METHOD FOR EVALUATING WASTE PLASTIC-DERIVED POROUS CARBON AND METHOD FOR MANUFACTURING POROUS CARBON

Abstract

An evaluation method capable of evaluating whether or not waste plastic-derived porous carbon can be applied on an industrial scale, according to the present disclosure, may include the steps of evaluating CO.sub.2 capture performance using a 5-step temperature vacuum swing adsorption (TVSA) process, assessing economic feasibility in an industry using a techno-economic assessment (TEA) method, and quantifying environmental impacts of the porous carbon production pathway and global warming potential (GWP) using cradle-to-gate life-cycle assessment (LCA).

A method for manufacturing porous carbon, according to the present disclosure, may include the steps of carbonizing a polyethylene terephthalate plastic, activating the carbonized plastic with CO.sub.2, and performing cooling.

Claims

1. A method for evaluating waste plastic-derived porous carbon, the method comprising the steps of: evaluating CO.sub.2 capture performance using a 5-step temperature vacuum swing adsorption (TVSA) process; assessing economic feasibility in an industry using a techno-economic assessment (TEA) method; and quantifying environmental impacts of the porous carbon production pathway and global warming potential (GWP) using cradle-to-gate life-cycle assessment (LCA).

2. The method of claim 1, wherein the five-step temperature vacuum swing adsorption process is included of: (1) a pressurization step in which a feed gas (CO.sub.2/N.sub.2) flows into one port of an adsorption chamber at a constant velocity (v.sub.f); (2) an adsorption step in which the feed gas is flown in at a constant velocity (v.sub.f) from one port of the adsorption chamber and the other port is opened; (3) a heating step in which a desorbed gas (CO.sub.2) is flown out from one port of the adsorption chamber and the other port is closed; (4) a vacuuming step in which the desorbed gas (CO.sub.2) is discharged from one port of the adsorption chamber by a vacuum pump and the other port is closed; and (5) a cooling step in which both ports are closed and gas does not flow inside and outside the adsorption chamber, and the five-step temperature vacuum swing adsorption process is used to derive and evaluate productivity, purity, recovery, specific energy consumption, and exergy efficiency.

3. The method of claim 2, wherein the specific energy consumption is calculated by Equation below: $E=w_{\mathrm{vac}}+q_{\mathrm{heat}}\left(\frac{T_{\mathrm{heat}}-T_{\mathrm{cool}}}{T_{\mathrm{heat}}}\right)$ where, w.sub.vac (specific work consumption) is a work consumed by the vacuum pump in the (4) vacuuming step, and is calculated by Equation below: $w_{\mathrm{vac}}=\frac{n_{\mathrm{vac}}}{N_{{\mathrm{CO}}_2,\mathrm{des}}}\frac{22.4}{{\eta }_{\mathrm{vac}}}\frac{k}{k-1}{P}_H\left[{\left(\frac{P_H}{P_{\mathrm{vac}}}\right)}^{\frac{k-1}{k}}-1\right]$ where, k and η.sub.vac are an adiabatic coefficient of air and an efficiency of the vacuum pump respectively, and are 1.4 and 0.7 respectively, and where, q.sub.heat is a specific heat input in the (3) heating step and is calculated as follows: $Q_{\mathrm{heat}}=\left(1-\epsilon \right)V_{\mathrm{bed}}\left[C_{p,\mathrm{ad}}\left(T_H-T_L\right)+{\rho }_{\mathrm{ad}}\left(\Delta n_{{\mathrm{CO}}_2,\mathrm{des}}\Delta H_1+\Delta n_{N_3,\mathrm{des}}\Delta H_2\right)\right]$ $+V_{\mathrm{wall}}{C}_{p,w}\left(T_H-T_L\right)$ $q_{\mathrm{heat}}=\frac{Q_{\mathrm{heat}}}{N_{{\mathrm{CO}}_3,\mathrm{des}}{M}_{{\mathrm{CO}}_3}}$ where, M.sub.CO2 is a molar mass of CO.sub.2.

4. The method of claim 2, wherein the exergy efficiency is calculated by Equation below:
E.sub.ex=w.sub.min/E where, W.sub.min is a Gibbs free energy change (ΔG) as a minimum separation work for CO.sub.2 separation, and E is specific energy consumption.

5. The method of claim 1, wherein in the step of assessing economic feasibility in the industry using the TEA method, evaluation is performed using a revenue (R.sub.PC) obtained from porous carbon according to Equation below and a revenue (R.sub.E) obtained from electricity:
R.sub.PC=Σ.sub.t=1.sup.nQ.sub.PC×SP.sub.PC, where, R.sub.PC is the revenue obtained from porous carbon, Q.sub.PC is an amount (tons) of porous carbon produced, and SP.sub.PC is a selling price (in Euros) of porous carbon per ton, and
R.sub.E=Σ.sub.t=1.sup.nU.sub.E×FiT.sub.E, where, R.sub.E is the revenue obtained from electricity generated by a combined heat and power (CHP) plant, U.sub.E is the number of power (1%, 10%, 20%, 50%, and 75%) generated in kWh unit with respect to a power conversion rate after considering heat loss, and FiT.sub.E is a supply tariff with respect to electricity units in Europe.

6. The method of claim 1, wherein the step of quantifying the porous carbon production pathway and global warming potential (GWP) using the cradle-to-gate life-cycle assessment (LCA) uses a ReCiPe (H) impact assessment method.

7. A method for manufacturing porous carbon, the method comprising steps of: carbonizing a polyethylene terephthalate plastic; activating the carbonized plastic with CO.sub.2; and performing cooling.

8. The method of claim 7, wherein in the step of performing activation with CO.sub.2, the activation is performed at a temperature of 800° C. to 1,000° C.

9. The method of claim 7, wherein in the step of performing activation with CO.sub.2, CO.sub.2 is supplied at 100 mL/min to 300 mL/min.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0019] FIG. 1 is a schematic diagram of a 5-step temperature vacuum swing adsorption (TVSA) process.

[0020] FIG. 2 is changes in temperature and pressure with time of the TVSA processor.

[0021] FIG. 3A is SEM images of porous carbon according to Examples, FIG. 3B is X-ray photoelectron spectrum irradiation results, FIG. 3C is Raman spectra, FIG. 3D is N.sub.2 adsorption/desorption isothermal lines, and FIG. 3E is pore size distributions.

[0022] FIG. 4A is a graph of CO.sub.2 adsorption performance of PET6-CO.sub.2-9, FIG. 4B is a graph of CO.sub.2 adsorption performance of PET6-K7, FIG. 4C is a graph of CO.sub.2 adsorption performance of PET6-KU7, FIG. 4D is a graph of isosteric heats of adsorption (Q.sub.st), FIG. 4E is dynamic CO.sub.2 adsorption test results, and FIG. 4F is ten periodic CO.sub.2 adsorption test results using thermogravimetric analysis (TGA) at 30° C. and 1 bar.

[0023] FIG. 5A is a comparison result for each environmental impact category, and FIG. 5B is a result of considering a mitigated environment impact.

[0024] FIG. 6, as a diagram showing the environmental impacts and economic benefits of three samples, compares the global warming potential (GWP) and net present value (NPV).

[0025] FIG. 7 is results of comparing mitigated GWP and released GWP.

DETAILED DESCRIPTION

[0026] Unless defined otherwise, all technical and scientific terms used in the present specification have the same meaning as commonly understood by one of ordinary skill in the art to which the present disclosure pertains. In general, the nomenclature used in the present specification is those well-known and commonly used in the art.

[0027] Hereinafter, the present disclosure will be described in more detail with reference to the accompanying drawings.

[0028] The present disclosure, which relates to a method for evaluating waste plastic-derived porous carbon, relates to a method for evaluating feasibilities such as whether or not waste plastic-derived porous carbon can be applied on an industrial scale and whether or not it is sustainable and economically feasible.

[0029] Specifically, the method for evaluating waste plastic-derived porous carbon according to various embodiments of the present disclosure may include the steps of: evaluating CO.sub.2 capture performance using a 5-step temperature vacuum swing adsorption (TVSA) process; assessing economic feasibility in an industry using a techno-economic assessment (TEA) method; and quantifying environmental impacts of the porous carbon production pathway and global warming potential (GWP) using the cradle-to-gate life-cycle assessment (LCA).

[0030] The steps are not constrained in order and may be evaluated regardless of the order.

[0031] First, the step of evaluating the CO.sub.2 capture performance using a five-step temperature vacuum swing adsorption (TVSA) process may be performed as the process as shown in FIG. 1. The TVSA process has the advantages that mild operating conditions for adsorbent regeneration that may be driven by low grade thermal solar energy are required, and it has high CO.sub.2 productivity.

[0032] Specifically, referring to FIGS. 1 and 2, the five-step temperature vacuum swing adsorption process may be included of: (1) a pressurization step in which a feed gas (CO.sub.2/N.sub.2) flows into one port of an adsorption chamber at a constant velocity (v.sub.f); (2) an adsorption step in which the feed gas is flown in at a constant velocity (v.sub.f) from one port of the adsorption chamber and the other port is opened; (3) a heating step in which a desorbed gas (CO.sub.2) is flown out from one port of the adsorption chamber and the other port is closed; (4) a vacuuming step in which the desorbed gas (CO.sub.2) is discharged from one port of the adsorption chamber by a vacuum pump and the other port is closed; and (5) a cooling step in which both ports are closed and gas does not flow inside and outside the adsorption chamber.

[0033] (1) In the pressurization step, when the other port is closed, the pressure inside the chamber rises from a low value (P.sub.L) to a high value (P.sub.H). The heat of adsorption is removed by the cooling medium so that the chamber is maintained at a constant temperature (T.sub.L).

[0034] (2) In the adsorption step, the pressure inside the chamber is maintained at a constant value P.sub.H. In addition, the heat of adsorption is removed by the cooling medium so that the chamber is maintained at a constant temperature T.sub.L.

[0035] (3) In the heating step, the pressure inside the chamber is maintained at a constant value P.sub.H. Further, the adsorption chamber is heated by the heating medium to reach the desorption temperature T.sub.H.

[0036] (4) In the vacuuming step, the pressure inside the chamber is reduced due to the continuous operation of the vacuum pump to achieve the vacuum pressure P.sub.vac. The temperature of the adsorption chamber is slightly decreased and maintained at a constant temperature T.sub.vac.

[0037] (5) In the cooling step, when the temperature drops, the pressure inside the closed adsorption chamber is further reduced to achieve the desorption pressure P.sub.L. The adsorption chamber is cooled by the cooling medium to reach the adsorption temperature T.sub.L.

[0038] Productivity, purity, recovery, specific energy consumption, and exergy efficiency may be derived and evaluated using such a TVSA process.

[0039] At this time, the specific energy consumption may be calculated by Equation below.

[00001]$E=w_{\mathrm{vac}}+q_{\mathrm{heat}}\left(\frac{T_{\mathrm{heat}}-T_{\mathrm{cool}}}{T_{\mathrm{heat}}}\right)$

[0040] where, w.sub.vac (specific work consumption) is the work consumed by the vacuum pump in the (4) vacuuming step, and is calculated by Equation below.

[00002]$w_{\mathrm{vac}}=\frac{n_{\mathrm{vac}}}{N_{{\mathrm{CO}}_2,\mathrm{des}}}\frac{22.4}{{\eta }_{\mathrm{vac}}}\frac{k}{k-1}{P}_H\left[{\left(\frac{P_H}{P_{\mathrm{vac}}}\right)}^{\frac{k-1}{k}}-1\right]$

[0041] Where, k and η.sub.vac are the adiabatic coefficient of air and the efficiency of the vacuum pump respectively, and are 1.4 and 0.7 respectively.

[0042] where, q.sub.heat is the heat provided in the (3) heating step and is calculated as follows.

[00003]$Q_{\mathrm{heat}}=\left(1-\epsilon \right)V_{\mathrm{bed}}\left[C_{p,\mathrm{ad}}\left(T_H-T_L\right)+{\rho }_{\mathrm{ad}}\left(\Delta n_{{\mathrm{CO}}_2,\mathrm{des}}\Delta H_1+\Delta n_{N_3,\mathrm{des}}\Delta H_2\right)\right]$$+V_{\mathrm{wall}}{C}_{p,w}\left(T_H-T_L\right)$$q_{\mathrm{heat}}=\frac{Q_{\mathrm{heat}}}{N_{{\mathrm{CO}}_2,\mathrm{des}}{M}_{{\mathrm{CO}}_2}}$

[0043] where, C.sub.p,ad is the bed heat capacity, C.sub.p,w is the chamber wall heat capacity, and M.sub.CO2 is the molar mass of CO.sub.2.

[0044] Exergy efficiency, as an energy level, may be calculated by Equation below.

E.sub.ex=w.sub.min/E

[0045] where, W.sub.min is the Gibbs free energy change (ΔG) as a minimum separation work for CO.sub.2 separation, and is calculated as in Equation below.

W.sub.min=ΔG.sub.sep=ΔG.sub.B+ΔG.sub.C−ΔG.sub.A

[0046] The Gibbs free energy change for CO.sub.2 separation (ΔG.sub.sep) is calculated from the Gibbs free energy (ΔG.sub.A) of the flue gas containing CO.sub.2 emitted from the CO.sub.2 emission plant, the Gibbs free energy (ΔG.sub.B) of the CO.sub.2 rich gas captured through the CO.sub.2 capture plant, and the Gibbs free energy (ΔG.sub.C) of the remaining flue gas. Meanwhile, E is the specific energy consumption described above.

[0047] In the step of assessing economic feasibility in the industry using the TEA method, it is characterized by performing evaluation using the revenue (R.sub.PC) obtained from porous carbon according to Equation below and the revenue (R.sub.E) obtained from electricity.

[0048] Specifically, the revenue (R.sub.PC) obtained from porous carbon may be calculated as follows.

R.sub.PC=Σ.sub.t=1.sup.nQ.sub.PC×SP.sub.PC,

[0049] Where, R.sub.PC is the revenue obtained from porous carbon, Q.sub.PC is the amount (tons) of porous carbon produced, and SP.sub.PC is the selling price (in Euros) of porous carbon per ton.

[0050] The revenue (R.sub.E) obtained from electricity may be calculated as follows.

R.sub.E=Σ.sub.t−1.sup.nU.sub.E×FiT.sub.E,

[0051] Where, R.sub.E is the revenue obtained from electricity generated by the combined heat and power (CHP) plant, U.sub.E is the number of power (1%, 10%, 20%, 50%, and 75%) generated in kWh unit with respect to the power conversion rate after considering heat loss, and FiT.sub.E is a supply tariff with respect to electricity units in Europe.

[0052] The step of quantifying environmental impacts of the porous carbon production pathway and global warming potential (GWP) using the cradle-to-gate life-cycle assessment (LCA) may use a ReCiPe (H) impact assessment method.

[0053] In the present disclosure, it may be possible to evaluate the environmental impact in the porous carbon activation process and the economic benefit for industrial scale application through TEA and LCA evaluation.

[0054] That is, using the evaluation method according to the present disclosure, waste plastic-derived porous carbon capable of mitigating climate change and promoting recycling of waste plastics through CO.sub.2 capture can be evaluated and compared from various angles, and selected rationally in terms of aspects of CO.sub.2 capture performance, economic feasibility, and environmental sustainability.

[0055] The method for manufacturing porous carbon according to the present disclosure may manufacture waste plastic-derived porous carbon capable of mitigating climate change and promoting recycling of waste plastics through CO.sub.2 capture. Specifically, the present disclosure may include the steps of: carbonizing a polyethylene terephthalate (PET) plastic; activating the carbonized plastic using different agents such as CO.sub.2, KOH, Urea.

[0056] In the carbonization step, PET may be cut into small pieces (about 5 mm×5 mm) and carbonized at 500° C. to 700° C. for 30 minutes to 2 hours in N.sub.2 atmosphere.

[0057] Next, in the activation step, it may be activated by supplying CO.sub.2 at a flow rate of 100 mL/min to 300 mL/min at a temperature of 800° C. to 1,000° C.

[0058] In the cooling step, it may be cooled by lowering the temperature to room temperature.

[0059] It can be confirmed that porous carbon manufactured by the manufacturing method according to the present disclosure has both of the lowest environmental impact and high economic benefits for industrial scale application when evaluated by the above-described evaluation method according to the present disclosure. In other words, porous carbon physically activated with CO.sub.2 is economically feasible and has low environmental impact.

[0060] Hereinafter, the present disclosure will be described in more detail through Examples. These Examples are for illustrating the present disclosure in more detail, and the scope of the present disclosure is not limited to these Examples.

EXAMPLE 1

Manufacturing of PET Plastic-Derived Porous Carbon

[0061] As a raw material for porous carbon, polyethylene terephthalate PET bottles were collected from our daily environment (i.e., trash cans, streets). Before carrying out carbonization and activation/modification, the bottle caps and labels were removed, and then the bottles were washed, dried, and cut into small pieces (about 5 mm×5 mm) to pretreat the bottles. One whole PET sample was carbonized at 600° C. for 1 hour in N.sub.2 atmosphere using a horizontal cylindrical furnace. The carbonized sample was named “PET6”, and it was prepared with three porous carbons using different activation methods.

EXAMPLE 1-1

Physical Activation Using CO.SUB.2

[0062] After 5 g of PET6 was put in a horizontal tubular reactor (50 mm inner diameter), the reactor was heated to 900° C. at a heating rate of 10° C./min, and held at 900° C. for 2 hours under a CO.sub.2 flow rate of 200 mL/min. After the tubular reactor was cooled from the operating temperature to room temperature, the obtained sample was named “PET6-CO.sub.2-9”.

EXAMPLE 1-2

Chemical Activation Using Potassium Hydroxide (KOH)

[0063] After a mixture (mass ratio of KOH:PET6 is 2:1) of 5 g of PET6 and 10 g of KOH was added to 25 mL of deionized water at 60° C. for 1 hour, the mixture was dried overnight at 110° C. to remove water. This dried mixture was further activated in a horizontal tubular reactor at a heating rate of 10° C./min at 700° C. for 1 hour under a N.sub.2 flow rate of 200 mL/min, and then treated with 0.5 N HCl solution and removed. After drying it overnight at 110° C., a sample activated with KOH was collected and named “PET6K7”.

EXAMPLE 1-3

Simultaneous Activation Using KOH/Urea

[0064] Considering that effective N-doping may improve the adsorption and selectivity of CO.sub.2 compared to other gases, N-doped porous carbon derived from waste PET plastic waste through one-pot synthesis was prepared. 5 g of PET6, KOH, and urea (mass ratio of PET6:KOH:urea is 1:2:1) were mixed with 25 mL of distilled water, and then the mixture was dried overnight at 110° C. to remove water. The dried mixture was activated at 700° C. at a heating rate of 10° C./min for 1 hour under a N.sub.2 flow rate of 200 mL/min. The same washing and drying treatment as the previous activation method was applied and the final sample was named “PET6KU7”.

EXAMPLE 2

Morphological Analysis of Porous Carbon

[0065] SEM images were checked with respect to Example 1-1 (PET6-CO.sub.2-9), Example 1-2 (PET6K7), and Example 1-3 (PET6KU7), and as the results, it was confirmed that there was no obvious morphological difference between the three types of porous carbons referring to FIG. 3A.

[0066] Meanwhile, texture properties, XPS analysis, and CO.sub.2 adsorption were compared with respect to three porous carbon samples, and the results are as shown in Table 1 below.

TABLE-US-00001 TABLE 1 CO.sub.2 uptake S.sub.BET.sup.a V.sub.total.sup.b Atomic (%).sup.d (mmol/g).sup.e Samples m.sup.2/g cm.sup.3/g V.sub.micro.sup.c V.sub.micro/V.sub.total C O N 0° C. 25° C. 50° C. PET6-CO.sub.2-9 1482 0.607 0.592 0.975 92.99 7.11 — 6.25 3.63 2.29 PET6-K7 * 1263 0.519 0.501 0.965 93.27 6.73 — 5.30 3.87 2.29 PET6-KU7 * 1165 0.469 0.460 0.981 77.97 18.80 3.23 6.23 4.58 2.82 .sup.aCalculated using Brunauer-Emmett-Teller model. .sup.bTotal pore volume at p/p.sub.0 = 0.99 using Horvath-Kawazoe equation. .sup.cMicropore volume using Dubinin-Radushkevich Equation. .sup.dPeak area of X-ray photoelectron spectroscopy (XPS) spectra. .sup.eAcquired at less than 1 bar using a volumetric sorption analyzer.

[0067] Referring to Table 1 above and FIG. 3B, only PET6-KU7 among all samples showed an N content of 3.23% by weight to confirm that the N-doping treatment was effective. Referring to FIG. 3C, the D-peak at 1,350 cm.sup.−1 and the G-peak at 1,589 cm.sup.−1 were clearly observed in the Raman spectrum, and similar intensity ratios (I.sub.d/I.sub.g=˜1.0) of the D and G bands were obtained with respect to all three samples, which indicates that the degree of graphitization of the samples was not greatly different in different activation pathways. Referring to FIG. 3D, all N.sub.2 adsorption and desorption isothermal lines were classified as type I according to the International Federation of Pure and Applied Chemistry classification system, suggesting that the prepared sample is a typical microporous carbon material. As shown in FIG. 3E, different peaks were detected for each sample, and it can be seen that micropores were well developed in all porous carbons. The dominant pore size was <1.5 nm, suitable for CO.sub.2 capture.

[0068] Referring to FIGS. 4A to 4C, the CO.sub.2 adsorption performance values of three porous carbon samples were evaluated at 0 C, 25° C., and 50° C. at less than 1 bar, and the results are as shown in Table 1 above. Referring to FIG. 4D, the isosteric heat of adsorption (Q.sub.st) values were calculated using the Clausius-Clapeyron equation. ln(P) versus 1/T was indicated for the CO.sub.2 adsorption isothermal lines obtained at 0, 25 and 50° C. for each sample. Referring to FIG. 4E, the dynamic CO.sub.2 adsorption within 2 hours was evaluated using thermogravimetric analysis (TGA) at 30° C. and 1 bar. 95% or more of the total CO.sub.2 uptake by each sample was achieved within the first 5 minutes, indicating rapid adsorption kinetics. Further, referring to FIG. 4F, the cycle stability of each sample was evaluated using 10 adsorption-desorption cycles at 30° C. and 1 bar. As a result, the same cycle curves of the CO.sub.2 adsorption and desorption processes were obtained. In addition, stable working capacities of 2.68 mmol/g for PET6-CO.sub.2-9, 3.03 mmol/g for PET6-K7, and 3.28 mmol/g for PET6-KU7 were observed. These are numerical values much higher than the absorption amount (1.5 mmol/g) of industrial MEA (aqueous monoethanolamine). In particular, they could be easily desorbed by converting the purge gas from the target gas to N.sub.2.

EXAMPLE 3

TVSA Process Performance Evaluation

[0069] The periodic performance evaluation using the 5-step TVSA process of FIGS. 1 and 2 was performed 46 times. CO.sub.2 gas was captured and separated from the mixed gas using a temperature and pressure driven adsorption and desorption process. Considering the adsorption chamber containing the CO.sub.2 adsorbent and gas as a single system, a numerical simulation run in MATLAB (MathWorks, USA) was used to streamline the process to a steady-state process. This assumed that 1) the gas inside the adsorption chamber is an ideal gas and 2) the pressure drops throughout the adsorption chamber. In addition, 3) the mass transfer resistance between the solid and gas phases is negligible, 4) the temperature of the adsorption chamber was assumed to be homogeneous, and 5) the physical properties (specific heat capacity, density, and void fraction) of the system to be considered were assumed to remain constant.

[0070] Meanwhile, when selecting porous carbon with optimal CO.sub.2 capture performance in terms of industrial applications and energy consumption, five key indicators including productivity, purity, recovery, specific energy consumption, and exergy efficiency were considered. Detailed operating parameters and simulation results are as shown in Table 2 below.

TABLE-US-00002 TABLE 2 Operation parameters Value Unit Heating medium temperature, T.sub.heat 120 ° C. Cooling medium temperature, T.sub.cool 25 ° C. Heat transfer temperature difference 5 ° C. Adsorption pressure, P.sub.H 1.0 bar Vacuuming pressure, P.sub.vac 0.1 bar Performance indicators PET6-CO.sub.2-9 PET6-K7 PET6-KU7 Productivity 32.88 27.03 44.23 kg/t h Purity 70.52 71.57 77.73 % Recovery 89.88 84.93 90.02 % Specific energy consumption, E 1.04 1.44 0.97 GJ/t Exergy efficiency, E.sub.ex 7.21 5.06 8.94 %

[0071] Referring to Table 2 above, PET6-KU7 is shown to be considered as the most promising candidate for CO.sub.2 capture from the point of view of industrial application and energy consumption compared with PET6-CO.sub.2-9 and PET6-K7.

EXAMPLE 4

Evaluation of Economic feasibility in Industry Using TEA Method

[0072] Evaluation was performed on Example 1-1 (PET6-CO.sub.2-9), Example 1-2 (PET6K7), and Example 1-3 (PET6KU7) in consideration of the total capital investment (TCI), yearly operation cost (YOC), and revenue which are generated for the scale-up process modeling.

[0073] First, the sum of the costs for manufacturing porous carbon was estimated in order to derive the total capital investment (TCI), and this was subdivided into various processes such as pretreatment, pyrolysis, carbon activation process, power generation, flue gas treatment, other costs, and infrastructure costs, and these are as shown in Table 3 below.

TABLE-US-00003 TABLE 3 Capacity Cost PET6- PET6- PET6- PET6- PET6- PET6- Reference Equipment cost CO.sub.2-9 K7 KU7 CO.sub.2-9 K7 KU7 or Source Waste PET Pre-treatment Cost Weighbridges 50 t  €21,500.00 .sup.S27 Feedstock store 1500 t   €5,680.50 .sup.S28 Belt conveyer system  10 m  €1,700.00 * Shredder  1 t  €7,682.40 .sup.S29 Trommel screen  1 t  €18,000.00 * with conveyers Loading shovels 0.5 t   €11,250.00 * Excavator 0.5 t   €11,250.00 * Sub-total: 1 (ST1)   €77062.90 — Pyrolysis Unit Auger screw-flue gas   1 t/h  €799,044.80 .sup.S30 heated pyrolizer with vapour collection Auger conveyor belt  5 m    €840.00 * Horizontal belt 3 motors 5 motors    €360.00    €600.00 * conveyors motors Sub-total: 2 (ST2) €800,244.80 €800,484.80  — Carbon Activation Process Activation reactor 0.11 t    €3,200.00 * KOH solution storage tank 15 t    €780.00 * Urea solution storage tank  6 t    €320.00 * HCL solution storage tank 20 t  €1,040.00 * Mixing tank — 1 t 2 t —  €3,500.00  €7,000.00 * Dryer 2 —  €8,000.00 * Washer — 1 —  €5,000.00 * Silo/Bin (Porous carbon 2.5 t   €1,600.00 * storage) Sub-total: 3 (ST3)  €6,940.00 €23,440.00 €26,940.00 — Power Generation High pressure turbine 306.6 kW €246,636.00 .sup.S27 Medium pressure turbine 347.8 kW €280,326.80 .sup.S27 Low pressure turbine 614.6 kW €495,367.50 .sup.S27 Organic Rankine cycle 95.4 kW + 5 t (Working fluid) €571,323.62 .sup.S31, S32, *.sup.a turbine Water chiller unit   5 t/h  €5,725.00 * Cold water storage tank 150 t   €30,750.00 * Sub-total: 4 (ST4) 1341.97 kW   €1,630,128.92   — Flue gas treatment €20,388.62 Pressure swing adsorption 1 unit (20 kg/h to 300 kg/h) €203,950.00 * unit and associated components Sub-total: 5 (ST5) €203,950.00 — Miscellaneous expenses Additional machinery —  €82,950.00 .sup.S33 Sub-total: 6 (ST6)  €82,950.00 — Infrastructure costs Land cost 12,000 m.sup.2 at €93.60/m.sup.2 €1,123,200.00   Estimated Office and laboratory — €400,000.00 .sup.S33 equipment Buildings — €200,000.00 Estimated Sub-total: 7 (ST7) €1,723,200.00   — Total Capital Investment — €4,524,476.62   €4,541,186.61   €4,544,716.62   — (TCI) = ST1 + ST2 + ST3 + ST4 + ST5 + ST6 + ST7 * indicates data from https://www.alibaba.com/. All values are converted from RMB to euro to represent a conversion ratio of RMB 1 = €0.13 (a is the cost value of the working fluid).

[0074] Referring to Table 3, it was confirmed that the total capital investments (TCI) for Example 1-1 (PET6-CO.sub.2-9), Example 1-2 (PET6K7), and Example 1-3 (PET6KU7) were similar.

[0075] Meanwhile, the yearly operation cost (YOC) was estimated after considering the input of raw materials required for manufacturing Example 1-1 (PET6-CO.sub.2-9), Example 1-2 (PET6K7), and Example 1-3 (PET6KU7). The recurring costs of carbon and other infrastructure overhead required to sustain a production unit are presented in Table 4 below. Operational data were obtained according to process requirements. Energy consumption amount was the most commonly required input amount and was supplied internally through the CHP plant. The net exergy efficiency of the CHP system was low in such an amount that the costs associated with energy consumption were not negligible. Cost data related to consumables, particularly cost data used in the activation process, were obtained through Alibaba, an Internet company having long-term contracts with suppliers.

[0076] Water required for the power generation process was supplied monthly by a Tianjin industrial water supplier at a price of RMB 7.9/t (Price Monitoring Center, NDRC) S34. In the case of yearly operation costs, the costs accompanied by capturing the emitted CO.sub.2 emissions were also priced taking into account the cost values for the purchased porous carbon.

TABLE-US-00004 TABLE 4 Capacity Cost Reference Equipment cost PET6-CO.sub.2-9 PET6-K7 PET6-KU7 PET6-CO.sub.2-9 PET6-K7 PET6-KU7 or Source Carbon Activation Process CO.sub.2 gas 1.05 t/h — —     0.00 .sup.a — — — KOH — 0.421 t/h — €232.00 * Urea — — 0.23 t/h — —    €57.00 * HCL —  0.8 t/h — €174.67 * Sub-total: 8 (ST8) .sup.c Estimated per year — €3,253,360.00   €3,709,360.00   — Power Generation Water 3.9 t/h     €3.89 .sup.S34 Sub-total: 9 (ST9) .sup.c Estimated per year  €31,120.00 — Flue Gas Treatment Energy Energy from the combined heat and power plant within the system boundary Capture cost for 76 t 66 t 46 t  €95,852.16  €83,005.56  €57,852.36 Estimated plant emission .sup.b Sub-total: 10 (ST10)  €95,852.16  €83,005.56  €57,852.36 — Human Resource Workforce includes plant Salaries and other expenses €126,096.17 Estimated operators, administrative for 15 people per year team etc. Sub-total: 11 (ST11) .sup.c Estimated per year €126,096.17 — Miscellaneous Expenses .sup.c Maintenance 6% of TCI €271,468.59 €272,471.19 €272,682.99 .sup.35 Insurance 2.5% of TCI    €113111.92 €113,529.67 €113,617.92 .sup.36 Contingencies 5% of TCI  €226223.83 €227,059.33 €227,235.83 .sup.37 ICT infrastructure cost Per year  €5,000.00 Estimated Sub-total: 12 (ST12) Estimated per year €615,804.34 €618,060.19 €618,536.74 First Year Operation Estimated per year €868,872.67 €4,111,641.92   €4,542,965.27   — Cost (FYOC) = ST8 + (first year) ST9 + ST10 + ST11 + S12 Yearly Operation Estimated per year €773,020.57 €4,028,636.36   €4,485,112.91   — Cost (YOC) = (Second year onwards) ST8 + S9 + ST11 + S12

[0077] The CO.sub.2 required for physical activation was obtained from a pressure swing adsorption (PSA) unit, one-time cost in the first year, yearly cost, and * represent data obtained from https://www.alibaba.com/;, and all values were converted to RMB 1=0.13 Euros.

[0078] Referring to Table 4, the yearly operation cost was evaluated to be the lowest in Example 1-1 (PET6-CO.sub.2-9).

[0079] Next, in order to evaluate the revenue, the revenue obtained by selling porous carbon in the market and the revenue obtained by selling electricity were calculated according to Equation below.

[00004]$R_{\mathrm{PC}}=\underset{t=1}{\overset{n}{.Math.}}{Q}_{\mathrm{PC}}\times {\mathrm{SP}}_{\mathrm{PC}}$

[0080] Where, R.sub.PC is the revenue obtained from porous carbon, Q.sub.PC is the amount (tons) of porous carbon produced, and SP.sub.PC is the selling price (in Euros) of porous carbon per ton.

[00005]$R_E=\underset{t=1}{\overset{n}{.Math.}}{U}_E\times {\mathrm{FiT}}_E$

[0081] Where, R.sub.E is the revenue obtained from electricity generated by the combined heat and power (CHP) plant, U.sub.E is the number of power (1%, 10%, 20%, 50%, and 75%) generated in kWh unit with respect to the power conversion rate after considering heat loss, and FiT.sub.E is a supply tariff with respect to electricity units in Europe.

[0082] TR is the total revenue obtained by selling porous carbon and electricity, and is calculated using Equation below.

[0083] Meanwhile, revenue generation (in euro unit) through the sale of porous carbon is as shown in Table 5 below.

TABLE-US-00005 TABLE 5 Revenue (when sold Revenue (when sold Porous carbon (ton) at the minimum price) at an average price) PET6- PET6- PET6- PET6- PET6- PET6- PET6- PET6- Year CO.sub.2-9 K7 KU7 CO.sub.2-9 K7 KU7 CO.sub.2-9 K7 1 704 800 720 201,555.20 229,040.00 206,136.00 1,107,494.08 1,259,716.00 2 704 800 720 201,555.20 229,040.00 206,136.00 1,107,494.08 1,259,716.00 3 704 800 720 201,555.20 229,040.00 206,136.00 1,107,494.08 1,259,716.00 4 704 800 720 201,555.20 229,040.00 206,136.00 1,107,494.08 1,259,716.00 5 704 800 720 201,555.20 229,040.00 206,136.00 1,107,494.08 1,259,716.00 6 704 800 720 201,555.20 229,040.00 206,136.00 1,107,494.08 1,259,716.00 7 704 800 720 201,555.20 229,040.00 206,136.00 1,107,494.08 1,259,716.00 8 704 800 720 201,555.20 229,040.00 206,136.00 1,107,494.08 1,259,716.00 9 704 800 720 201,555.20 229,040.00 206,136.00 1,107,494.08 1,259,716.00 10 704 800 720 201,555.20 229,040.00 206,136.00 1,107,494.08 1,259,716.00 11 704 800 720 201,555.20 229,040.00 206,136.00 1,107,494.08 1,259,716.00 11 704 800 720 201,555.20 229,040.00 206,136.00 1,107,494.08 1,259,716.00 13 704 800 720 201,555.20 229,040.00 206,136.00 1,107,494.08 1,259,716.00 14 704 800 720 201,555.20 229,040.00 206,136.00 1,107,494.08 1,259,716.00 15 704 800 720 201,555.20 229,040.00 206,136.00 1,107,494.08 1,259,716.00 Life 10,560 t 12,000 t 10,800 t €3,023,328.00 €3,435,600.00 €3,092,040.00 €16,612,411.20 €18,895,740.00 time Revenue (when sold Revenue (when sold at an average price) at the maximum price) PET6- PET6- PET6- PET6- Year KU7 CO.sub.2-9 K7 KU7 1 1,133,744.40 2,015,544.96 2,290,392.00 2,061,352.80 2 1,133,744.40 2,015,544.96 2,290,392.00 2,061,352.80 3 1,133,744.40 2,015,544.96 2,290,392.00 2,061,352.80 4 1,133,744.40 2,015,544.96 2,290,392.00 2,061,352.80 5 1,133,744.40 2,015,544.96 2,290,392.00 2,061,352.80 6 1,133,744.40 2,015,544.96 2,290,392.00 2,061,352.80 7 1,133,744.40 2,015,544.96 2,290,392.00 2,061,352.80 8 1,133,744.40 2,015,544.96 2,290,392.00 2,061,352.80 9 1,133,744.40 2,015,544.96 2,290,392.00 2,061,352.80 10 1,133,744.40 2,015,544.96 2,290,392.00 2,061,352.80 11 1,133,744.40 2,015,544.96 2,290,392.00 2,061,352.80 11 1,133,744.40 2,015,544.96 2,290,392.00 2,061,352.80 13 1,133,744.40 2,015,544.96 2,290,392.00 2,061,352.80 14 1,133,744.40 2,015,544.96 2,290,392.00 2,061,352.80 15 1,133,744.40 2,015,544.96 2,290,392.00 2,061,352.80 Life €17,006,166.00 €30,233,174.40 €34,355,880.00 €30,920,292.00 time

[0084] The revenue obtained by selling electricity was estimated by considering the heat loss scenario as shown in Table 6 below.

TABLE-US-00006 TABLE 6 Parameters PET6-CO.sub.2-9 PET6-K7 Total Q 1.00 10.00 20.00 50.00 75.00 1.00 10.00 20.00 loss; % Tfg 1202.00 1185.00 1167.00 1113.00 1067.00 1259.00 1243.00 1225.00 (Rankine in); C Rankine 4010.00 3915.00 3810.00 3490.00 3220.00 3925.00 3845.00 3750.00 H.sub.2O; kg/h Net; kW 706.56 678.25 646.97 551.55 470.99 706.56 682.80 654.53 Act Q; −581.42 −581.42 −581.42 −581.42 −581.42 −252.89 −252.89 −252.89 MJ/h Pyro Q; −2859.14 −2859.14 −2859.14 −2859.14 −2859.14 −2859.14 −2859.14 −2859.14 MJ/h Cooling 4043.00 3971.00 3878.00 3623.00 3403.00 3983.00 3910.00 3831.00 water; kg/h Act Q −5.81 −58.14 −116.28 −290.71 −436.07 −2.53 −25.28 −50.578 Loss; MJ/h Pyro Q −28.60 −285.91 −571.83 −1429.57 −2144.35 −28.60 −285.91 −571.83 Loss; MJ/h Parameters PET6-K7 PET6-KU7 Total Q 50.00 75.00 1.00 10.00 20.00 50.00 75.00 loss; % Tfg 1170.00 1125.00 1245.00 1228.00 1208.00 11150.00 1100.00 (Rankine in); C Rankine 3460.00 3220.00 3850.00 3760.00 3655.00 3345.00 3085.00 H.sub.2O; kg/h Net; kW 568.00 496.50 703.35 676.60 645.25 552.84 475.31 Act Q; −252.89 −252.89 −486.0596 −486.06 −486.06 −486.06 −486.06 MJ/h Pyro Q; −2859.14 −2859.14 −2859.136 −2859.14 −2859.14 −12859.14 −2859.14 MJ/h Cooling 3600.00 3411.00 3799.00 3712.00 3639.00 3385.00 3175.00 water; kg/h Act Q −126.45 −189.68 −4.86 −48.61 −97.22 −243.03 −364.55 Loss; MJ/h Pyro Q −1429.57 −2144.35 −28.59 −285.91 −571.83 −1429.57 −2144.35 Loss; MJ/h

[0085] The results of calculating revenue generation by electricity sales are as shown in Table 7 below.

TABLE-US-00007 TABLE 7 Lifetime varying different heat loss percentage Sample 0% 1% 10% 20% 50% 75% PET6-CO.sub.2-9 85,200,000 84,787,200 81,390,000 77,636,400 66,186,000 56,518,800 PET6-K7 87,988,800 84,787,200 81,936,000 78,543,600 68,160,000 59,580,000 PET6-KU7 87,988,800 84,402,000 81,192,000 77,430,000 66,340,320 57,036,960

[0086] The results showed that PET6-CO.sub.2-9 production was the most feasible process, followed by PET6-K7 and PET6-KU7 production. According to TEA results, all three of these pathways can produce porous carbon, energy loss during the process is 20%, and the product can be sold at the lowest market price (Euro 200/t).

EXAMPLE 5

Life Cycle Assessment (LCA) Method Evaluation

[0087] Cradle-to-gate LCA was evaluated on Example 1-1 (PET6-CO.sub.2-9), Example 1-2 (PET6K7), and Example 1-3 (PET6KU7). Calculation was performed on the environmental impact categories of Table 8 below using the ReCiPe(H) Midpoint method of SimaPro(v8.5.2) software.

TABLE-US-00008 TABLE 8 Impact category Unit Global warming kg CO.sub.2 eq Stratospheric ozone depletion kg CFC11 eq Ionising radiation kBq Co-60 eq Ozone formation, human health kg NO.sub.x eq Fine particulate matter formation kg PM.sub.2.5 eq Ozone formation, terrestrial ecosystems kg NO.sub.x eq Terrestrial acidification kg SO.sub.2 eq Freshwater eutrophication kg P eq Marine eutrophication kg N eq Terrestrial ecotoxicity kg 1,4-DCB Freshwater ecotoxicity kg 1,4-DCB Marine ecotoxicity kg 1,4-DCB Human carcinogenic toxicity kg 1,4-DCB Human non-carcinogenic toxicity kg 1,4-DCB Land use m2a crop eq Mineral resource scarcity kg Cu eq Fossil resource scarcity kg oil eq Water consumption m.sup.3

[0088] As results, referring to FIG. 5A, it was shown that the KOH/urea chemical activation pathway that is Example 1-3 (PET6KU7) had a greater environmental impact in almost all 18 environmental impact categories. That is, Example 1-3 (PET6KU7) was about 200% higher than the CO.sub.2 physical activation pathway that is Example 1-1 (PET6-CO.sub.2-9), and was −1.74% to 125% higher than the KOH chemical activation pathway that is Example 1-2 (PET6K7). FIG. 5B is a result of considering a mitigated environment impact.

[0089] Meanwhile, GWP among all impact categories is the most important. Referring to FIGS. 6 and 7, the CO.sub.2 physical activation pathway that is Example 1-1 (PET6-CO.sub.2-9) had the lowest GWP, and the KOH/urea chemical activation pathway that is Example 1-3 (PET6KU7) had the highest GWP.

[0090] Referring to FIG. 6, a net present value (NPV) was calculated for the production of each porous carbon in various scenarios by changing the heat-power conversion loss and the selling price of porous carbon. Each scenario describes the capital investment in the plant, operating costs over 15 years, and revenue obtained from the sale of porous carbon and electricity produced in the process. As results, PET6-CO.sub.2-9 production was shown to be the most feasible process, followed by PET6-K7 and PET6-KU7 production. When the TEA result evaluated in Example 4 above and the LCA result of Example 5 above were integrated and evaluated, it was confirmed that the CO.sub.2 physical activation pathway that is Example 1-1 (PET6-CO.sub.2-9) had both of the lowest environmental impact and high economic benefits for industrial scale application. That is, it was confirmed that Example 1-1 (PET6-CO.sub.2-9) was economically feasible and had a low environmental impact.

[0091] Hereinabove, a specific part of the present disclosure content has been described in detail. Therefore, it will be clear to those of ordinary skill in the art that this specific description is only a preferred embodiment, and the scope of the present disclosure is not limited thereby. Accordingly, the substantial scope of the present disclosure will be said to be defined by the appended claims and their equivalents.