WO2016071871A1 - Procédé de transalkylation basé sur un composé liquide ionique - Google Patents

Procédé de transalkylation basé sur un composé liquide ionique Download PDF

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WO2016071871A1
WO2016071871A1 PCT/IB2015/058576 IB2015058576W WO2016071871A1 WO 2016071871 A1 WO2016071871 A1 WO 2016071871A1 IB 2015058576 W IB2015058576 W IB 2015058576W WO 2016071871 A1 WO2016071871 A1 WO 2016071871A1
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aromatic compound
compound
ionic liquid
heavy
formula
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PCT/IB2015/058576
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English (en)
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Viswanath KOTRA
Mangesh SAKHALKAR
Pavan Kumar Aduri
B. Suresh IYENGAR
Rahul DHAWADE
Parasuveera Uppara
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Reliance Industries Limited
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Publication of WO2016071871A1 publication Critical patent/WO2016071871A1/fr

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    • 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
    • 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
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
    • B01J31/0279—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the cationic portion being acyclic or nitrogen being a substituent on a ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/06—Halogens; Compounds thereof
    • C07C2527/125—Compounds comprising a halogen and scandium, yttrium, aluminium, gallium, indium or thallium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • 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
    • C10G2300/70—Catalyst aspects
    • 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

Definitions

  • the present disclosure relates to organic chemistry in general. Particularly, the present disclosure relates to a transalkylation process for converting heavy aromatic compounds to light alkyl aromatic compounds in the presence of salt such as liquid salt including but not limited to ionic liquid compound.
  • the ionic liquid compound for transalkylation process is amine and metal salt based ionic liquid compound.
  • the present disclosure further relates to a system for carrying out the transalkylation process in the presence of the ionic liquid compound.
  • alkylation of aromatics with olefins produces alkyl aromatics that have various commercial applications e.g., benzene with olefins of 8 to 15 carbon atoms produce linear alkyl benzenes which can be sulphonated to produce detergents.
  • various side reactions will take place leading to the formation of dialkylaromatics, oligomers of olefins (referred to as heavier' s) which have very low commercial value as compared to the lighter alkyl aromatics.
  • Use of excess reactant helps in minimizing the heavier' s but they cannot be eliminated.
  • the catalysts currently used are not selective and other reactions of olefins will occur to produce heavier' s, i.e., dimers and dialkylaryl compounds. Also skeletal isomerization of the olefin will occur, resulting in a loss of selectivity to the alkylbenzene.
  • a process called Transalkylation is adapted to convert the heavier's back to alkyl aromatics.
  • the transalkylation process in the prior arts for the conversion of heaver's to lighter aromatic compound uses solid aromatic compound, which has its own limitation towards the transalkylation process.
  • United States Patent No. 2222632 discloses a clay comprising of alumina and silica for transalkylation of poly aromatics.
  • United States Patent No. 3385906 describes a process for transalkylating benzene and diisopropylbenzene to make Cumene in the presence of a zeolite molecular sieve catalyst wherein not more than 90% of aluminium atoms in the zeolite are associated with monovalent cations.
  • United States Patent No. 2222632 discloses a clay comprising of alumina and silica for transalkylation of poly aromatics.
  • United States Patent No. 3385906 describes a process for transalkylating benzene and diisopropylbenzene to make Cumene in the presence of a zeolite molecular sieve catalyst wherein not more than 90% of aluminium atoms in the zeolite are associated with monovalent cations.
  • 3410921 describes transalkylating a polyalkylated aromatic compound by reacting the compound in admixture with hydrogen, with an alkylatable aromatic compound in contact with a catalyst comprising an active catalytic component, preferably a group VIII metal, on an aluminium support having suspended therein less than about 20wt% of a finely divided crystalline aluminosilicate under transalkylation conditions.
  • the transalkylation reaction is carried out at 250°C - 700°C and latm -200 atm pressure and the hydrogen to hydrocarbon mole ratio is 2: 1 to 20: 1.
  • United States Patent Nos. 3751504 and 3571506 show transalkylation and alkylation in the vapour phase over ZSM-5 type zeolite catalysts.
  • ZSM-5 is a medium pore size zeolite having an effective pore size between 5A° and 6A°.
  • United States Patent Nos. 3769360, 3776971, 3778415, 3843739 and 4459426 relate to methods for combining alkylation and transalkylation to obtain improved yields of monoalkylated aromatics.
  • Rare earth exchanged Y and steam stabilized Y zeolites are cited in these patents as being particularly effective catalysts.
  • United States Patent No. 4891458 describes a process for the alkylation or transalkylation of an aromatic hydrocarbon which comprises contacting the aromatic hydrocarbon with C2 to C4 olefin alkylating agent or a polyalkylaromatic hydrocarbon transalkylating agent under at least partial liquid phase conditions and in the presence of a catalyst comprising zeolite beta.
  • United States Patent No. 5157180 discloses a process for producing alkylated organic compound via alkylation and /or transalkylation in the presence of a molecular sieve catalyst.
  • the catalyst comprises of a molecular sieve having alkylation and/or transalkylation activity and contains 250 -20000 ppm of ammonium ions calculated as (NH 4 ) 2 0 on a volatiles free basis.
  • the present disclosure relates to a process for converting heavy aromatic compound to light alkyl aromatic compound, said process comprising a step of contacting a mixture comprising heavy aromatic compound and unsubstituted aromatic compound or methyl substituted aromatic compound with ionic liquid compound of formula I-[(NRiR 2 R3)iMi] n+ [(M2Y k ) L Xj] n"
  • NR1R2R3 is amine
  • Ri, R 2 and R 3 are independently selected from a group comprising alkyl, aryl and
  • Mi and M 2 are independently metals selected from a group comprising Al, Fe, Zn, Mn, Mg, Ti, Sn, Pd, Pt, Rh, Cu, Cr, Co, Ce, Ni, Ga, In, Sb and Zr or any combinations thereof;
  • X and Y are independently selected from a group comprising halide ion, nitrate, sulphate, sulfonate, carbonate, phosphonate, citrate, cyanide ion, nitrite, phosphate and acetate, or any combination thereof;
  • 'n' is an integer ranging from about 1 to 4;
  • 'i' is an integer ranging from about 1 to 6;
  • 'j ' is an integer ranging from about 1 to 4.
  • 'k' is an integer ranging from about 1 to 4.
  • 'L' is an integer ranging from about 1 to 7;
  • Mi M 2 or Mi ⁇ M 2 .
  • the present disclosure relates to a system for transalkylation process for converting a heavy aromatic compound to light alkyl aromatic compound, said system comprises:
  • At least one mixer adapted to independently receive mixture comprising heavy aromatic compound and unsubstituted aromatic compound or methyl substituted aromatic compound and ionic liquid compound of formula I ⁇ [(NRiR 2 R 3 ) 1 M 1 ] n+ [(M 2 Y k ) L X j f ;
  • NRiR 2 R3 is amine:
  • Mi and M 2 are independently metal selected from a group comprising Al, Fe, Zn,
  • X or Y is selected from a group comprising halide ion, nitrate, sulphate, sulfonate, carbonate, phosphonate, citrate, cyanide ion, nitrite, phosphate and acetate, or any combinations thereof;
  • 'n' is an integer ranging from about 1 to 4;
  • 'i' is an integer ranging from about 1 to 6;
  • 'j ' is an integer ranging from about 1 to 4.
  • 'k' is an integer ranging from about 1 to 4.
  • 'L' is an integer ranging from about 1 to 7;
  • Mi M 2 or Mi ⁇ M 2 .
  • the mixer is adapted to convert the heavy aromatic compound to the light alkyl aromatic compound in presence of ionic liquid compound of formula I b) at least one settler unit fluidly connected to at least one mixer, wherein the settler unit is adapted to receive at least one of the heavy aromatic compound, the unsubstituted aromatic compound or the methyl substituted aromatic compound and the ionic liquid compound of formula I and the light alkyl aromatic compound from the mixer, and wherein the settler unit is adapted to separate at least one of light alkyl aromatic compound, ionic liquid compound of formula I, heavy aromatic compound, unsubstituted aromatic compound or methyl substituted aromatic compound;
  • the purifier is adapted to receive at least one of the light alkyl aromatic compound, the ionic liquid compound of formula I, the heavy aromatic compound, the unsubstituted aromatic compound or the methyl substituted aromatic compound and alkali solution and wherein the purifier is adapted to purify the light alkyl aromatic compound;
  • At least one fractionating column adapted to receive at least one of the light alkyl aromatic compound, the heavy aromatic compound, unsubstituted aromatic compound or methyl substituted aromatic compound and ionic liquid compound of formula I from at least one settler unitand wherein the fractionating column is adapted to separate at least one of the light alkyl aromatic compound, the heavy aromatic compound, the unsubstituted aromatic compound or the methyl substituted aromatic compound, the ionic liquid compound of formula I and paraffi; and
  • At least one catalyst recovery unit adapted to receive at least one of the ionic liquid compound of formula I, the heavy aromatic compound, the unsubstituted aromatic compound or the methyl substituted aromatic compound and the light alkyl aromatic compound, independently from at least one of the settler unit and at least one of the fractionating column and wherein the catalyst recovery unit is adapt to regenerate the ionic liquid compound of formula I.
  • FIG. 1 illustrates system of the present disclosure employed for carrying out transalkylation process of the present disclosure.
  • the present disclosure relates to transalkylation process for conversion of heavy aromatic compounds to light alkyl aromatic compounds, using salt such as liquid salt including but not limited to ionic liquid compound.
  • the heavy aromatic compound is a heavy alkyl aromatic compound, wherein the alkyl group comprises carbon atom ranging from about 3 to
  • the ionic liquid compound employed in the transalkylation process of the present disclosure comprises at least one electron-pair acceptor and at least one electron-pair donor.
  • the electron-pair acceptor of the ionic liquid compound includes but is not limited to a Lewis acid and the electron-pair donor of the ionic liquid compound includes but is not limited to a Lewis base.
  • the Lewis acid of the ionic liquid compound for the transalkylation process of the present disclosure is a salt of cation selected from a group comprising Aluminium (Al 3+ ), Magnesium (Mg 2+ ), Calcium (Ca 2+ ), Chromium
  • the Lewis acid of the ionic liquid compound for the transalkylation process of the present disclosure is complexed with an alkyl amine.
  • the Lewis base or anion of the ionic liquid compound for transalkylation process of the present disclosure is selected from a group comprising halide ion, Sulphate (S0 4 ), Sulphonate (HSO 3 ), Nitrate (NO 3 ), Carbonate (CO3 2" ), Phosphonate (C-PO(OH) 2 ), Citrate (C 6 H 5 0 7 3" ), Cyanide ion (CN " ), Nitrite
  • the halide ion of the ionic liquid compound for transalkylation process of the present disclosure is selected from a group comprising fluoride (F ⁇ ), chloride (Cl ⁇ ), bromide (Br ⁇ ), iodide ( ⁇ ) and astatide (At ⁇ ), or any combination thereof.
  • the ionic liquid compound for the transalkylation process comprises metal selected from a group comprising Aluminium (Al), Iron (Fe), Zinc (Zn), Manganese (Mn), Magnesium (Mg), Titanium (Ti), Tin (Sn), Palladium (Pd), Platinum (Pt), Rhodium (Rh), Copper (Cu), Chromium (Cr), Cobalt (Co), Cerium (Ce), Nickel (Ni), Gallium (Ga), Indium (In), Antimony (Sb) and Zirconium (Zr) or any combinations thereof, wherein the metal of the ionic liquid compound is complexed with alkyl amine.
  • the ionic liquid compound is an amine and metal salt based ionic liquid compound.
  • the ionic liquid compound for the transalkylation process of the present disclosure is represented by Formula I
  • NRiR 2 R3 is amine
  • Ri, R 2 and R3 are independently selected from a group comprising alkyl, aryl and H or any combinations thereof, wherein
  • Mi and M 2 are independently metals selected from a group comprising Al,
  • X and Y are independently selected from a group comprising halide ion, nitrate, sulphate, sulfonate, carbonate, phosphonate, citrate, cyanide ion, nitrite, phosphate and acetate, or any combination thereof;
  • 'n' is an integer ranging from about 1 to 4;
  • 'i' is an integer ranging from about 1 to 6;
  • 'j' is an integer ranging from about 1 to 4.
  • 'k' is an integer ranging from about 1 to 4;
  • 'L' is an integer ranging from about 1 to 7;
  • Mi M 2 or Mi ⁇ M 2 .
  • the ionic liquid compound for the transalkylation process of the present disclsoure is [(N(C 2 I3 ⁇ 4)3-A1] + [Al 2 Ci7] " 3.
  • the ionic liquid compound for the transalkylation process of the present disclosure is a pure substance (form).
  • the ionic liquid compound for the transalkylation of the present disclosure is mixed with an organic compound or inorganic compound to lower its viscosity by the formation of an Ionic liquid compound complex with organic compound or inorganic compound, wherein the organic compound is an aromatic compound or aliphatic compound.
  • the aromatic compound is selected from a group comprising benzene and toluene, or a combination thereof.
  • the process of transalkylation of the present disclosure for converting heavy aromatic compound to light alkyl aromatic compound or hydrocarbon layer comprises step of:
  • the light alkyl aromatic compound or hydrocarbon layer is deacidified followed by distilling to remove components comprising unreacted alkylated products.
  • the transalkylation process comprises the step of recycling the ionic liquid of formula I after obtaining the light alkyl aromatic compound.
  • the heavy alkyl aromatic compound of the mixture is alkyl benzene wherein the alkyl group comprises carbon atom ranging from about 3 to 50; and wherein the unsubstituted aromatic compound of the mixture is selected from a group comprising benzene and methyl substituted aromatic compound is selected from a group comprising toluene.
  • the heavy alkyl aromatic compound comprises benzene attached to alkyl group having carbon atom ranging from about 3 to 50, wherein the heavy alkyl aromatic compound is selected from a group comprising 1,4- didecylbenzene, 1,4-dodidecyl benzene and trimethyl benzene, or any combination thereof.
  • the light alkyl aromatic compound is selected from a group comprising benzene attached to alkyl group containing carbon atoms ranging from about 1 to 14.
  • the heavy alkly aromatic compound 1,4-dodidecyl benzene undergoes trans-alkylation process as per the present disclosure with benzene to produce light alkyl alkyl aromatic compound 1,4-decyl benzene.
  • tri methyl benzene undergoes trans-alkylation process as per the present disclosure with benzene to produce toluene or diethyl benzene.
  • the heavy alkyl aromatic compound is 1,4- dodidecyl benzene (benzene with C-24) upon undergoing the transalkylation as described in the instant invention, it forms 1-dodecyl benzene (benzene with C-12), which is considered as light aromatic compound.
  • tri-methyl benzene undergoes transalkylation as described in the instant invention, it forms dimethyl benzene or methyl benzene (benzene with C-2 or C-l). In this case tri-methyl benzene is the heavier aromatic compound and dimethyl benzene is the light aromatic compound. Therefore, the heavy aromatic alkyl aromatic compound comprises alkyl group having carbon atoms ranging from about 3 to 50 and lighter aromatic compound comprises alkyl group having carbon atoms ranging from about 1 to 14.
  • the mixture of heavy alkyl aromatic compound and unsubstituted aromatic compound or methyl substituted aromatic compound and ionic liquid compound of formula I during the transalkylation process is contacted in a reactor such as but not limited to transalkylation reactor for the conversion of the heavy alkyl aromatic compound to light alkyl aromatic compound, followed by allowing the components of the conversion to settle to obtain light alkyl aromatic compound or hydrocarbon layer.
  • the heavier alkyl aromatic compound consists of mostly benzene attached to alkyl having carbon C-20 or more.
  • molar ratio of the unsubstituted aromatic compound or methyl substituted aromatic compound to the heavy alkyl aromatic compound in the mixture is ranging from about 1 : 1 to 20: 1, preferably the molar ratio of the unsubstituted aromatic compound or methyl substituted aromatic compound to the heavy alkyl aromatic compound is ranging from about 2: 1 to 8: 1.
  • the mixture comprising heavy alkyl aromatic compound and unsubstituted aromatic compound or methyl substituted aromatic compound is contacted with pure form (pure substance) of ionic liquid compound of formula I.
  • the mixture comprising heavy alkyl aromatic compound and unsubstituted aromatic compound or methyl substituted aromatic compound is contacted with mixed form of ionic liquid compound of formula I, wherein the mixed form of ionic liquid compound of formula I refers to ionic liquid compound of formula I mixed with benzene or toluene to lower the viscosity of the ionic liquid compound of formula I.
  • the mixture comprising heavy alkyl aromatic compound and unsubstituted aromatic compound or methyl substituted aromatic compound is contacted with recycled form of ionic liquid compound of formula I, wherein the recycled form of ionic liquid compound of formula I refers to ionic liquid compound of formula I obtained after regeneration, post conversion of heavy alkyl aromatic compound to light alkyl aromatic compound.
  • the mixture comprising heavy alkyl aromatic compound and unsubstituted aromatic compound or methyl substituted aromatic compound is contacted with ionic liquid compound of formula I at a temperature ranging from about 5°C to 170°C, preferably at a temperature ranging from about 50°C to 150°C and at a pressure ranging from about 1 atmosphere to 50 atmosphere, preferably at a pressure ranging from about 1 atmosphere to 10 atmosphere.
  • the volume ratio of the ionic liquid compound of formula I to the mixture comprising heavy alkyl aromatic compound and unsubstituted aromatic compound or methyl substituted aromatic compound is 0.01 to 1.5.
  • the deacidification during the process of transalkylation is carried out using techniques including but not limited to washing with aqueous solution such as alkali solution including but not limited to sodium hydroxide (NaOH), calcium hydroxide (Ca(OH) 2 ) and potassium hydroxide (KOH), centrifugation, alumina treatment, and acid stripping.
  • aqueous solution such as alkali solution including but not limited to sodium hydroxide (NaOH), calcium hydroxide (Ca(OH) 2 ) and potassium hydroxide (KOH), centrifugation, alumina treatment, and acid stripping.
  • the volume ratio of alkali solution to the light alkyl aromatic compound is 0.2 to 1 and concentration of alkali in the solution is ranging from about 2% to 50%.
  • the ionic liquid compound of formula I after the conversion of heavy aromatic compound to light alkyl aromatic compound is either recycled as such or recycled after regeneration.
  • the transalkylation process of the present disclosure in the presence of ionic liquid compound of formula I lead to about 50% to 60% conversion of heavy aromatic compound including but not limiting to heavy alkyl benzene, wherein the alkly group comprises about 3 to 50 carbon atoms.
  • the present disclosure further relates to a system for transalkylation process in the presence of the ionic liquid compound of formula I.
  • the system for transalkylation process in the presence of the ionic liquid compound of formula I comprises:
  • At least one mixer adapted to independently receive mixture comprising heavy aromatic compound and unsubstituted aromatic compound or methyl substituted aromatic compound and ionic liquid of compound of formula I; wherein the mixer is adapted to convert heavy aromatic compound to light alkyl aromatic compound;
  • At least one settler unit fluidly connected to at least one mixer, the settler unit is adapted to receive at least one of the heavy aromatic compound, the unsubstituted aromatic compound or the methyl substituted aromatic compound, the ionic liquid compound of formula I and the light alkyl aromatic compound, and wherein the settler unit is adapted to separate at least one of light alkyl aromatic compound, ionic liquid compound of formula I, heavy aromatic compound, unsubstituted aromatic compound or methyl substituted aromatic compound;
  • the purifier is adapted to receive at least one of the light alkyl aromatic compound, ionic liquid compound of formula I, heavy aromatic compound, unsubstituted aromatic compound or methyl substituted aromatic compound and alkali solution and wherein the purifier is adapted to purify the light alkyl aromatic compound;
  • At least one fractionating column adapted to receive at least one of the light alkyl aromatic compound, the heavy aromatic compound, unsubstituted aromatic compound or methyl substituted aromatic compound and ionic liquid compound of formula I from at least one settler unit and wherein the fractionating column is adapted to separate at least one of the light alkyl aromatic compound, the heavy aromatic compound, the unsubstituted aromatic compound or the methyl substituted aromatic compound, the ionic liquid compound of formula I ;
  • At least one catalyst recovery unit adapted to receive at least one of the ionic liquid compound of formula I, the heavy aromatic compound, the unsubstituted aromatic compound or the methyl substituted aromatic compound and the light alkyl aromatic compound, independently from at least one of the settler unit and at least one of the fractionating column; wherein the catalyst recovery unit is adapted to regenerate the ionic liquid compound of formula I.
  • figure 1 illustrates the system (100) for transalkylation process for converting heavy aromatic compounds to light alkyl aromatic compounds in the presence of ionic liquid compound of formula I.
  • the system (100) for the transalkylation process in the presence of ionic liquid compound of formula I is operated in a mode selected from a group comprising batch mode semi-continuous mode and continuous mode, or any combination thereof.
  • the system (100) comprises one or more mixers Ml, M2, M3... Mn (collectively referred as M) configured to carry out transalkylation process between the heavy alkyl aromatic compound and the unsubstituted aromatic compound or the methyl substituted aromatic compound, in the presence of the ionic liquid compound of formula I; one or more settler units SI, S2, S3..Sn (collectively referred as S) which are fluidly connected to one or more mixers (M).
  • the settler units (S) are configured to receive at least one of the heavy alkyl aromatic compound, the unsubstituted aromatic compound or the methyl substituted aromatic compound, the ionic liquid compound of formula I and the light alkyl aromatic compound from the one or more mixers (M), and are adapted to carry out layer separation of at least one of the heavy alkyl aromatic compound, the unsubstituted aromatic compound or the methyl substituted aromatic compound, the ionic liquid compound of formula I and the light alkyl aromatic compound .
  • the system (100) also includes a purifier (PU) fluidly connected to the one or more settlers (S), and is configured to receive separated layer comprising the light alkyl aromatic compound from the one or more settlers (S).
  • PU purifier
  • the purifier (PR) is adapted to purify the light alkyl aromatic compound. Further, the purified light alkyl aromatic compound from the purifier (PR) is fed back to the one or more settler unit (S) for further layer separation.
  • the system (100) also comprises one or more fractionating columns Dl, D2, D3... Dn (collectively referred as D) fluidly connected to the one or more settlers units (S) for receiving further the separated layer comprising light alkyl aromatic compound from the one or more settler (S).
  • the one or more fractionating columns (D) are configured to further separate the light alkyl aromatic compounds and recycle at least one of the heavy aromatic compound, the unsubstituted aromatic compound or the methyl substituted aromatic compound and the ionic liquid compound of formula I, use to the one or more mixers (M).
  • a catalytic recovery unit (CRU) is provided in the system (100), and is fluidly connected to one or more settler units (S) for recovering or regenerating ionic liquid compound of formula I after layer separation, and recycle the ionic liquid compound of formula I to the one or more mixers (M).
  • the system (100) comprises first mixer (Ml), second mixer (M2) and third mixer (M3).
  • the mixers Ml , M2 and M3 are selected from a group comprising stirred vessel, plug flow reactor, static mixer, jet mixer and pump mixer, or any combination thereof.
  • the system also comprises a first settler unit (SI), a second settler unit (S2) and a third settler unit (S3).
  • the settler units SI, S2 and S3 is a settling vessel such as but not limited to gravity settling vessel, arranged either horizontally or vertically, comprising single step settling or multi-step settling with a series of settlers arranged inside the settler units, either horizontally or vertically.
  • the purifier (PR) of the system is selected from a group comprising vessel such as stirred vessel, a separator such as centrifuge separator a column packed with alumina, an evaporator, and an acid stripper.
  • the purifier of the system removes acid traces from the light alkyl aromatic compound.
  • the working of the system (100) for transalkylation process employing the ionic liquid compound of formula I comprises following steps: Initially, the reaction raw material is prepared by mixing an unsubstituted aromatic compound such as but not limited to benzene; and heavy aromatic compound such as but not limited to heavy alkyl benzene (HAB) coming from lines 1 and 2, respectively to obtain pre-mixed feed. The pre-mixed feed is then fed to first mixer (Ml) where pure form/ mixed form /recycled/regenerated ionic liquid compound of formula I is added via line 3. The first mixer (Ml) is maintained at a temperature ranging from about 30°C to 150°C and maintained at a pressure ranging from about 1 atmosphere to 20 atmosphere .
  • first mixer (Ml) is maintained at a temperature ranging from about 30°C to 150°C and maintained at a pressure ranging from about 1 atmosphere to 20 atmosphere .
  • the molar ratio of unsubstituted aromatic compound to heavy alkyl aromatic compound is ranging from about 2: 1 to 8: 1.
  • the volume ratio of the ionic liquid compound of formula I to the mixture comprising heavy aromatic compound and unsubstituted aromatic compound is 0.01 to 1.5, preferably the volume ratio is 0.03 to 0.5.
  • the conversion of heavy aromatic compound to light alkyl aromatic compound in the presence of ionic liquid compound of formula I takes place in the first mixer (Ml).
  • the outlet of the first mixer (Ml) is directly fed into second mixer (M2) where further conversion of heavy aromatic compound to light alkyl aromatic compound in the presence of ionic liquid compound of formula I takes place.
  • the temperature and pressure conditions in the second mixer (M2) are same as the first mixer (Ml).
  • the temperature of the second mixer is ranging from about 5°C to 170°C, preferably ranging from about 50°C to 150°C
  • the outlet from the second mixer (M2) is fed into first settler unit (SI) where the light alkyl aromatic compound and the ionic liquid compound of formula I layer are separated.
  • the heavier catalyst layer which is denser than the light alkyl aromatic compound, from first settler unit (SI) via line 4 is recycled to at least one of first mixer (Ml), and the third mixer (M3) through catalyst recovery unit (CRU).
  • the upper layer from the settler unit (SI) comprises the light alkyl aromatic compound which is fed to third mixer (M3) via line 5 where pure form/ mixed form/recycled/regenerated ionic liquid compound of formula I is added via line 3.
  • the outlet from the third mixer (M3) is fed into second settler unit (S2) where the light alkyl aromatic compound layer and the ionic liquid compound of formula I are separated
  • the heavier catalyst layer which is denser than the light alkyl aromatic compound, from the second settler unit (S2) via line 6 is recycled to at least one of the first mixer (Ml) and the third mixer (M3) through catalytic regeneration unit (CRU).
  • the upper light alkyl aromatic compound layer from settler unit (S2) is fed to purifier (PR) via line 7, where the light alkyl aromatic compound is washed with alkali solution such as but not limiting to sodium hydroxide (NaOH) via line 8; or directly centrifuged without addition of alkali solution to remove trace acid content in the light alkyl aromatic compound.
  • alkali solution such as but not limiting to sodium hydroxide (NaOH) via line 8; or directly centrifuged without addition of alkali solution to remove trace acid content in the light alkyl aromatic compound.
  • the volume ratio of alkali solution to the light alkyl aromatic compound is 0.2 to 1 and the concentration of alkali in the solution is ranging from about 2% to 50%, preferably about 5% to 20%.
  • the purifier (PR) is a packed column filled with alumina to remove acidic traces in the light alkyl aromatic compound.
  • the outlet from (PR) is directly fed to third settler unit (S3) where further separation of light alkyl aromatic compound occurs.
  • the bottom layer in the settler unit (S) is the layer of alkali solution, which is sent for effluent treatment plant (ETP) via line 9 while in case of centrifugation or crystallization is performed in the purifier (PR), the bottom layer is ionic liquid compound of formula I which is fed to catalyst recovery unit (CRU) via line 9.
  • the upper layer comprising the light alkyl aromatic compound from third settler unit (S3) is fed to first fractionating column (Dl) via line 10 where the unsubstitued aromatic compound such as benzene is distilled off and recycled to line 1 via line 11.
  • first fractionating column (Dl) is fed to second fractionating column (D2) via line 12 to remove and recover light alkyl aromatic compound via line 13.
  • the residue of second fractionating column (D2) is fed to third fractionating column (D3) via line 14 to separate light alkyl aromatic compound such as linear alkyl benzene product by line 15 and unreacted heavy alkyl aromatic compound by line 16 is recycled to line 2.
  • the fractionating columns (Dl, D2 and D3) of the system are operated under pressure ranging from about 1.05Kg/cm 2 to 1.5kg/cm 2 .
  • the fractionating columns (Dl, D2 and D3) of the system are operated under vacuum ranging from about 0.05 kg/cm 2 to 0.5 kg/cm 2
  • Comparative experimentation 1 Molar ratio of about 1 :3 of heavy alkyl benzene to benzene is subjected to transalkylation process employing about 5% ionic liquid of formula 1, [(N(C 2 H 5 ) 3 -A1] + [Al 2 Clv] " 3 at a temperature of about 80°C. The transalkylation process is carried for about 1.5hours under stirring condition.
  • Comparative experimentation 2 Molar ratio of about 1 :3 of heavy alkyl benzene to benzene is subjected to transalkylation process employing about 5% [BMIM] + [Al 2 Cl 6 Br] " at a temperature of about 80°C. The transalkylation process is carried for about 1.5hours under stirring condition.
  • Line 1 Carries aromatic compound for mixing with contents from Line 2.
  • Line 2 Carries heavy alkyl aromatic compound for mixing with contents of Line 1.
  • Line 4 Connects first settler to first/third mixer for recycling heavier catalyst layer from first settler to first/third mixer.
  • Line 5 Connects first settler to third mixer for feeding upper light alkyl aromatic compound layer.
  • Line 6 Connects second settler to first/third mixer for recycling heavier catalyst layer.
  • Line 7 Connects second settler to purifier for feeding upper light alkyl aromatic compound layer.
  • Line 8 Connected to purifier for feeding aqueous/alkali solution for washing the light alkyl aromatic compound layer.
  • Line 9 Connects third settler to catalyst recovery unit for sending bottom aqueous layer for effluent treatment/feeding bottom catalyst layer into CRU.
  • Line 10 Connects third settler to first fractionating
  • Line 11 Connects first fractionating column to line 1 for recycling distilled aromatic compound.
  • Line 12 Connects first fractionating column to second fractionating column for feeding residue.
  • Line 13 Connected to second fractionating column for removing and recovering light alkyl aromatic compound.
  • Line 14 Connects second fractionating column to third fractionating column for feeding residue.
  • Line 15 Connected to third fractionating column for separating alkyl aromatic compound.
  • Line 16 Connects third fractionating column to line 2 for recycling unreacted heavy alkyl aromatic compound.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

La présente invention concerne un procédé de transalkylation pour la conversion de composés aromatiques lourds en composés aromatiques d'alkyle légers au moyen d'un sel liquide, tel que, mais pas exclusivement, un composé liquide ionique. Dans un autre mode de réalisation, le composé liquide ionique est un composé liquide ionique à base de sel d'amine et de sel métallique. La présente invention concerne également un système s'appliquant au procédé de transalkylation en présence du composé liquide ionique.
PCT/IB2015/058576 2014-11-07 2015-11-06 Procédé de transalkylation basé sur un composé liquide ionique WO2016071871A1 (fr)

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IN2551MU2014 2014-11-07

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Cited By (1)

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WO2020121154A1 (fr) * 2018-12-09 2020-06-18 Reliance Industries Limited Procédé de préparation d'alkylbenzène linéaire

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US2222632A (en) 1938-10-08 1940-11-26 Socony Vacuum Oil Co Inc Dealkylation process
US3385906A (en) 1965-05-25 1968-05-28 Union Carbide Corp Production of cumene
US3410921A (en) 1966-06-27 1968-11-12 Universal Oil Prod Co Transalkylation of polyalkylated aromatic compounds using a crystalline aluminosilicate catalyst
US3571506A (en) 1967-02-07 1971-03-16 Rank Organisation Ltd Pulse shaping means for blanking pulses
US3843739A (en) 1971-04-09 1974-10-22 Gulf Research Development Co Process for transalkylating diethyl benzene
US3769360A (en) 1971-04-09 1973-10-30 Gulf Research Development Co Process for transalkylating diethyl benzene
US3776971A (en) 1971-08-13 1973-12-04 Gulf Research Development Co Process for preparing a monoalkyl aromatic
US3778415A (en) 1971-08-13 1973-12-11 Gulf Research Development Co Process for preparing a monoalkyl aromatic
US3751504A (en) 1972-05-12 1973-08-07 Mobil Oil Corp Vapor-phase alkylation in presence of crystalline aluminosilicate catalyst with separate transalkylation
US4459426A (en) 1980-04-25 1984-07-10 Union Oil Company Of California Liquid-phase alkylation and transalkylation process
US4599470A (en) 1982-11-18 1986-07-08 The British Petroleum Company P.L.C. Process for the transalkylation or dealkylation of alkyl aromatic hydrocarbons
US4885426A (en) 1987-09-02 1989-12-05 Mobil Oil Corporation Transalkylation of polyaromatics
EP0358792A1 (fr) 1987-09-11 1990-03-21 Uop Procédé d'alkylation/transalkylation pour la production sélective d'hydrocarbures aromatiques mono-alkylés
US4891458A (en) 1987-12-17 1990-01-02 Innes Robert A Liquid phase alkylation or transalkylation process using zeolite beta
US5157180A (en) 1989-05-26 1992-10-20 Union Oil Company Of California Alkylation and transalkylation processes
WO2000041809A1 (fr) * 1999-01-15 2000-07-20 Bp Chemicals Limited Catalyseur a base de liquide ionique pour alkylation
EP1358141A1 (fr) 2001-02-07 2003-11-05 ExxonMobil Chemical Patents Inc. Obtention d'un compose alkylaromatique
EP1572838A1 (fr) 2002-12-19 2005-09-14 Uop Llc Processus integre pour la production d'aromatiques
CN101020619A (zh) * 2006-02-13 2007-08-22 黑龙江大学 离子液体催化转移烷基化制备2,6－二甲基萘的方法
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US7414163B1 (en) 2006-07-28 2008-08-19 Uop Llc Iridium and germanium-containing catalysts and alkylaromatic transalkylation processes using such catalysts
US7456124B2 (en) 2006-09-12 2008-11-25 Uop Llc Rhenium-containing transalkylation catalysts and processes for making the same
US7642389B2 (en) 2007-02-12 2010-01-05 Uop Llc Energy integrated processes including alkylation and transalkylation for making detergent range alkylbenzenes
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WO2014178075A2 (fr) * 2013-04-19 2014-11-06 Reliance Industries Limited Composé liquide ionique

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020121154A1 (fr) * 2018-12-09 2020-06-18 Reliance Industries Limited Procédé de préparation d'alkylbenzène linéaire
US11370723B2 (en) 2018-12-09 2022-06-28 Reliance Industries Limited Process for preparing linear alkyl benzene

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