PLASTIC WASTE CONVERSION TO LUBRICANT PRODUCTION
20230109450 · 2023-04-06
Inventors
- Pingping Sun (Downers Grove, IL, US)
- Guiyan Zang (Woodridge, IL, US)
- Theodore R. Krause (Naperville, IL, US)
- Amgad A. Elgowainy (Lisle, IL, US)
- Ryan Hackler (Chicago, IL, US)
- Massimiliano Delferro (Chicago, IL)
- Vincenzo Cappello (Chicago, IL, US)
Cpc classification
C10M177/00
CHEMISTRY; METALLURGY
C10N2070/00
CHEMISTRY; METALLURGY
International classification
C10M177/00
CHEMISTRY; METALLURGY
Abstract
A process for converting plastic feedstock into a lubricant on an industrial scale can include a reactor having a filter integrated therein to allow for separation and recovery of catalyst so it can be washed and reused in subsequent conversion processes. Such recycling of the catalyst can allow for an industrial scale conversion process.
Claims
1. A process for conversion of a plastic feedstock to a liquid lubricant product, comprising: heating the plastic feedstock in the presence of a hydrogenolysis/hydrocracking catalyst in a conversion reactor with a flow of H.sub.2 to a conversion temperature to form a slurry; holding the slurry at the conversion temperature for a retention time sufficient to convert substantially all of the plastic feedstock to a liquid lubricant; removing the liquid lubricant from the conversion reactor and flowing the liquid lubricant into a distillation column, wherein the liquid lubricant is separated from the hydrogenolysis/hydrocracking catalyst before the liquid lubricant is flowed into the distillation column; recovering the hydrogenolysis/hydrocracking catalyst separated from the liquid lubricant and transferring the recovered catalyst to a catalyst filter unit after the liquid lubricant is removed from the conversion reactor; washing the recovered catalysts in the catalyst filter using a washing solvent introduced into the catalyst filter, wherein any lubricant remaining on the recovered catalysts will be dissolved into the washing solvent during washing; returning the washed catalyst to the conversion reactor for reuse; flowing the washing solvent after catalyst washing to the distillation column; purifying the liquid lubricant and washing solvent in the distillation column to recover solvent; recovering the purified washing solvent for reuse; and collecting the liquid lubricant product.
2. The process of claim 1, wherein the washing solvent after catalyst washing is flowed into the distillation column at a level above which the liquid lubricant is flowed into the distillation column.
3. The process of claim 1, wherein the purified solvent is recovered and removed from the distillation column at a head of the distillation column and the liquid lubricant product is collected from a bottom of the distillation column.
4. (canceled)
5. The process of claim 1, wherein the hydrogenolysis/hydrocracking catalyst comprises one or more platinum group metals and/or transition metals.
6. The process of claim 5, wherein the platinum group metal and/or transition metal is one or more of Pt, Ni, Co, and Pd.
7. The process of claim 5, wherein the platinum group metal and/or transition metal is deposited on a support.
8. The process of claim 7, wherein the support is a metal oxide or active carbon.
9. The process of claim 7, wherein the support is one or more of SrTiO3, TiO2, MgO, WO.sub.3, ZrO.sub.2, amorphous aluminosilicate, (modified) zeolite, active carbon, mesoporous support, etc.
10. The process of claim 5, wherein the catalyst comprises about 0.1 wt % to about 20 wt % Pt based on the total weight of the catalyst.
11. (canceled)
12. (canceled)
13. The process of claim 1, wherein unreacted H.sub.2 and/or C.sub.1-C.sub.8 hydrocarbon gases formed during conversions of the plastic feedstock in the conversion reactor are vented from the conversion reactor and diverted to a boiler for combustion.
14. (canceled)
15. The process of claim 1, wherein C.sub.4-C.sub.8 hydrocarbon gases formed during the conversion of the plastic feedstock in the conversion reactor are processed through a Joule-Thomson unit for recovery of naphtha.
16. (canceled)
17. The process of claim 1, wherein the plastic feedstock comprises one or more of HDPE, LDPE, and LLDPE.
18. (canceled)
19. The process of claim 1, further comprising admixing a hydrocarbon solvent with the plastic feedstock.
20. The process of claim 19, wherein the hydrocarbon solvent is one or more of butane, pentene, hexane, and naphtha.
21. The process of claim 19, wherein the hydrocarbon solvent and plastic feedstock are co-fed into the conversion reactor.
22. The process of claim 20, wherein purifying the liquid lubricant comprises separating the hydrocarbon solvent from the liquid lubricant in the distillation column.
23. The process of claim 22, wherein the separated hydrocarbon solvent is recovered from the distillation column and flowed back into the conversion reactor.
24. The process of claim 1, wherein the conversion reactor comprises a filter arranged such that the liquid lubricant passes through the filter and can be removed from the conversion reactor while the hydrogenolysis/hydrocracking catalyst remains on the filter and within the conversion reactor thereby separating the liquid lubricant from the hydrogenolysis/hydrocracking catalyst.
25. The process of claim 1 wherein the slurry is removed from the conversion reactor and flowed to a slurry filtration unit for separating the hydrogenolysis/hydrocracking catalysts from the liquid lubricant before the liquid lubricant is flowed into the distillation column, or wherein the slurry is removed from the conversion reactor and flowed to the catalyst filter unit for separating the hydrogenolysis/hydrocracking catalyst from the liquid lubricant, the liquid lubricant is then flowed from the catalyst filter unit to the distillation column, while the catalyst remains in the catalyst filter unit for washing.
26. (canceled)
27. The process of claim 1, wherein the washing solvent is one or more of hexane, pentane, or a paraffin.
28. (canceled)
29. (canceled)
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0008]
[0009]
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[0015]
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[0021]
DETAILED DESCRIPTION
[0022] An industrially relevant process for converting plastic waste into lubricants can beneficially include separation and recycling of the catalyst after the reaction with the plastic waste. Such separation and recovery is needed for a cost-effective process. Particularly, the high viscosity of both feedstock (after melting) and product requires efficient separation at elevated temperature.
[0023] A process for conversion of a plastic feedstock to a liquid lubricant product can include heating the plastic feedstock in the presence of a hydrogenolysis/hydrocracking catalyst to convert the plastic feedstock to a hydrocarbon product. The hydrocarbon can have from about 1 to about 50 carbons. For example, a C.sub.44 hydrocarbon can be produced from conversion of the plastic feedstock.
[0024] The plastic feedstock can be or include one or more of HDPE, LDPE, and LLDPE. For example, the plastic feedstock can be post-consumer recycled plastic waste. This can include a mixture of different plastics. The plastic feedstock can be in the form or treated to be in the form of pellets, chips, and/or flakes.
[0025] The process can include a plastic pretreatment depending on the type of plastic to be converted. For example, conversion of post-consumer plastic would benefit from a pretreatment process. The pretreatment can include, washing, drying, and crushing steps. The pretreatment equipment of phase of the facility can include a washer, dryer, and crusher. For example, the feedstock during pretreat can be washed to remove residual product contained in the plastics. For example, the feedstock can be crushed to be in pellet, chip or flake form.
[0026] The process can include heating the plastic feedstock in the presence of the catalyst to a conversion temperature of about 200° C. to about 450° C. For example, the conversion temperature can be about 300° C.
[0027] Once the conversion temperature is reached, the plastic feedstock can be held for a retention time of about 6 hours to about 96 hours. For example, the retention time can be about 72 hours.
[0028] H.sub.2 is flowed into the conversion reactor during the heating. The H.sub.2 can be flowed at a flow rate of about 30 kg/hr to about 600 kg/hr, at a pressure of 170 psi to 500 psi.
[0029] The process can include flowing a hydrocarbon solvent into the conversion reactor with the plastic feedstock. The hydrocarbon solvent can be a light hydrocarbon, such as, but not limited to, butane, pentene, hexane, and naphtha. The hydrocarbon solvent can be co-fed to the reactor with the plastic feedstock. This can aid mass transfer to further reduce retention time. When a hydrocarbon solvent is included, the resulting liquid lubricant will be admixed with the hydrocarbon solvent. The admixture can be separated from the catalyst and the hydrocarbon solvent can be separated from the liquid lubricant in the distillation column. The hydrocarbon solvent can be recovered from the distillation column and reintroduced into the conversion reactor for reuse.
[0030] The process includes separating the catalyst from the produced liquid lubricant prior to the liquid lubricant being flowed into the distillation column. Separation can be performed in the conversion reactor itself or in an external filtration unit. For example, the catalyst filter unit can be used to separate the catalyst from the liquid lubricant prior to washing the catalyst. Alternatively, a separate filter unit could be provided such that the slurry is first flowed to the filter unit to separate the catalyst and the liquid lubricant. After separation, the liquid lubricant can be flowed to the distillation column and the catalyst can be introduced into the catalyst filter unit for washing.
[0031] In embodiments in which the separation occurs in the conversion reactor, the conversion reactor, with a mixing agitator, can include a filter arranged in the interior volume of the reactor (built in filter). Solid catalyst and solid plastic feedstock can be introduced into the reactor such that it resides above or on a top surface of the filter. The filter can prevent the solids from passing through and entering a bottom region of the reactor but can allow liquid lubricant generated during the conversion process to pass through such that it resides on the bottom of the reactor, thereby providing separation from the solids. The liquid lubricant can be removed from the bottom of the reactor, while the solid catalyst remains within the reactor. The liquid lubricant can be flowed to a distillation column for purification as detailed below.
[0032] The solid catalyst can be removed from the reactor after removal of the liquid lubricant, for example by vacuum, then conveyed for washing. Any suitable method of collecting and introducing the catalyst into a washing unit can be used, referred to herein as a catalyst filter unit The catalyst filter unit can be a candle filter. For example, a FUNDABAC® (DrM, Dr. Mueller AG) could be used. A candle filter could similarly be used as separate unit, separate from the washing unit to separate the catalyst from the liquid lubricant prior to washing, but external from the conversion unit.
[0033] The catalyst can be washed with hexane or other solvent (e.g. pentane or other paraffin) that can dissolve paraffinic lubricant in the filter unit. The hexane can be flowed to an external source. During washing, hexane will dissolve residual lubricant on the catalysts thereby cleaning the lubricant from the catalyst. The washed catalyst can be recovered from the filter unit and the recovered catalyst can be used in the conversion reactor for further conversion reactions. Hexane used during the washing can be flowed from the filter unit to the distillation column, wherein the solved lubricant is separated from the hexane and purified hexane is recovered from the distillation column for reuse in the catalyst washing process.
[0034] The solid catalyst can be a one or more catalytic metal selected platinum group metals and/or transition metals. For example, the catalytic metal can be Pt, Pd, Ni, Co, and combinations thereof. The catalytic metal can be provided on a support. The support can be for example, a metal oxide. Examples of support materials include, but are not limited to one or a combination of SrTiO3, TiO2, MgO, WO.sub.3, ZrO.sub.2, amorphous aluminosilicate, and modified zeolite. For example, the hydrogenolysis/hydrocracking catalyst can be one or more of Pt disposed on a metal oxide support, Pt alloy catalysts, NiMo catalyst, and CoMo catalyst. The catalytic metal can be provided on the support in an amount, based on the total weight of the catalyst, of about 0.1 wt % to about 20 wt %, about 0.1 wt % to 2 wt %, about 1 wt % to about 2 wt %, about 1 wt % to about 5 wt %, about 2 wt % to about 5 wt %, and any values or ranges there between. For example, the catalytic metal can be provided on the support in an amount, based on the total weight of the catalyst of about, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 wt %. For example, the catalyst can be about 5 wt % Pt as the catalytic metal, based on the total weight of the catalyst.
[0035] The catalyst can be used in ratio of about 1:10 to 1:20 per kg of plastic feed stock.
[0036] Hexane and liquid lubricant can be purified in the distillation column. Hexane from the washing of the catalyst can be purified to remove any solved lubrication, which can be further purified with the liquid lubricant to form the liquid lubricant product. The liquid lubricant product can be a high quality liquid, for example. Hexane can be recovered from the distillation column and reused for subsequent washing cycles.
[0037] The catalyst can be washed and reused in the process of the disclosure for long periods of time. This makes the process of the disclosure available as a large scale process as it is both economical and efficient. For example, the catalyst can be used in a process of the disclosure for repeated conversion cycles for 2-3 years or more.
[0038]
[0039] In the process diagram
[0040]
[0041] In any of the arrangements, unreacted H.sub.2 gas and/or C.sub.1-C.sub.8 hydrocarbon gas may form during the conversion process. The gas can be vented from the reactor. In some embodiments, the gas can be burned to provide heat energy back into the system. In some embodiments, the gas can be separated after venting and H.sub.2 can be recycled back into the reactor for subsequent conversion reaction. The C.sub.4-C.sub.8 hydrocarbons can be separated (e.g. distillation, compression, refrigeration) and introduced into the conversion reactor as a solvent. For example, the C.sub.4-C.sub.8 hydrocarbons can be used as a solvent to co-feed with plastic waste feedstock.
[0042] Referring to
[0043]
[0044] Hydrocarbons ranging from C.sub.3-C.sub.8 are recovered using a Joule-Thomson unit. The catalyst is washed with hexane at A300. The remaining fuel gas is combusted to produce power and steam.
[0045]
[0046] As described above, in some embodiments of the process, a hydrocarbon solvent can be introduced into the conversion reactor with the plastic feed stock. In such embodiments, the gas produced in the conversion reactor can include a hydrocarbon. The gas can be vented from the reactor and diverted for combustion for heat supply or diverted to refrigerated separation for the recovery of naphtha and/or LPG or as hydrocarbon solvent.
[0047] In any of the arrangements, after washing, the solids will be dried via gas pressure and then discharged as a dry cake. Further, as shown in
[0048] Liquid lubricant produced in the reactor can be removed from the bottom of the reactor (reactor with built in filtration) or after external filtration unit and flowed to a distillation column for purification and ultimately collection.
[0049] Washed catalyst can be recovered from the catalyst filter and reintroduced into the conversion reactor for reuse. Washing and drying of the catalyst can be achieved inside the filter unit, after discharging the lubricant products as filtrate. The catalyst is collected after disrupting the dry cake via gas pressure.
[0050] In the distillation column, liquid lubricant remained dissolved in the filter is separated from the washing solvent (e.g., hexane), which is then recovered. The purified hexane is removed from the distillation column and recycled into the process for reuse in the catalyst washing procedure, while the bottom product is sent to increase the LHV of the fuel.
[0051] Processes of the disclosure can advantageously achieve high yields HQL, such as 60% or more, 70% or more, 80% or more, and 90% or more. For example, the processes of the disclosure can achieve yields of HQL from 60% to 90%.
[0052] Processes of the disclosure can have significant environmental benefit. For example, the process can result in significant reduction of solid waste in landfills and waterways, without production of and required disposal of solid char. Further, as compared to production of refinery lubricant or polyalphaolefin (PAO), the process of the disclosure has significantly reduced green-house gas emissions.
[0053] The production of lubricant is energy and emission intensive.
[0054] In addition, the lubricant production also incurs indirect emissions or the upstream burdens related to the production of feedstock or materials that are used by refineries. By including the CO.sub.2 emission associated with refinery upstream burdens (e.g. crude oil recovery, electricity and hydrogen production), the refinery lubricant wells to gate CO.sub.2 emission is about 0.98 kg/kg lubricant product. Raimondi, A., Girotti, G., Blengini, G. A. et al. LCA of petroleum-based lubricants: state of art and inclusion of additives. Int J Life Cycle Assess 17, 987-996 (2012). https://doi.org/10.1007/s11367-012-0437-4
[0055] It is worth noting that the lubricant produced from plastic waste has higher quality than the refinery lubricant (group I, II and III), but rather similar with that of group IV or synthetic lubricant, or PAO (polyalphaolefin). The PAO catalyst has a well to gate CO.sub.2 emission of 1.9 kg CO.sub.2 eq/kg lubricant. Giorgia Girotti, Andrea Raimondi, Gian A. Blengini and Debora Fino, The Contribution of Lube Additives to the Life Cycle Impacts of Fully Formulated Petroleum-Based Lubricants, American Journal of Applied Sciences DOI: 10.3844/ajassp.2011.1232.1240, Volume 8, Issue 11, Pages 1232-1240
[0056] Processes of the disclosure can have significantly reduced green-house gas emissions as compared to refinery processes and PAO production process. In contrast, the lubricant product derived from plastic waste has well to gate CO.sub.2 emission of 0.5-1.7 kg CO.sub.2e/kg lubricant, depending on catalyst loading and operating conditions, lower than the CO.sub.2 emission from the current lubricant production, 0.98-1.9 kg/kg lubricant for group I, II, III and IV.
[0057] A process to upgrade HDPE waste to high-quality liquid in accordance with the disclosure can advantageously provide a means to address the plastic management issues while being economically profitable with an estimated MSP of the lubricant-like product of $1.83 gal.sub.HQL.sup.−1 ($0.60 kg.sub.HQL.sup.−1), considering the market price for group III and PAO lubricants in the range $6-10 gal.sup.−1. The main parameters that affected the production costs were the cost of plastic waste and the amount of Pt/SrTiO.sub.3 catalyst needed.
[0058] The process for lubricant production in accordance with the disclosure can have significant environmental and national energy security benefits. For the former, our proposed technology has extraordinary benefit in solid waste reduction in landfill and in waterways, without producing and disposing solid char. This is especially important for the U.S. as the waste export market continues to dwindle as foreign countries ban the importing of waste. For the latter, the process of the disclosure could reduce GHG emissions significantly compared to refineries by displacing the energy intensive lubricant production process. The LCA showed that lubricant produced from plastic waste had an onsite CO.sub.2 emission as low as 0.24 kg.sub.CO2 kg.sub.Lub.sup.−1 (0.72 kg.sub.CO2 gal.sub.HQL.sup.−1), which was significantly lower than the CO.sub.2 emission from petroleum lubricant (0.89-1.35 kg.sub.CO2 kg.sub.Lub.sup.−1). Based on the U.S. lubricant production of 60.87 million barrels in 2019, replacing petroleum-derived lubricant with plastic waste-derived lubricant could reduce CO.sub.2 emissions between 3 and 9 million MT per year in the U.S.
EXAMPLES
Example 1: Lab Scale Hydrogenolysis
[0059] Hydrogenolysis of polyethylene was done in a Parr autoclave reactor using about 3 g of polymer and varying amounts of Pt/STO catalyst, along with variations in H.sub.2 pressure (
Example 2: Facility Model
[0060] A conceptual facility to convert 250 MT per day of PE post-consumer waste into lubricant-range molecules was designed, based laboratory results about polyethylene hydrogenolysis detailed in previous studies. G. Celik, R. M. Kennedy, R. A. Hackler, M. Ferrandon, A. Tennakoon, S. Patnaik, A. M. LaPointe, S. C. Ammal, A. Heyden, F. A. Perras, M. Pruski, S. L. Scott, K. R. Poeppelmeier, A. D. Sadow and M. Delferro, ACS Cent. Sci., 2019, 5, 1795-1803; and R. A. Hackler, K. Vyavhare, R. M. Kennedy, G. Celik, U. Kanbur, P. J. Griffin, A. D. Sadow, G. Zang, A. Elgowainy, P. Sun, K. R. Poeppelmeier, A. Erdemir and M. Delferro, ChemSusChem, DOI:10.1002/cssc.202100912. The process was modelled by using the software Aspen Plus v12. Two case studies were considered: a high-yield case (HY) based on the best up to date test results, and a conservative case characterized by a low-yield (LY). The operating conditions for both cases are listed in Table 1, below. The simulated process to convert recovered plastic wastes to high-quality liquids (HQL) consisted of four main process areas.
TABLE-US-00001 TABLE 1 Operating conditions for the low-yield and high-yield case studies. Parameter LY HY Lubricant yield 0.6 0.9 Catalyst:PE 0.1 0.05 Reaction time/h 72 40 Pt:SrTiO.sub.3 0.1 0.02 Reaction temperature/° C. 300 Pressure/bar 11.7 Feedstock/MT day.sup.−1 250
[0061] In Area 100 (A100), four pretreatment lines consisting of washer, dryer, and crusher handled the bales of mixed HDPE before conveying the pelletized feedstock to the reactor. In A200, the hydrogenolysis was carried out in an agitated reactor at 300° C. and 11.7 bar. In the presence of Pt/SrTiO3 catalyst, HDPE (Mw=35,000 Da) was fully converted to HQL and other lighter hydrocarbon products based on the following chemical equations for the low-yield and high-yield cases, respectively:
(C.sub.2H.sub.4).sub.1250+528.5H.sub.2=270CH.sub.4+90C.sub.2H.sub.6+43.3C.sub.3H.sub.8+40C.sub.4H.sub.10+14C.sub.5H.sub.12+13.3C.sub.6H.sub.14+10C.sub.7H.sub.16+5C.sub.8H.sub.18+42.9C.sub.35H.sub.72.
(C.sub.2H.sub.4).sub.1250+185.7H.sub.2=67.5CH.sub.4+22.5C.sub.2H.sub.6+10.8C.sub.3H.sub.8+10C.sub.4H.sub.10+3.5C.sub.5H.sub.12+3.3C.sub.6H.sub.14+2.5C.sub.7H.sub.16+1.3C.sub.8H.sub.18+64.3C.sub.35H.sub.72.
[0062] The catalyst can be designed to achieve a narrow product distribution. The n-C.sub.35H.sub.72 component was used to characterize the properties of the HQL (LHV=44.26 MJ kg-1, density=800 kg m.sup.−3). For the low-yield case, the stoichiometry was obtained considering a 60% yield in C.sub.35H.sub.72 and the fraction of lighter gases. The plastic feedstock was not available in the Aspen Plus database; hence, physical and thermodynamic properties of interest were implemented in the model. The enthalpy of formation was obtained from the gross heat of combustion value reported in the literature (i.e. 47.7 MJ kg.sup.−1). The plastic was melted and heated up to a temperature of 300° C. with heat generated by the combustion of light gases produced on site. For the heat of fusion, the value 4.14 kJ mol.sup.−1 was considered. Hydrogen was used in excess (i.e. 2 times the stoichiometric amount) to aid H.sub.2 adsorption on catalyst surface, promote hydrogenolysis kinetics, and reduce mass transfer limitations. In the process design, the reactor was fed with 680 Nm.sup.3 of hydrogen per MT of PE. The unreacted H.sub.2 was recovered by pressure swing adsorption (PSA). The PSA was simulated at 9.2 bar to separate hydrogen from hydrocarbons with an overall recovery ratio of 85%. The adsorbed gases were then released after depressurization and diverted to a Joule-Thomson (JT) unit, while the recovered hydrogen was compressed to 11.7 bar. The JT unit (
TABLE-US-00002 TABLE 2 Simulation parameters of the main equipment. Process area Unit Aspen block Parameter/unit Value A100 H.sub.2 compressor Compr Discharge pressure/bar 11.7 Isentropic efficiency 0.86 A200 Plastic heater Heater Temperature/° c. 300 Duty/cal s.sup.−1 81.59* Reactor Rstoic Pressure/bar 11.7 Temperature/° c. 300 HDPE conversion 100%** Flash separator Flash2 Pressure/bar 9.5 Gas chiller Heater Temperature 43 PSA Sep H.sub.2 recovery 85% Ch.sub.4 recovery 0.1% A200.jt plant Gas compressor Mcompr Number of stages 4 Intercooler temperature/° c. 43 Discharge pressure/bar 120 Isentropic efficiency 0.86 KO drum Flash2 Δp/bar 0 Heat/cal .Math. sec.sup.−1 0 Gas-liq. Heater Heatx Heat transfer coefficient/w .Math. m.sup.−2 .Math. k.sup.−1 63.6 Δt.sub.outlet/k (countercurrent) 10 Gas-gas heater Heatx Heat transfer coefficient/w .Math. m.sup.−2 .Math. k.sup.−1 30 Δt.sub.outlet/k (countercurrent) 10 Jt valve Valve Δp/bar −115 Cold separator Flash2 Δp/bar 0 A300 Catalyst filter Sep Solid recovery 100% Liquid entrainment 1% Hexane dist. Distl Number of stages 15 Column Feed stage 2 Reflux ratio 0.5 Distillate:feed 0.99 Pressure/bar 1 A400 Boiler.sup.† Heater #1 Water t.sub.out/° c. 300 Heater #2 Degree superheating 0 Heater #3 Steam t.sub.out/° c. 550 Heater #4-6 Δp/bar 0 Air blower Compr Δp/bar 0.3 Isentropic efficiency 0.86 Steam turbine Compr Discharge pressure/bar 0.04.sup.†† Isentropic efficiency 0.86 Water condenser Heater Δp/bar 0 Vapor fraction 0 Water pump Pump Discharge pressure/bar 112 Efficiency 0.78 *Based on the heat of fusion of HDPE. .sup.†The boiler was made of an economizer, vaporizer, and superheater, each heater modeled as a couple of heater blocks to describe the water/steam side and the hot gases side. .sup.††Obtained from Calculator, based on the water saturation pressure at the outlet conditions (T = 30° C.).
TABLE-US-00003 TABLE 3 Conversions and stoichiometry defined for the reactor model. The conversion values to C1-C8 were based on the data published in Celik et al. .sup.1A total conversion of HDPE was assumed for both cases. HDPE CONVERSION HDPE CONVERSION (60% YIELD) (90% YIELD) STOICHIOMETRY 0.108 0.027 HDPE + 2500 H.sub.2 = 2500 CH.sub.4 0.072 0.018 2 HDPE + 2500 H.sub.2 = 2500 C.sub.2H.sub.6 0.052 0.013 3 HDPE + 2500 H.sub.2 = 2500 C.sub.3H.sub.8 0.064 0.016 4 HDPE + 2500 H.sub.2 = 2500 C.sub.4H.sub.10 0.028 0.007 5 HDPE + 2500 H.sub.2 = 2500 C.sub.5H.sub.12 0.032 0.008 6 HDPE + 2500 H.sub.2 = 2500 C.sub.6H.sub.14 0.028 0.007 7 HDPE + 2500 H.sub.2 = 2500 C.sub.7H.sub.16 0.016 0.004 8 HDPE + 2500 H.sub.2 = 2500 C.sub.8H.sub.18 0.600 0.900 35 HDPE + 2500 H.sub.2 = 2500 C.sub.35H.sub.72
Life Cycle Assessment (LCA)
[0063] A LCA based technique was applied to estimate the carbon footprint for lubricant synthesis processes from plastic waste, using data from GREET 2020 (Greenhouse gases, Regulated Emissions, and Energy use in Technologies model). GREET provides the inventory of data for a variety of processes with detailed information of energy use, material consumption and the resulting emissions.
[0064] The system boundary used for the LCA is shown in
[0065] To quantify the potential environmental benefit of converting plastic waste to HQL lubricant, the conventional processes for group III and PAO lubricants were taken as baselines. In
[0066] To quantify the effects of solid waste upcycling, it was important to assess the reduction in solid waste as a part of this environmental analysis. Therefore, solid waste reduction analysis was carried out in addition to establishing carbon reduction profile using LCA. For this estimation, the net amount of solid waste reduction was calculated accounting for the plastic used as raw material and the average catalyst support material disposed, which was calculated from the total catalyst support used over the lifetime of the plant. The average catalyst support material disposed was also used as a basis for solid waste reduction comparison to an average lubricant production process.
[0067] The total material and energy streams are listed in Tables 4-6.
TABLE-US-00004 TABLE 4 Summary stream table for the two scenarios. The catalyst consumption rate was calculated based on the full replacement of the catalyst every three years during the total life of the plant (i.e. 40 years). LY HY UNIT INPUT HDPE 1.64 1.10 KG KG.sub.HQL.sup.−1 H.sub.2 0.0562 0.02 KG MAKEUP KG.sub.HQL.sup.−1 AIR 7.80 1.92 KG KG.sub.HQL.sup.−1 HEXANE 0.004 0.002 KG MAKEUP KG.sub.HQL.sup.−1 OUTPUT HQL 153 227 MT DAY.sup.−1 NAPHTHA 0.304 0.034 KG KG.sub.HQL.sup.−1 FLUE GAS 8.19 2.01 KG KG.sub.HQL.sup.−1 CO.sub.2 IN 1.08 0.24 KG FLUE GAS KG.sub.HQL.sup.−1 COOLING 377.96 116.97 KG WATER KG.sub.HQL.sup.−1 PROCESS 0.73 0.22 KG WATER KG.sub.HQL.sup.−1 CATALYST CONSUMPTION 4.70 8.81 KG RATE 10.sup.−4 10.sup.−5 MT.sub.HQL.sup.−1
TABLE-US-00005 TABLE 5 Summary stream table of the process with lubricant yield of 60%. The components flow rates are listed in mole basis. 1 2 3 4 5 6 Temperature/° C. 25.00 25.00 25.00 41.87 43.28 29.13 Pressure/bar 1.01 20.00 1.01 11.72 1.01 10.95 Phase Solid Gas Solid Gas G + L G + L Mass flowrate/t day.sup.−1 250.00 8.59 250.00 14.21 152.88 47.12 Mole flowrate/kmol h.sup.−1 0.30 177.54 0.30 293.10 14.21 31.20 HDPE 0.30 0 0.30 0 0 0 H.sub.2 0 177.54 0 293.02 0.16 0.01 CH.sub.4 0 0 0 0.08 0.19 0.94 C.sub.2H.sub.6 0 0 0 0 0.10 3.10 C.sub.3H.sub.8 0 0 0 0 0.07 5.43 C.sub.4H.sub.10 0 0 0 0 0.11 9.85 C.sub.5H.sub.12 0 0 0 0 0.07 3.96 C.sub.6H.sub.14 0 0 0 0 0.43 3.80 C.sub.7H.sub.16 0 0 0 0 0.20 2.76 C.sub.8H.sub.18 0 0 0 0 0.14 1.34 C.sub.35H.sub.72 0 0 0 0 12.73 0 O.sub.2 0 0 0 0 0 0 N.sub.2 0 0 0 0 0 0 CO.sub.2 0 0 0 0 0 0 H.sub.2O 0 0 0 0 0 0 7 8 9 10 11 Temperature/° C. 43.03 25.00 3.76 25.00 130.06 Pressure/bar 8.00 1.01 5.00 1.01 1.30 Phase Gas Liquid Gas Gas Gas Mass flowrate/t day.sup.−1 5.62 0.59 59.18 1192.25 1251.43 Mole flowrate/kmol h.sup.−1 115.56 0.29 132.41 1721.89 1866.47 HDPE 0 0 0 0 0 H.sub.2 115.48 0 20.36 0 0 CH.sub.4 0.08 0 79.07 0 0 C.sub.2H.sub.6 0 0 23.53 0 0 C.sub.3H.sub.8 0 0 7.36 0 0 C.sub.4H.sub.10 0 0 1.92 0 0 C.sub.5H.sub.12 0 0 0.13 0 0 C.sub.6H.sub.14 0 0.29 0 0 0 C.sub.7H.sub.16 0 0 0 0 0 C.sub.8H.sub.18 0 0 0 0 0 C.sub.35H.sub.72 0 0 0 0 0 O.sub.2 0 0 0 361.60 60.27 N.sub.2 0 0 0 1360.29 1360.29 CO.sub.2 0 0 0 0 156.75 H.sub.2O 0 0 0 0 289.16
TABLE-US-00006 TABLE 6 Summary stream table of the process with lubricant yield of 90%. The components flow rates are listed in mole basis. 1 2 3 4 5 6 Temperature/° C. 25.00 25.00 25.00 54.28 44.16 33.98 Pressure/bar 1.01 20.00 1.01 11.72 1.01 10.95 Phase Solid Gas Solid Gas G + L G + L Mass flowrate/t day.sup.−1 250.00 4.41 250.00 14.18 226.80 7.67 Mole flowrate/kmol h.sup.−1 0.30 91.21 0.30 293.04 20.03 4.43 HDPE 0.30 0 0.30 0 0 0 H.sub.2 0 91.21 0 293.02 0.43 0.01 CH.sub.4 0 0 0 0.02 0.07 0.10 C.sub.2H.sub.6 0 0 0 0 0.04 0.30 C.sub.3H.sub.8 0 0 0 0 0.03 0.45 C.sub.4H.sub.10 0 0 0 0 0.04 1.03 C.sub.5H.sub.12 0 0 0 0 0.02 0.65 C.sub.6H.sub.14 0 0 0 0 0.25 0.86 C.sub.7H.sub.16 0 0 0 0 0.04 0.69 C.sub.8H.sub.18 0 0 0 0 0.03 0.34 C.sub.35H.sub.72 0 0 0 0 19.10 0 O.sub.2 0 0 0 0 0 0 N.sub.2 0 0 0 0 0 0 CO.sub.2 0 0 0 0 0 0 H.sub.2O 0 0 0 0 0 0 7 8 9 10 11 Temperature/° C. 43.03 25.00 19.36 25.00 130.00 Pressure/bar 8.00 1.01 10.95 1.01 1.30 Phase Gas Liquid Gas Gas Gas Mass flowrate/t day.sup.−1 9.77 0.46 20.41 435.10 455.51 Mole flowrate/kmol h.sup.−1 201.83 0.22 66.97 628.39 687.37 HDPE 0 0 0 0 0 H.sub.2 201.81 0 35.61 0 0 CH.sub.4 0.02 0 19.88 0 0 C.sub.2H.sub.6 0 0 6.35 0 0 C.sub.3H.sub.8 0 0 2.74 0 0 C.sub.4H.sub.10 0 0 1.90 0 0 C.sub.5H.sub.12 0 0 0.37 0 0 C.sub.6H.sub.14 0 0.22 0 0 0 C.sub.7H.sub.16 0 0 0 0 0 C.sub.8H.sub.18 0 0 0 0 0 C.sub.35H.sub.72 0 0 0 0 0 O.sub.2 0 0 0 131.96 21.99 N.sub.2 0 0 0 496.43 496.43 CO.sub.2 0 0 0 0 50.99 H.sub.2O 0 0 0 0 117.96
[0068] The scenario characterized by a lubricant yield of 60% led to a HQL production of 153 MT day.sup.−1 and about 46 MT day.sup.−1 of naphtha. Increasing the lubricant yield from 60% to 90% led to a 50% increase in lubricant production. The case with 90% yield was also characterized by a lower amount of hydrogen consumption per kg of HQL, due to the lower production of light hydrocarbons, the formation of which requires more H.sub.2 than liquid products. Moreover, the on-site CO.sub.2 emissions decreased by 78% due to the lower amount of fuel gas burnt for power generation. The amount of co-product decreased to about 8 MT day.sup.−1, as well as the net electric power produced, that decreased by 42%.
[0069] The energy balance is summarized in Table 7.
TABLE-US-00007 TABLE 7 Energy balance and process efficiency for both low-yield and high-yield cases. LY HY UNIT INPUT HDPE 128.3 128.3 MW H.sub.2 11.9 6.1 MW POWER 5.8 4.3 MW OUTPUT HQL 78.3 116.2 MW NAPHTHA 24.6 4.1 MW POWER 10.6 3.1 MW EFFICIENCY 78% 89%
[0070] The process energy efficiency was calculated based on the energy of the product, co-product, and feedstock materials:
[0071] Here, E is the energy content of feedstock and products based on the low heating value (LHV), while W.sub.e is the electric power needed (IN) and generated (OUT). For the cases with 90% yield, both the increase in HQL productivity and decrease in hydrogen demand led to a more efficient process overall, with an energy efficiency of 89%.
LCA Results
[0072] The CO.sub.2 emissions associated with the production of plastic-derived lubricant are a vital parameter to ensure the environmental benefit synergy between solid waste reduction and air emission reduction. This section provides results for the emissions profile of HQL process, a discussion on petroleum lubricant emissions as a baseline, and the sensitivity case of conventional synthetic lubricant (PAO) production process.
[0073] Solid waste reduction by plastic upcycling. The process for conversion of plastics to HQL product used 91,250 mt year.sup.−1 of HDPE feedstock. From a solids material balance viewpoint this corresponds to the total input solid HDPE that is converted to HQL. In this process, the only solid waste generated over the lifetime of the plant comes from catalyst support that is disposed, since the metal, Pt, is recovered owing to its high cost and value. Therefore, based on the amount of support catalyst generating the sole source of solid waste, on a yearly average of 6.63 mt year.sup.−1, this process is likely to bring about a reduction in solid waste by 99.9%.
[0074] A conventional process for mineral lube production is estimated to yield an average of 40 mt of solid waste, in the form of clay. Compared to this value, the current process accounts for over 83% reduction in solid waste, for lubricant production. It is important to point here that along with this reduction in solid waste, the lubricant product obtained from the process in this research is of a higher quality than mineral lube.
[0075] Emissions from the plastic waste derived lubricant. The total CO.sub.2 emissions produced from the combustion of fuel gas are listed in Table 8 for both scenarios. In the LY case study, the combustion of fuel gas generated a surplus of power, which was accounted as power injected into the grid. The HY case produced nearly 80% less co.sub.2 from power generation, due to the lower amount of light hydrocarbons produced from the HDPE hydrogenolysis.
TABLE-US-00008 TABLE 8 Carbon emissions generated by the HQL process from combustion of light gases. LY HY UNIT 1.08 0.24 KG.sub.CO2 KG.sub.HQL.sup.−1 3.25 0.72 KG.sub.CO2 GAL.sub.HQL.sup.−1
[0076] The cradle-to-gate CO.sub.2 emissions of the lubricant production from plastic waste was calculated by accounting for the upstream burdens of feedstocks and other material and energy inputs. In
[0077] Petroleum lubricant well-to-gate co.sub.t emission as a baseline.
[0078] Despite the existence of some energy consumption data for lubricant product, the CO.sub.2 emission has been rarely reported, as most studies focused on the refinery emissions allocated to major products, such as gasoline, diesel, jet, naphtha, pet coke, etc. The CO.sub.2 emission is highly depended on refinery crude slates, refinery product slates, and refinery's operating conditions. We conducted a unit-based process analysis to obtain a detailed breakdown of energy sources, in order to obtain CO.sub.2 emissions by using emission factors of various energy sources. In addition, we developed a detailed input inventory list, to calculate the upstream burden for lubricant production.
[0079] The results presented here consolidate a baseline for the lubricant production process calculated from available literature. Table 6 shows sources from the literature which provided a comparison of emissions data for the current technology to literature available for emissions associated with lubricant production. According to the energy and environmental profile for US refineries, the total fuel and electricity consumption for lubricant production is reported to be 11.26 MJ kg.sub.Lub.sup.−1 and 0.5 MJ kg.sub.Lub.sup.−1, respectively. Other sources reported fuel and electricity use at 11.56 MJ/kg.sub.Lub and 0.06 MJ kg.sub.Lub.sup.−1, respectively, for a paper that reports criteria air pollutant and greenhouse gas emissions allocated to refinery products for US refineries. Best Available Techniques (BAT) for refining of mineral oil and gas, a European Commission report, also provides fuel and electricity use at 6.07 MJ kg.sub.Lub.sup.−1 and 0.21 MJ kg.sub.Lub.sup.−1, respectively. The corresponding onsite CO.sub.2 for lubricant production fall in the range of 0.89-1.35 kg.sub.CO2 kg.sub.Lub.sup.−1.
[0080] Synthetic lubricant (PAO) emissions profile. The total onsite energy input of the process includes power, heat, and steam. The energy consumption is 2.37 MJ kg.sub.Lub.sup.−1 and 9.60 MJ kg.sub.Lub.sup.−1, for power and thermal components, respectively. This energy consumption together corresponds to a total CO.sub.2 emission of 0.81 kg.sub.CO2 kg.sub.Lub.sup.−1, wherein emissions from U.S. grid mix electricity and natural gas-based boiler. Upstream emissions for ethylene production were obtained from GREET and it amounted to 0.84 kg.sub.CO2 kg.sub.Lub.sup.−1, 9 bringing the total emissions for PAO lubricant to 1.65 kg.sub.CO2 kg.sub.Lub.sup.−1.
[0081] As seen in
[0082] Plastics upcycling is a field with high potential for waste-to-value generation and has as such garnered active interest from researchers. A variety of high-value products such as fuels, construction materials, nanomaterials, hydrogen, and lubricants have been obtained using pre-consumer and waste plastics alike, thereby developing novel waste-to-value routes..sup.21,58,59 In terms of emissions, with the validated 90% yield, the HQL synthesis from HDPE led to 0.48 kg.sub.CO2 kg.sub.HQL.sup.−1. This represented a 52% reduction in the WTG CO.sub.2 emission relative to group III lubricant oil and a 72% reduction respect to PAO, as well as 99.9% of solid waste reduction
[0083] Accordingly, the foregoing description is given for clearness of understanding only, and no unnecessary limitations should be understood therefrom, as modifications within the scope of the disclosure may be apparent to those having ordinary skill in the art.
[0084] All patents, patent applications, government publications, government regulations, and literature references cited in this specification are hereby incorporated herein by reference in their entirety. In the case of conflict, the present description, including definitions, will control.
[0085] Throughout the specification, where the compounds, compositions, methods, and/or processes are described as including components, steps, or materials, it is contemplated that the compounds, compositions, methods, and/or processes can also comprise, consist essentially of, or consist of any combination of the recited components or materials, unless described otherwise. Component concentrations can be expressed in terms of weight concentrations, unless specifically indicated otherwise. Combinations of components are contemplated to include homogeneous and/or heterogeneous mixtures, as would be understood by a person of ordinary skill in the art in view of the foregoing disclosure.