Purification of Saline Water Using Desalination Pellets
1.1. Other Applications for the Pellets
1.2. Potential Markets
1.3. Zero Valent Iron Desalination
1.3.1. Continuous Flow, Flow line, Contact Flow Approach
1.3.2. Batch Flow Emulsified n-Fe0, Approach
1.3.3. Fluidised Bed n-Fe0, Approach
1.3.4. Batch Flow, Diffusion Bed n-Fe0, m-Fe0, Fe0 Approach
- The discovery and proof of concept studies for the diffusion reactors are provided in six academic book chapters, and six academic papers, e.g., [1,2]. They consider the desalination of water, in : (i) static water, static bed reactors, using n-Fe0, m-Fe0, Fe0 and processed ZVI; (ii) a batch flow, circulating water, static bed diffusion reactor. The ZVI body is static and is located outside of the path of the circulating water. The water circulation is driven by either, thermal convection or pumped flow; (iii) A batch flow, bubble column, static bed diffusion reactor. The gas is bubbled through the water body but not through the ZVI. (iv) A batch flow, bubble column, static bed, recirculating, diffusion reactor. The gas is bubbled through the water body, but not through the ZVI. The water is continually recirculated between the bubble column and a storage tank. The circulating water does not flow through the ZVI.
- A proto-type commercial scale, desalination reactor train (0.24 m3), capable of processing up to 1.9 m3 d−1, using a steel wool charge, has been constructed and tested . It produced a 24.5% average desalination over 70 sequential water batches . This reactor train uses a catalytic, rapid-pressure-swing-adsorption–desorption/separation process, to achieve the observed desalination. The reactor train is designed to provide a solution to the desalination of saline irrigation water, and the desalination of saline aquifers, over the product delivery range 1 to 2000 m3 d−1. The reactor used was a batch flow, bubble column, static bed diffusion reactor . The reactor train demonstrated that 1 t Fe0 had the potential to partially desalinate >42,000 m3 of saline water .
- Approach A: Proto-type commercial scale, desalination reactor train (0.86 m3), capable of processing up to 24 m3 d−1, using a n-Fe0 charge, and producing a 40% average desalination over 50 sequential water batches (an a single Fe0 charge). This reactor uses a catalytic, rapid-pressure-swing-adsorption–desorption/separation process, to achieve the observed desalination. This technology is designed to provide a cost-effective solution to the desalination of saline irrigation water, the desalination of reject brine from conventional desalination plants and the desalination of saline aquifers, over the product delivery range 1 to 2000 m3 d−1. The reactor used in this trial series was a batch flow, bubble column, static bed, recirculating, diffusion reactor.
- Approach B: Proto-type engineering scale, reactor designed to commercially manufacture desalination pellets, which when placed in a saline water body gradually desalinate the water body. Unlike all previous desalination technologies, the pellets produced by this approach require no onsite energy, or infrastructure to undertake the desalination, and produce no reject brine. They are suitable for the desalination of saline impoundments, salinized soil and salinized groundwater. This desalination technology forms the focus of this paper. This study builds on the initial discovery documented in 2015, in reference . The reactor type used in this study to desalinate water is a static water, static bed, diffusion reactor.
- Approach C: Proto-type continuous flow, contact flow reactors, where a 10 to 70% desalination is achieved within 10 min of the diffusion desalination catalyst being added to the water. This technology is being developed to provide a rapid, low cost, low technology, zero energy solution for saline irrigation water, capable of delivering 20 to 2000 m3 d−1 of partially desalinated water.
2. Methodology, Materials and Equipment Used
Interpretation of R2
- PCC = 0.9 to 1.0 (R2 = 0.81 to 1.00): Interpretation—very strong correlation
- PCC = 0.7 to 0.89 (R2 = 0.49 to 0.79): Interpretation—strong correlation
- PCC = 0.4 to 0.69 (R2 = 0.16 to 0.47): Interpretation—moderate correlation
- PCC = 0.1 to 0.39 (R2 = 0.01 to 0.15): Interpretation—weak correlation
- PCC = 0.0 to 0.10 (R2 = 0.00 to 0.01): Interpretation—negligible correlation
2.3. Gas Measurement Equipment
2.4. Adjusting for Gas Contraction within a Reactor
2.6.1. Basic Reactor Operating Principles
- A reactant is physically adsorbed onto a catalytic site and is then desorbed as a product;
- The rapid pressure swing is designed to reduce the incidence of site blocking, and increase the availability of sites for adsorption to occur;
- The rate constant increases with decreasing space velocity;
- The adsorbed species is less voluminous than the reactant species;
- The adsorption rate constant increases with increasing pressure;
- The desorption rate constant increases with decreasing pressure.
2.6.2. Reactor Construction
2.6.3. Reactor Train
2.6.4. The Halite Rector
2.6.5. The ZVI Reactor
3.1. Desalination Pellets: Characterisation
3.1.1. Fe(b) Polymers
- Under constant oxygen partial pressure conditions
- The polymer sites show rapid physical adsorption and extremely slow product desorption, i.e., no effective desalination. Any physical desorption of ions is into the water body.
- Under oscillating oxygen partial pressure conditions
- The polymer sites show rapid physical adsorption and rapid product desorption;
- The rate of ion removal decreases rapidly with time as the proportion of sites blocked with competing ions, e.g., OH−, increases. The effective desalinating operating life of this catalyst type in a batch of water is 3 to 35 h. Switching to a new, lower pH, batch of water results in OH- desorption from the sites and allows the desalination process to be repeated. The desalination products have not been fully elucidated from this process, but will include HClO, ClOxn−, NaClO, etc.
- Under constant oxygen partial pressure conditions
- The polymer sites show rapid physical adsorption and extremely slow product production and desorption.
- The physically adsorbed ions are desorbed into the dead-end pores, without change (resulting in an observed desalination), or the open pores (resulting in no change to the water salinity).
- The salinity of the water will remain unchanged over time, if the pellets contain no accessible dead-end pores.
- The salinity of the water will change over time, if the pellets contain accessible dead-end pores.
- Once the salinity in the dead-end pores reaches an equilibrium level, no further movement of saline ions from the open pores to the dead-end pores occurs and the desalination process effectively ceases.
3.1.2. Fe(b) Polymer Construction
3.1.3. Pellet Operation
Cl− Ions Removed on Each Cycle
3.2. Desalination Pellets: Desalination Results
3.3. Desalination Pellet: Reaction Kinetics
- The reaction rate is independent of ion concentration in the open pellet porosity. The associated kinetic controls in this type of environment are provided in reference 
- The observed reaction rate is constant and is independent of the concentration of the reactants .
- The reaction rate at high substrate concentration is independent on its availability .
- The ion removal ceases abruptly after a period of ion removal (e.g., Figure 12).
3.3.1. Impact of Changing Temperature
3.3.2. Impact of Changing Pressure
3.4. Predicting Desalination as a Function of Reaction Time
Controls on the Desalination Rate
- The pellets initially increase water pH. The subsequent decline in water pH is associated with a decline in water salinity. Desalination effectively ceases when the water pH drops below about 8.2.
- Desalination is associated with a general increase in Eh within the range 200 to 450 mV. Cessation of desalination is associated with a drop in Eh towards −400 mV.
3.5. Pellet Construction: ZVI Reactor Water Salinity
Comparison of Desalination Using a Pellet with Desalination Using n-Fe0
- All three approaches increase the pH of the product water, by increasing the availability of OH− ions, i.e., desalination is associated with an increase in water salinity;
- The desalination pellets typically produce a product water with a pH in the range 7.5 to 8.5. This compares with n-Fe0, which typically produces a product water in the pH range 8 to 11.
3.6. Pellet Construction: Polymer Type
3.7. Pellet Reuse
- Option 1: the pellets are dried and reduced to powder. They are then washed in warm water, to remove the NaCl, and returned to the ZVI Reactor to be reconstituted (with ZVI makeup), as a new ZVI desalination pellet, or
- Option 2: the pellets are dried and reduced to powder. They are then washed in warm water, to remove the NaCl, and returned to the ZVI Reactor to be reconstituted (with ZVI makeup or n-Fe-polymer makeup); dried and then powdered, for use as a new n-Fe-polymer powder. Alternatively (Option 2a): the pellets are dried and reduced to powder. They are then washed in warm water, to remove the NaCl, and are then mixed with and reconstituted (with ZVI makeup, or n-Fe-polymer makeup); dried and then powdered, for use as a new n-Fe-polymer powder, or
- Option 3: the pellets are placed in warm fresh water under low Eh conditions (hydrogen stability zone 1 or hydrogen stability zone 2) to reverse the desalination storage reaction. The warm fresh water will become saline during this process.
3.7.1. Option 2: Example Pellet Reuse
3.7.2. Potential Applications for Option 2a
3.8. Finished Product
4.1. Pellet Applications
4.2. Pellet Markets
- Partial desalination of livestock feed water;
- Partial desalination of irrigation water;
- Partial desalination of salinized soils to allow arable usage.
4.2.1. Partial Desalination of Saline Livestock Feed Water
4.2.2. Impact of Desalination on Crop Yield
4.2.3. Desalination of Salinized Soils
- With no irrigation, the soil water salinity will increase sharply with increasing soil depth ;
- With fresh water irrigation the overland flow runoff and shallow throughflow will accumulate in the ditch surrounding the raised field (Figure 23). The soil water salinity will increase with soil depth. Lateral infiltration from the ditch will create a fresh water influx under the base of the raised field ;
- Constructing the raised field, with the ZVI desalination pellets, placed within the mound and the ditch (Figure 23), may allow the raised field to be irrigated with saline water, and the water recovered from the associated ditch (Figure 23). This is expected to reduce the groundwater salinity within the raised field (Figure 24).
5. Commercial Manufacture of the Desalination Pellets
5.1. Manufacturing the Desalination Pellets Using ZVI Reactors Placed in Series
5.2. Manufacturing the Desalination Pellets Using a Single ZVI Reactor with Product Gas Recycle
- New feed gas flow rate = JF
- Recycle gas flow rate = JR
- Gas feed flow rate entering the reactor, GF = JF + JR
- The gas product flow rate leaving the reactor = GP
- The recycle gas flow rate, JR = aGP
- The product gas flow rate leaving the reactor, JP = GP − JR
5.3. Manufacturing Costs and Economics
- 20 t coal d−1 (at USD360 t−1) = USD2,628,000 a−1: Purchase Cost
- 9.4 t coke d−1 (at USD600 to 720 t−1) = USD2,058,600 to 2,470,320 a−1: Sale Price
- Net Loss: USD157,680 to 569,000 a−1;
- Liquids converted to fuel gas
- Fuel gas: 72 m3 d−1 (1051.4 kJ mol−1) = USD500 MWh = USD171,322 a−1 sale price;
- Synthesis gas sold as fuel gas
- Fuel Gas: 20,164 m3 d−1 (250 kJ mol−1) = USD500 MWh = USD11,406,250 a−1: sale price.
- Net revenue (profit) if the synthesis gas is sold as a carbon rich fuel gas = USD11,008,570 a−1 to USD11,419,970 a−1.
- This study converts this synthesis gas to a hydrogen rich fuel gas. The appropriate cashflow adjustments are:
- Synthesis gas converted to a hydrogen rich fuel gas:
- Fuel Gas: 28,658 m3 d−1 (215 kJ mol−1) = USD500 MWh = USD13,943,325 a−1: sale price.
- ZVI: Around 8000 t a−1 = USD1000 t−1 = USD8,000,00 a−1; purchase cost
- Net revenue (profit) if the synthesis gas is sold as a hydrogen rich fuel gas
- Net revenue: if the ZVI pellet sale price is USD0 t−1 = USD5,545,645 a−1 to USD5,957,046 a−1. The desalination pellet sale price will be a function of local market conditions.
- Net revenue: if the ZVI used is completely recycled following use as a desalination pellet = USD13,545,645 a−1 to USD13,957,046 a−1. Selling, or lending, the pellets to a customer for $0 t−1, coupled with an automatic return of the used pellets to the plant will allow the Year 3 onwards profit from the plant to be closer to USD13,545,645 a−1 to USD13,957,046 a−1.
- Initially being used to process around 40 m3 t−1 pellets for irrigation;
- Reconstitution of the pellets to process reject brine from a desalination plant where about 2000 m3 of reject brine are processed by 1 t of reconstituted desalination pellet (Figure 20).
5.4. Improving the Desalination Efficiency of the Desalination Pellets
- Prior ZVI desalination studies have established that ZVI can partially desalinate water. The desalination rates are very variable and tend to represent a first order, or second order, removal reaction. The desalination products from these ZVI processes remain unknown.
- The desalination pellets are unusual in that they operate with a zero-order reaction, and sequester the removed NaCl to dead-end porosity within the pellets.
- A zero-order reaction produces a desalination rate, which is independent of the feed water salinity;
- Desalination ceases after a pre-determined (and predictable) amount of time;
- The rate constant for the pellets zero-order desalination reaction, is set in the manufacturing process within the ZVI Reactor. It predictably changes, with increasing feed water salinity, within the ZVI reactor during the manufacturing process.
- The standard deviation associated with the pellets desalination rate constant is demonstrated in this study to be small. These observations, mean that it is possible to use the pellets to predictably desalinate water with a high of degree of statistical confidence in the expected desalination outcome range.
- Table 6 Compares the pellet desalination outcomes with other published studies.
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
Appendix A. Reactor Design Issues and Results
Appendix A.1. Reactor Fluid Flow Design
- each EPB separates an Upstream Storage Area (USA, e.g., an upstream plenum) from a Downstream Storage Area (DSA, e.g., a downstream plenum), and
- each EPB is constructed from one or more of a fluid, membrane, particulate material, reactant, inert material, and catalyst, and
- each EPB has a permeability, k, which changes in response to changes in driving force, ΔP, where ΔP = PU − PD − PL, and PL = pressure losses (Pa) associated with the fluid flow, Q, across the EPB; PU = pressure (Pa) in the area located immediately upstream of the EPB; PD = pressure (Pa) in the area located immediately downstream of the EPB; k = permeability of the EPB (m3m−2s−1Pa−1), and
- the permeability, k, of each EPB increases as ΔP increases, and
- the permeability, k, of each EPB decreases as ΔP decreases, and
- the changes in permeability, k, of each EPB, can be gradual, or abrupt, or a combination, and
- ΔP associated with each EPB cyclically increases and decreases with time, and
- ΔP, PU, and PD are in a constant state of flux, and
- PU, and PD cyclically increase and decrease with time, and
- PL changes with time or remains constant, and
- fluid flow, Q, through each EPB is: Q = k ΔP, or Q = k (ΔP−Δχ), where Δχ = correction for fugacity; Q = fluid flow through each EPB (m3 m−2 s−1), and
- fluid flow, Q, through each EPB decreases as k ΔP decreases, or k (ΔP−Δχ) decreases, and
- fluid flow, Q, through each EPB increases as k ΔP increases, or k (ΔP−Δχ) increases, and
- the reactor contains one or more USA, and the reactor contains one or more DSA, and
- each USA is associated with one or more EPB, and
- each DSA is associated with one or more EPB, and
- each USA is associated with one or more DSA, and
- each DSA is associated with one or more USA, and
- each USA contains a volume of fluid, and
- each DSA contains a volume of fluid, and
- the volume of fluid in each USA associated with a specific EPB cyclically increases and decreases with time, and
- the volume of fluid in each DSA associated with a specific EPB cyclically increases and decreases with time, and
- cyclic decreases in the volume of fluid in a USA correspond to cyclic increases in the volume of fluid in the associated DSA, and
- cyclic increases in the volume of fluid in a USA correspond to cyclic decreases in the volume of fluid in the associated DSA, and
- each USA has a pressure, PU, which cyclically increases and decreases with time, and
- ΔP decreases and PU decreases, as the volume of fluid in each USA associated with a specific EPB decreases, and
- ΔP increases and PU increases, as the volume of fluid in each USA associated with a specific EPB increases, and
- each DSA has a pressure, PD, which cyclically increases and decreases with time, and
- ΔP decreases and PD increases, as the volume of fluid in each DSA associated with a specific EPB increases, and
- ΔP increases and PD decreases, as the volume of fluid in each DSA associated with a specific EPB decreases, and
- at any instant in time, the pressure, PU, in each USA is greater than, or equal to, the pressure, PD, in the associated DSA, and
- the reactor is used to undertake catalytic reactions, and
- catalyst is present in one or more parts of the reactor, and
- the catalyst is a solid, or a fluid, or a combination thereof, and
- the reactor processes one or more fluids, and
- reactants include one or more fluids, and products include one or more fluids, and
- fluids enter the reactor through one or more upstream conduits, which are attached to each USA, and
- the maximum fluid flow through each EPB is greater than the average fluid flow entering the associated USA through one or more upstream conduits, and
- the minimum fluid flow through the EPB is less than the average fluid flow entering the associated USA through one or more upstream conduits, and
- fluids entering the reactor through one or more upstream conduits are either reactants, or are reactants and non-reactants, and
- fluids are removed from the reactor through one or more downstream conduits, which are attached to each DSA, and
- fluids leaving the reactor through one or more downstream conduits are either products and residual reactants, or are products, residual reactants, and non-reactants, and
- conduits which allow fluids to enter the reactor and fluids to leave the reactor are controlled by valves, and
- fluids entering each USA through one or more upstream conduits are liquids or gases, and
- liquid fluid flow into each USA is independent of PU, ΔP, the volume of fluid in the USA, fluid flow, Q, through the associated EPB, and the permeability, k, of the associated EPB, and
- gaseous fluid flow into each USA cyclically increases and decreases with time, where decreases in gaseous fluid flow into the USA are associated with increases in PU, and increases in gaseous fluid flow into the USA are associated with decreases in PU, and the pressure in the upstream conduits is always greater than PU.
Appendix A.2. ZVI Pellet Manufacturing Reactor Train
Appendix A.2.1. Halite Reactor
- CO:CH4; R2 = 0.9981; PCC = 0.999; Very strong positive linear statistical relationship containing a data clump, where CO = >12%. This results from CO desorption, which is associated with low rates of CH4 adsorption. Where CO = <12%, both CH4 and CO adsorption have occurred.
- CO:CO2; R2 = 0.9733; PCC = 0.9865; Very strong positive linear statistical relationship containing a data clump, where CO = >12% and CO2 >8.33%, indicating desorption of both CO and CO2. The relationship contains outliers which could be interpreted as indicating CO2 adsorption associated with CO desorption. This linear correlation, and the linear correlation between CO and CH4, are interpreted as indicating a common intermediary adsorbed product of C0. This concept was first demonstrated in 1905 in French Patent 355,900.
- CO:H2; R2 = 0.908; PCC = 0.952; Very strong positive linear statistical relationship containing a data clump, where CO = >12% and H2 outliers. The data could be interpreted as indicating that H2 desorption is associated with CO desorption, e.g.,
- CO:C2+; R2 = 0.078; PCC = 0.279; Weak positive linear statistical relationship containing a data clump, where CO = >12% and C2+ outliers are >0.5%. The data could be interpreted as indicating that C2+ and H2 desorption is associated with CO desorption, e.g.,
- CO2:CH4; R2 = 0.9749; PCC = 0.987; Strong positive linear statistical relationship containing a data clump, where CO2 = >8.33%. The data could be interpreted as indicating that CH4 adsorption is associated with both CO2 adsorption and CO2 desorption, through the provision of C0 for desorption, and hydrogen for adsorption, e.g.,
- CO2:H2; R2 = 0.9749; PCC = 0.987; Strong positive linear statistical relationship containing a data clump, where CO2 = >8.33% and H2 >0.5%.
- CO2:C2+; R2 = 0.0763; PCC = 0.276; Weak positive linear statistical relationship containing a data clump, where CO2 = 8.33% and C2+ outliers are >0.5%. This relationship indicates that the C2+ outliers may result from a desorption reaction of the form:
- CH4:H2; R2 = 0.9127; PCC = 0.955; Strong positive linear statistical relationship containing a data clump, where CH4 = >12% and H2 >0.5%. This is interpreted as indicating that H2 desorption occurs during periods when low levels of CH4 adsorption occur. The primary interpreted process associated with CH4 adsorption is interpreted as:
- CH4:C2+; R2 = 0.077; PCC = 0.277; Weak positive linear statistical relationship containing a data clump, where CH4 = >12% and some C2+ = >0.5%. This is consistent with the primary role of the CH4 being to provide a source of C0.
- H2:C2+; R2 = 0.1423; PCC = 0.377; Weak positive linear statistical relationship containing a data clump, where H2 = <1.5% and C2+ = <0.5%. The data could be interpreted using a polynomial expression, where C2+ = 39.129[H2]2 − 0.6058[H2] + 0.0028. This gives a R2 = 0.3184; PCC = 0.564; representing a moderate positive statistical correlation where C2+ increases with the availability of H2.
- CH4: Product Gas volume: R2 = 0.9646; PCC = 0.982; Strong positive linear statistical relationship, indicating that product gas volumes are always less than the feed gas volumes.
Appendix A.2.2. ZVI Reactor
- CO:CH4; R2 = 0.9449; PCC = 0.972; Very strong positive linear statistical relationship containing outliers, where CO = >10%.
- CO:CO2; R2 = 0.5679; PCC = 0.7535; Strong positive linear statistical relationship containing a data, where CO = >10.75% and CO2 >10.9%, indicating desorption of both CO and CO2 can occur.
- CO:H2; positive linear statistical relationship where substantial H2 discharges are associated with CO discharges.
- CO:C2+; Negligible positive linear statistical relationship where high levels of CO desorption are associated with C2+ outliers of >0.5%.
- CO2:CH4; Negligible linear statistical relationship containing a data clump, between CH4 = 5% to 15% where CO2 outliers can exceed 50%.
- CO2:H2; Positive linear statistical relationship indicated by outliers where CO2 = >8.33% and H2 >20%.
- CO2:C2+; Weak positive linear statistical relationship where C2+ outliers are >0.5%.
- CH4:H2; No obvious statistical relationship between these two parameters, suggesting that the H2 is not produced directly from the CH4.
- CH4:C2+; No obvious statistical relationship between these two parameters, suggesting that the C2+ is not produced directly from the CH4.
- H2:C2+; No obvious statistical relationship between these two parameters, suggesting that the C2+ is not produced by the same process as the H2.
- CH4: Product Gas volume: Positive linear statistical relationship, with high volume outliers resulting from hydrogen production.
|Feed from FBR||0.89%||46.03%||10.75%||10.91%||12.90%||0.08%|
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|Trial||Water||pH||Eh, mV||Temperature, C||Cl−, g L−1||Na+, g L−1|
|Product + 24 h||7.68||327||11.2||74.73||5.17|
|Product + 24 h||12.58||−53||11.9||1.39||0.97|
|Product + 24 h||12.24||−97||7.4||2.48||0.97|
|Number of ZVI Reactors in Series||N2||CO||CO2||CH4||H2||Pellets Manufactured, t a−1||Water Desalination Potential, m3 a−1|
|Recycle Ratio||N2||CO||CO2||CH4||H2||Product Gas, m3m−1||Recycle Gas, m3m−1||Carbon Removed|
|Recycle Ratio||Pellets Manufactured, t a−1||Water Desalination Potential, m3 a−1|
|Fe0 Particle Size||0.002 to 0.08 mm||50 nm||Steel Wool||Steel Wool *|
|as, m2 g−1||not measured||20||not measured||not measured|
|Pw, g L−1||25–50||25||1.67||1.67|
|Reactor Size, L||1||0.2||240||240|
|Time, h, to Achieve 24.5% desalination||1500||720 to 1400||Not Achieved||3|
|Time, h, to Achieve 60% desalination||3000||1400 to 2800||Not Achieved||Not Achieved|
|Air flow, L h−1 kg Fe0||0||0||0||150|
|Reaction Order||Zero||First||n/a||First or second|
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Antia, D.D.J. Purification of Saline Water Using Desalination Pellets. Water 2022, 14, 2639. https://doi.org/10.3390/w14172639
Antia DDJ. Purification of Saline Water Using Desalination Pellets. Water. 2022; 14(17):2639. https://doi.org/10.3390/w14172639Chicago/Turabian Style
Antia, David Dorab Jamshed. 2022. "Purification of Saline Water Using Desalination Pellets" Water 14, no. 17: 2639. https://doi.org/10.3390/w14172639