RELATED APPLICATIONS

[0001] This application claims benefit to U.S. Patent Application No. 62/064, 159, filed on October 15, 2014, the disclosure of which is incorporated herein in its entirety for any and all purposes.

TECHNICAL FIELD

[0002] This application relates to the refining of crude oil and use of the products produced therefrom in further chemical plant operations.

BACKGROUND

[0003] Typically, refinery plants and the chemical plants that use refinery's products are operated independently from one another. As a result, shipping costs, purification to a common purity (often more than required by a particular industrial process), and tariffs all add to the overall cost of operation of the chemical plant. In addition, various streams at a refinery plant are flamed or otherwise disposed of. This disposal results in the loss of materials that have the potential to be converted into high value products. Accordingly, there is a need in the art for operations having improved environmental and economic impact.

SUMMARY

[0004] In some aspects, the disclosure concerns methods of production, comprising refining a crude oil at a refinery train; communicating products of the refinery train to a steam cracker, operating the steam cracker so as to give rise to at least ethylene and an offgas;

communicating products of the refinery train to a high olefin fluid catalytic cracker; operating the high olefin fluid catalytic cracker to as to give rise to propylene and olefins; and synthesizing one or more of the following from products of the steam cracker and the catalytic cracker - H2, syngas, polyethylene, polyvinyl chloride, ethylene dichloride, phenol, acetone, polycarbonate, butadiene, ethylene vinyl acetate, benzene, cumene, propylene, an alkylbenzene, terephthalic acid, or xylene.

[0005] In other aspects, the disclosure concerns methods for the production of cumene comprising refining crude oil in a first refinery train so as to produce a first plurality of streams, said first plurality of streams comprising one or more of offgas, liquefied petroleum gas, naphtha, C4 olefins, and vacuum gas oil; feeding said offgas, liquefied petroleum gas, naphtha and C4 olefins to a steam cracker to produce one or more streams comprising one or more of propylene, ethylene, butadiene, and offgas; reacting said ethylene and said offgas so as to produce one or more streams comprising one or more of hydrogen, syngas, and polyethylene; feeding one or more streams comprising vacuum gas oil, naphtha to a fluid catalytic cracker so as to produce a stream comprising propylene; refining crude oil in a second refinery train so as to produce a second plurality of streams comprising one or more of kerosene and reformates; feeding said reformates to a paraxylene separations unit that outputs one or more streams comprising one or more of benzene, paraxylene, linear alkylbenzenes, CI 1 hydrocarbons and therphthalic acid; and reacting said benzene and said propylene so as to produce cumene.

[0006] In yet another aspect, the disclosure concerns integrated system comprising

~ a first refinery train, the refinery train configured to receive crude oil and convert it to a plurality of streams comprising one or more of offgas, liquefied petroleum gas, naphtha, C4 olefins, vacuum gas oil and naphtha;

~ a steam cracker comprising in fluid communication with said first refinery train, said steam cracker configured to receive one or more of said offgas, liquefied petroleum gas, naphtha and C4 olefins and produce propylene, ethylene, butadiene, and offgas;

~ a first reaction unit in fluid communication with said steam cracker, said first reaction unit configured to react said ethylene and said offgas so as to produce one or more streams comprising one or more of hydrogen, syngas, and polyethylene;

~ a fluid catalytic cracker in fluid communication with said first refinery train, said fluid catalytic cracker configured to accept one or more streams comprising vacuum gas oil, naphtha and produce a stream comprising propylene;

~ a second refinery train in fluid communication with said first refining train, said second refinery train configured to convert crude oil to a plurality of streams comprising one or more of kerosene and reformates;

~ a paraxylene separations unit in fluid communication with said second refinery train, said paraxylene separations unit configured to accept said reformates and produce one or more streams comprising one or more of benzene, paraxylene, linear alkylbenzenes, CI 1 hydrocarbons and therphthalic acid; and

~ a first reaction unit in fluid communication with said paraxylene separations unit and said fluid catalytic cracker, said reaction unit configured to react said benzene and said propylene to produce cumene. BRIEF DESCRIPTION OF THE DRAWINGS

[0007] The following is a brief description of the drawings wherein like elements are numbered alike and which are exemplary of the various embodiments described herein.

[0008] FIG. 1 presents a schematic of an integrated process that includes a crude oil refinery unit, a cracker and petrochemical complex as well as integrated downstream syngas, chemical products value chain and polycarbonate plant. Other oil products include gasoline, jet/kerosene, diesel/gasoil, fuel oil, lubricants, waxes, asphalt, petcoke, etc. Heavy liquid streams include pyrolysis fuel oil, etc.

[0009] FIG. 2 presents an example of an integrated C3-C6 polycarbonate value chain process. Propylene and benzene produced in the front end of the refinery and cracker complex are reacted to produce cumene which in turn is used to produce phenol and acetone and ultimately Bisphenol A and polycarbonate. Carbon monoxide and hydrogen produced by the syngas facility are used to produce methanol, dimethyl carbonate and diphenyl carbonate which is ultimately used to react with Bisphenol A to produce polycarbonate.

[0010] FIG. 3 presents a schematic a gasification unit that can intake cracker offgas as well as other fuel sources to produce syngas that can be used in production of polycarbonate intermediates, methanol, and methanol to olefins (MTO) and methanol to propylene (MTP) processes.

[0011] FIG. 4 presents an exemplary schematic for operation of an integrated process for the production of cumene from crude oil.

[0012] FIG. 5 presents an exemplary schematic of a process for the production of phenol and acetone from crude oil.

[0013] FIG. 6 presents an exemplary schematic of backward integrated Bisphenol A (BPA) production unit.

[0014] FIG. 7 presents an exemplary schematic of a backward integrated cumene, phenol, acetone and diphenyl carbonate unit. DPC is diphenyl carbonate, FCC is fluid catalytic cracker and ASU is an air separations unit.

[0015] FIG. 8 shows an exemplary schematic of a crude oil to syngas integrated production unit.

[0016] FIG. 9 presents an exemplary schematic of a chemical operation using offgas, LPG, naphtha to feed a cracker and ultimately produce a variety of endproducts such as polyethylene (HDPE and LLDPE), polypropylene (PP), butadiene, benzene, paraxylene, methyl ethyl glycol (MEG), and polyvinylchloride (PVC). Other streams such as natural gas and kerosene can be converted into a variety of products such as linear alkyl benzene (LAB), purified terephthalic acid (PTA) and ethylene vinyl acetate (EVA).

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

[0017] Before the present methods and systems are disclosed and described, it is to be understood that the methods and systems are not limited to specific synthetic methods, specific components, or to particular compositions. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

[0018] Various combinations of elements of this disclosure are encompassed by this disclosure, e.g., combinations of elements from dependent claims that depend upon the same independent claim.

[0019] Moreover, it is to be understood that unless otherwise expressly stated, it is in no way intended that any method set forth herein be construed as requiring that its steps be performed in a specific order. Accordingly, where a method claim does not actually recite an order to be followed by its steps or it is not otherwise specifically stated in the claims or descriptions that the steps are to be limited to a specific order, it is no way intended that an order be inferred, in any respect. This holds for any possible non-express basis for interpretation, including: matters of logic with respect to arrangement of steps or operational flow; plain meaning derived from grammatical organization or punctuation; and the number or type of aspects described in the specification.

[0020] It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. As used in the specification and in the claims, the term "comprising" may include the aspects "consisting of and "consisting essentially of." Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. In this specification and in the claims which follow, reference will be made to a number of terms which shall be defined herein.

[0021] As used in the specification and the appended claims, the singular forms "a," "an" and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a polycarbonate" includes mixtures of two or more such polycarbonates. Furthermore, for example, reference to a filler includes mixtures of two or more such fillers. [0022] Ranges can be expressed herein as from "about" one particular value, and/or to "about" another particular value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about," it will be understood that the particular value forms another aspect. A value modified by a term or terms, such as "about" and "substantially," is intended to include the degree of error associated with measurement of the particular quantity based upon the equipment available at the time of filing this application. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. It is also understood that there are a number of values disclosed herein, and that each value is also herein disclosed as "about" that particular value in addition to the value itself. For example, if the value "10" is disclosed, then "about 10" is also disclosed. It is also understood that each unit between two particular units are also disclosed. For example, if 10 and 15 are disclosed, then 11, 12, 13, and 14 are also disclosed.

[0023] The suffix "(s)" is intended to include both the singular and the plural of the term that it modifies, thereby including at least one of that term (e.g., the colorant(s) includes at least one colorants).

[0024] "Optional" or "optionally" means that the subsequently described event or circumstance can or cannot occur, and that the description includes instances where the event occurs and instances where it does not.

[0025] Unless defined otherwise, technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art to which this disclosure belongs.

[0026] A number of industrial processes are described herein. From an efficiency and economic standpoint, it is advantageous to design a process where each process step is in fluid communication with the process step that immediately precedes or follows the process step. As such, a process where each step is performed on a single plant site with the differing units integrated and in fluid communication provides a preferred embodiment of the disclosure. One exemplary integrated facility is illustrated in FIG. 1 where a crude oil refinery unit, a cracker and petrochemical complex as well as integrated downstream syngas, chemical products value chain and polycarbonate plant are integrated to produce an efficient facility. Various descriptions and schemes provided herein can be integrated, in full or in part, to illustrate processes of the instant disclosure. Refinery Train(s)

[0027] Crude oil contains different hydrocarbon molecules that are separated in a refinery into streams which can be used in various end uses such as fuels, lubricants, and as feedstocks in petrochemical processes. In some aspects, crude oil can be refined via distillation to produce a variety of products. Such distillation columns are well known to those skilled in the art.

[0028] Typically, high boiling components are removed at or near the bottom of the column, mid-range boiling components are removed between the top and bottom of the column and low temperature boiling components are removed at or near the top of the columns.

Typically, the distillation is performed at atmospheric pressure. In some embodiments, crude oil can be refined trough one or more refinery trains to produce streams comprising, e.g., one or more of (i) offgas, (ii) liquefied petroleum gas, (iii) naphtha, (iv) vacuum gas oil, (v) C3 hydrocarbons, (vi) hydrogen, (vii) syngas, (viii) kerosene, (ix) gasoline, (x) fuel oil, and (xi) reformate which are captured at different levels of the distillation column. The refining process can further comprise refining the one or more streams comprising kerosene, gasoline, and fuel oil to produce individual streams of kerosene, gasoline, and fuel oil. Some refinery columns produce petcoke at or near the bottom of the column.

[0029] Some aspects of the disclosure concern integrated systems comprising: (i) a refinery train, the refinery train being configured to refine crude oil into at least offgas, liquefied petroleum gas, naphtha, and a C-3 rich stream; (ii) a separations unit in fluid communication with said refinery train, said separations unit configured to separate said offgas into a plurality of streams, said plurality of streams comprising a stream enriched in ethylene and propylene and a stream with reduced ethylene and propylene content; (iii) a gasification unit in fluid

communication with said separations unit, said gasification unit configured to convert stream with reduced ethylene and propylene content to syngas; and (iv) a steam cracker in fluid communication with said separations unit, said steam cracker configured to receive said stream enriched in ethylene and propylene.

[0030] The Nelson Index is a rating of the complexity of a refinery and its ability to produce higher value products. Some refining processes of the instant disclosure have a Nelson Index of between about 5 and about 17 or about 11 to about 14. In certain embodiments, the Nelson Index is from about 12 to about 14. Cracker(s)

[0031] Cracking is the process where compounds such heavy (high boiling) hydrocarbons are broken down into smaller molecules such as light hydrocarbons. This is accomplished by breaking carbon-carbon bonds to form smaller molecules. The composition of the product of a cracking unit is strongly dependent on the temperature the unit is operated at and presence of catalysts. Steam crackers and fluid cracker are commonly used crackers. Typically, fluid catalytic crackers are used to produce gasoline and LPG, while hydrocracking is a major source of jet fuel, diesel fuel, naphtha, and LPG. Operation of crackers is known to those skilled in the art.

[0032] Some processes of the disclosure concern refining crude oil at a refinery train, communicating products of the refinery train to a steam cracker, operating the steam cracker so as to give rise to at least ethylene and offgas; communicating products of the refinery train to a catalytic cracker, and operating the catalytic cracker to as to give rise to propylene;

[0033] Some embodiments of the disclosure concern feeding one or more streams comprising vacuum gas oil, and naphtha to a fluid catalytic cracker so as to produce a stream comprising propylene.

[0034] In certain embodiments, steam crackers can be fed naphtha and/or LPG gas at a point or at points mid-range in the cracker and produce streams comprising one or more of ethylene, propylene, mixed C4 hydrocarbons mid-range in the column with higher boiling components removed from the bottom of the column. Ethylene can be polymerized to produce polyethylene such as HDPE and LLDPE. Propylene can be polymerized to produce

polypropylene. Mixed C4 hydrocarbons can be separated to produce purified components such as butadiene. High boiling components can be further processed to produce purified components such as benzene, paraxylene and other aromatic components.

[0035] FIG. 9 presents an exemplary schematic of a chemical operation using offgas, LPG, naphtha to feed a cracker and ultimately produce a variety of end products such as polyethylene (HDPE and LLDPE), polypropylene (PP), butadiene, benzene, paraxylene, methyl ethyl glycol (MEG), and polyvinylchloride (PVC). Other streams such as natural gas and kerosene can be converted into a variety of products such as linear alkyl benzene (LAB), purified terephthalic acid (PTA) and ethylene vinyl acetate (EVA).

Paraxylene Refining Unit [0036] An illustrative paraxylene refining unit comprises a distillation column that inputs a stream comprising two or more of benzene, paraxylene, linear alkylbenzenes, CI 1 hydrocarbons, and therphthalic acid and separates the stream into a plurality of streams rich in one or more of the aforementioned components. In some embodiments, an output stream from the paraxylene refining unit comprising at least some of the C 11 hydrocarbons are recycled to a refinery train. See, FIG. 1. Benzene, useful in other reactions described herein can be isolated. In addition, para-xylene can be separated from meta-xylene, ortho-xylene and ethylbenzene by use of a series of distillation steps. A benzene rich stream may be used in other chemical processes described herein. See, for example, FIGs. 5-7.

Integrated Syngas Unit

[0037] One aspect of an integrated syngas unit is the separation of useful hydrocarbons from the offgas product of the crude oil refinery for further processing and taking the remaining gas and subjecting it to a gasifier to produce syngas. This process not only recovers valuable products that might be flared or otherwise disposed of, it produces syngas that can be useful in the production of higher value chemicals including some chemicals used in the processes described herein. In some embodiments, the process concerns refining crude oil to produce a stream comprising offgas; separating the stream comprising offgas to produce a stream enriched in ethylene and proplylene and a stream having reduced ethylene and propylene content; and introducing the stream having reduced ethylene and propylene content to a gasifier so as to produce syngas comprising hydrogen and carbon monoxide. The stream rich in ethylene and propylene can be further processed to utilize the individual components.

[0038] In some aspects, the disclosure concerns reacting at least a portion of the hydrogen and the carbon monoxide from the syngas to produce methanol; and further reacting the methanol, the carbon monoxide and oxygen to produce dimethyl carbonate. In certain aspects, dimethyl carbonate is transesterified with phenol so as to produce diphenyl carbonate.

[0039] The separations described above can be accomplished using a fractionation train that can be integrated with the cracker. The fractionation train can include a demethaniser, deethanizer and depropanizer. The C2 splitter and C3 splitter that are used in traditional operations are optional and not required. This contributes to higher process efficiencies, higher energy efficiencies, and lower capital expenses.

[0040] Offgas feed streams can be fed to a demethaniser. Methane and lighter offgas are split off as top products and fed to the offgas gasification syngas unit. The demethanizer bottoms stream (enriched in ethylene and propylene) enters the deethanizer at the midsection. The deethanizer bottoms, comprising propylene, propane, and heavier components, are fed to the depropanizer. The deethanizer overhead comprises a mixture of ethylene and ethane. This mixture may bypass the cracker furnaces and be fed directly to a C2 splitter downstream from the cracker. No separate C2 Splitter before the cracker will be required as in normal setups. The depropanizer produces refinery -grade propylene as overheads and this stream may be fed directly, bypassing the cracker furnaces, to a C3 splitter so as to produce propane and chemical- grade propylene.

[0041] In certain embodiments, the stream enriched in ethylene and propylene comprises from about 15 to about 35 percent by weight (or by vol/mols) of the stream comprising offgas (from about 20 to about 30 percent by weight or by vol/mols of the stream comprising offgas in some embodiments). Some process can process 300,000 to 700,000 tons of light gas.

[0042] The methane and other lighter offgases that are split off as top products and fed to the offgas gasification syngas unit, produce hydrogen and carbon monoxide. The hydrogen and carbon monoxide may be reacted to produce methanol in the presence of catalyst. While any suitable catalyst may be utilized, some preferred catalysts include those having one or more of copper, zinc oxide, or alumina.

[0043] Steam reforming of hydrocarbons is one known method for producing syngas and involves contacting the hydrocarbon with steam. Steam reforming is highly endothermic and requires high reaction temperatures of e.g. 700-1100°C. Accordingly, care should be taken to avoid thermodynamic constraints. Furthermore, steam reforming of hydrocarbons can require relatively long contact times. Typically, the syngas mixture produced by steam reforming of a hydrocarbon such as methane has a comparatively high H ₂ /CO ratio of approximately 4.5-5.2. The H ₂ /CO ratio of syngas produced by steam reforming methane may be adapted, e.g., by adding CO or by removing ¾. Alternatively, the H ₂ /CO ratio of a syngas composition may be adapted to a desired value by subjecting the composition to the reverse water-gas shift reaction.

[0044] A syngas composition with a H ₂ /CO ratio of approximately 1 can be produced directly by catalytic dry reforming of methane with CO ₂ . Also catalytic dry reforming of methane is highly endothermic and should be executed at high reaction temperatures. Many catalytic dry reforming processes are known to involve rapid coke deposition leading to catalyst inactivation. In these catalytic dry reforming processes the reactor can be regenerated by feeding oxygen to the catalyst under high temperatures. [0045] Partial oxidation in the presence of a hydrocarbon feed is a further means to produce a syngas mixture. A disadvantage of partial oxidation is that carbon dioxide is produced as a by-product, which limits the selectivity for aliphatic and aromatic C2-C6 hydrocarbons of the hydrocarbon reforming process.

[0046] By combining different reforming reactions including those described herein above, the reforming process can be optimized e.g. by circumventing thermodynamic constraints and/or by reducing the costs for heating or process heat removal.

[0047] A nickel/lanthana (Ni/LaiC ) catalyst system is found to be useful in syngas production is described in international patent application WO2010/105788, the description of which is incorporated herein in its entirety.

[0048] In certain embodiments, the refining crude oil additionally produces a plurality of streams comprising one or more of naphtha, liquefied petroleum gas, a C3 rich stream, or a C4 rich stream. The C4 rich stream can be further processed to produce one or more of butadiene, n-butane, and isobutene.

[0049] Some processes of the disclosure concern operation of a crude oil cracking unit comprising: refining crude oil to produce a stream comprising offgas; feeding the offgas to a demethanizer to remove at last a portion of methane from the offgas and produce a reduced- methane gas and methane-rich stream; feeding the reduced-methane gas to a de-ethanizer column to remove at least a portion of any ethane and ethylene from the reduced-methane gas and produce a reduced-ethane stream and an ethane-rich stream; feeding the reduced-ethane stream to a depropanizer column to remove at least a portion of any propane and propylene in the reduced-ethane stream and produce a propane-rich stream and a reduced-propane stream; feeding the ethane-rich stream and the propane-rich stream to a steam cracker to produce one or more streams comprising one or more of propylene, ethylene, and butadiene; and feeding the reduced- propane stream to a gasification unit to produce syngas to produce syngas comprising hydrogen and carbon monoxide.

[0050] At least a portion of the hydrogen and the carbon monoxide can advantageously be reacted to produce methanol. A further reaction may comprise reacting the methanol, the carbon monoxide and oxygen to produce dimethyl carbonate. Dimethyl carbonate can be reacted with phenol to produce diphenyl carbonate which can be reacted with bisphenol A to produce polycarbonate.

[0051] In preferred embodiments, each process step is in fluid communication with the process step that immediately precedes or follows the process step. [0052] One aspect of the disclosure is an integrated system, comprising

~ a refinery train, the refinery train being configured to refine crude oil into at least a plurality of products including offgas;

~ separating unit in fluid communication with the refinery train, the separating unit configured to receive the offgas and separate the offgas into a plurality of streams including a stream enriched in ethylene and proplylene and a stream with reduced ethylene and propylene content;

~ a gasification unit in fluid communication with the separating unit, the gasification unit configured to accept the stream with reduced ethylene and propylene content and producing syngas, the syngas comprising hydrogen and carbon monoxide; and

~ a first reaction unit in fluid communication with the gasification unit, the reaction unit configured to convert at least a portion of the hydrogen and the carbon monoxide to methanol.

[0053] Gasification of hydrocarbon sources to produce syngas can be used to make a variety of chemicals including polycarbonate precursors, methanol, and olefins such as propylene. Illustrations of integrated schemes are found in FIG. 3 and FIG. 8. FIG. 8 shows introduction of crude oil into the refinery. Coke or other higher boiling products can be introduced to a gasification unit to produce syngas.

Polycarbonate Value Chain

[0054] In some aspects, the disclosure concerns an integrated process for the production of polycarbonate at one production location, the process comprising, at the production location: (i) refining crude oil in a refinery train so as to produce a first plurality of streams, the first plurality of streams comprising one or more of offgas, liquefied petroleum gas, naphtha, C3 olefins, C4 olefins, or vacuum gas oil; (ii) processing at least a portion of the offgas, liquefied petroleum gas (LPG), naphtha, C3 or C4 olefins with a steam cracker at the production location so as to produce one or more streams comprising one or more of propylene, ethylene, butadiene, and offgas; (iii) reacting the ethylene and the offgas so as to produce one or more streams comprising one or more of hydrogen, syngas, and polyethylene; (iv) processing one or more of the vacuum gas oil, the naphtha, or both, with a fluid catalytic cracker so as to produce a stream comprising propylene; (v) reacting benzene isolated at the production location from crude oil with the propylene so as to produce cumene, (vi) reacting the cumene so as to produce phenol and acetone; (vii) reacting the phenol and the acetone so as to produce bisphenol A; (viii) contacting carbon monoxide, oxygen and methanol under such conditions so as to produce dimethyl carbonate; (ix) reacting the dimethyl carbonate and phenol to produce diphenyl carbonate; and(x) reacting the diphenyl carbonate with the bisphenol A so as to produce polycarbonate. See, for example, FIG. 2.

[0055] In certain aspects, the disclosure concerns processes for the production of polycarbonate comprising: (i) refining crude oil in a first refinery train so as to produce a first plurality of streams, the first plurality of streams each comprising one or more of offgas, liquefied petroleum gas, naphtha, C4 olefins, and vacuum gas oil; (ii) feeding the offgas, liquefied petroleum gas, naphtha and C4 olefins to a steam cracker to produce one or more streams comprising one or more of propylene, ethylene, butadiene, and offgas; (iii) reacting the ethylene and the offgas so as to produce one or more streams comprising one or more of hydrogen, syngas, and polyethylene; (iv) feeding one or more streams comprising vacuum gas oil and naphtha to a fluid catalytic cracker so as to produce a stream comprising propylene; (v) refining crude oil in a second refinery train so as to produce a second plurality of streams comprising one or more of kerosene and reformates; (vi) feeding the reformates to a paraxylene separations unit that outputs one or more streams comprising one or more of benzene, paraxylene, linear alkylbenzenes, CI 1 hydrocarbons and therphthalic acid; (vii) feeding benzene and propylene to an alkylation reactor to produce a cumene-rich stream; (viii) feeding the cumene-rich stream to a depropanizer distillation column to recover at least a portion of propane and producing a stream having reduced propane; (ix) feeding the stream having reduced propane into a benzene distillation column to recover at least a portion of benzene and produce a stream having reduced benzene; (x) feeding the stream having reduced benzene to a cumene distillation column to recover at least a portion of cumene and produce a bottoms stream; (xi) feeding the bottoms stream to a distillation column to produce a polyisopropylbenzenes rich stream and a heavies stream ; (xii) feeding the polyisopropylbenzenes rich stream to a transalkylation reactor and feeding the product of the transalkylation reactor to the benzene distillation column; (xiii) reacting the cumene so as to produce phenol and acetone; (xiv) reacting the phenol and the acetone so as to produce bisphenol A; (xv) contacting carbon monoxide, oxygen and methanol so as to produce dimethyl carbonate; (xvi) reacting the dimethyl carbonate and phenol to produce diphenyl carbonate; and (xvii) reacting the diphenyl carbonate with the bisphenol A so as to produce polycarbonate. See, for example, FIGs 2 and 8.

[0056] A schematic illustration of one integrated polycarbonate value chain operation is presented in FIG. 2. A process for the production of the intermediate cumene from crude oil in found in FIG. 4. FIG. 5 presents a schematic of a process for the production of phenol and acetone from crude oil. FIG. 6 presents a schematic of backward integrated Bisphenol A (BPA) production unit. FIG. 7 presents a schematic of a backward integrated cumene, phenol, acetone and diphenyl carbonate unit. In FIG. 7, DPC is diphenyl carbonate, FCC is fluid catalytic cracker and ASU is air separations unit. These schemes, as well as others included in this application, can be combined in total or in any part to illustrate aspects of the disclosure.

[0057] The Hock process is an industrial process that may be used to produce phenol and acetone from benzene and propylene. This process converts benzene and propylene, into cumene and then into phenol and acetone. Typically, propylene and benzene are reacted in the presence of a catalyst to produce a mixture of cumene and propane. Suitable catalysts include heterogeneous zeolite catalysts and acid catalysts, for example, phosphoric acid and aluminum chloride. Heterogeneous zeolite catalysts are known in the art and commercially available.

[0058] In a first step, a cumene feed can enter an oxidation reactor along an oxidizing agent. The oxidation reactor outputs a cumene oxidation product comprising cumene hydroperoxide and side products of cumene oxidation.

[0059] The oxidation reactor can circulate the cumene flow through a cascade of large bubble columns. In the bubble columns, the air is added at the bottom of each reactor and the oxygen can transfer from the air bubbles into the cumene. The oxidation reaction can be auto- catalyzed by the cumene hydroperoxide. The oxidation reactor can operate at pressures ranging from atmospheric to around 200 psi. The temperature of the oxidation reactor can range from 80°C - 130°C. The residence time in the reactor can range from 10 minutes to several hours.

[0060] The oxidizing agent can be any agent capable of oxidizing the cumene. In one aspect, the oxidizing agent is oxygen. The oxygen can be pure or as a mixture with other gases, for example the mixture of gases found in air. In another aspect, the oxidizing agent is air.

[0061] The cumene oxidation product comprises cumene hydroperoxide and dimethyl benzyl alcohol. The oxidation reactor can also output one or more by-products. The one or more by-products can include acetophenone (ACP), methyl hydroperoxide (MHP), or a combination thereof.

[0062] In one aspect, the cumene oxidation product comprises from about 20 weight percent to about 30 weight percent cumene hydroperoxide and from about 0.1 weight percent to about 2 weight percent dimethyl benzyl alcohol.

[0063] The system may optionally further comprises a stripping element in communication with the oxidation reactor, the stripping element configured to receive the cumene oxidation product and to modify a concentration of the cumene oxidation product, wherein the conversion reactor is configured to receive the modified cumene oxidation product. Typically the concentration of cumene hydroperoxide (CHP) would be increased in this element.

[0064] The cleavage reaction in the manufacture of phenol and acetone from cumene is well known. In the system, a feed stream from the conversion reactor (CHP cleavage reactor) of the cumene oxidation product and the converted oxidation product passes into the cleavage reactor. An acid catalyst in the cleavage reactor decomposes the cumene oxidation product and the converted oxidation product into an output product comprising phenol, acetone, and alpha- methylstyrene (AMS), and other by-products.

[0065] In some embodiments, the cleavage takes place in a two reactor system. In a first system, comprising one or more reactors, cumene hydroperoxide is decomposed in the presence of a catalyst mixture to form phenol and a ketone. A portion of the CHP reacts with dimethyl benzyl alcohol (DMBA) to form a dicumyl peroxide (DCP) mixture in a first stage. In a second stage, the product of the first stage can be fed to a second system (comprising one or more reactors) to form a phenol, acetone, and AMS mixture from decomposition of the dicumyl peroxide mixture formed in the first stage. As described herein, the first and the second systems are connected in series.

[0066] In certain embodiments, the second stage reaction is carried out at a temperature from about 90 °C to about 160 °C. and a pressure from about 5 to about 200 psi.

[0067] The cleavage reaction can be extremely fast due to it exothermic nature and is essentially to completion in most processes. In one aspect, the cleavage reaction can occur within 30 seconds to 5 minutes. In fact it is common to use a constant boiling or refluxing type system for the isothermal cleavage reaction. This is generally the constant boiling temperature of the CHP decomposition product. Generally this can vary from about 70° to about 90° C. Because this is the general cumene oxidation product and the converted oxidation product feed stream as well as the output product; the phenol to acetone molar ratio is essentially 1 to 1 throughout the course of the reaction. The ratio of acetone to phenol may be optionally increased depending on the amount of recycle acetone used to control the decomposition process.

[0068] The acid catalyst in the cleavage reactor can be any acidic material. To avoid corrosion, heavily corrosive inorganic acids, for example, hydrochloric acid or hydrobromic acid are not usually used in the cleavage reactor. Acid catalysts often used, but not limited to, include, for example, phosphoric acid or sulfuric acid or a combination thereof. In one aspect, the acid catalyst can be present in the quantity of about 10 to about 3000 parts per million of sulfuric acid per weight of composition mass. [0069] In some embodiments, the cleavage reaction may be run in the presence of excess acetone. In this regard, the addition of recycle acetone may be used in the stream entering the cleavage reactor.

[0070] In some embodiments, these reactors have a specific surface not less than about 30 to 35 meter squared per ton of 100% CHP per hour. CHP conversion in the reactors in is 30 to 45%, 30 to 40%, or 10 to 30% when three reactors are utilized. In the event that more or less 1st stage decomposition reactors are utilized, the %conversion will be different.

[0071] Other by-products that can be formed in the cleavage reactor include, for example, hydroxyacetone, 2-methylbenzofuran, or diacetone alcohol or a combination thereof. The by-products formed in the cleavage reactor can also include some aldehydes, for example, acetaldehyde.

[0072] The output product from the cleavage reactor can be cooled. In a further aspect, the output product can be neutralized in a neutralization unit to stop the acid-catalyzed reaction from the cleavage reactor. In one aspect, the output product can be neutralized using an neutralizing agent, such as sodium phenate.

[0073] A condensation reactor (or BPA production reactor) may be configured to receive the output product and to produce Bisphenol A.

[0074] The system may further comprise a purification system that is configured to receive the output product and to purify the one or more of phenol, acetone, and alpha- methylstyrene to produce a purified output product. The purified output material may optionally be fed to a condensation reactor that is configured to receive the purified output product and to produce one or more of Bisphenol A and para-cumylphenol.

[0075] Polycarbonate can be produced by the reaction of Bisphenol A and diphenyl carbonate. This reaction is more environmentally friendly than the tradition reaction of

Bisphenol A with phosgene to produce polycarbonate.

[0076] Diphenyl carbonate can be made by the transesterifcation of dimethyl carbonate with phenol. Carbon monoxide, methanol and oxygen are reacted to form dimethyl carbonate by a known commercial process.

[0077] The reaction of Bisphenol A and diphenyl carbonate to produce polycarbonate can occur using a melt reaction process known in the art.

[0078] In some processes, the benzene used to produce cumene has a purity of 95- 99.5% by weight based on the weight of the benzene. In certain processes, the propylene used to produce cumene has a purity of 95-99.5% by weight based on the propylene. Conventional processes use higher purity benzene and propylene which add to the cost of production. In some preferred processes, benzene and propylene are reacted in the presence of a zeolite catalyst to produce cumene.

[0079] In some aspects the disclosure also concerns an integrated system comprising (i) a first refinery train, the first refinery train being capable of producing a first plurality of streams, the first plurality of streams plurality of streams each comprising one or more of offgas, liquefied petroleum gas, naphtha, C4 olefins, and vacuum gas oil; (ii) a steam cracker configured to intake one or more streams comprising one or more of offgas, liquefied petroleum gas, naphtha and C4 olefins and output one or more streams comprising one or more of propylene, ethylene butadiene and offgas; (iii) one or more further processing units configured to convert ethylene and offgas to one or more of hydrogen, syngas, and polyethylene; (iv) a fluid catalytic cracker configured to intake one or more streams comprising vacuum gas oil and naphtha and output a stream comprising propylene; (v) a second refinery train, the second refinery train configured to input crude oil and output a second plurality of streams, the second plurality of streams comprising one or both of kerosene and reformates; (vi) a paraxylene separations unit configured to input reformates and output one or more streams comprising one or more of benzene, paraxylene, linear alkylbenzenes, CI 1 hydrocarbons and therphthalic acid; (vii) a recycle stream that supplies the C 11 hydrocarbons to the second refinery train; (viii) a reactor configured to convert the benzene and the propylene to cumene; (ix) a reactor configured to convert the cumene to phenol and acetone; (x) a reactor configured to input phenol and acetone to produce bisphenol A; and (xi) a reactor configured to contact diphenyl carbonate with the bisphenol A to produce polycarbonate.

[0080] Some integrated processes additionally comprise: a separations unit to separate the offgas into a stream enriched in ethylene and propylene and a stream with reduced ethylene and propylene content. Certain integrated systems additionally comprise a process unit to feed the stream enriched in ethylene and propylene to the stream cracker; and a process unit to feed the stream with reduced ethylene and propylene to a gasifier to produce syngas.

Illustrative and Non-Limiting Aspects

[0081] Aspect 1. A method of production, comprising:

refining a crude oil at a refinery train;

communicating products of the refinery train to a steam cracker,

operating the steam cracker so as to give rise to at least ethylene and an offgas; communicating products of the refinery train to a high olefin fluid catalytic cracker; operating the high olefin fluid catalytic cracker to as to give rise to propylene and olefins; synthesizing one or more of the following from products of the steam cracker and the catalytic cracker - H ₂ , a syngas, polyethylene, polyvinyl chloride, ethylene dichloride, phenol, acetone, polycarbonate, butadiene, ethylene vinyl acetate, benzene, cumene, propylene, an alkylbenzene, terephthalic acid, or xylene.

[0082] Aspect 2. The method of aspect 1, wherein the refinery train is in fluid communication with the steam cracker and the catalytic cracker.

[0083] Aspect 3. The method of aspect 2, wherein the steam cracker, the catalytic cracker, or both, are in fluid communication with a reaction train configured to produce one or more of H ₂ , a syngas, polyethylene, polyvinyl chloride, ethylene dichloride, phenol, acetone, polycarbonate, butadiene, ethylene vinyl acetate, benzene, cumene, propylene, an alkylbenzene, terephthalic acid, or xylene.

[0084] Aspect 4. The method of any one of aspects 1-3, further comprising communicating a product of the refinery train to a paraxylene separation unit.

[0085] Aspect 5. The method of aspect 4, further comprising communicating a product of the paraxylene separation unit to a reaction train configured to produce one or more of paraxylene, terephthalic acid, alkylbenzene, benzene, cumene, phenol, polycarbonate, or any combination thereof.

[0086] Aspect 6. The process of any one of aspects 1-5, wherein said process has a Nelson Index of between about 5 and about 16.

[0087] Aspect 7. The process of any one of aspects 1-5, wherein said process has a Nelson Index of greater than 12.

[0088] Aspect 8. The process of any one of aspects 1-5, wherein the process has a Nelson Index of greater than 14.

[0089] Aspect 9. The process of any one of aspects 1-8, wherein a stream enriched in ethylene and propylene is isolated from said offgas, said stream comprising from about 15 to about 35 percent by one of weight or vol/mol, of said stream comprising offgas.

[0090] Aspect 10. The process of aspect 9, wherein the stream enriched in ethylene and propylene comprises from about 20 to about 30 percent by one of weight or vol/mols of said stream comprising offgas.

[0091] Aspect 11. A process for the production of cumene comprising ~ refining crude oil in a first refinery train so as to produce a first plurality of streams, said first plurality of streams comprising one or more of offgas, liquefied petroleum gas, naphtha, C4 olefins, and vacuum gas oil;

~ feeding said offgas, liquefied petroleum gas, naphtha and C4 olefins to a steam cracker to produce one or more streams comprising one or more of propylene, ethylene, butadiene, and offgas;

~ reacting said ethylene and said offgas so as to produce one or more streams comprising one or more of hydrogen, syngas, and polyethylene;

~ feeding one or more streams comprising vacuum gas oil, naphtha to a fluid catalytic cracker so as to produce a stream comprising propylene;

~ refining crude oil in a second refinery train so as to produce a second plurality of streams comprising one or more of kerosene and reformates;

~ feeding said reformates to a paraxylene separations unit that outputs one or more streams comprising one or more of benzene, paraxylene, linear alkylbenzenes, CI 1 hydrocarbons and therphthalic acid;

~ reacting said benzene and said propylene so as to produce cumene.

[0092] Aspect 12. The process of aspect 11, wherein said naphtha has a boiling point between about 90 oC and about 200 oC.

[0093] Aspect 13. The process of aspect 11 or aspect 12, wherein said benzene has a purity of 95-99% by weight based on the weight of the benzene.

[0094] Aspect 14. The process of any one of aspects 11-13, wherein said propylene has a purity of less than about 95-99% by weight based on the propylene.

[0095] Aspect 15 The process of any one of aspects 11-14, wherein said benzene and said propylene are reacted in the presence of a zeolite catalyst.

[0096] Aspect 16. The process of anyone of aspects 11-15, further comprising returning at least a portion of said CI 1 hydrocarbons to said second refinery train.

[0097] Aspect 17. The process of any one of aspects 11-16, further comprising

~ reacting said cumene so as to produce phenol and acetone;

~ reacting said phenol and said acetone so as to produce bisphenol A;

~ contacting carbon monoxide, oxygen and methanol so as to produce dimethyl carbonate;

~ reacting said dimethyl carbonate and phenol to produce diphenyl carbonate; and

~ reacting said diphenyl carbonate with said bisphenol A so as to produce polycarbonate. [0098] Aspect 18. The process of any one of aspects 11-17, wherein reacting said benzene and said propylene occurs in the presence of a zeolite catalyst.

[0099] Aspect 19. The process of any one of aspects 11-18, wherein said cumene is further reacted to produce acetone and phenol.

[00100] Aspect 20. The process of aspect 19, wherein said cumene is oxidized in the presence of oxygen to produce acetone and phenol.

[00101] Aspect 21. The process of aspect 20, wherein said reacting said phenol and said acetone so as to produce bisphenol A occurs in the presence of an ion exchange resin.

[00102] Aspect 22. The process of anyone of aspects 11-21, wherein said syngas is fed to a gasification unit to produce a stream comprising carbon monoxide and hydrogen.

[00103] Aspect 23. The process of aspect 22, wherein said carbon monoxide is reacted with chlorine to produce phosgene.

[00104] Aspect 24. The process of aspect 11, further comprising reacting methanol to produce dimethyl ether.

[00105] Aspect 25. The process of any one of aspects 11-24, wherein each step is in fluid communication with the process step that immediately precedes or follows aid process step.

[00106] Aspect 26. The process of any one of aspects 11-25, wherein said process has a Nelson Index of between about 5 and about 16.

[00107] Aspect 27. The process of any one of aspects 11-25, wherein said process has a Nelson Index of greater than 12.

[00108] Aspect 28. The process of any one of aspects 11-25, wherein the process has a Nelson Index of greater than 14.

[00109] Aspect 29. The process of any one of aspects 11-28, wherein a stream enriched in ethylene and propylene is isolated from said offgas, said stream comprising from about 15 to about 35 percent by one of weight or vol/mol, of said stream comprising offgas.

[00110] Aspect 30. The process of aspect 29, wherein the stream enriched in ethylene and propylene comprises from about 20 to about 30 percent by one of weight or vol/mols of said stream comprising offgas.

[00111] Aspect 31. An integrated system comprising

~ a first refinery train, the refinery train configured to receive crude oil and convert it to a plurality of streams comprising one or more of offgas, liquefied petroleum gas, naphtha, C4 olefins, vacuum gas oil and naphtha; ~ a steam cracker comprising in fluid communication with said first refinery train, said steam cracker configured to receive one or more of said offgas, liquefied petroleum gas, naphtha and C4 olefins and produce propylene, ethylene, butadiene, and offgas;

~ a first reaction unit in fluid communication with said steam cracker, said first reaction unit configured to react said ethylene and said offgas so as to produce one or more streams comprising one or more of hydrogen, syngas, and polyethylene;

~ a fluid catalytic cracker in fluid communication with said first refinery train, said fluid catalytic cracker configured to accept one or more streams comprising vacuum gas oil, naphtha and produce a stream comprising propylene;

~ a second refinery train in fluid communication with said first refining train, said second refinery train configured to convert crude oil to a plurality of streams comprising one or more of kerosene and reformates;

~ a paraxylene separations unit in fluid communication with said second refinery train, said paraxylene separations unit configured to accept said reformates and produce one or more streams comprising one or more of benzene, paraxylene, linear alkylbenzenes, CI 1 hydrocarbons and therphthalic acid; and

~ a first reaction unit in fluid communication with said paraxylene separations unit and said fluid catalytic cracker, said reaction unit configured to react said benzene and said propylene to produce cumene.

[00112] Aspect 32. The integrated system of aspect 31, further comprising:

~ a second reaction unit in fluid communication with said first reaction unit, said second reaction unit configured to react said cumene to produce phenol and acetone;

~ a third reaction unit in fluid communication with said second reaction unit, said third reaction unit configured to react said phenol with said acetone so as to produce bisphenol A;

~ a fourth reaction unit configured to react carbon monoxide, oxygen and methanol so as to produce dimethyl carbonate;

~ a fifth reaction unit in fluid communication with said fourth reaction unit, said fifth reaction unit configured to react said dimethyl carbonate and phenol to produce diphenyl carbonate; and

~ a sixth reaction unit in fluid communication with said fifth reaction unit, said sixth reaction unit configured to react said diphenyl carbonate with said bisphenol A so as to produce polycarbonate.

[00113] Aspect 33. The integrated system of aspect 32, further comprising: ~ a gasifier in fluid communication with said steam cracker, said gasifier configured to react said offgas and produce syngas comprising hydrogen and carbon monoxide; said gasifier further in fluid communication so as to supply said carbon monoxide and said hydrogen to said fourth reaction unit.

[00114] Aspect 34. The integrated system of any one of aspects 31-33, wherein said process has a Nelson Index of between about 5 and about 16.

[00115] Aspect 35. The integrated system of any one of aspects 31-33, wherein said process has a Nelson Index of greater than 12.

[00116] Aspect 36. The integrated system of any one of aspects 31-33, the process has a Nelson Index of greater than 14.

[00117] Aspect 37. The integrated system of any one of aspects 31-36, comprising a separator wherein a stream enriched in ethylene and propylene is isolated from said offgas, said stream comprising from about 15 to about 35 percent by one of weight or vol/mol, of said stream comprising offgas.

[00118] Aspect 38. The integrated system of any one of aspects 31-36, comprising a separator wherein a stream enriched in ethylene and propylene comprises from about 20 to about 30 percent by one of weight or vol/mols of said stream comprising offgas.

Definitions

[00119] All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if a term in the present application contradicts or conflicts with a term in the incorporated reference, the term from the present application takes precedence over the conflicting term from the incorporated reference.

[00120] While typical embodiments have been set forth for the purpose of illustration, the foregoing descriptions should not be deemed to be a limitation on the scope herein.

Accordingly, various modifications, adaptations, and alternatives can occur to one skilled in the art without departing from the spirit and scope herein.

[00121] As used herein, the term "hydrocarbyl" and "hydrocarbon" refers broadly to a substituent comprising carbon and hydrogen, optionally with 1 to 3 heteroatoms, for example, oxygen, nitrogen, halogen, silicon, sulfur, or a combination thereof. "Alkyl" refers to a straight or branched chain, saturated monovalent hydrocarbon group. "Alkylene" refers to a straight or branched chain, saturated, divalent hydrocarbon group. [00122] The terms "polycarbonate" or "polycarbonates" as used herein includes copolycarbonates, homopoly carbonates and (co)polyester carbonates.

[00123] "Naphtha" is a fraction of hydrocarbons that boils between 30 °C and 200 °C. Naphtha consists of a complex mixture of hydrocarbon molecules typically having between about 5 and about 12 carbon atoms. Most crude oil contains about 15 to about 30 weight % of naphtha by weight. Light naphtha is the fraction boiling between 30 °C and 90 °C and mainly consists of molecules with 5 to 6 carbon atoms. Heavy naphtha boils between 90 °C and 200 °C and mainly consists of molecules with 6 to 12 carbons.

[00124] "Reformates" are high-octane liquid petroleum products.

[00125] A gasifer runs a process that converts carbonaceous materials to CO, H2 and C02. The conversion is accomplished by reacting the material at high temperatures (>700 °C), without combustion and in the presence of a controlled amount oxygen and/or steam.

[00126] "Offgas" comprises one or more of hydrogen, methane, ethane and ethylene as well as other low molecular weight hydrocarbons (typically C1-C5 or C1-C4 or C1-C3). Offgas is the product of a distillation of crude oil where a substantial portion of naphtha is separated from the resultant offgas.

[00127] "Liquefied petroleum gas" comprises one or both of propane and butane.

[00128] "C4 olefins" are a mixture of olefins having four carbon atoms that may be linear or branched and have one carbon-carbon double bond.

[00129] "C3 olefins" are a mixture of olefins having three carbon atoms that may be linear or branched and have one carbon-carbon double bond.

[00130] "CI 1 hydrocarbons" are a mixture of linear and branched hydrocarbons having 11 carbon atoms. These hydrocarbons may be saturated or unsaturated.

[00131] "Vacuum gas oil" is also known as heavy gas oil. This oil is a high molecular weight portion of product derived from the refining train and vacuum gas oil units.

[00132] "Linear alkylbenzenes" are substituted benzene rings having a linear alkyl substituent. In some embodiments, linear alkylbenzene is of the formula C ₆ H ₅ C _n H ₂ n+i . In certain embodiments, n is 10-16.

[00133] "Syngas" is a gas mixture consisting primarily of hydrogen, carbon monoxide, and very often some carbon dioxide.

[00134] As used herein a "demethanizer" is a distillation column that recovers at least a portion of methane from a process stream and produces a stream having reduced methane content. [00135] By 'deethanizer" it is meant a distillation column that recovers at least a portion of ethane and ethylene from a process stream and produces a stream having reduced ethane and ethylene content.

[00136] As used herein a "depropanizer" is a distillation column that recovers at least a portion of propane from a process stream and produces a stream having reduced propane and propylene content.

[00137] "Petroleum coke" (also known as pet coke) is a carbonaceous solid recovered from oil refinery units or other cracking processes.

[00138] "Heavies" comprise high molecular weight/high boiling products. In some embodiments, heavies have a boiling point above 400 °C (750 °F).

[00139] The "Nelson Index" or "Nelson Complexity Index" is a measure of the secondary conversion capacity of a petroleum refinery relative to the primary distillation capacity, as described by Wilbur L. Nelson in a series of articles that appeared in the Oil & Gas Journal from 1960 to 1961 (Mar. 14, p. 189; Sept. 26, p. 216; and June 19, p. 109) and in 1976 (Sept. 13, p. 81; Sept. 20, p. 202; and Sept. 27, p. 83). A higher index number indicates the ability to refine lower value crude oil and the ability to produce higher value products. Nelson Index numbers range from 7-14 for conventional to highly advanced complex refineries globally.