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EP-4739646-A1 - PROCESS AND CATALYSTS FOR THE PRODUCTION OF ETHYLENE AND PROPYLENE FROM LOW-CARBON SYNGAS

EP4739646A1EP 4739646 A1EP4739646 A1EP 4739646A1EP-4739646-A1

Abstract

An improved process and catalysts for efficiently producing ethylene and propylene from low-carbon syngas is described. The process comprises contacting the low-carbon syngas with a ZnO-impregnated ZnMoO4 spinel catalyst or a ZnO-impregnated ZnAhO4 spinel catalyst; wherein the said catalysts demonstrate selectivities of up to about 80% for C2-C4 alkenes, at syngas H2/CO ratios of 1.0 to 3.0, at temperatures of 250 to 425 °C (482-797 °F), at pressures of 150 to 350 psi, and at space velocities of 4,000 to 15,000 hr"1 with CO conversion efficiencies of 40-55%.

Inventors

  • SCHUETZLE, ROBERT
  • SCHUETZLE, DENNIS

Assignees

  • Greyrock Technology, LLC

Dates

Publication Date
20260513
Application Date
20240627

Claims (19)

  1. 1. A process for producing ethylene and propylene from syngas, wherein the process comprises: contacting a low-carbon syngas with a catalyst, wherein the catalyst is a spinel, and wherein the catalyst is either ZnO impregnated on Z11M0O4 or ZnO impregnated on ZnAhO4, wherein the catalyst provide for a combined selectivity ranging from 50% to 80% for C2-C4 olefins at syngas H2/CO ratios ranging from 1.0 to 3.0, at temperatures ranging from 250 °C to 425 °C, at pressures ranging from 100 psi to 350 psi, at space velocities ranging from 4,000 hr"' ' to 15,000 hr -1 and CO conversion efficiencies ranging from 40% to 75%, thereby producing ethylene and propylene from syngas.
  2. 2. The process of claim 1, wherein there is a loading percentage of the ZnO impregnated on ZnMoO4 or ZnAhO4, and wherein the loading percentage ranges from 0.10 weight percent to 25.0 weight percent.
  3. 3. The process of claim 1, wherein there is a catalyst efficiency, and wherein the catalyst efficiency decreases between 0% and 1.0% after 1,000 hrs. of operation.
  4. 4. The process of claim 1, wherein CH4 and CO are also produced, and wherein there is a selectivity associated with the production, and wherein the selectivity ranges from 0% to 5%.
  5. 5. The process of claim 1, wherein the process further comprises the step of producing the low-carbon syngas by the gasification of a renewable feedstock with a low-carbon footprint.
  6. 6. The process of claim 1, wherein the ZnO is at least partially reduced to metallic zinc while in contact with the syngas.
  7. 7. The process of claim 1, wherein the produced ethylene and propylene are in a product stream, and wherein the ethylene and propylene are separated from one another by distillation or adsorption to provide purified ethylene and propylene.
  8. 8. The process of claim 7, wherein the purified ethylene and propylene each have a carbon intensity value, and wherein the carbon intensity value ranges from 0% to 50% of ethylene and propylene produced from petroleum-derived feedstocks.
  9. 9. The process of claim 5, wherein the low-carbon syngas is produced by the gasification of agricultural waste or municipal solid waste.
  10. 10. The process of claim 5, wherein the low-carbon syngas is produced by the gasification of biomass.
  11. 11. The process of claim 5, wherein the low-carbon syngas is produced by the gasification of carbonaceous resources, and wherein the carbonaceous resources are flare gas, oil refinery waste, stranded gas, disadvantaged gas, used engine oil, waste tires, tar sands, and oil shale.
  12. 12. The process of claim 5, wherein the low-carbon syngas is produced by the catalytic conversion of captured CO2 and renewable H2.
  13. 13. A catalyst for producing ethylene and propylene from syngas, wherein the catalyst comprises either ZnO impregnated on ZnMoC>4 or ZnO impregnated on ZnAhO4.
  14. 14. The catalyst of claim 13, wherein there is a loading percentage of the ZnO impregnated on Z11M0O4 or ZnAhO4, and wherein the loading percentage ranges from 0.10 weight percent to 25.0 weight percent.
  15. 15. The catalyst of claim 14, wherein the impregnated ZnO comprises particles, and wherein the particles have an average dimension ranging from 1 nm to 150 nm.
  16. 16. The catalyst of claim 14, wherein the catalyst has a surface area ranging from 10 m2/g to 200 m2/g and pore volumes ranging from 0.20 cc/g to 0.80 cc/g.
  17. 17. A process for producing a catalyst for the production of ethylene and propylene from syngas, wherein the process comprises: preparing either Z11M0O4 spinel or Z11AI2O4 spinel; impregnating either the ZnMoO4 spinel or Z11AI2O4 spinel with ZnO to provide either zinc oxide impregnated zinc aluminate spinel or zinc oxide impregnated zinc molybdate spinel; and, calcining either the zinc oxide impregnated zinc aluminate- spinel or zinc oxide impregnated zinc molybdate spinel at a temperature ranging from 900 °C to 1,000 °C.
  18. 18. The process of claim 17, wherein the catalyst is zinc oxide impregnated zinc aluminate spinel, and wherein impregnation comprises a solid-state reaction of ZnO and AI2O3 at a temperature ranging from 900 °C to 1,000 °C, and wherein the ZnO and AI2O3 are reacted in molar ratios, and wherein the molar ratios range from 1.01 to 1.35.
  19. 19. The process of claim 17, wherein the catalyst is zinc oxide impregnated zinc molybdate spinel, and wherein impregnation comprises a solid-state reaction of ZnO and MoOs at a temperature ranging from 625 °C to 675 °C, and wherein the ZnO and MoOs are reacted in molar ratios, and wherein the molar ratios range from 1.01 to 1.75.

Description

PROCESS AND CATALYSTS FOR THE PRODUCTION OF ETHYLENE AND PROPYLENE FROM LOW-CARBON SYNGAS FIELD OF THE INVENTION A process and catalysts for efficiently producing ethylene and propylene from low- carbon syngas. BACKGROUND OF THE INVENTION Plastics have undoubtedly revolutionized numerous industries, providing countless benefits and conveniences. However, the production of plastics comes at a significant environmental cost, particularly in relation to carbon emissions. Crackers play a crucial role in the conventional production of plastics. They are responsible for breaking down hydrocarbon molecules derived primarily from fossil fuels, such as crude oil and natural gas. The cracking process releases ethylene and propylene, which serve as the building blocks for the production of various plastic polymers. While crackers are essential in meeting the ever-growing demand for plastics, they come with a significant carbon emissions footprint. The cracking process involves the release of substantial amounts of greenhouse gases, including carbon dioxide and methane, into the atmosphere. These emissions contribute to global warming, climate change, and other environmental concerns. , Multiple factors contribute to the generation of carbon emissions during the cracking process, including: 1. Energy Intensity: Crackers require vast amounts of energy, primarily in the form of fossil fuels, to break down the hydrocarbon molecules. This energy expenditure results in substantial carbon dioxide emissions. 2. Feedstock Composition: The type and quality of feedstock used in crackers can impact the carbon emissions. Fossil fuels with higher carbon content, such as heavier petroleum fractions, tend to release more carbon emissions during cracking. 3. Byproduct Emissions: The cracking process can produce unintended byproducts, including methane, a potent greenhouse gas. Methane emissions arise from leaks, flaring, or incomplete combustion of gases released during the cracking process. The reliance on crackers for ethylene and propylene production poses significant challenges in mitigating carbon emissions within the plastics industry. Limiting or eliminating the use of crackers entirely is not feasible due to the essential role they play in plastics manufacturing. However, a paradigm shift is necessary to adopt more sustainable and eco- friendly alternatives. There are many crackers that are operating today throughout the world. Some of the more well-known crackers in Europe and their locations include: Borealis Olefins Plant (Stenungsund, Sweden); INEOS Cracker Plant (Koln, Germany); LyondellBasell Cracker Plant (Maasvlakte, Netherlands); SABIC Cracker Plant (Gelsenkirchen, Germany); Shell Cracker Plant (Moerdijk, Netherlands); Total Cracker Plant (Antwerp, Belgium); Versalis Cracker Plant (Ferrara, Italy); Yara Cracker Plant (Sluiskil, Netherlands); Polimery Police Ethylene and Propylene Plant (Police, Poland); Borealis Ethylene and Propylene Plant (Stenungsund, Sweden). Some of the more well-known crackers in the United States and their locations include: Chevron Phillips Chemical Company - Cedar Bayou Plant (Texas); ExxonMobil Chemical Company - Baytown Plant (Texas); Dow Chemical Company - Freeport Plant (Texas); Shell Chemical LP - Deer Park Plant (Texas); LyondellBasell Industries - La Porte Plant (Texas); Formosa Plastics Corporation - Point Comfort Plant (Texas); INEOS Olefins & Polymers USA - Chocolate Bayou Plant (Texas); Occidental Chemical Corporation - Ingleside Plant (Texas); Chevron Phillips Chemical Company - Sweeny Plant (Texas); ExxonMobil Chemical Company - Baton Rouge Plant (Louisiana). Some of the more well-known crackers in Asia and the Middle East and their locations include: Qatofin Olefins Plant (Qatar); Borouge Olefins Plant (UAE); Sadara Olefins Plant (Saudi Arabia); Jamnagar Olefins Plant (India); S-Oil Onsan Olefins Plant (South Korea); Formosa Petrochemical Olefins Plant (Taiwan); JGC Olefins Plant (Japan); Zhejiang Petrochemical Olefins Plant (China); Thai Olefins Plant (Thailand); Petronas Melaka Olefins Plant (Malaysia). The most recent advancement in the conversion of syngas to olefins was reported by Mao, et al. (2023). They studied A12Si2O5(OH)4 modified SAPO-34 molecular sieves for the production of C2-C4 olefins. They found that this catalyst converted CO with an efficiency of 50% to C2-C4 olefins with a selectivity of 24%, and a CO2 selectivity of 17%, at an H2/CO ratio of 2.0, a temperature of 400 °C, and a pressure of 450 psi. This 24% olefin selectivity is much lower than the 80% olefin selectivity achieved by the improved catalyst described herein. In addition, the 17% CO2 selectivity is not commercially viable. Yu et al (2022) tested a sodium (Na) promoted ruthenium (Ru) catalyst on SiOa for the conversion of syngas to C2-C5 olefms. Their catalyst had a Ru concentration of 5% and a Ru/Na ratio of 2.0. This catalyst was tested at 260 °C, at a space velocity of 3,000 ml/g/hr, at 1