Process for producing polyvinyl alcohol and polyvinyl acetal that have reproduction component

Abstract

To provide a process for producing polyvinyl alcohol (r-PVOH) having a reproduction component, and optionally polyvinyl acetal.SOLUTION: A process for producing polyvinyl alcohol having a reproduction component includes the steps of: (a) synthesizing vinyl acetate by reacting a first ethylene and a first acetic acid / anhydride with oxygen; (b) polymerizing at least a part of the vinyl acetate to thereby produce a polyvinyl acetate; and (c) reacting at least a part of the polyvinyl acetate with a first alcohol to thereby produce a polyvinyl alcohol (PVOH). The PVOH includes a reproduction component from one or more of the following raw materials: (i) a waste plastic; (ii) a reproduction component ethylene (r-ethylene); (iii) a reproduction component alcohol (r-alcohol); and / or (iv) a reproduction component acetic acid / anhydride (r-acetic acid / anhydride).SELECTED DRAWING: None

Description

[Background technology]

[0001]

[0001] Polyvinyl alcohol is an important chemical used in a wide variety of applications. For example, polyvinyl alcohol is used as a thickener or protective colloid for high viscosity solutions where low solids content is desired. Polyvinyl alcohol is also used in paper and textile sizing applications and as an intermediate in the production of polymers such as polyvinyl butyral, which is used as an adhesive interlayer in forming laminated safety glass.

[0002]

[0002] Although the demand for recycled chemical products is ever-increasing, there is no clear method for recycling polyvinyl alcohol by mechanical recycling. Therefore, there is a need for a commercial process to produce the recycled component polyvinyl alcohol. Summary of the Invention

[0003]

[0003] In one aspect, the present technology relates to a process for producing polyvinyl alcohol (r-PVOH) having recycled content, the process comprising: (a) synthesizing vinyl acetate by reacting a first ethylene and a first acetic acid / anhydride with oxygen; (b) polymerizing at least a portion of the vinyl acetate to produce polyvinyl acetate; and (c) reacting at least a portion of the polyvinyl acetate with a first alcohol to produce polyvinyl alcohol (PVOH), wherein the PVOH comprises recycled content from one or more of the following raw materials: (i) waste plastic, (ii) recycled ethylene (r-ethylene), (iii) recycled alcohol (r-alcohol), and / or (iv) recycled acetic acid / anhydride (r-acetic acid / anhydride).

[0004]

[0004] In one aspect, the present technology relates to a process for producing polyvinyl acetal having a recycled component, the process comprising: (a) reacting a first ethylene and a first acetic acid / anhydride with a first oxygen to produce vinyl acetate; (b) polymerizing at least a portion of the vinyl acetate to produce polyvinyl acetate; (c) subjecting at least a portion of the polyvinyl acetate to alcoholysis with ethanol to produce polyvinyl alcohol; and (d) acetalizing at least a portion of the polyvinyl alcohol with a first aldehyde to produce polyvinyl acetal, wherein the polyvinyl acetal comprises a recycled component from one or more of the following raw materials: (i) waste plastic, (ii) recycled component synthesis gas (r-syngas), (iii) recycled component ethylene (r-ethylene), (iv) recycled component carbon monoxide, and (v) recycled component acetic acid / anhydride (r-acetic acid / anhydride). [Brief explanation of the drawings]

[0005] [Figure 1]

[0005] A block flow diagram showing the major steps and equipment of a process for producing recycled polyvinyl alcohol (r-PVOH) and optionally recycled polyvinyl acetal (r-PVAc), where the r-PVOH (and r-PVAc) have been physically recycled from one or more raw materials. [Figure 2]

[0006] 1 is a block flow diagram showing the major steps and equipment of a process for producing recycled polyvinyl alcohol (r-PVOH) and optionally recycled polyvinyl acetal (r-PVAc), where the r-PVOH (and r-PVAc) have a credit-based recycled content from one or more feedstock materials. [Figure 3]

[0007] 1 is a block flow diagram showing the major steps and equipment of a process for producing recycled polyvinyl alcohol (r-PVOH) and optionally recycled polyvinyl acetal (r-PVAc), where the r-PVOH (and r-PVAc) have both physical and credit-based recycled components from one or more source materials. DETAILED DESCRIPTION OF THE INVENTION

[0006]

[0008] The present inventors have discovered new methods and systems for producing polyvinyl alcohol (PVOH), and optionally polyvinyl acetal, with recycled content. More particularly, the present inventors have discovered a process and system for producing PVOH that utilizes recycled content from waste materials, such as waste plastics, in the PVOH in a manner that promotes recycling of the waste plastics, resulting in PVOH with a significant amount of recycled content.

[0007]

[0009] Generally, PVOH can be formed via the oxidative addition reaction of ethylene with acetic acid / anhydride in the presence of oxygen to produce vinyl acetate. At least a portion of the vinyl acetate is then polymerized to form polyvinyl acetate, which can then be hydrolyzed with an alcohol (usually methanol or ethanol) to produce polyvinyl alcohol. In some embodiments, polyvinyl alcohol can then be condensed with an aldehyde to form polyvinyl acetal. PVOH can contain recycled components from one or more source materials, including, for example, waste plastics, recycled ethylene (r-ethylene), recycled carbon monoxide (r-CO), recycled acetic acid / anhydride (r-acetic acid / anhydride), and recycled alcohol (r-alcohol). When PVOH is reacted with an aldehyde to form polyvinyl acetal (PVAc), the PVAc can contain recycled components from one or more source materials, including, for example, waste plastics, r-ethylene, r-acetic acid / anhydride, r-CO, r-alcohol (r-methanol or r-ethanol), and r-synthesis gas. The recycled content in the PVOH (and PVAc, if produced) may be a physically recycled content, derived directly from at least one of these streams, and / or the recycled content may be a credit-based recycled content, utilized from one or more of these feed streams into a target stream in the PVOH (or PVAc) process.

[0008]

[0010] Referring now to Figure 1, one embodiment of a process and equipment for forming PVOH with physically (directly) recycled content is shown. The recycled content in the PVOH may be derived from the pyrolysis and cracking of waste plastics and / or carbon reforming of recycled hydrocarbon-containing feed (r-HC). The resulting PVOH can have a total recycled content of at least 5%, at least 10%, at least 25%, at least 50%, or at least 65%, and / or less than 99%, less than 95%, less than 90%, or less than 85%.

[0009]

[0011] As shown in Figure 1, waste plastics can be pyrolyzed to form recycled pyrolysis gas (r-pygas) and recycled pyrolysis oil (r-pyoil). All or a portion of the r-pygas and / or r-pyoil can be introduced into a cracking facility where it can be used to produce recycled olefins, such as recycled ethylene (r-ethylene). The feed to the cracking facility can include only r-pyoil and / or r-pygas, or it can also include non-recycled hydrocarbons, such as naphtha (e.g., C5-C22) or light hydrocarbons (e.g., C2-C5).

[0010]

[0012] As shown in Figure 1, all or a portion of the recycled component ethylene from cracking and / or pyrolysis can be used in an oxidative addition reaction with acetic acid / anhydride and oxygen to form recycled component vinyl acetate (r-vinyl acetate). In one embodiment, at least a portion of the feed to the oxidative addition can include non-regenerated component ethylene. In some embodiments, the ethylene used in the addition reaction is at least 50%, at least The recycled content may be at least 75%, at least 90%, or 100% recycled content.

[0011]

[0013] In some embodiments, the PVOH production facility may also include carbon reforming of a renewable hydrocarbon-containing feed stream (r-HC) to produce a renewable synthesis gas (r-syngas) having a physically renewable component and renewable carbon monoxide (r-CO). In one embodiment, the feed to the carbon reforming may include both renewable feed components (e.g., waste plastics) and non-renewable feed components (e.g., coal, liquid hydrocarbons, and / or gaseous hydrocarbons). In one embodiment, the carbon reforming is a partial oxidation gasification fed with coal and waste plastics. In another embodiment, the carbon reforming is a plasma gasification of a feed consisting primarily of waste plastics. In yet another embodiment, the carbon reforming is a partial oxidation gasification fed with non-renewable liquid or gaseous hydrocarbons and renewable pyrolysis oil produced by the pyrolysis of waste plastics. In some embodiments, the carbon reforming may include catalytic reforming, and in other embodiments, the carbon reforming may include steam reforming.

[0012]

[0014] In some embodiments, at least a portion of the r-syngas from carbon reforming can be reacted in the presence of a catalyst to form regenerant component methanol (r-methanol). This r-methanol can then undergo carbonylation to form regenerant component acetic acid / anhydride (r-acetic acid / anhydride). All or a portion of the acetic acid / anhydride used to produce r-vinyl acetate can be r-acetic acid / anhydride formed from r-syngas (and / or r-methanol). In some embodiments, at least a portion of the syngas, methanol, and / or acetic acid / anhydride can be non-regenerant component materials. In some embodiments, the syngas, methanol, and / or acetic acid can each comprise at least 50%, at least 75%, at least 90%, or 100% regenerant component.

[0013]

[0015] As shown in FIG. 1 , r-vinyl acetate formed in the PVOH production facility can then be polymerized to form recycled component polyvinyl acetate (r-polyvinyl acetate), which can be further reacted with an alcohol (e.g., ethanol or methanol) to form recycled component polyvinyl alcohol (r-polyvinyl alcohol). In one embodiment, at least a portion of the alcohol can comprise a recycled component alcohol. For example, if ethanol is used in the alcoholysis reaction, all or a portion of the ethanol can be formed by hydrolysis of recycled component ethylene (r-ethylene), which can be derived from cracking and / or thermal cracking as shown in FIG. 1 . Other suitable processes for producing r-ethanol, such as hydrogenation of acetaldehyde, can also be used. In some cases, at least a portion of the acetaldehyde (a by-product of the vinyl acetate-producing reaction) in the PVOH facility can be used to form r-ethanol. Similarly, if methanol is used in the alcoholysis of r-polyvinyl acetate, all or a portion of the methanol can be derived from the catalytic synthesis of r-syngas, as described above.

[0014]

[0016] After alcoholysis, the resulting r-PVOH stream can have at least 5%, at least 10%, at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, at least 55%, or at least 65%, and / or 100%, or less than 99%, less than 95%, less than 90%, less than 85%, less than 80%, less than 75%, or less than 70% recycled content.

[0015]

[0017] The amount of physically recycled content in r-PVOH can be determined by tracing the amount of recycled material along a chemical pathway that starts with waste plastic and ends with PVOH. The chemical pathway includes all chemical reactions between the starting material (e.g., waste plastic) and PVOH, and other In Figure 1, the chemical pathways include pyrolysis, cracking, carbon reforming, catalytic synthesis, carbonylation, oxidative addition, polymerization, and alcoholysis.

[0016]

[0018] In one or more embodiments, a conversion rate can be associated with each step along a chemical pathway. The conversion rate describes the amount of recycled component that is converted or lost at each step along the chemical pathway. For example, the conversion rate can describe the conversion, yield, and / or selectivity of a chemical reaction along the chemical pathway.

[0017]

[0019] The amount of recycled content utilized in r-PVOH can be determined using one of a variety of methods for quantifying, tracking, and accounting for recycled content in various materials in various processes. One suitable method, known as "mass balance," quantifies, tracks, and accounts for recycled content based on the mass of recycled content in the process. In certain embodiments, the method for quantifying, tracking, and accounting for recycled content is overseen by a certification body that verifies the accuracy of the method and provides certification for the utilization of recycled content in r-PVOH.

[0018]

[0020] In some embodiments, as shown as an option in Figures 1-3, all or a portion of the r-PVOH can be further condensed (e.g., acetalized) with an aldehyde to form a recycled polyvinyl acetal (r-PVAc). The aldehyde can be a C2-C24, C3-C10, or C4-C6 aldehyde, or can include, for example, butyraldehyde. In some embodiments, the aldehyde can include recycled components (e.g., from hydroformylation of olefins using recycled syngas, as shown in Figure 1) or can include non-recycled aldehydes. Although not shown in Figure 1, all or a portion of the olefins may also have recycled components, and in some cases may be derived from the thermal cracking and decomposition of syngas (e.g., recycled propylene). When the aldehyde used is a C4 aldehyde, the resulting polyvinyl acetal can include polyvinyl butyral.

[0019]

[0021] Referring now to Figure 2, an embodiment is shown in which r-PVOH does not have a physical regeneration component but has a credit-based regeneration component. In the process and system shown in Figure 2, r-acetic acid / anhydride and r-ethylene are not directly fed to the vinyl acetate synthesis reaction, and r-methanol is not used for alcoholysis. In addition, r-ethylene is not directly used to produce r-ethanol for alcoholysis, and r-CO is not directly used to form acetic acid / anhydride.

[0020]

[0022] Instead, the recycled component credits from the recycled component streams shown in FIG. 2 (e.g., r-ethylene, r-methanol, r-acetic acid / anhydride, r-CO2, and, if used, r-synthesis gas) may be attributed to one or more streams within the production facility. For example, recycled component credits from one or more of the above streams may be attributed to the ethylene and / or acetic acid / anhydride fed to the vinyl acetate synthesis step, the ethanol or methanol fed to the alcoholysis step, and / or the syngas fed to the hydroformylation step (if implemented). In this manner, the r-ethylene, r-methanol, r-acetic acid / anhydride, r-CO2, and, if used, the r-synthesis gas, each serve as the "feedstock" for the recycled component credits, and the ethylene and / or acetic acid / anhydride fed to the vinyl acetate synthesis step, the ethanol or methanol fed to the alcoholysis step, and / or the syngas fed to the hydroformylation step (if implemented) each serve as the "target material" to which the recycled component credits are attributed.

[0021]

[0023] In one or more embodiments, the source material has a physical regenerating component and the target material has a For example, the source material can have at least 10%, at least 25%, at least 50%, at least 75%, at least 90%, at least 99%, or 100% physically recycled content, and / or the target material can have less than 100%, less than 99%, less than 90%, less than 75%, less than 50%, less than 25%, less than 10%, or less than 1% physically recycled content.

[0022]

[0024] The ability to attribute recycled content credits from source materials to target materials eliminates the requirement for co-location of facilities that produce source materials (with physical recycled content) with facilities that produce PVOH (or polyvinyl acetal). This allows a chemical recycling facility / site at one location to process waste into one or more recycled content source materials and then apply recycled content credits derived from those source materials to one or more target materials being processed at an existing commercial facility located away from the chemical recycling facility / site. Furthermore, the use of recycled content credits allows different entities to produce the source material and the r-PVOH. This allows for efficient use of existing commercial assets to produce r-PVOH. In one or more embodiments, the feedstock material is generated at a facility / site that is at least 0.16 km (0.1 mile), at least 0.5 km (0.80 km), at least 1 mile (1.60 km), at least 5 miles (8.04 km), at least 16.09 km (10 miles), at least 80.46 km (50 miles), at least 160.93 km (100 miles), at least 804.67 km (500 miles), or at least 1609.34 km (1000 miles) away from the facility / site where the target material is used to produce PVOH.

[0023]

[0025] Attribution of recycled component credits from a source material (e.g., r-ethylene produced by pyrolysis / cracking of waste plastics) to a target material (e.g., ethylene fed to a vinyl acetate synthesis step) can be achieved by directly transferring the recycled component credits from the source material to the target material. Alternatively, as shown in Figure 2, recycled component credits can be utilized for PVOH (or polyvinyl acetal) from either waste plastics, recycled component hydrocarbon feed (r-HC) to the carbon reforming step, r-syngas, r-CO2, r-methanol, r-ethylene, and / or r-acetic acid / anhydride via a recycled component inventory. The recycled component inventory can be a digital inventory or database used to record and track recycled components of various materials at various sites over various time periods.

[0024]

[0026] When a recycled component inventory is used, recycled component credits from feedstock materials with physical recycled components (e.g., waste plastics, r-HC, r-ethylene, r-syngas, r-CO, r-methanol, and / or r-acetic acid / anhydride in FIG. 2) are recorded in the recycled component inventory. The recycled component inventory can also contain recycled component credits from other feedstocks and other time periods. In one embodiment, recycled component credits in the recycled component inventory can only be allocated to target materials with the same or similar composition as the feedstock. For example, as shown in FIG. 2, recycled component credits recorded in the recycled component inventory from r-ethylene by pyrolysis / cracking can be allocated to ethylene fed to synthesis. This is because the two ethylene streams have the same or similar composition. However, recycled component credits from r-ethylene cannot be allocated to methanol fed to alcoholysis. This is because the feedstock and target materials are not the same or similar.

[0025]

[0027] In some embodiments, all or a portion of the recycled component credits may be utilized for one or more target materials (e.g., syngas) upon receipt of one or more waste plastic-containing materials at the facility. That is, prior to utilizing the credit-based recycled component for the target material, the waste plastic (or recycled component hydrocarbon feed) may be utilized. Processing is not required. Instead, waste plastics (or waste plastic-containing materials) may be received at a facility, allowing recycled content credits to be utilized for one or more target materials. However, in most cases, such waste plastics are subsequently processed at a facility within 30, 60, or 90 days to produce one or more target materials. Once recycled content credits are attributed to the target material (e.g., ethylene and / or acetic acid / anhydride fed to catalytic synthesis and / or methanol or ethanol fed during alcoholysis in Figure 2), the credit-based recycled content amount assigned to PVOH is calculated by tracing the recycled content along a chemical pathway from the target material to PVOH. The chemical pathway includes all chemical reactions and other processing steps (e.g., separations) between the target material and PVOH, and a conversion rate can be associated with each step along the chemical pathway of the credit-based recycled content. The conversion rate describes the amount of recycled content converted or lost at each step along the chemical pathway. For example, the conversion rate can describe the conversion, yield, and / or selectivity of a chemical reaction along a chemical pathway.

[0026]

[0028] As with physical recycled content, the amount of credit-based recycled content utilized in r-PVOH can be determined using one of a variety of methods, such as mass balance, to quantify, track, and account for recycled content in various materials in various processes. In certain embodiments, the method for quantifying, tracking, and accounting for recycled content is overseen by a certification body that verifies the accuracy of the method and provides certification for the utilization of recycled content in r-PVOH.

[0027]

[0029] 4 can have a credit-based recycled content of 25-90%, 40-80%, or 55-65% and a physical recycled content of less than 50%, less than 25%, less than 10%, less than 5%, or less than 1%. In certain embodiments, the PVOH can have a credit-based recycled content of 10-80%, 20-75%, or 25-70% from one or more of r-syngas, r-CO2, r-methanol, r-ethylene, and r-acetic acid / anhydride, respectively.

[0028]

[0030] In one or more embodiments, the recycled content of the r-PVOH product can include both physical recycled content and credit-based recycled content. For example, the r-PVOH can have at least 10%, at least 20%, at least 30%, at least 40%, or at least 50% physical recycled content and at least 10%, at least 20%, at least 30%, at least 40%, or at least 50% credit-based recycled content. As used herein, the term "total recycled content" refers to the cumulative amount of physical recycled content and credit-based recycled content from all feedstocks.

[0029]

[0031] FIG. 3 illustrates several embodiments of r-PVOH production processes and systems, in which a physical recycled component and a credit-based recycled component are attributed to the r-PVOH. Any combination of the physical recycled component (solid line) and credit-based recycled component (dashed line) shown in FIG. 3 can be used to form and / or attribute to the PVOH and produce the r-PVOH. For example, the physical recycled component can be provided by at least one, at least two, at least three, at least four, at least five, or all of the feedstocks shown in FIG. 3, including r-ethylene, r-CO, r-acetic acid / anhydride, r-methanol, and, if used, r-syngas, and the credit-based recycled component can be provided by one or more of the other feedstocks shown in FIG. 3. In some embodiments, the r-PVOH can include 10-60%, 20-50%, or 25-40% of the physical recycled component and 10-60%, 20-50%, or 25-40% of the credit-based recycled component. Alternatively, the r-PVOH has less than 15%, less than 10%, or less than 5% physically recycled content (or credit-based recycled content), and at least 85%, at least 90%, or at least 9 May include a 5% credit-based recycled component (or physical recycled component).

[0030]

[0032] For example, in some embodiments, the physical regeneration component can be provided by r-ethylene fed to the catalytic synthesis, and the credit-based regeneration component can be provided by acetic acid / anhydride fed to the same process. In other embodiments, the physical regeneration component can be provided by acetic acid / anhydride, and ethylene can provide the credit-based regeneration component. Alternatively, both acetic acid / anhydride and ethylene can be feedstocks for the physical regeneration component, and both can provide the credit-based regeneration component.

[0031]

[0033] Similarly, when ethanol is used for alcoholysis, the physical and / or credit-based recycled component can be provided from ethylene. In some cases, the ethylene used to form r-ethanol may be formed by the pyrolysis of waste plastics. Similarly, when methanol is used for alcoholysis, the physical and / or credit-based recycled component can be provided, typically from syngas. In some cases, the syngas used to form r-methanol may be formed by carbon reforming of a recycled component hydrocarbon-containing feed.

[0032]

[0034] Referring again to the embodiment shown in Figure 1, the carbon reforming facility and / or the pyrolysis / cracking facility may be collocated with the r-PVOH production facility. In the embodiment shown in Figure 2, the carbon reforming facility and / or the pyrolysis / cracking facility may be located remotely from the r-PVOH production facility. In the embodiment shown in Figure 3, the portion of the pyrolysis / cracking facility that supplies the r-PVOH facility with physical recycled components may be collocated, and the portion of the pyrolysis / cracking facility that supplies the r-PVOH facility with credit-based recycled components may be located remotely. If remotely located, the two facilities may be at least 0.5 miles, 1 mile, 5 miles, 10 miles, 100 miles, 500 miles, 1,000 miles, or 10,000 miles from one another. If co-located, the two facilities can be within 5 miles, 1 mile, 0.5 miles, or 0.25 miles of each other. If acetalization is performed, one or more of the above regarding pyrolysis / cracking facilities, carbon reforming facilities, and PVOH facilities also apply to PVAc facilities. As previously mentioned, when located at remote locations, two or more facilities may be owned and / or operated by the same or different commercial entities.

[0033]

[0035] The recycled PVOH can be used in a variety of end uses. For example, r-PVOH can be used as a sizing agent in fiber and paper applications, or can be incorporated into adhesive formulations with one or more polymers. r-PVOH can also be used as an emulsifier and / or a component of coatings, and can be further processed / reacted to form recycled polymers (such as polyvinyl acetals, as described herein).

[0034] Supplementary explanation of claims - First embodiment

[0036] In a first embodiment of the present technology, a process for producing recycled polyvinyl alcohol (r-PVOH) includes: (a) synthesizing vinyl acetate by reacting a first ethylene and a first acetic acid / anhydride with oxygen; (b) polymerizing at least a portion of the vinyl acetate to produce polyvinyl acetate; and (c) reacting at least a portion of the polyvinyl acetate with a first alcohol to produce polyvinyl alcohol (PVOH), wherein the PVOH is produced from the following raw materials: (i) waste plastic, (ii) recycled ethylene (r-ethylene), (iii) recycled alcohol (r-ethylene), -alcohol), and / or (iv) the regenerated component acetic acid / anhydride (r-acetic acid / anhydride).

[0035]

[0037] The first embodiment described in the previous paragraph may also include one or more of the additional aspects listed below. Each of the following additional aspects of the first embodiment may be an independent feature or may be combined with one or more of the other additional aspects to the extent consistent. In addition, the following bulleted paragraphs may be considered features of dependent claims, with the level of dependency indicated by the degree of indentation in the bulleted list (i.e., a feature that is indented further than the feature listed above it is considered dependent on the feature listed above it).

[0036] ●r-alcohol contains methanol. r-methanol is formed from the regenerated component synthesis gas (r-syngas). ■ At least a portion of the r-syngas is formed by carbon reforming of a regenerated component hydrocarbon feedstream.

[0037] ●r-alcohol contains ethanol. ○ r-ethanol is formed from the recycled component ethylene (r-ethylene). At least a portion of the r-ethylene is formed by the thermal decomposition of waste plastics.

[0038] • The PVOH contains physically and credit-based recycled components from one or more source materials. • PVOH contains physically recycled components from r-ethylene and / or r-acetic acid / anhydride.

[0039] The PVOH contains credit-based recycled content from r-alcohol and / or r-CO. At least a portion of the r-ethylene is produced from waste plastic, and the first ethylene comprises at least a portion of the r-ethylene.

[0040] • further comprising the step of reacting at least a portion of the r-ethylene to form regenerating component ethanol (r-ethanol), wherein the first alcohol comprises at least a portion of the r-ethanol.

[0041] ● further comprising the steps of carbon reforming the regenerative component hydrocarbon-containing feedstock to produce an r-synthesis gas stream (r-syngas), and subjecting at least a portion of the r-synthesis gas to methanol synthesis to produce regenerative component methanol (r-methanol), wherein the first alcohol comprises at least a portion of the r-methanol.

[0042] • Carbon reforming includes partial oxidation gasification of a hydrocarbon-containing feedstock, and a first acetic acid / anhydride is formed from at least a portion of the r-syngas. At least a portion of the first acetic acid / anhydride is produced by converting a second synthesis gas to a first methanol and then subjecting at least a portion of the methanol to carbonylation with carbon monoxide to produce the acetic acid / anhydride, wherein the second synthesis gas comprises at least a portion of the r-syngas from carbon reforming, and / or the carbon monoxide comprises the regenerated component carbon monoxide (r-CO) produced during the r-syngas production.

[0043] The synthesis, polymerization, and reaction are carried out at a PVOH manufacturing facility, and at least one of the raw materials that provide the recycled component for the PVOH is manufactured at a raw material facility located at least 100 miles away from the PVOH manufacturing facility, and the PVOH is produced from the remote raw material. The facility includes a credit-based recycled component from at least one source material produced at the facility.

[0044] ● The synthesis, polymerization, and reaction occur at a PVOH manufacturing facility, at least one of the feedstock materials is produced at an on-site feedstock facility located within 8.04 km (5 miles) of the PVOH manufacturing facility, and the PVOH includes physically recycled components from at least one of the feedstock materials produced at the on-site feedstock facility.

[0045] • further comprising the step of acetalizing at least a portion of the recycled PVOH with at least one aldehyde to form a recycled component polyvinyl acetal. ●The aldehyde is a C3 to C6 aldehyde.

[0046] • Further comprising utilizing credit-based recycled content from one or more feedstock materials in the PVOH. ● The utilizing step includes the steps of: (i) attributing the recycled component from at least one of the source materials having a physical recycled component to at least one target material via a recycled component credit; (ii) tracing the recycled component along at least one chemical pathway from the at least one target material to the PVOH; and (iii) allocating the recycled component to the PVOH based at least in part on the tracing of the recycled component along the chemical pathway.

[0047] • At least one of the following criteria is met: (i) both the source material and the target material contain ethylene, (ii) both the source material and the target material contain acetic acid / anhydride, (iii) both the source material and the target material contain methanol, and / or (iv) both the source material and the target material contain carbon monoxide.

[0048] ● The attributing step includes (i) recording recycled component credits attributable to at least one source material in a digital inventory; and (ii) allocating the recycled component credits from the digital inventory to the target material, wherein the tracking step includes determining one or more conversion rates for one or more chemical reactions along the chemical pathway, and the attributing step includes allocating credit-based recycled components from the digital inventory to the target material, wherein the conversion rate determines the amount of credit-based recycled components utilized in the target material that is allocated to PVOH.

[0049] ● further comprising the steps of synthesizing methanol from a synthesis gas stream comprising a regenerated component synthesis gas (r-syngas) to form regenerated component methanol (r-methanol), and subjecting at least a portion of the r-methanol to carbonylation to form regenerated component acetic acid / anhydride (r-acetic acid / anhydride), wherein the first acetic acid / anhydride used in the synthesis of vinyl acetate comprises r-acetic acid / anhydride.

[0050] ● further comprising a step of hydroformylating the first propylene with a first synthesis gas to form regenerated component n-butyraldehyde (rn-butyraldehyde), wherein at least one of the first propylene and the first synthesis gas comprises regenerated component propylene (r-propylene) or regenerated component synthesis gas (r-synthesis gas), and the first n-butyraldehyde comprises at least a portion of the rn-butyraldehyde.

[0051] The first propylene comprises r-propylene. ■ r-Propylene is formed by the pyrolysis of waste plastics. The first syngas comprises r-syngas.

[0052] ■r-syngas is produced by carbon reforming of recycled hydrocarbon feedstocks, including waste plastics. is formed. • The PVOH contains physically recycled components from one or more raw materials.

[0053] • The PVOH contains credit-based recycled content from one or more source materials. • The PVOH contains physically and credit-based recycled components from one or more source materials.

[0054] ●PVOH contains recycled components from r-ethylene. PVOH contains a physically recycled component from r-ethylene. PVOH contains recycled content on a credit basis from r-ethylene.

[0055] ●PVOH contains recycled components from r-CO. ○PVOH contains a physically recycled component from r-CO. ○PVOH contains recycled content on a credit basis from r-CO.

[0056] ●PVOH contains recycled components from r-methanol. ○PVOH contains components physically recycled from r-methanol. PVOH contains a credit-based recycled content from r-methanol.

[0057] ●PVOH contains recycled components from r-acetic acid / anhydride. PVOH contains a physically regenerated component from r-acetic acid / anhydride. PVOH contains credit-based recycled components from r-acetic acid / anhydride.

[0058] ●The synthesis, polymerization, and reaction occur at a PVOH manufacturing facility, and at least one of the feedstock materials that provide the recycled component for the PVOH is produced at a feedstock facility located at least 0.80 km (0.5 mile), 1.60 km (1 mile), 8.04 km (5 miles), 16.09 km (10 miles), 160.93 km (100 miles), 804.67 km (500 miles), 1609.34 km (1000 miles), or 16093.44 km (10,000 miles) away from the PVOH manufacturing facility.

[0059] The PVOH comprises a credit-based recycled component from at least one feedstock material produced at a remote feedstock facility. The reaction, polymerization, hydrolysis, and acetalization occur at a PVOH manufacturing facility, and at least one of the feedstock materials is produced at an adjacent feedstock facility located within 8.04 km (5 miles), 1.60 km (1 mile), 0.80 km (0.5 miles), or 0.40 km (0.25 miles) of the PVOH manufacturing facility.

[0060] The PVOH contains a physically recycled component from at least one source material produced at a remote source facility. • further comprising producing r-syngas from at least one regenerated component hydrocarbon-containing feedstock.

[0061] The producing step comprises partial oxidation gasification and / or steam reforming of a hydrocarbon-containing feedstock. ○The following criteria: (i) the first alcohol comprises methanol formed from at least a portion of the r-syngas; and / or (ii) the first acetic acid / anhydride is formed from at least a portion of the r-synthesis gas.

[0062] At least a portion of the first acetic acid / anhydride is produced by converting the second synthesis gas into methanol and then subjecting at least a portion of the methanol to carbonylation to produce acetic acid / anhydride.

[0063] ■ The second synthesis gas comprises at least a portion of the r-synthesis gas formed from the regenerated component hydrocarbon-containing feedstock. At least a portion of the r-ethylene is produced from waste plastics.

[0064] At least a portion of the r-ethylene is produced by pyrolysis and / or cracking of waste plastics. The first ethylene comprises at least a portion of r-ethylene.

[0065] • Further comprising utilizing credit-based recycled content from one or more feedstock materials in the PVOH. The utilizing step includes (i) attributing the recycled component from at least one of the raw materials having a physical recycled component to at least one target material via a recycled component credit; (ii) tracing the recycled component along at least one chemical pathway from the at least one target material to the PVOH; and (iii) allocating the recycled component to the PVOH based at least in part on tracing the recycled component along the chemical pathway.

[0066] ■At least one of the following criteria is met: (i) both the source material and the target material contain ethylene, (ii) both the source material and the target material contain acetic acid / anhydride, (iii) both the source material and the target material contain carbon monoxide, and / or (iv) both the source material and the target material contain methanol.

[0067] • At least one target material comprises one or more of a first acetic acid / anhydride, a first ethylene, and / or a first alcohol. ■The following criteria (i) to (iv): (i) the feedstock comprises r-syngas having a physically recycled component; (ii) the source material comprises r-acetic acid / anhydride with a physical regeneration component, and the target material comprises a first acetic acid / anhydride; (iii) the source material comprises r-CO with a physically regenerated component; and / or (iv) At least one of the following is satisfied: the source material comprises r-ethylene having a physical regeneration component; and the target material comprises the first ethylene.

[0068] ■ The attributing step includes (i) recording in a digital inventory recycled component credits attributable to at least one source material, and (ii) allocating the recycled component credits from the digital inventory to the target material.

[0069] ● The tracking step includes determining one or more conversion rates for one or more chemical reactions along the chemical pathway, and the attributing step includes allocating credit-based recycled components from the digital inventory to the target material, and the conversion rate determines an amount of the credit-based recycled components utilized in the target material that is allocated to PVOH.

[0070] • The process further includes obtaining certification from a certification body for the use of credit-based recycled content. ●The recycled components of the raw material are derived from waste plastic.

[0071] - The source material and the target material have substantially the same physical composition. • At least 50, 75, 90, 95, 99, or 100% by weight of the source material is identical to the target material.

[0072] • The r-PVOH has at least 10, 20, 30, 40, 50, 75, 90, 95, or 100% recycled content. • The r-PVOH has at least 10, 20, 30, 40, or 50% physical recycled content and at least 10, 20, 30, 40, or 50% credit-based recycled content.

[0073] • The source material has a physically recycled component and the target material has less than 100% of the physically recycled component. • The source material has at least 10, 25, 50, 75, 90, or 99% physically recycled content.

[0074] • The target material has less than 99, 90, 75, 50, 25, 10, or 1% physical regenerating components. • The source material has 100% physical regeneration components and the target material has no physical regeneration components.

[0075] - Neither the first ethylene, the first acetic acid / anhydride, nor the first alcohol has a physical regenerating component. • At least one (at least two, at least three, all) of the first ethylene, the first acetic acid / anhydride, and the first alcohol has a physical regenerating component.

[0076] The utilizing step further includes utilizing a physical recycled component to at least a portion of the PVOH, whereby the r-PVOH has both a physical recycled component and a credit-based recycled component.

[0077] • The physical regenerating component utilized in the PVOH is derived from at least one of r-ethylene, r-acetic acid / anhydride, r-methanol, or r-ethanol. • The target material comprises ethylene, and at least a portion of the credit-based recycled component allocated to PVOH is tracked via a first chemical pathway from ethylene to PVOH.

[0078] • The target material comprises acetic acid / anhydride, and at least a portion of the credit-based recycled component allocated to PVOH is tracked via a second chemical pathway from acetic acid / anhydride to PVOH.

[0079] • The target material includes an alcohol, and at least a portion of the credit-based recycled component allocated to PVOH is tracked via a third chemical pathway from alcohol to PVOH.

[0080] Supplementary explanation of claims - second embodiment

[0038] In a second embodiment of the present technology, a process for producing polyvinyl acetal having a recycled component includes the steps of: (a) reacting a first ethylene and a first acetic acid / anhydride with oxygen to produce vinyl acetate; (b) polymerizing at least a portion of the vinyl acetate to produce polyvinyl acetate; (c) subjecting at least a portion of the polyvinyl acetate to alcoholysis with a first ethanol to produce polyvinyl alcohol; and (d) acetalizing at least a portion of the polyvinyl alcohol with a first aldehyde to produce polyvinyl acetal, The process includes a recycled component from one or more of the following feedstock materials: (i) waste plastics, (ii) recycled component syngas (r-syngas), (iii) recycled component ethylene (r-ethylene), (iv) recycled component carbon monoxide, and (v) recycled component acetic acid / anhydride (r-acetic acid / anhydride).

[0081] The second embodiment described in the previous paragraph may also include one or more of the additional aspects listed below. Each of the following additional aspects of the second embodiment may be an independent feature or may be combined with one or more of the other additional aspects to the extent that they are not inconsistent.

[0082] The method further comprises the step of acetalizing at least a portion of the PVOH with n-butyraldehyde to produce polyvinyl butyral (PVB), wherein the PVB comprises recycled components from one or more of the raw materials (i)-(iv).

[0083] Further comprising the step of hydroformylating olefins with a first synthesis gas to provide a first aldehyde, wherein the first synthesis gas comprises at least a portion of the r-synthesis gas, such that the aldehyde is a regenerated component aldehyde (r-aldehyde).

[0084] The olefin comprises propylene. (3) At least a portion of the propylene is recycled propylene formed by thermal decomposition of waste plastics.

[0085] ● The reaction, polymerization, alcoholization, and acetalization occur at a polyvinyl acetal (PVAc) manufacturing facility, at least one of the feedstock materials that provides the recycled component to the PVAc is produced at a feedstock facility located at least 8.04 km (5 miles) away from the PVAc manufacturing facility, and the PVAc includes a credit-based recycled component from the at least one feedstock material produced at the remote feedstock facility.

[0086] ●Further comprising utilizing a credit-based recycled component from one or more feedstock materials to the PVAc, wherein the utilizing step comprises (i) attributing the recycled component from at least one of the feedstock materials having a physical recycled component to at least one target material via a recycled component credit; (ii) tracking the recycled component along at least one chemical pathway from the at least one target material to the PVAc; and (iii) assigning the recycled component to the PVAc based at least in part on tracking the recycled component along the chemical pathway, wherein at least one of the following criteria is met: (i) both the feedstock material and the target material contain syngas, (ii) both the feedstock material and the target material contain acetic acid / anhydride, (iii) both the feedstock material and the target material contain methanol, (iv) both the feedstock material and the target material contain carbon monoxide, and / or (v) both the feedstock material and the target material contain ethylene.

[0087] definition It should be understood that the following is not intended to be an exhaustive list of defined terms. Other definitions may be provided in the preceding description, for example, as accompanying the use of a defined term in context.

[0088] As used herein, the terms "a," "an," and "the" mean one or more. As used herein, the term "and / or," when used in a list of two or more items, means that any one of the listed items may be used by itself, or any combination of two or more of the listed items may be used. For example, if a composition is described as containing components A, B, and / or C, the composition can contain A alone; B alone; C alone; a combination of A and B; a combination of A and C, a combination of B and C; or a combination of A, B, and C.

[0089] As used herein, the phrase "at least a portion" includes at least a portion and up to the entire amount or period of time.

[0044] As used herein, the term "chemical pathway" refers to the chemical processing steps (e.g., chemical reactions, physical separations, etc.) between input materials and products, where the input materials are used to produce the products.

[0090]

[0045] As used herein, the term "chemical recycling" refers to a waste plastic recycling process that involves chemically converting waste plastic polymers into lower molecular weight polymers, oligomers, monomers, and / or non-polymer molecules (e.g., hydrogen, carbon monoxide, methane, ethane, propane, ethylene, CO) that are useful in their own right and / or as feedstocks for other chemical manufacturing processes.

[0091]

[0046] As used herein, the term "co-located" refers to the characteristic of at least two objects being located at a common physical location and / or within 5 miles, 1 mile, 0.5 miles, or 0.25 miles of each other.

[0092]

[0047] As used herein, the terms "comprising," "comprises," and "comprise" are open-ended transitional phrases used to transition from the subject matter described before the term to one or more elements described after the term, and the elements described after the transitional phrase are not necessarily the only elements that make up the subject matter.

[0093]

[0048] As used herein, the terms "credit-based recycled content," "non-physically recycled content," and "indirectly recycled content" all refer to materials that cannot be physically traced to waste but that have recycled content credits attached to them.

[0094]

[0049] As used herein, the term "directly derived" refers to having at least one physical component that is derived from waste.

[0050] As used in this specification, the terms "including," "include," and "included" have the same open-ended meaning as "comprising," "comprises," and "comprise" set forth above.

[0095]

[0051] As used herein, the term "indirectly derived" refers to the utilization of recycled components that (i) can be attributed to waste, but (ii) are not based on having physical components derived from waste.

[0096] As used herein, the term "remotely located" refers to a distance of at least 0.16 km (0.1 mile), 0.80 km (0.5 mile), 1.60 km (1 mile), 8.04 km (5 miles), 16.09 km (10 miles), 80.46 km (50 miles), 160.93 km (100 miles), 804.67 km (500 miles), or 1609.34 km (1000 miles) between two facilities, sites, or reactors.

[0097]

[0053] As used herein, the term "mass balance" refers to a method of tracking recycled components based on their mass in various materials. As used herein, the terms "physically recycled components" and "directly recycled components" both refer to materials that can be physically traced back to the waste.

[0098] As used herein, the term "majority" means greater than 50% by weight. For example, a predominantly propane stream, composition, feedstock, or product is a stream, composition, feedstock, or product that contains greater than 50% by weight of propane.

[0099] As used herein, the term "recycled content" refers to a composition that is or includes a composition that is derived directly and / or indirectly from recycled materials. Recycled content is used as a generic term to refer to both physically recycled content and credit-based recycled content. Recycled content is also used as an adjective to describe materials that have physically recycled content and / or credit-based recycled content.

[0100]

[0057] As used herein, the term "recycled content credit" refers to a non-physical measure of a physical recycled content that can be attributed directly or indirectly (i.e., via digital inventory) from a first material having a physical recycled content to a second material having less than 100% physical recycled content.

[0101]

[0058] As used herein, the term "total recycled content" refers to the cumulative amount of physically recycled content and credit-based recycled content from all feedstocks. As used herein, the term "waste" refers to used, scrap, and / or discarded materials.

[0102]

[0060] As used herein, the terms "waste plastic" and "plastic waste" refer to post-consumer, scrap, and / or discarded plastic materials.

[0103] Claims not limited to the disclosed embodiments

[0061] The preferred embodiments of the present invention described above should be used only as examples and should not be used in a limiting sense to interpret the scope of the present invention. Modifications to the above exemplary embodiments can be easily made by those skilled in the art without departing from the spirit of the present invention.

[0104]

[0062] The inventors hereby express their intention to rely on the doctrine of equivalents to determine and assess the reasonably fair scope of the present invention for any device that does not substantially depart from the present invention as set forth in the following claims, but that falls outside the literal scope thereof.

Claims

1. 1. A process for producing recycled polyvinyl alcohol (r-PVOH), comprising: (a) synthesizing vinyl acetate by reacting a first ethylene and a first acetic acid / anhydride with oxygen; (b) polymerizing at least a portion of the vinyl acetate to produce polyvinyl acetate; (c) reacting at least a portion of the polyvinyl acetate with a first alcohol to produce polyvinyl alcohol (PVOH); The process wherein the PVOH comprises recycled content from one or more of the following feedstocks: (i) waste plastics, (ii) recycled content ethylene (r-ethylene), (iii) recycled content alcohol (r-alcohol), and / or (iv) recycled content acetic acid / anhydride (r-acetic acid / anhydride).

2. 10. The process of claim 1, wherein the PVOH comprises physical and credit-based recycled content from one or more source materials.

3. 3. The process of claim 1 or 2, wherein the PVOH includes a physical regenerating component from the r-ethylene and / or the r-acetic acid / anhydride.

4. 4. The process of any one of claims 1 to 3, wherein the PVOH comprises a credit-based recycled component from the r-alcohol and / or the r-CO.

5. 5. The process of any one of claims 1 to 4, wherein at least a portion of the r-ethylene is produced from waste plastic and the first ethylene comprises at least a portion of the r-ethylene.

6. 6. The process of claim 5, further comprising reacting at least a portion of the r-ethylene to form regenerating component ethanol (r-ethanol), wherein the first alcohol comprises at least a portion of the r-ethanol.

7. 6. The process of any one of claims 1 to 5, further comprising carbon reforming a regenerative hydrocarbon-containing feedstock to produce an r-synthesis gas stream (r-syngas) and subjecting at least a portion of the r-synthesis gas to methanol synthesis to form regenerative methanol (r-methanol), wherein the first alcohol comprises at least a portion of the r-methanol.

8. 8. The process of claim 7, wherein the carbon reforming comprises partial oxidation gasification of the hydrocarbon-containing feedstock and the first acetic acid / anhydride is formed from at least a portion of the r-syngas.

9. 9. The process of claim 8, wherein at least a portion of the first acetic acid / anhydride is produced by converting a second synthesis gas to a first methanol and then subjecting at least a portion of the methanol to carbonylation with carbon monoxide to produce acetic acid / anhydride, wherein the second synthesis gas comprises at least a portion of the r-syngas from the carbon reforming, and / or the carbon monoxide comprises regenerated component carbon monoxide (r-CO) produced during the r-syngas production.

10. The synthesis, polymerization, and reaction are carried out in a PVOH manufacturing facility, and the PVOH is not enriched with recycled components.

10. The process of any one of claims 1 to 9, wherein at least one of the feedstock materials provided is produced at a feedstock facility located at least 100 miles away from the PVOH manufacturing facility, and the PVOH comprises a credit-based recycled content from the at least one feedstock material produced at the remote feedstock facility.

11. 11. The process of any one of claims 1 to 10, wherein the synthesis, polymerization, and reaction occur at a PVOH manufacturing facility, at least one of the feedstock materials is produced at an on-site feedstock facility located within 5 miles of the PVOH manufacturing facility, and the PVOH comprises physically recycled components from the at least one feedstock material produced at the on-site feedstock facility.

12. 12. The process of any one of claims 1 to 11, further comprising acetalizing at least a portion of the recycled PVOH with at least one aldehyde to form a recycled component polyvinyl acetal.

13. 13. The process of claim 12, wherein the aldehyde is a C3 to C6 aldehyde.

14. 14. The process of any one of claims 1 to 13, further comprising utilizing a credit-based recycled content from the one or more feedstock materials in the PVOH.

15. 15. The process of claim 14, wherein the utilizing step includes: (i) attributing recycled content from at least one of the source materials having a physical recycled content to at least one target material via recycled content credits; (ii) tracing recycled content along at least one chemical pathway from the at least one target material to the PVOH; and (iii) allocating recycled content to the PVOH based at least in part on the tracing of recycled content along the chemical pathway.

16. 16. The process of claim 15, wherein at least one of the following criteria is met: (i) both the source material and the target material comprise ethylene; (ii) both the source material and the target material comprise acetic acid / anhydride; (iii) both the source material and the target material comprise methanol; and / or (iv) both the source material and the target material comprise carbon monoxide.

17. 16. The process of claim 15, wherein the attributing step comprises: (i) recording recycled content credits attributable to the at least one raw material in a digital inventory; and (ii) allocating recycled content credits from the digital inventory to the target material; the tracking step comprises determining one or more conversion rates for one or more chemical reactions along the chemical pathway; and the attributing step comprises allocating credit-based recycled content from a digital inventory to the target material; and the conversion rate determines an amount of the credit-based recycled content utilized in the target material allocated to the PVOH.

18. 1. A process for producing polyvinyl acetal with recycled content (r-PVAc), comprising: (a) reacting a first ethylene and a first acetic acid / anhydride with oxygen to produce vinyl acetate; (b) polymerizing at least a portion of the vinyl acetate to produce polyvinyl acetate; (c) subjecting at least a portion of said polyvinyl acetate to alcoholysis with a first ethanol to produce polyvinyl alcohol; (d) acetalizing at least a portion of the polyvinyl alcohol with a first aldehyde to produce polyvinyl acetal; 1. A process wherein the polyvinyl acetal comprises recycled components from one or more of the following feedstocks: (i) waste plastics, (ii) recycled synthesis gas (r-syngas), (iii) recycled ethylene (r-ethylene), (iv) recycled carbon monoxide, and (v) recycled acetic acid / anhydride (r-acetic acid / anhydride).

19. 20. The process of claim 18, further comprising hydroformylating olefins with a first synthesis gas to provide said first aldehyde, said first synthesis gas comprising at least a portion of said r-syngas such that said aldehyde is a regeneration component aldehyde (r-aldehyde).

20. 20. The process of claim 18, further comprising utilizing recycled components on a credit basis from the one or more feedstock materials to the polyvinyl acetal, the utilizing comprising: (i) attributing recycled components from at least one of the feedstock materials having a physical recycled component to at least one target material via recycled component credits; (ii) tracing recycled components along at least one chemical pathway from the at least one target material to the polyvinyl acetal; and (iii) assigning recycled components to the polyvinyl acetal based at least in part on the tracing of recycled components along the chemical pathway, wherein at least one of the following criteria is met: (i) both the feedstock material and the target material comprise ethylene; (ii) both the feedstock material and the target material comprise acetic acid / anhydride; (iii) both the feedstock material and the target material comprise syngas; and / or (iv) both the feedstock material and the target material comprise carbon monoxide.

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