water and increased viscosity of the substance by overheating. Thus, it is necessary to determine the optimal power and reaction temperature for decomposing a particular target pollutant
[9,14,17,18,19,20,21][9][14][17][18][19][20][21].
It should be noted that the technological and economic efficiency of MW heating for the water environment is currently actively explored by contrasting it to other methods of heating and processing
[14,23,24][14][23][24]. The Department of Water Supply and Sanitation (Industrial University of Tyumen, Russia) laboratory has carried out several experiments related to the MW-heating of wastewater sludge
[14,24][14][24]. Firstly, a comparison is made between microwave and electric heating. The distinctive feature of microwave heating is its thermal effect, which is volumetric and does not involve thermal diffusion from the surface into the material, as conventional heating does, which explains its high thermoset reaction rates. According to observations, ultrahigh-frequency irradiation of liquid sewage sludge has a rapid thermal effect: samples of sludge with a 50–300 mL volume started to boil within one to two minutes (
Figure 3)
[14].
Figure 3. (a) Comparison of two methods of WWS-heating. (b) Boiling time dependence of the WWS on the sample volume at a constant power MW.
Figure 3a compares the heating curves of sewage sludge (mixture of the raw sludge and activated sludge) in two different ways, with the rate of heating the sludge to a given temperature using microwaves being four to six times faster than the usual heating on an electric stove. In addition, in the process of microwave irradiation, an improvement in the sedimentation and compaction of WWS was obtained by 13–15% compared to traditional convective heating to the same temperature
[14].
Secondly, the maximum time for MW treatment of WWS samples to reach boiling point
[24] was determined experimentally.
Figure 3b illustrates dependency t = f (V) at constant power MW based on the experience data. Obviously, the higher the microwave processing power, the faster the sludge samples reach the boiling point. At MW 200 W, the heating rate of sewage sludge is 3.7–4.0 times lower than at MW 1000 W and 3–2.8 times lower than at MW 600 W. Heating sludge with a power of 1000 W is 1.2 times more effective than heating with 600 W. Rapid and voluminous MW-heating of wastewater and sediments entails other positive effects discussed below.
3. Decontamination (Disinfection)
In the last century, the biophysical impact of the MW field on the viability and other properties of bacteria was discovered
[43,44][28][29]. The sterilising efficiency of the MW field produced by the GZ–10A generator when irradiated for 10 min, for example, was used to assess the biological effect of microwaves on microorganisms
[45][30]. The bacteria’s viability was determined by the number of colonies developed within two days on the breeding ground. As a result, researchers discovered a bactericidal effect of pulsed and continuous microwaves on Escherichia coli and staphylococcus cultures.
Experiments on the influence of centimetre waves on the growth of Escherichia coli M–17 in a continuous mode (frequency 10.6 GHz, PPM = 0.1–5.5 MW/cm
2) are presented in the paper
[46][31]. According to the material results, microwave radiation has a harmful effect on escherichia coli (n = 10) at a power of 130 W for five minutes
[47][32]. Water heating and disinfection systems were invented and patented in the 1970s and 1980s
[48,49][33][34].
The modern use of MW for wastewater disinfection is based on earlier studies
[50,51][35][36]. Less often it is mentioned that sewage sludge is also disinfected during microwave irradiation
[14,26,27,31,33,34,37,42,52][14][26][27][37][38][39][40][41][42]. Water disinfection usually occurs at a power of MW from 300 W and higher (frequency 2.45 GHz) when heated from 45 to 100 °C. Therefore, the processing time depends on the sample volume and the MW heating power. This knowledge is very relevant concerning the further disposal of such liquid municipal waste. For example, faecal sludge formed in public toilets was treated using a laboratory microwave installation (MW)
[26,27][26][27].
Total bacterial inactivation was achieved in 30–240 min after sewage sludge treatment in a special MW reactor
[42][41]. According to findings in
[52][42], high–level disinfection for enterococci and salmonella is possible to achieve in 9.5 min at MW energy consumption of 580 W∙s/g and temperature 72 °C. In some studies
[53[43][44],
54], microwave irradiation proved to effectively reduce the bacterial content of sewage sludge prior to anaerobic digestion. In addition, a high degree of removal of faecal coliforms in the sediment is recorded in
[55][45] (the content of 2.66 logs or less).
Similarly, researchers
[56][46] confirmed that a single pretreatment with microwaves resulted in a 50% reduction of bacteria C.Perfringens. Furthermore, according to the article
[14], the microwave treatment of a mixture of sewage sludge can achieve 99% decontamination from all pathogenic bacteria subject to control.
The MW technology can be further investigated for potential expansion as a rapid treatment alternative for faecal effluents and sediments in emergencies
[26[26][27],
27], such as a pandemic.
4. Decomposition of Organic Substances
Organic pollution of natural and wastewater is a source of concern for scientists and environmentalists worldwide, as these contaminants have a detrimental impact on the natural environment, human life, and health. Approximately 3000 different organic contaminants have been identified
[57,58][47][48] and classified into three groups: (1) organic substances of natural origin, (2) synthetic organic pollutants, and (3) chemicals reformed in water as a result of its purification. Many organic pollutants of the second and third groups are toxins and carcinogens
[59][49]. Therefore, the international community is looking for creative, highly efficient advanced oxidative water treatment technologies that involve various pollutant exposure processes to address this problem.
In order to increase the performance of WW treatment from different contaminants and minimise reaction time, microwave exposure should be combined with oxidising agents OX (MW + OX), adsorbents activated carbon AC (MW + OX + AC), catalysts carbon C (MW + OX + C), and advanced oxidation processes with the addition of UV irradiation such as photo-Fenton (MW + OX + C + UV), direct photolysis using an electrodeless discharge lamp EDL (MW+OX+EDL), and photocatalysis using TiO
2 photocatalyst (MW + OX + UV + TiO
2)
[60,61,62,63,64,65,66,67,68,69,70,71,72][50][51][52][53][54][55][56][57][58][59][60][61][62].
The review data were summarised reasonably well in the papers
[9,73][9][63]. Other studies of the efficacy of MW oxidation of organic compounds under various treatment conditions are seen in
Table 61 [22,61,62,63,64,65,66,67,68,69,70,71,72][22][51][52][53][54][55][56][57][58][59][60][61][62].
Table 61. The efficiency of MW oxidation of organic substances in WW.
Type of an Organic Substance |
Sample Volume |
Concentration |
Oxidizing Agent, Catalyst, pH |
MW Power |
MW Duration, Temperature |
Effect |
[Ref./No] |
Sample was only MW-treated |
Ammonia (laboratory installation) |
100 mL |
0.5–12 g/L |
Air 1 L/min pH = 11 |
750 W |
3 min 80 °C |
D * 98.4–96.1% |
[63][53] |
Ammonia (pilot plant) |
28,000 mL |
2.4–11 g/L |
Air 30 L/min pH = 11.6–12 |
4.8 kW |
60 min 80–100 °C |
D * 80% |
[63][53] |
With an addition of the oxidizer: MW + OX |
Naphthalene Disulfonic Acid |
10 mL |
1.0 mmol/L |
H2O2 |
300 W |
20 min 30 min 80 °C |
D * 90% M ** 50% |
[64][54] |
Dimethoate (phosphoric compound) |
No Data |
0.1 mmol/L |
K2S2O8 pH = 6.8 |
750 W |
4 min 100 °C |
D * 100% |
[22] |
Perflurooctanic acid |
50 mL |
0.25 mmol/L |
Na2S2O8 |
800 W |
240 min 60–130 °C |
D * 99.3% M ** 74.3% |
[66][56] |
The photo-Fenton process: MW + OX + C + UV |
Polyacrylamide (PAA) |
No Data |
150 mg/L |
H2O2/AC pH = 3 |
70 W 490 W |
6 min |
D * 20% D * 80% |
[61][51] |
Pesticides (dimethoate, triazophos, malathion) |
1000 mL |
6.11–31.65 mg/L |
H2O2 Fe2+; pH = 5 |
80 W |
120 min 25 °C |
M ** 72.1% |
[62][52] |
Direct photolysis: MW + OX + EDL |
Phenol |
50 mL |
200 mg/L |
H2O2 |
1000 W |
9 min 30 min 50 °C |
D * 90% M ** 95% |
[67][57] |
Atrazine |
50 mL |
50 mg/L |
pH = 6.3 |
900 W |
30 min 30 °C |
D * 100% |
[68][58] |
Photocatalysis: MW + OX + UV + TiO2 |
Methylene Blue (aromatic compound) |
50 mL |
100 mg/L |
TiO2 load pH = 7 |
900 W |
15 min 100 °C |
D * 96% M ** 50% |
[69][59] |
2,4–D chlorophenoxyacetic herbicide |
10 mL |
0.04 mmol/L |
TiO2 load pH = 4.9 |
700 W |
20 min 200 °C |
D * 100% |
[70][60] |
Bisphenol A (Endocrine disruptor) |
30 mL |
0.1 mM |
TiO2 load pH = 6.7 |
1500 W |
90 min 150 °C |
M ** 100% |
[71][61] |
Phenol |
50 mL |
10 mg/L |
TiO2/AC |
900 W |
30 min 1000 °C |
D * 87% |
[72][62] |
Atrazine |
50 mL |
20 mg/L |
TiO2 nanotubes pH = 8.1 |
900 W |
5 min 20 min |
D * 100% M ** 98.5% |
[72][62] |