Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
  • B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
  • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
  • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
  • C07C15/02—Monocyclic hydrocarbons
  • C07C15/067—C8H10 hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
  • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
  • C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
  • C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
  • C07C6/08—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond
  • C07C6/12—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring
  • C07C6/126—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring of more than one hydrocarbon
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C7/00—Purification; Separation; Use of additives
  • C07C7/04—Purification; Separation; Use of additives by distillation
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
  • C10G29/20—Organic compounds not containing metal atoms
  • C10G29/205—Organic compounds not containing metal atoms by reaction with hydrocarbons added to the hydrocarbon oil
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1096—Aromatics or polyaromatics
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/40—Characteristics of the process deviating from typical ways of processing
  • C10G2300/4087—Catalytic distillation
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
  • C10G2400/30—Aromatics
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/10—Process efficiency

Definitions

• Embodiments disclosed herein relate generally to processes for the production of alkylbenzenes, such as ethylbenzene and cumene, among others.
• Ethylbenzene and cumene are currently produced by the reaction of benzene and the respective olefin, i.e., ethylene and propylene by acid catalysis. More recently, benzene alkylation processes have used the corresponding alcohols as an alkylating agent. Cumene, also known as isopropylbenzene, is useful for the production of phenol, acetone, and alphamethylstyrene. Ethylbenzene is useful in the production of styrene. Alkyl-substituted aromatics also are useful as high octane transportation fuels. Various processes for their manufacture are known.
• Fresh ethanol, unreacted ethanol, diethyl ether by-product (also an alkylating agent), and optionally a portion of the recovered benzene and/or polyalkylated benzene may be fed to the column between the alkylation catalyst, located in the upper portion of the column, and the transalkylation catalyst, located in the lower portion of the column.
• the three systems of distillation, alkylation, and transalkylation may be consolidated into a single column, eliminating at least one major reactor from the conventional configuration for producing ethylbenzene. Cumene and other alkylated benzene species may be produced in a similar manner using the corresponding alcohols.
• embodiments disclosed herein relate to a process for the production of alkylbenzene, the process including: feeding a Ci to C 6 alcohol and benzene to a catalytic distillation reactor system comprising an upper reaction zone containing an alkylation catalyst and a lower reaction zone containing a transalkylation catalyst, which may be the same or different than the alkylation catalyst; concurrently in the catalytic distillation reactor system: reacting a portion of the alcohol with the benzene within the upper reaction zone to form a reaction mixture containing water, alkylbenzene, dialkyl ether, unreacted alcohol, unreacted benzene, and polyalkylate including dialkylbenzene; reacting a portion of the polyalkylate with benzene in the lower reaction zone to form additional alkylbenzene; and fractionally distilling the reaction mixture; recovering an overheads fraction from the catalytic distillation reactor system comprising benzene, unreacted alcohol, water, and dialkyl ether; recovering
• embodiments disclosed herein relate to a process for the production of ethylbenzene, the process including: feeding ethanol and benzene to a catalytic distillation reactor system comprising an upper reaction zone containing an alkylation catalyst and a lower reaction zone containing a transalkylation catalyst, which may be the same or different than the alkylation catalyst; concurrently in the catalytic distillation reactor system: reacting a portion of the ethanol with the benzene within the upper reaction zone to form a reaction mixture containing water, ethylbenzene, diethyl ether, unreacted ethanol, unreacted benzene, and polyalkylate including diethylbenzene; reacting a portion of the polyalkylate with benzene in the lower reaction zone to form additional ethylbenzene; and fractionally distilling the reaction mixture; recovering an overheads fraction from the catalytic distillation reactor system comprising benzene, ethanol, water, and diethyl
• embodiments disclosed herein relate to a process for the production of cumene, the process including: feeding isopropanol and benzene to a catalytic distillation reactor system comprising an upper reaction zone containing an alkylation catalyst and a lower reaction zone containing a transalkylation catalyst, which may be the same or different than the alkylation catalyst; concurrently in the catalytic distillation reactor system: reacting a portion of the isopropanol with the benzene within the upper reaction zone to form a reaction mixture containing water, cumene, diisopropyl ether, unreacted isopropanol, unreacted benzene, and polyalkylate including diisopropylbenzene; reacting a portion of the polyalkylate with benzene in the lower reaction zone to form additional cumene; and fractionally distilling the reaction mixture; recovering an overheads fraction from the catalytic distillation reactor system comprising benzene, isopropanol, water, and diiso
• Figure 1 is a simplified process flow diagram of a process for the alkylation of benzene according to embodiments disclosed herein.
• Figure 2 is a simplified process flow diagram of a process for the alkylation of benzene according to embodiments disclosed herein.
• Figure 3 is a simplified process flow diagram of a portion of a process for the alkylation of benzene according to embodiments disclosed herein.
• Figure 4 is a simplified process flow diagram of a process for the alkylation of benzene according to embodiments disclosed herein.
• Figure 5 is a simplified process flow diagram of a process for the alkylation of benzene according to embodiments disclosed herein.
• the expression "catalytic distillation reactor system” denotes an apparatus in which the catalytic reaction and the separation of the products take place at least partially simultaneously.
• the apparatus may comprise a conventional catalytic distillation column reactor, where the reaction and distillation are concurrently taking place at boiling point conditions, or a distillation column operatively connected with at least one side reactor to which a side draw from the distillation column is introduced as a feed and from which a reactor effluent is withdrawn and returned to the distillation column, where the side reactor may be operated as a liquid phase reactor, a vapor phase reactor, or a boiling point reactor.
• a catalytic distillation column reactor may have the advantages of decreased piece count, reduced capital cost, efficient heat removal (heat of reaction may be absorbed into the heat of vaporization of the mixture), and a potential for shifting equilibrium.
• Divided wall distillation columns, where at least one section of the divided wall column contains a catalytic distillation structure, may also be used, and are considered "catalytic distillation reactor systems" herein.
• Processes disclosed herein may include any number of reactors, including catalytic distillation reactor systems, both up-flow and down-flow.
• Use of catalytic distillation reactor systems may prevent foulants and heavy catalyst poisons in the feed from contacting the catalyst.
• clean reflux may continuously wash the catalyst zone.
• embodiments herein relate to processes for the production of alkylbenzenes, such as ethylbenzene and cumene, among others.
• Alkylation of benzene with an alcohol may be represented by the following reactions.
• Alkylation of benzene with other alcohols may proceed in a similar manner, producing water and the corresponding alkylate.
• alkylation of toluene may be effected in a similar manner.
• Production of alkylbenzene via catalytic distillation may be attained by feeding a Q to C 8 alcohol and benzene to a catalytic distillation reactor system including an upper reaction zone containing an alkylation catalyst and a lower reaction zone containing a transalkylation catalyst, which may be the same or different than the alkylation catalyst.
• the upper reaction zone may be located in the rectifying section of the column and the lower reaction zone may be located in the stripping portion of the column.
• the benzene and alcohol distills upward within the column and the benzene may be reacted with the alcohol over the alkylation catalyst to produce an alkyl benzene and water.
• the alcohol may also react with itself to form a dialkyl ether.
• alkyl benzene may be further alkylated over the alkylation catalyst to produce dialky benzene, trialkyl benzene, and higher polyalkylated benzenes.
• the alkylbenzene and polyalkylate produced in the upper reaction zone may then traverse downward through the column, for contact with the transalkylation catalyst and recovery of the alkylbenzene and polyalkylate as a bottoms fraction.
• Benzene present in the lower reaction zone is available for transalkylation with the polyalkylate, producing additional monoalkylate.
• benzene may react with the alcohol or the dialkyl ether over the transalkylation catalyst, also producing additional monoalkylate.
• the feed components and reaction products are separated (fractionally distilled) within the catalytic distillation reactor system.
• Benzene, unreacted alcohol, water, and dialkyl ether may be recovered from the column as an overheads product, and benzene, alkylbenzene, and polyalkyl benzene may be recovered as a bottoms fraction.
• the operation of the catalytic distillation column should be such that reaction conditions suitable for the alkylation of benzene with an alcohol are achieved in the reaction zones.
• the reaction zones may be maintained at a temperature in the range from 200°F to 700°F; from 200°F to 400°F in other embodiments.
• the mole ratio of alcohol to benzene fed to the reactor may range from 0.1:1 to 10: 1 in some embodiments; from 0.5:1 to 5:1 in other embodiments; from 0.8:1 to 2:1 in other embodiments; and from 0.9:1 to 1.1:1 in other embodiments.
• Alcohols useful in embodiments disclosed herein may include Q to C 6 primary and secondary alcohols.
• examples of alcohols useful in embodiments disclosed herein include methanol, ethanol, n-propanol, i-propanol, n-butanol, i- butanol and t-butanol, among others.
• Any catalyst useful for the alkylation and/or transalkylation of benzene with an alcohol may be used in the processes disclosed herein.
• molecular sieves or zeolitic catalysts may be useful for the alkylation and/or transalkylation of benzene.
• Molecular sieves useful in embodiments disclosed herein may include porous, crystalline, three-dimensional alumina-silicates of the zeolite mineral group. The crystal skeleton is composed of silicon and aluminum atoms each surrounded by four oxygen atoms to form.
• the term molecular sieve can be applied to both naturally occurring zeolites and synthetic zeolites. Naturally occurring zeolites have irregular pore size and are not generally considered as equivalent to synthetic zeolites. Amorphous forms of synthetic silicas and aluminas may also be used.
• Synthetic zeolites are typically prepared in the sodium form, wherein a sodium cation is in close proximity to each aluminum tetrahedron and thereby balancing its charge.
• seven principal types of molecular sieves have been reported, namely A, X, Y, L, erionite, omega and mordenite.
• the type A zeolite has relatively small effective pore size (diameter).
• Types X and Y have larger pore size and differ with regard to the ratio of A1 2 0 3 to Si0 2 .
• the type L zeolite has a higher ratio of AI2O3 to Si0 2 .
• catalysts useful in the processes disclosed herein may contain a zeolite sometimes referred to as medium pore or ZSM-5 type.
• the zeolite may be a medium pore shape selective acidic metallosilicate zeolite selected from the group consisting of ZSM-5, H-ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-50, MCM-22, as well as larger pore zeolite Y and zeolite Beta.
• a particular catalyst found to effectively facilitate alkylation and/or transalkylation of benzene is zeolite beta in proton form.
• catalysts useful in embodiments disclosed herein may include phosphorous-modified zeolites, aluminas, and silicas.
• one particular catalyst useful in embodiments disclosed herein is A1P0 4 .
• the AIPO 4 may be supported on alumina.
• the above described catalysts may be prepared in the form of a distillation structure.
• the catalytic distillation structure must be able to function as catalyst and as mass transfer medium.
• the catalyst must be suitably supported and spaced within the column to act as a catalytic distillation structure.
• the catalyst is contained in a structure as disclosed in
• U.S. Patent No. 5,730,843 which is hereby incorporated by reference.
• one or more of the above-described catalysts may be contained in a plurality of wire mesh tubes closed at either end and laid across a sheet of wire mesh fabric such as demister wire. The sheet and tubes are then rolled into a bale for loading into the distillation column reactor.
• This embodiment is described, for example, in U.S. Patent No. 5,431,890, which is hereby incorporated by reference.
• Other useful catalytic distillation structures are disclosed in U.S. Patent Nos. 4,302,356, 4,443,559, 4,731,229, 5,073,236, 5,431,890, 5,266,546, and 5,730,843, which are each incorporated by reference.
• dialkyl ether may be formed as a byproduct via alcohol dehydration over the alkylation catalyst.
• Dialkyl ether is an alkylating agent, and may react with benzene to form alkylbenzene over the alkylation and/or transalkylation catalysts. Any dialkyl ether recovered in the column overheads may be recycled to the column for reaction with benzene. In this manner, dialkyl ether formation may be balanced by the dialkyl ether consumption, resulting in no net dialkyl ether production.
• FIG. 1 a simplified process flow diagram for the production of alkyl benzene according to embodiments disclosed herein is illustrated.
• Fresh alcohol feed is introduced to catalytic distillation reactor system 10 via flow line 12.
• Fresh benzene is introduced to catalytic distillation reactor system 10 via flow line 14.
• benzene may additionally be added via separate stream(s) (not illustrated) to catalytic distillation reactor system 10, such as when additional benzene or localized benzene flow may be beneficial to the optimization of column operations.
• Catalytic distillation reactor system 10 includes an upper reaction zone 16 containing a bed of alkylation catalyst and a lower reaction zone 18 containing a bed of transalkylation catalyst.
• benzene and alcohol are contacted with the alkylation catalyst and react to form alkyl benzene, water, and byproducts, such as dialkyl benzene, trialkylbenzene, and other polyalkylate products, as well as dialkyl ether, formed by the dehydration of the alcohol over the alkylation catalyst.
• the rectifying section of the column (above the alcohol feed) also separates the alkylbenzene and polyalkyl benzene from unreacted benzene, unreacted alcohol, water, and dialkyl ether, which may be recovered from catalytic distillation reactor system 10 as an overheads fraction via flow line 20.
• benzene may be alkylated with dialkyl ether and/or alcohol. Additionally, benzene may react with polyalkylated benzene to form additional monoalkylate.
• the stripping section of the column (below the alcohol feed) also provides for the separation of the light components (water, alcohol, dialkyl ether) from the alkylbenzene product. Unreacted benzene, the alkylbenzene and polyalkyl benzenes may be recovered from catalytic distillation reactor system 10 as a bottoms fraction via flow line 22.
• the catalytic distillation reactor system 10 is operated downflow with respect to benzene.
• the fresh benzene which may also be mixed with various recycle streams, serves as the reflux feed to catalytic distillation reactor system 10.
• flow line 14 may be a reflux feed, returning a portion of the overheads to the column, and the fresh benzene may be introduced at a lower feed point, such as intermediate the upper and lower reaction zones, among other possible locations.
• Figure 1 is also described as feeding the alcohol to the catalytic distillation reactor system 10 intermediate the upper and lower reaction zones.
• two or more alcohol feeds may be used, introducing the alcohol along the length of the column. In this manner, an area of high alcohol concentration in the column may be avoided, thereby limiting the extent of the dehydration reaction.
• the fresh alcohol fed to the column may also be mixed with various recycle streams, embodiments of which are described below.
• FIG 2 a simplified process flow diagram of a process for the production of alkylbenzene according to embodiments disclosed herein is illustrated, where like numerals represent like parts.
• the general flow scheme as described with respect to Figure 1 is used, where fresh benzene is fed to the top of the column via flow line 14, along with recycle components, and fresh alcohol is fed between the upper and lower reaction zones via flow line 12, along with recycle components.
• the bottoms fraction recovered from catalytic distillation reactor system 10 via flow line 22 may include benzene, alkyl benzene, and polyalkyl benzene, including dialkyl benzene, trialkyl benzene, and higher alkylated benzenes.
• the bottoms fraction may then be fed to a first separation column 24, for separating the benzene from the alkylbenzene and the polyalkyl benzene.
• the benzene may be recovered as an overheads fraction from first separation column 24 via flow line 26.
• the recovered benzene may then be recycled via flow line 26 back to catalytic distillation reactor system 10 for additional pass(es) through the reaction zones.
• the alkylbenzene and polyalkyl benzene may be recovered as a bottoms fraction from first separation column 24 via flow line 28.
• the alkylbenzene and polyalkyl benzene may then be fed to second separator 30 for separating the alkylbenzene from the polyalkyl benzene.
• the alkylbenzene may be recovered as an overheads fraction from second separator 30 via flow line 32
• dialkyl benzene or dialkyl benzene and trialkylbenzene may be recovered from second separator 30 as a side draw fraction via flow line 34
• heavier polyalkylate may be recovered from second separator 30 as a bottoms fraction via flow line 36.
• the side draw fraction may be recycled back to catalytic distillation reactor 10 for continued reaction with benzene in the lower portion of the column to produce additional alkylbenzene.
• the overheads fraction recovered from catalytic distillation reactor system 10 via flow line 20 may include benzene, alcohol, dialkyl ether, and water.
• the overheads fraction may then be condensed and phase separated, such as via indirect heat exchanger and settling drum 40. To achieve adequate liquid-liquid separation, it may be necessary to cool the condensate to a temperature of about 50°C or less. Phase separation may result in an upper hydrocarbon liquid fraction, which may include benzene as well as some dialkyl ether and/or alcohol, and a lower aqueous fraction, which may include water, alcohol, and dialkyl ether.
• the upper liquid fraction may be recovered from drum 40 via flow line 42, a portion of which may be recycled to the column with the fresh benzene as reflux, and a portion of which may be recycled to the column with the fresh alcohol feed.
• the column reflux line 44 includes fresh benzene, recycle benzene from first separator 24, and recycle benzene from drum 40.
• the lower liquid fraction including water, alcohol, and dialkyl ether, may be recovered from drum 40 via flow line 46 and fed to third separator 48 for separating the water from the alcohol and the dialkyl ether.
• Water may be recovered from third separator 48 as a bottoms fraction via flow line 50, and may be treated or disposed as necessary.
• Alcohol and dialkyl ether may be recovered from third separator 48 as an overheads fraction via flow line 52 and recycled back to catalytic distillation reactor system 10 via flow line 54 for continued reaction.
• the column feed line 56 includes fresh alcohol feed, recycle benzene from drum. 40, recycle alcohol and dialkyl ether from third separator 48, and recycle polyalkyl benzene from second separator 30.
• Separation of the water, dialkyl ether, and alcohol in third separator 48 may result in the overheads fraction containing some water.
• water may be carried over in the overheads recovered via flow line.
• a separation system as illustrated in Figure 3 may be used.
• the aqueous fraction recovered from drum 40 via flow line 46 is fed to third separator 48 for separation as described above.
• the overheads fraction recovered via flow line 52 may include water, alcohol and dialkyl ether.
• the overheads fraction may then be mixed with a benzene-containing stream 58, such as a portion or all of the fresh benzene stream 14, a portion or all of the benzene recovered from first separator 24 via flow line 26, or a portion or all of the upper liquid fraction recovered from drum 40 via flow line 42, or a mixture of two or more of these streams or portions thereof.
• the resulting mixture may then be phase separated in drum 60 to recover a hydrocarbon fraction via flow line 62, including the benzene, alcohol, and dialkyl ether, and an aqueous water fraction via flow line 64.
• the aqueous fraction may include some alcohol and dialkyl ether, and may be recycled to third separator 48 for continued separation and recovery of the alcohol and dialkyl ether.
• FIG. 4 a simplified process flow diagram of a process for the production of alkylbenzene according to embodiments disclosed herein is illustrated, where like numerals represent like parts.
• the fresh benzene feed and the fresh alcohol feed are introduced intermediate the upper and lower reaction zones 16, 18 and reacted/distilled as described with respect to Figure 1.
• the overheads fraction recovered from catalytic distillation reactor system 10 via flow line 20 is condensed and phase separated via indirect heat exchanger 38 and drum 40, as described above.
• the lower liquid fraction recovered via flow line 46 is fed to separator 48, and separated as described in Figure 3.
• the benzene mixed with the overheads fraction from third separator 48 fed to drum 60 includes both the fresh benzene 14 and the recycle benzene recovered as an overheads from first separator 24 via flow line 26.
• a portion of the upper liquid fraction recovered via flow line 42 is fed to catalytic distillation reactor system 10 as reflux via flow line 70.
• the remaining portion of the upper liquid fraction is combined with the hydrocarbon fraction recovered from drum 60 via flow line 62 and the fresh alcohol feed fed via flow line 12 for introduction as the column feed via flow line 56.
• alkylbenzene may be recovered as an overheads via flow line 32, and the polyalkylate, inclusive of the dialkyl benzene and trialkyl benzene may be recovered from second separator 30 as a bottoms fraction via flow line 72.
• the polyalkylate may then be subsequently processed, separated, or used as a fuel blendstock, as may be appropriate for the production facility.
• FIG. 5 a simplified process flow diagram of a process for the production of alkylbenzene according to embodiments disclosed herein is illustrated, where like numerals represent like parts.
• the overheads fraction recovered from catalytic distillation reactor system 10 is processed similar to that as described with respect to Figure 4, where a portion of the upper liquid fraction 42 is used as column reflux 70, and fresh benzene 14 is combined with the overheads 52 from third separator 48 to limit the amount of water recycled to catalytic distillation reactor system 10.
• catalytic distillation column 10 is maintained under operating conditions to result in the bottoms fraction recovered via flow line 22 containing less than 0.03 wt.% benzene.
• the bottoms fraction may then be fed directly to separator 30 for separation of the alkylbenzene, recovered as an overheads fraction via flow line 32, from the polyalkyl benzene, recovered as a bottoms fraction 36.
• a side draw fraction may be recovered from column 30 via flow line 34, the side draw containing dialkyl benzene and trialkyl benzene, which may be recycled to catalytic distillation reactor system 10 for production of additional alkyl benzene.
• the resulting alkylbenzene product stream 32 may have a purity of at least 99.95 wt.% alkylbenzene.
• reducing the temperature of the overheads fraction recovered from catalytic distillation reactor system 10 may be achieved by contacting the overheads fraction in indirect heat exchange with the bottoms fraction recovered from third separator 48 via flow line 50, the overhead fraction recovered from second separator 24 via flow line 26. Additionally, the overhead fraction may be contacted in indirect heat exchange with water/steam for the production of warm water or low or medium pressure steam, which may be used elsewhere in the process, such as for indirect heat exchange to condense the overhead fraction recovered from third separator 48 via flow line 52.
• the lower liquid fraction recovered from drum 40 via flow line 46 may also be heated prior to feed to third separator 48 using the bottoms fraction recovered from third separator 48 via flow line 50.
• Using heat integration in this manner may effectively minimize or negate the need for cooling water and may result in the utilization of all the heat generated in the process due to the exothermic alkylation reaction.
• embodiments disclosed herein provide for the production of ethylbenzene, cumene, and other alkyl benzenes via a catalytic distillation process integrating the systems of distillation, catalytic alkylation, and catalytic transalkylation.
• embodiments disclosed herein may provide for one or more of the following advantages as compared to a conventional process configuration for producing alkyl benzenes:
• Equipment piece count is reduced, and capital costs may be reduced by up to 60% over current commercial ethylene-based alkylation processes. Specifically, the following major equipment pieces may be eliminated from the process: (1) a finishing reactor, (2) a transalkylation reactor, (3) a diethylbenzene/triethylbenzene column, (4) a light end stripper, (5) a vent absorber, (6) an ethylene compressor, and (7) all auxiliary equipment such as pumps, reboilers, condensers, drums, and control systems associated with items (1) through (6).
• Electricity consumption may be reduced by more than 50% as compared to current commercial ethylene-based alkylation processes. Specifically, the number of pumps required is reduced by more than half and a compressor is not required.
• Cooling water usage may be reduced by up to 100%, and cooling water used may be utilized to generate low pressure steam effectively.
• Catalyst consumption and cycle times are enhanced over fixed bed processes, which are limited due to coking and poisoning.
• the catalyst may be consistently washed and cleaned due to the liquid traffic in the column, and hot spots should not exist in the column. Consequently, the catalyst life is expected to be enhanced and stable operations may be achieved.

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