WO2016205194A1 - Antifouling oligomerization catalyst systems - Google Patents

Antifouling oligomerization catalyst systems Download PDF

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Publication number
WO2016205194A1
WO2016205194A1 PCT/US2016/037366 US2016037366W WO2016205194A1 WO 2016205194 A1 WO2016205194 A1 WO 2016205194A1 US 2016037366 W US2016037366 W US 2016037366W WO 2016205194 A1 WO2016205194 A1 WO 2016205194A1
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Prior art keywords
catalyst system
antifouling agent
titanate
compound
mol
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PCT/US2016/037366
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English (en)
French (fr)
Inventor
Sohel Shaikh
Motaz KHAWAJI
Hussain AL YAMI
Wei Xu
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Saudi Arabian Oil Co
Aramco Services Co
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Saudi Arabian Oil Co
Aramco Services Co
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Priority to EP19188473.3A priority Critical patent/EP3578256B1/en
Application filed by Saudi Arabian Oil Co, Aramco Services Co filed Critical Saudi Arabian Oil Co
Priority to KR1020187001672A priority patent/KR102545317B1/ko
Priority to CN201680035981.0A priority patent/CN107810057B/zh
Priority to EP16732154.6A priority patent/EP3310476B1/en
Priority to JP2017565808A priority patent/JP7014609B2/ja
Priority to EP23186812.6A priority patent/EP4257234B1/en
Priority to EP25168237.3A priority patent/EP4582181A1/en
Priority to EP21155202.1A priority patent/EP3868472B1/en
Publication of WO2016205194A1 publication Critical patent/WO2016205194A1/en
Priority to SA521422206A priority patent/SA521422206B1/ar
Priority to SA517390554A priority patent/SA517390554B1/ar
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0255—Phosphorus containing compounds
    • B01J31/0267—Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen
    • B01J31/0268—Phosphonium compounds, i.e. phosphine with an additional hydrogen or carbon atom bonded to phosphorous so as to result in a formal positive charge on phosphorous
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    • 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
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    • B01J31/122—Metal aryl or alkyl compounds
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    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
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    • B01J2231/20—Olefin oligomerisation or telomerisation
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    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
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    • C07C2531/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24
    • C07C2531/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24 of titanium, zirconium or hafnium

Definitions

  • Embodiments of the present disclosure generally relate to catalyst systems used in ethylene oligomerization, and more specifically relate to antifouling catalyst systems used in ethylene oligomerization which may reduce undesired polymerization.
  • 1-Butene and 1-hexene are important petrochemicals, especially for the production of polyethylene.
  • LLDPE linear low density polyethylene
  • a source of 1-butene is the butene fraction from the effluent of a hydrocarbon cracker, such as a steam cracker or fluidized catalytic cracker.
  • a hydrocarbon cracker such as a steam cracker or fluidized catalytic cracker.
  • the process for recovering 1-butene from such an effluent requires several difficult process steps that may make the process undesirable.
  • a commercially successful dimerization process is the AlphabutolTM Process, developed by the Institute Francais du Petrole (IFP), described in A. Forestiere, et al., "Oligomerization of Monoolefins by Homogenous Catalysts", Oil & Science and Technology— Review de l'lnstitute Francais du Petrole, pages 663-664 (Volume 64, Number 6, November 2009).
  • IFP Institute Francais du Petrole
  • This process uses a bubble-point reactor that contains 1- butene as a process fluid to oligomerize ethylene selectively into 1-butene.
  • a hot spot is an area where external cooling is ineffective and catalyst activity is high. It represents a loss of process control.
  • a hot spot can be an area of collected polymer that includes catalytically active material that fosters side-reactions, including polymerization. If left unchecked, the hot spot can eventually lead to a process shutdown due to the loss of cooling capacity, a runaway polymerization reaction, or both.
  • a catalyst system that may reduce polymeric fouling may comprise at least one titanate compound, at least one aluminum compound, and an antifouling agent.
  • the antifouling agent may be chosen from one or more of a phosphonium or phosphonium salt; a sulfonate or a sulfonate salt; a sulfonium or sulfonium salt; an ester comprising a cyclic moiety; an anhydride; a polyether; and a long-chained amine-capped compound.
  • the catalyst system may further comprise a non-polymeric ether compound.
  • 1-butene may be selectively produced by a method that may comprise contacting ethylene with a catalyst system to oligomerize the ethylene to selectively form 1-butene.
  • the catalyst system may comprise at least one titanate compound, at least one aluminum compound, and an antifouling agent.
  • the antifouling agent may be chosen from one or more of a phosphonium or phosphonium salt; a sulfonate or a sulfonate salt; a sulfonium or sulfonium salt; an ester comprising a cyclic moiety; an anhydride; a polyether; and a long-chained amine-capped compound.
  • One or more embodiments of the present disclosure are directed to catalyst systems which may be utilized in promoting ethylene oligomerization, such as the dimerization of ethylene to form 1-butene or 1-hexene, while reducing reactor fouling caused by undesired polymerization.
  • These catalyst systems are sometimes referred to in this disclosure as “antifouling ethylene oligomerization catalyst systems" or “antifouling catalyst systems”.
  • the antifouling catalyst systems described may comprise at least one titanate compound, at least one aluminum compound, and at least one antifouling agent.
  • the antifouling catalyst systems may further comprise one or more non-polymeric ether compounds, and the components of the antifouling catalyst system may be mixed in a solvent such as hexane.
  • the antifouling catalyst systems may be used to selectively oligomerize ethylene to produce 1- butene, while reducing undesirable polymerization, sometimes referred to in this disclosure as "fouling".
  • reactor fouling may occur due to the formation of solid polyethylene-based residues which may reduce fluid flow and fully block or at least partially block fluids in a reactor system from flowing at a desired rate.
  • the "antifouling ethylene oligomerization catalyst systems" or “antifouling catalyst systems” described may not completely eliminate fouling during a reaction. However, these catalyst systems reduce fouling as compared with catalyst systems which do not include an antifouling agent as described in the present disclosure.
  • catalyst systems of the present disclosure may be useful in ethylene oligomerization reactions, such as ethylene dimerization to form 1-butene, they may also be useful for the catalysis of other chemical reactions, and the antifouling catalyst systems described in this disclosure should not be considered limited in their use to the dimerization of ethylene to 1- butene. It should further be understood that the antifouling agents described in this disclosure may be incorporated with other catalyst systems which contain, for example, non-titanium based catalysts.
  • embodiments of the described antifouling catalyst systems may comprise one or more titanate compounds which may serve as a catalyst in the catalyst systems described in this disclosure. While several titanate compounds may be included in the antifouling catalyst system, in some embodiments a single titanate compound may be included in the antifouling catalyst system.
  • the titanate compound may be an alkyl titanate.
  • An alkyl titanate may have the structure Ti(OR) 4 in which R is a branched or straight chain alkyl group.
  • each alkyl group may comprise from 2 to 8 carbons, where each R group may be the same or different.
  • Suitable alkyl titanates may include tetraethyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate (sometimes referred to as titanium butoxide or tetrabutyl ortho titanate), 2-tetraethylhexyl titanate, or combinations thereof.
  • the titanate compound of the antifouling catalyst system consists of tetra-n- butyl titanate.
  • embodiments of the described antifouling catalyst systems may comprise one or more aluminum compounds which may act as co-catalysts in the catalyst systems described in this disclosure. While several aluminum compounds may be included in the antifouling catalyst system, in some embodiments a single aluminum compound may be included. In one or more embodiments, one or more aluminum alkyl compounds may be included in the antifouling catalyst system.
  • Aluminum alkyl compounds may have a structure of A1R' 3 or A1R' 2 H, where R' is a straight chain or branched alkane comprising from 1 to 20 carbons, or an aluminoxane structure (that is, a partial hydrolysate of trialkylaluminum compounds).
  • the R' groups of the aluminum alkyl compounds may be the same or different from one another.
  • suitable aluminum alkyl compounds may include triethylaluminum, tripropylaluminum, tri-iso-butylaluminum, trihexylaluminum, or combinations thereof.
  • the aluminum compound of the antifouling catalyst system consists of triethylaluminum.
  • the antifouling catalyst systems described in this disclosure include at least one antifouling agent.
  • An antifouling agent may be any additive to a catalyst system which decreases fouling by polymer production.
  • Antifouling agents contemplated include phosphoniums or phosphonium salts, sulfonates or sulfonate salts, sulfoniums or sulfonium salts, esters, anhydrides, polyethers, and long-chained amine-capped compounds.
  • a "sulfonate antifouling agent” is an antifouling agent which includes a sulfonate moiety
  • a "phosphonium antifouling agent” is an antifouling agent which includes a phosphonium moiety.
  • the antifouling catalyst system comprises one or more phosphonium antifouling agents.
  • phosphonium antifouling agents include any compound comprising the phosphonium structure depicted in Chemical Structure #1, where Ri, R 2i R 3, and R 4 represents chemical groups which may contain other moieties, and the various R groups may be identical or different from one another.
  • phosphonium antifouling agents may be introduced into the antifouling catalyst system as phosphonium salts, where the phosphonium cation forms an ionic bond with an anion compound.
  • phosphonium antifouling agents include phosphonium salts or dissociated phosphonium cations.
  • Suitable phosphonium antifouling agents include, without limitation, tetraaikyl phosphonium salts.
  • the antifouling agent may include tetraaikyl phosphonium haiides (such as, for example, tetrabutyl phosphonium haiide), phosphonium malonates (such as, for example, tetrabutylphosphonium malonate), trihexyltetradecylphsophonium haiides (such as, for example, trihexyltetradecylphsophonium bromide), tetrabutylphosphonium haiides (such as, for example, tetrabutylphosphonium iodide), tetrabutylphosphonium tetrahaloborates (such as, for example, tetrabutylphosphonium tetrafluoroborate), tetrabutylphosphonium haiides (such as, for example,
  • a haiide may include fluoride, chloride, bromide, or iodide (and "halo" may include the elements fluorine, chlorine, bromine, or iodine).
  • the R groups (that is, Rj, R 2 , R 3 , and R 4 ) may be branched or unbranched alkanes, alkenes, or aryls, and the R groups may be identical or different from one another.
  • the antifouling catalyst system comprises one or more sulfonate antifouling agents.
  • sulfonate antifouling agents include any compound comprising the structure depicted in Chemical Structure #2, where R represents a chemical group, which may contain other moieties.
  • R represents a chemical group, which may contain other moieties.
  • sulfonate antifouling agents may be introduced into the antifouling catalyst system as a sulfonate salt, where the sulfonium anion forms an ionic bond with a cation compound.
  • sulfonium antifouling agents include sulfonium salts or dissociated sulfonium anions.
  • Suitable sulfonate antifouling agents include, without limitation, sulfonate salts.
  • sulfonate antifouling agents may include, without limitation, sodium dodecylbenzenesulfonate, sodium dioctylsulfonsuccinate, tetrabutylphosphonium methanesulfonate, tetrabutylphosphonium p-toluenesulfonate, and hexadecyltrimethylammonium p-toluene sulfonate.
  • suitable antifouling agents may include non-salt sulfonates (that is, sulfonates which do not dissociate as salts), such as ammonium sulfonates.
  • non-salt sulfonates suitable as antifouling agents include, without limitation, 3-(dimethyl(octadecyl)ammonio)propane-l- sulfonate, 3,3'-(l,4-didodecylpiperazine-l,4-diium-l,4-diyl)bis(propane-l-sulfonate), and 3- (4-(tert-butyl)pyridinio)-l-propanesulfonate.
  • the antifouling catalyst system comprises one or more sulfonium antifouling agents.
  • Sulfonium antifouling agents are generally depicted in Chemical Structure #3, where Ri, R 2i and R 3 represent chemical groups which may contain other moieties, and the various R groups (that is, Ri, R 2i and R 3 ) may be identical or different from one another.
  • sulfonium antifouling agents may be introduced into the antifouling catalyst system as sulfonium salts, where the sulfonium cation forms an ionic bond with an anion compound.
  • sulfonium antifouling agents include sulfonium salts or dissociated sulfonium cations.
  • the antifouling agent may include an ester antifouling agent or an anhydride antifouling agent where, in some embodiments, the ester or anhydride antifouling agent comprises a cyclic moiety.
  • Suitable ester or anhydride antifouling agents which contain a cyclic moiety may include, without limitation, ⁇ -caprolactone, 2-phenylethyl acetate, and polyisobutenyl succinic anhydride.
  • the ester or anhydride moiety is included in the cyclic moiety. However, in other embodiments, the ester or anhydride moiety is separate from the cyclic moiety.
  • Example cyclic moieties include, without limitation, cyclic alkyls, and aryls, but may include any chemical moiety which includes a ringed structure of atoms.
  • the ester or anhydride antifouling agent may be an ester or anhydride-capped polymer that has a number average molecular weight ( n) of from 150 grams per mole (g/mol) to 200,000 g/mol (for example, from 150 g/mol to 1,000 g/mol, from 150 g/mol to 2,000 g/mol, from 150 g/mol to 3,000 g/mol, from 150 g/mol to 5,000 g/mol, from 150 g/mol to 10,000 g/mol, from 150 g/mol to 50,000 g/mol, from 150 g/mol to 100,000 g/mol, from 150 g/mol to 150,000 g/mol, from 1 ,000 g/mol to 200,000 g/mol, from 5,000 g/mol to 200,000 g/mol,
  • the antifouling agent may include one or more polyether antifouling agents.
  • the polyether antifouling agents may include monomer units comprising carbon chains with one, two, three, four, or even more carbons separating ether moieties.
  • one polyether contemplated in this disclosure includes that depicted in Chemical Structure # 4, where m is equal to from 1 to 10 (for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, or even more, such as m equal to at least 10, at least 25, at least 50, or at least 75, and less than or equal to 100), and n is from 1 to 50,000.
  • R in Chemical Structure 4 may represent a hydrogen atom, or an alkyl with or without branches or substitutions.
  • R may include at least 5, at least 10, or even more carbon atoms).
  • the polyether antifouiing agent may have a number average molecular weight (Mrs) of from 150 grams per mole (g/mol) to 200,000 g/mol (for example, from 150 g/mol to 1,000 g/mol, from 150 g/mol to 2,000 g/mol, from 150 g/mol to 3,000 g/mol, from 150 g/mol to 5,000 g/mol, from 150 g/mol to 10,000 g/mol, from 150 g/mol to 50,000 g/mol, from 150 g/mol to 100,000 g/mol, from 150 g/mol to 150,000 g/mol, from 1 ,000 g/mol to 200,000 g/mol, from 5,000 g/mol to 200,000 g/mol, from 10,000 g/mol to
  • Mrs number average molecular weight
  • the antifouiing agent may include one or more long- chained amine-capped antifouiing agents.
  • the long-chained amine-capped antifouiing agent may have a number average molecular weight (Mrs) of from 150 grams per mole (g/mol) to 200,000 g/mol (for example, from 150 g/mol to 1,000 g/mol, from 150 g/mol to 2,000 g/mol, from 150 g/mol to 3,000 g/mol, from 150 g/mol to 5,000 g/mol, from 150 g/mol to 10,000 g/mol, from 150 g/mol to 50,000 g/mol, from 150 g/mol to 100,000 g/mol, from 150 g/mol to 150,000 g/mol, from 1,000 g/mol to 200,000 g/mol, from 5,000 g/mol to 200,000 g/mol, from 10,000 g/mol to 200,000 g/mol, from 50,000 g/mol/mol, from 50,000 g//mol
  • Suitable long-chained amine- capped antifouiing agent include, without limitation, polyisobutene-mono-succinimide and polyisobutene-bis-succinimide.
  • polyisobutene-mono-succinimide and polyisobutene-bis-succinimide.
  • two or more different antifouling agent species may be present as the antifouling agent.
  • two or more different antifouling agent species of the same type may be present.
  • the catalyst system may comprise two different species of phosphonium, two different species of sulfonate, two different species of sulfonium, two different species of esters, an anhydride, two different species of poly ethers, or two different species of long-chained amine-capped compounds.
  • the catalyst system may comprise two or more different types of antifouling agents (that is, two or more of any of a phosphonium or phosphonium salt, a sulfonate or a sulfonate salt, a sulfonium or sulfonium salt, an ester comprising a cyclic moiety, an anhydride, a polyether, and a long-chained amine-capped compound).
  • two or more of antifouling agents that is, two or more of any of a phosphonium or phosphonium salt, a sulfonate or a sulfonate salt, a sulfonium or sulfonium salt, an ester comprising a cyclic moiety, an anhydride, a polyether, and a long-chained amine-capped compound.
  • Some antifouling agent species may include two or more types of antifouling agents.
  • salts which have an anion of one type of antifouling agent and a cation of a different antifouling agent may generally comprise two types of antifouling agents.
  • antifouling agents include tetrabutylphosphonium methanesulfonate and tetrabutylphosphonium p-toluenesulfonate, which are salts that include a sulfonate and a phosphonium.
  • the antifouling catalyst system may comprise one or more non-polymeric ether compounds.
  • the one or more ether compounds may include cyclic non-polymeric ethers such as, but not limited to, tetrahydrofuran (THF), a dioxane, a tetrahydropyran (THP), or combinations thereof.
  • non-polymeric ethers refer to compounds which include one or more ethers but do not include long ether polymer chains. Usually, these non-polymeric ethers comprise one or two ether moieties, and comprise less than 10 ether moieties.
  • antifouling catalyst systems which include esters or anhydrides as antifouling agents may be particularly suited for not including an ester. It is believed that the ester or anhydride functionalities of some antifouling agents may at least partially replicate or mimic the functionality of ethers in the antifouling catalyst systems, rendering some embodiments of antifouling catalyst systems which include esters or anhydrides sufficient for their purpose without an additional ether compound.
  • the antifouling catalyst systems may comprise at least one or more titanate compounds, one or more aluminum compounds, and one or more antifouling agents.
  • the molar ratio of total titanate compound to total aluminum compound may be from 1: 10 to 1: 1 (such as, for example, from 1: 10 to 1:2, from 1: 10 to 1:3, from 1: 10 to 1:4, from 1:10 to 1:5, from 1: 10 to 1:6, from 1: 10 to 1:7, from 1: 10 to 1:8, from 1: 10 to 1:9, from 1:9 to 1: 1, from 1:8 to 1: 1, from 1:7 to 1: 1, from 1:6 to 1:1, from 1:5 to 1: 1, from 1:4 to 1: 1, from 1:3 to 1: 1, or from 1:2 to 1).
  • the molar ratio of total titanate compounds to total antifouling agent may be from 1: 10 to 1:0.01 (such as, for example, from 1: 10 to 1:0.05, from 1: 10 to 1:0.1, from 1: 10 to 1:0.3, from 1: 10 to 1:0.5, from 1: 10 to 1:0.7, from 1: 10 to 1: 1, from 1: 10 to 1:2, from 1: 10 to 1:3, from 1: 10 to 1:5, from 1:5 to 1:0.01, from 1:3 to 1:0.01, from 1:2 to 1:0.01, from 1: 1 to 1:0.01, from 1:0.7 to 1:0.01, or from 1:0.3 to 1:0.01).
  • 1: 10 to 1:0.01 such as, for example, from 1: 10 to 1:0.05, from 1: 10 to 1:0.1, from 1: 10 to 1:0.3, from 1: 10 to 1:0.5, from 1: 10 to 1:0.7, from 1: 10 to 1: 1, from 1: 10 to 1:2, from 1: 10 to 1:3, from 1: 10 to 1
  • the molar ratio of total titanate compounds to total non-polymeric ether compounds may be from 1: 10 to 1:0 (such as, for example, from 1:5 to 1:0, from 1:3 to 1:0, from 1:2 to 1:0, from 1: 1 to 1:0, from 1:0.5 to 1:0, from 1:0.3 to 1:0, from 1:0.1 to 1:0, from 1: 10 to 1:0.1, from 1: 10 to 1:0.5, from 1: 10 to 1: 1, from 1: 10 to 1:2, or from 1: 10 to 1:5).
  • 1: 10 to 1:0 such as, for example, from 1:5 to 1:0, from 1:3 to 1:0, from 1:2 to 1:0, from 1: 1 to 1:0, from 1:0.5 to 1:0, from 1:0.3 to 1:0, from 1:0.1 to 1:0, from 1: 10 to 1:0.1, from 1: 10 to 1:0.5, from 1: 10 to 1: 1, from 1: 10 to 1:2, or from 1:
  • the molar ratios of components of the antifouling catalyst systems described previously in this disclosure are representative of the total amount of each component of the antifouling catalyst system relative to the total amount of titanate compound, where the "total" amount refers to the molar amount of all species of the antifouling catalyst system which may be considered as a particular component type (that is, titanate compound, aluminum compound, non-polymeric ether compound, or antifouling agent).
  • the total amount of a component may include two or more chemical species which are titanate compounds, aluminum compounds, non-polymeric ether compounds, or antifouling agents, respectively.
  • 1-butene may be produced by contacting ethylene with the antifouling catalyst system described previously to oligomerize the ethylene to form 1-butene.
  • the ethylene and antifouling catalyst system are supplied to a reactor and mixed.
  • the reaction may be performed as a batch reaction or as a continuous process reaction, such as a continuous stir tank reactor process.
  • the pressure of the reactor may be from 5 bar to 100 bar, and the reactor temperature may be from 30 degrees Celsius (°C) to 180 °C.
  • process conditions outside of these ranges are contemplated, especially in view of the specific design of the reactor system and concentrations of the reactants and catalysts.
  • the reactions of the present disclosure primarily limit or do not include polymerization of ethylene (for example, polymers comprising 100 or more monomer ethylene units).
  • polymer formation may be limited to less than 500, less than 300, or even less than 100 parts per million of reactant.
  • heteroatoms of the antifouling agents may form weak coordination with the titanate compound utilized as the catalyst in the catalyst system. It is believed that, in one or more embodiments, the alkyl groups or other relatively long-chained groups of the antifouling agents may serve in some capacity to prevent ethylene access to the catalytic center of the titanate compound. The restriction of access of the ethylene to the titanate catalytic site may reduce the polymerization of ethylene and thus reduce reactor fouling.
  • the introduction of the antifouling agent into a catalyst system may suppress polymer formation while not greatly reducing catalytic activity of 1-butene formation.
  • polymer formation may be reduced by at least 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or even 95% by the inclusion of an antifouling agent.
  • 1-butene production may be increased, stay the same, or may decrease by less than or equal to 50%, 40%, 30%, 20%, 10% or even 5% by the inclusion of an antifouling agent.
  • antifouling agents may both reduce the polymer formation (such as by at least 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% or even 95%) and increase, not effect, or decrease 1-butene production rate by less than or equal to 50%, 40%, 30%, 20%, 10% or even 5%.
  • Reduction in polymer formation rates and catalytic activity on a percentage basis are based on catalyst systems which include one or more antifouling agents described as compared with catalyst systems which are void of an antifouling agent.
  • the molar ratio of Ti:THF:TEAL in the examples was 1:6:7.5.
  • the oligomerization experiments were conducted in a rig which included 8 autoclave reactors each having a volume of 400 milliliters (mL). Prior to the experimental runs, the rig was subjected to inertization process which included evacuating the reactors with an oil vacuum pump and heating to 160 °C. After a stable temperature had been reached, the rig was pressurized to 4 bar with nitrogen and the stirrers were operated with a stirring speed of about 300 rpm. Then, three minutes following the start of the pressurization, the gas outlet valves were opened to release the nitrogen to the exhaust.
  • Heptane was utilized as a solvent, and an amount of heptane was utilized, such that the autoclave reactors were nominally filled.
  • the first solution contained the TEAL co-catalyst mixed with 90% of the heptane.
  • the second solution contained the titanium tetrabutoxide catalyst, the THF, and the antifouling agents mixed with 10% of the heptane. The first solution and the second solution were put into first solution chargers and second solution chargers, respectively.
  • the pressure in the rig was released to about 0.2 bar.
  • the chargers with the second solution of TEAL/heptane were injected into the reactors.
  • the charging was achieved by pressurizing the chargers with ethylene to 10 bar and opening the valve between the charger and the reactor.
  • the contents of the second solution charger were then injected, using ethene as the charging gas with a pressure of 35 bar.
  • the target pressure for the reactors was set to 23 bar.
  • the gas dosage into the reactor was started automatically.
  • the temperature in the reactor rose and the temperature was set to the target value of 53.5 °C. After the start of the ethene dosage, the reaction was run for 75 min.
  • reaction was terminated by the injection of 1 mL of ethanol.
  • the pressure was released from the reactors, and the temperature was set to 20 °C.
  • the reactors were opened and the contents of the reactor, including the baffles and stirrers, were removed and placed in a heating oven at 75 °C for one hour.
  • the residue in the reactor was then washed with a 10 wt.% aqueous sulfuric acid solution to dissolve any catalyst residues.
  • the remaining solid polymer was filtered and dried overnight in an oven at 110°C and weighed.
  • Table 1 shows the dimerization activity and weight of polymer deposit for reactions which utilized each of the sample catalyst systems. As is evident by the reaction data of Table 1, the addition of the antifouling additives reduced polymer formation to some degree while maintaining relatively high dimerization activity. Activity (grams of Polymer
  • Example #2 0.3: 1 9 0 (0) tetrabiityjphosphoniuin rn a iota ate
  • Example #4 3 1 208 96 (10) sodium dodecylbenzenesulfonate
  • Example #2 96.1 % 100.0%
  • Example #13 -4.4% 84.0%
  • a number of antifouling agents suppress polymer formation (for example, at least 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% or even 95% reduction) while not greatly reducing activity (for example, less than or equal to 50%, 40%, 30%, 20%, 10% or even 5% reduction in activity, or even increased activity).
  • any two quantitative values assigned to a property may constitute a range of that property, and all combinations of ranges formed from all stated quantitative values of a given property are contemplated in this disclosure.

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