KR-102963518-B1 - Catalytic cracking system and method for a true circular solution for converting pyrolysis oil produced from recycled waste plastics into virgin olefins and petrochemical intermediates

KR102963518B1KR 102963518 B1KR102963518 B1KR 102963518B1KR-102963518-B1

Abstract

Method and system for the production of raw materials and the production of a true circular polymer. The system and method may include the steps of treating a waste-derived hydrocarbon stream, such as waste plastic pyrolysis oil, with a catalyst mixture in a first reactor system, and treating a fossil-based feedstock with said catalyst mixture in a second reactor system. The catalyst mixture may be supplied to each of the first and second reactor systems from a common catalyst regenerator. An effluent containing fossil-derived hydrocarbon products may be recovered from the second reactor system, and an effluent containing waste-derived hydrocarbon products may be recovered from the first reactor system. After separation, the consumed catalyst from each of the first and second reactor systems may be returned to the common catalyst regenerator.

Inventors

포텔라, 조아큄 안토니오 데, 올리베이라
마리, 라마, 라오
그로튼, 윌리브로드, 에이.

Assignees

루머스 테크놀로지 엘엘씨

Dates

Publication Date: 20260511
Application Date: 20210928
Priority Date: 20201229

Claims (20)

As a method for manufacturing raw materials for the production of truly circular polymers, The above method is: A step of treating waste plastic pyrolysis oil with a catalyst mixture in a first reactor system; A step of treating a fossil-based feedstock with the catalyst mixture in a second reactor system; A step of supplying the catalyst mixture from a common catalyst regenerator to each of the first and second reactor systems; A step of recovering an effluent containing fossil-based hydrocarbon products from the second reactor system; A step of recovering an effluent containing a waste-derived hydrocarbon product from the first reactor system; and A step of returning the spent catalyst from each of the first and second reactor systems to the common catalyst regenerator; Including; Here, the catalyst consumed from the second reactor system is: An additive-type cracking catalyst or a mixture of additive-type cracking catalysts selected from the group consisting of medium-pore zeolites and pentasil family zeolites; and A contaminant trapping additive or a mixture of contaminant trapping additives selected from the group consisting of MgO, CaO , CeO2 , MgTiO3 , CaTiO3 , Li2Ti2O7 and ZnTiO3 , Ca/Mg, boron , or rare earth-based trapping additives, having a higher affinity for the captured contaminant than the additive-type decomposition catalyst or a mixture of the additive-type decomposition catalysts; A manufacturing method comprising both.
In paragraph 1, A manufacturing method further comprising the step of separating and maintaining the fossil-based hydrocarbon product recovered from the first reactor system from the waste-derived hydrocarbon product recovered from the second reactor system.
In paragraph 2, A manufacturing method further comprising the step of supplying the olefin fraction recovered from the above waste-derived hydrocarbon product to a polymerization system to produce a circulating polymer.
In any one of paragraphs 1 through 3, A manufacturing method further comprising the step of producing waste plastic pyrolysis oil by pyrolyzing a waste stream containing plastic, tire, or other polymeric material.
In any one of paragraphs 1 through 3, A manufacturing method further comprising the step of producing a circulating polymer by directly or indirectly supplying one or more of the above-mentioned waste-derived hydrocarbon products, or a waste-derived monomer produced from the treatment of the above-mentioned waste-derived hydrocarbon products, to a polymerization process.
As a method of converting waste plastic into a feedstock for manufacturing plastic, The above method is: A step of pyrolyzing waste polymeric feedstock to produce waste plastic pyrolysis oil; A step of regenerating a catalyst mixture in a catalyst regenerator, wherein the catalyst mixture comprises a first catalyst and a second catalyst; A step of supplying a portion of the catalyst mixture to a first reactor system; A step of supplying a portion of the above catalyst mixture to a second reactor system; In the first reactor system, a step of contacting a fossil-based feedstock with the catalyst mixture to decompose a portion of the fossil-based feedstock to produce a first effluent comprising a fossil-derived olefin, a first catalyst, and a second catalyst; In the above second reactor system: A step of decomposing a portion of the waste plastic pyrolysis oil by contacting the waste plastic pyrolysis oil with a concentrated catalyst mixture in a reactor, wherein the concentrated catalyst mixture comprises a portion of the catalyst mixture supplied to the second reactor system and an additional second catalyst, so that the concentration of the second catalyst in the catalyst mixture in the second reactor system is higher than in the first reactor system or the catalyst regenerator, and the contact produces a second reactor effluent comprising waste-derived olefins and other hydrocarbons, the first catalyst, and the second catalyst; A step of separating the effluent from the second reactor to produce a first stream comprising the first catalyst and the waste-derived olefin and other hydrocarbons, and a second stream comprising the second catalyst, wherein the catalyst consumed is: An additive-type cracking catalyst or a mixture of additive-type cracking catalysts selected from the group consisting of medium-pore zeolites and pentasil family zeolites; and A contaminant trapping additive or a mixture of contaminant trapping additives selected from the group consisting of MgO, CaO , CeO2 , MgTiO3 , CaTiO3 , Li2Ti2O7 and ZnTiO3 , Ca/Mg, boron , or rare earth-based trapping additives, having a higher affinity for the captured contaminants than the additive-type decomposition catalyst or a mixture of the additive-type decomposition catalysts; comprising both; A step of supplying the second stream as an additional second catalyst to the second reactor, thereby concentrating the second catalyst within the second reactor system; A step of separating the first effluent to recover (i) a mixture of the consumed first catalyst and the consumed second catalyst and (ii) a first reactor system product stream comprising the fossil-derived olefin; A step of separating the first stream to recover (i) the consumed first catalyst and (ii) a second reactor system product stream comprising the waste-derived olefin and other waste-derived hydrocarbons; and A step of supplying (i) a mixture of the consumed first catalyst and the consumed second catalyst and (ii) each of the consumed first catalysts to the catalyst regenerator; A method including
In paragraph 6, A method comprising one or more selected from the group consisting of amorphous silica alumina, Y-type zeolite, X-type zeolite, zeolite beta, zeolite MOR, mordenite, fauzashite, nanocrystalline zeolite and MCM mesoporous material.
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In paragraph 6 or 7, A step of supplying the first reactor system product stream to a first fractionation system to separate the first reactor system product stream and recover two or more fossil-derived hydrocarbon fractions; and A step of supplying the second reactor system product stream to a second fractionation system to separate the second reactor system product stream and recover two or more waste-derived hydrocarbon fractions; A method that further includes.
In Paragraph 9, A method further comprising the step of producing a circulating polymer by directly or indirectly supplying a monomer produced from the treatment of one or more of the two or more waste-derived hydrocarbon fractions, or one or more of the two or more waste-derived hydrocarbon fractions, to a polymerization process.
In Paragraph 10, The above pyrolysis comprises pyrolyzing a waste polymer feedstock to produce waste plastic pyrolysis oil having one or more contaminants selected from the group consisting of iron, calcium, copper, potassium, magnesium, sodium, silicon, titanium, zinc, and chlorine; The catalyst mixture comprising a first catalyst and a second catalyst comprises a second catalyst configured to capture one or more contaminants; The contact in the above second reactor system is: The above waste plastic pyrolysis oil is contacted with a concentrated catalyst mixture in a first stage reactor to remove contaminants from the waste plastic pyrolysis oil and decompose a portion of the waste plastic pyrolysis oil, wherein the concentrated catalyst mixture comprises a portion of the catalyst mixture supplied to the second reactor system and an additional second catalyst, so that the concentration of the second catalyst in the catalyst mixture in the first stage reactor is higher than in the catalyst regenerator, and the contact produces a first stage reactor effluent comprising treated waste plastic pyrolysis oil with reduced contaminant concentration, the first catalyst, and the second catalyst containing captured contaminants; Separating the effluent from the first stage reactor to produce a first stream comprising the first catalyst and treated waste plastic pyrolysis oil with reduced contaminant concentration, and a second stream comprising the second catalyst; Supplying the second stream as an additional second catalyst to the first stage reactor, thereby concentrating the second catalyst within the first stage reactor; and Supplying the first stream to a second stage reactor to decompose the treated waste plastic pyrolysis oil and recovering the second stage reactor effluent containing the consumed catalyst and waste-derived olefins and other waste-derived hydrocarbons; Includes, A method comprising, wherein separating the first stream comprises separating the second stage reactor effluent to recover (i) the consumed catalyst and (ii) the second stage reactor system product stream containing the waste-derived olefin and other waste-derived hydrocarbons.
In Paragraph 11, A method further comprising the step of separating and maintaining the fossil-derived hydrocarbon fraction recovered from the first reactor system from the waste-derived hydrocarbon product recovered from the second reactor system.
In Paragraph 11, A method further comprising the step of supplying one or more hydrocarbon fractions recovered from the waste-derived hydrocarbon product to the first reactor of the second reactor system.
In Paragraph 11, A method further comprising the step of supplying one or more hydrocarbon fractions recovered from the waste-derived hydrocarbon product to the second reactor of the second reactor system.
In Paragraph 11, A method further comprising the step of withdrawing a portion of the second catalyst from the first reactor.
As a method for converting waste plastic material into monomers for the production of circular polymers, The above method is: A step of pyrolyzing a waste polymeric feedstock to produce waste plastic pyrolysis oil having one or more contaminants (concentrations) selected from the group consisting of iron, calcium, copper, potassium, magnesium, sodium, silicon, titanium, zinc, and chlorine; A step of regenerating a catalyst mixture in a catalyst regenerator, wherein the catalyst mixture comprises a first catalyst and a second catalyst, and the second catalyst is configured to capture one or more contaminants; A step of supplying a portion of the catalyst mixture to a first reactor system; A step of supplying a portion of the above catalyst mixture to a second reactor system; In the above-mentioned first reactor system: A step of contacting the waste plastic pyrolysis oil in a first reactor with a concentrated catalyst mixture to remove contaminants from the waste plastic pyrolysis oil and decompose a portion of the waste plastic pyrolysis oil, wherein the concentrated catalyst mixture comprises a portion of the catalyst mixture supplied to the first reactor system and an additional second catalyst, so that the catalyst mixture in the first reactor system has a higher concentration of the second catalyst than in the catalyst regenerator, and the contact produces a first reactor effluent comprising treated waste plastic pyrolysis oil having a reduced contaminant concentration, the first catalyst, and the second catalyst containing captured contaminants; A step of separating the effluent from the first reactor to produce a first stream comprising the first catalyst and the treated waste plastic pyrolysis oil having a reduced contaminant concentration, and a second stream comprising the second catalyst; A step of supplying the second stream to the first reactor as an additional second catalyst, thereby concentrating the second catalyst within the first reactor system; and A step of supplying the above first stream to a separation system to recover a first separated effluent containing a consumed first catalyst and a second separated effluent containing the treated waste plastic pyrolysis oil; A step of supplying the second separated effluent to a fractionation system to fractionate the treated waste plastic pyrolysis oil into three or more hydrocarbon fractions, including a light olefin fraction, a naphtha fraction, and a treated pyrolysis oil fraction; A step of supplying at least one of the above naphtha fraction and the above treated pyrolysis oil fraction to a second reactor system, In the second reactor system, a step of contacting at least one of the naphtha fraction and the heavy oil fraction with the catalyst mixture to decompose a portion of the hydrocarbons therein to produce a second reactor system effluent comprising a waste-derived olefin, a first catalyst, and a second catalyst, wherein the consumed catalyst is: An additive-type cracking catalyst or a mixture of additive-type cracking catalysts selected from the group consisting of medium-pore zeolites and pentasil family zeolites; and A contaminant trapping additive or a mixture of contaminant trapping additives selected from the group consisting of MgO, CaO , CeO2 , MgTiO3 , CaTiO3 , Li2Ti2O7 and ZnTiO3 , Ca/Mg, boron , or rare earth-based trapping additives, having a higher affinity for the captured contaminants than the additive-type decomposition catalyst or a mixture of the additive-type decomposition catalysts; comprising both; A step of separating the effluent of the second reactor system to recover (i) a mixture of the consumed first catalyst and the consumed second catalyst and (ii) a second reactor system product stream comprising the waste-derived olefin; and (i) a mixture of the consumed first catalyst and the consumed second catalyst and (ii) each of the first separated effluents containing the consumed first catalyst is supplied to the catalyst regenerator; A method including
As a method for manufacturing raw materials for producing truly circular polymers, The above method is: A step of treating a waste polymer mixture in a first reactor system comprising a first stage reactor and a second stage reactor, wherein the treatment of the waste polymer mixture is: Supplying the above waste polymer mixture to the above first stage reactor to pyrolyze the polymer therein and recover the pyrolyzed effluent; Feeding a mixture of waste-derived plastic pyrolysis oil and catalyst to the second stage reactor to decompose hydrocarbons therein and recovering effluent containing decomposed hydrocarbons; Includes; A step of supplying the pyrolyzed effluent from the first stage reactor and the effluent from the second stage reactor to a first fractionation system to separate the effluent into two or more waste-derived hydrocarbon streams comprising the waste-derived plastic pyrolysis oil and one or more waste-derived olefin fractions; A step of treating a fossil-based feedstock with the catalyst mixture in a second reactor system; A step of supplying the catalyst mixture from a common catalyst regenerator to each of the first and second reactor systems; A step of recovering an effluent containing fossil-based hydrocarbon products from the second reactor system; A step of feeding the effluent containing the above-mentioned fossil-based hydrocarbon product to a second fractionation system; A step of returning the catalyst consumed from each of the first and second reactor systems to the common catalyst regenerator, wherein the consumed catalyst is: An additive-type cracking catalyst or a mixture of additive-type cracking catalysts selected from the group consisting of medium-pore zeolites and pentasil family zeolites; and A contaminant trapping additive or a mixture of contaminant trapping additives selected from the group consisting of MgO, CaO , CeO2 , MgTiO3 , CaTiO3 , Li2Ti2O7 and ZnTiO3 , Ca/Mg, boron , or rare earth-based trapping additives, having a higher affinity for the captured contaminant than the additive-type decomposition catalyst or a mixture of the additive-type decomposition catalysts; comprising both; and A step of separating and maintaining the fossil-based hydrocarbon product recovered from the first reactor system from the waste-derived hydrocarbon product recovered from the second reactor system; A manufacturing method comprising
In Paragraph 17, The catalyst mixture comprises a first catalyst and a second catalyst, and the second stage reactor is a catalyst-concentration reactor system, and The above method is: A step of recovering the second stage reactor effluent containing the catalyst mixture and decomposed hydrocarbons; A step of separating the effluent from the second stage reactor to produce a first stream containing the first catalyst and decomposed hydrocarbon, and a second stream containing the second catalyst; A step of separating the first stream to recover (i) the consumed catalyst and (ii) the second stage reactor effluent supplied to the first fractionation system; and A step of supplying the second stream to the second stage reactor, thereby concentrating the second catalyst circulating within the second reactor to a concentration greater than that of the catalyst mixture received from the regenerator; A manufacturing method comprising
In any one of paragraphs 16 through 18, Waste polymer pyrolysis oil comprises one or more thermoplastics selected from the group consisting of polystyrene, polypropylene, polyphenylene sulfide, polyphenylene oxide, polyethylene, polyetherimide, polyether ether ketone, polyoxymethylene, polyether sulfone, polycarbonate, polybenzimidazole, polylactic acid, nylon, acrylonitrile-butadiene-styrene (ABS) polymer, and polymethyl methacrylic acid (PMMA); and one or more thermosetting resins formed from monomers comprising one or more of acrylic, polyester, vinyl ester, epoxy, urethane, urea, and isocyanate; A method derived from one or more unsaturated or saturated elastomers selected from the group consisting of polybutadiene, isoprene, chloroprene, styrene-butadiene, nitrile, and ethylene vinyl acetate, or comprising a waste polymeric feed or waste polymer mixture.
As a system for manufacturing raw materials for manufacturing true circular polymers, The above system is: A first reactor system containing a catalyst mixture and configured to process waste plastic pyrolysis oil; A second reactor system configured to process fossil-based feedstocks with the above catalyst mixture; Feed lines for supplying the catalyst mixture from a common catalyst regenerator to each of the first and second reactor systems; Flow lines for recovering effluent containing fossil-based hydrocarbon products from the second reactor system; A flow line for recovering an effluent containing a waste-derived hydrocarbon product from the first reactor system; and A flow line for returning the catalyst consumed from each of the first and second reactor systems to the common catalyst regenerator, wherein the consumed catalyst is: An additive-type cracking catalyst or a mixture of additive-type cracking catalysts selected from the group consisting of medium pore zeolites and pentasil family zeolites; and A contaminant trapping additive or a mixture of contaminant trapping additives selected from the group consisting of MgO, CaO , CeO2 , MgTiO3 , CaTiO3 , Li2Ti2O7 and ZnTiO3 , Ca/Mg, boron , or rare earth-based trapping additives, having a higher affinity for the captured contaminants than the additive-type decomposition catalyst or a mixture of the additive-type decomposition catalysts; comprising both; A system including

Description

Catalytic cracking system and method for a true circular solution for converting pyrolysis oil produced from recycled waste plastics into virgin olefins and petrochemical intermediates Embodiments of the present disclosure generally relate to the recycling of waste materials, such as plastic waste. More specifically, embodiments of the present invention relate to systems and methods that provide a truly circular solution for returning end-of-life plastic materials to olefins and chemical intermediates that may be useful for manufacturing new plastic materials and compositions. Thermal pyrolysis of waste plastics recovers valuable carbon and hydrogen elements from used plastics by converting them into valuable molecules that can be upgraded into new chemical intermediates, and subsequently into new consumer materials. Because this process has the potential to repeatedly recycle used plastics into new materials, the polymers produced through this process are referred to as circular polymers. This results in less plastic waste in landfills and the environment and replaces the consumption of equivalent amounts of fossil-derived feedstocks. However, there are several factors affecting the economic viability of this recycling pathway. Liquid oil products derived from the pyrolysis of plastic waste may not be suitable for feeding into a liquid steam cracker or may require treatment or conditioning before being fed therein. High levels of nitrogen, chlorine, and mono- and di-olefins, as well as contaminants such as iron and calcium, may require further review or adjustment before being added directly as a feed to the steam cracker. To prepare for this feedstock steam cracking, a hydrogenation step may be required as a potential solution, for example, by saturating the diolefins first and then the mono-olefins before hydrogenation. However, such a step requires hydrogen supply, the addition of multiple high-pressure reactors, and associated investment (if vessels are not available) and operating costs. Another option for this approach is to dilute the negative effects of the pyrolysis oil properties by mixing it with a conventional naphtha feedstock in the cracker. However, since the olefins and petrochemical intermediates generated from the cracking of pyrolysis oil will contribute only a tiny fraction of the final olefin product when mixed with those from conventional naphtha, they require certification of having a specific circular content based on material balance methodology. However, co-mingling with new hydrocarbon feedstocks is merely a transitional solution and not a viable long-term solution for a circular plastics economy. Another factor affecting the feasibility of plastic recycling is the limited volume of waste plastic feedstock available through cost-effective channels. Due to infrastructure and logistical constraints, the amount of plastic accessible for recycling is limited at each geographical location. Most currently available plastic pyrolysis process technologies are designed to process less than 50 tons/day of plastic per train. This is driven not only by limitations on scaling up but also by the availability of waste plastic. At this scale, if the pyrolysis oil produced from one of these units (equivalent to 13,000 metric tons per year) were fed to a global naphtha cracker, it would account for only 2% by weight of the total feed for a single steam cracking heater. The capacity of waste plastic pyrolysis units is expected to grow to a much larger size in the future, ranging from 1,000 to 2,000 tons/day of plastic feedstock. However, even at these higher capacities, the contribution of the generated feedstock to the naphtha cracker would be only a fraction of the total feed for the steam cracker. Therefore, the generated product will not be 100% cyclic, but the generated product will have a very small percentage of cyclic components. The cost of acquiring plastic waste and the costs associated with sorting and washing it into feedstock suitable for pyrolysis are also high. Many proposed processes are inflexible to feedstock fluctuations and contaminant content, which requires large amounts of sorting and washing to produce usable feedstock. To address issues related to the quality and contamination of pyrolysis oil feedstocks for liquid naphtha crackers, many companies use expensive, clean, and pure recycled plastic feedstocks, such as pure PE or PP, in the pyrolysis unit, or hydroprocess and hydrotreat them, or use dilution effects by blending the pyrolysis oil with much larger volumes of fossil-derived naphtha. However, even at higher capacities, such as about 3,800 barrels per day, hydroprocessing and hydrotreating the pyrolysis oil to produce feedstock suitable for a typical steam cracking unit may still be uneconomical. Another factor affecting plastic recycling is that the design throughput capacity of plastic pyrolysis units is typically small, failing to leverage economies of scale, and