TWI505872B - Catalyst system and method of polymerization reaction thereof - Google Patents

Description

Catalyst system and polymerization method thereof

The present application claims priority to U.S. Patent Provisional Application Serial No. 61/312,869, which is hereby incorporated by reference in its entirety in its entirety in its entirety in In this way, it is included in this article.

The invention relates to catalysts used in the conversion of organic compounds. More specifically, the present invention relates to an activated metal oxide catalyst used in an organic compound conversion reaction.

Many different types of catalyst systems have been proposed for the organic compound conversion reaction. Such systems include, for example, (1) the use of a metal oxide-BF ₃ composite, (2) a combination of BF ₃ and liquid BF ₃ as a catalyst for the polymerization of isobutylene, and (3) a liquid BF ₃ methanol composite. a catalyst for the polymerization of isobutylene, and (4) a catalyst for the polymerization of isobutylene in a solid state. Prior art related to these prior art systems will be discussed below.

Metal oxide-BF ₃ Complex

In the past, inorganic metal oxides, such as alumina, have been subjected to catalytic activity by contacting the inorganic metal oxides with BF ₃ (usually in gaseous form). After the contact, it is usually followed by hydrolysis and calcination or some other post treatment. These catalysts are generally limited in activity, unstable, and release free BF ₃ into the reaction product, so the residues must be removed after the reaction.

One of the gelatinized aluminas treated with gaseous BF ₃ is disclosed in U.S. Patent No. 2,804,411, the disclosure of which is incorporated herein by reference. Free BF ₃ must be added to the reaction mixture.

And let the Esso U.S. Patent No. 2,976,338 describes one of the olefin polymerization catalyst, which may be a solid catalyst comprising a supported adsorbed BF of _3- H ₃ PO ₄ complex.

Let it through anhydrous θ- γ- alumina or alumina and the gaseous BF UOP under the U.S. Patent No. 3,114,785 describes one olefin isomerization catalyst to prepare the catalyst system of about ₃ at a temperature of 100 deg.] C to 150 deg.] C Contact for 10 hours or until the alumina is saturated. The olefin isomerization process using the BF ₃ -alumina catalyst has been advocated; the composition of the catalyst is not claimed.

U.S. Patent No. 4,407,731 to U.S. Patent No. 4,407,731, the disclosure of which is incorporated herein by reference. Next, the treated γ-alumina is treated with BF ₃ gas at a temperature of from 308 ° C to 348 ° C under pressure to obtain a final catalyst useful for the oligomerization and alkylation reaction.

Let the Mobil Oil Co. of the U.S. Patent No. 4,427,791 discloses an enhancing metal oxide, such as alumina, the activity of the method, the method of the alumina-based or NH ₄ F treatment of BF _3, so that the fluorinated product with The monoammonium exchange solution is contacted and the final product is then calcined.

A catalyst for the alkylation of isoalkanes is described in U.S. Patent No. 4,918,255, the disclosure of which is incorporated herein to In the presence of a controlled amount of water or water-producing material, it is treated with a Lewis acid (including BF ₃ ). Since the BF _{3 used} exceeds that required to saturate the metal oxide, excess BF ₃ must be removed after the reaction.

Let the Mobil Oil Co. and U.S. Patent No. 4,935,577 describes a catalytic distillation process, the process gas activation system using one non-zeolitic metal oxide BF _3. Since the BF _{3 used is} more than necessary to saturate the metal oxide, it is necessary to remove excess BF ₃ after the reaction.

BF ₃ And liquid BF ₃ Composite as a catalyst for polymerization of isobutylene

The in-phase catalyzed polymerization of olefins using gaseous BF ₃ and liquid BF ₃ complexes is well known. The polymers produced in this manner are generally of the highly reactive type in which a large proportion of the polymer comprises terminal double bonds or has a very high vinylidene component. All of these processes must be carried out after the reaction to remove the BF ₃ catalyst.

And Boetzel et al issued U.S. Patent No. 4,152,499 describes the use of a cover layer of BF ₃ gas as a catalyst, the synthesis of 10 to 100 units of a degree of polymerization of the polyisobutene. The polyisobutylene product is then reacted with maleic anhydride in a yield of from 60% to 90%, showing a substantial portion of the vinylidene end groups.

The production of polyisobutylene, which has at least 70% unsaturation at the terminal position, is described in U.S. Patent No. 4,605,808, issued toS. One of the BF ₃ alcohol complexes is used as a catalyst. This BF ₃ recombination appears to provide better control and higher vinylidene content for the reaction.

U.S. Patent No. 7,411,104 to Daelim Industrial Co. describes a process for producing highly reactive polyisobutylene from a raffinate oil R1 stream using a composite of a liquid BF ₃ secondary alkyl ether-triol. This process requires a low reaction temperature, and the catalyst composite is not stable and must be made in situ. The catalyst must be removed from the reactor outlet via a post reaction treatment process.

Issued to Rath et al.'S U.S. Patent No. 5,191,044 discloses one prepared polyisobutylene process, the manufacturing process, BF ₃ catalyst system completely with an alcohol compound to the reaction or without free of BF ₃ within the plurality of the reaction zone. To ensure that no free BF _{3 is} present, an excess of alcohol complexing agent must be used. The reaction time is about 10 minutes and the reaction temperature is below 0 °C.

Rath is described in U.S. Patent No. 5,408,018, the disclosure of which is directed to the polymerization of isobutylene or an isobutene-containing liquid hydrocarbon feed by means of boron trifluoride as a catalyst at temperatures between 0 ° C and -60 ° C. a multi-stage process of highly reactive polyisobutylene having a terminal vinylidene component of greater than 80 mole percent and an average molecular weight of from 500 to 5,000 amps; the multi-stage process is included The polymerization is carried out in the presence of a secondary alcohol of 3 to 20 carbon atoms and/or an ether having 2 to 20 carbon atoms.

Olefin polymerization, especially isobutylene polymerization, is an exothermic process. Control of the reaction temperature is critical to product quality, catalyst life, degree of polymerization, and obtaining the desired pre-selected properties. In the patents cited above, the reaction temperature is controlled by the concentration of the diluted olefin monomer, the composite catalyst, the multi-stage reaction and/or the long reaction time, and the low reaction temperature. Low reaction temperatures increase energy demand; long reaction times or diluted feed streams increase equipment size and equipment costs (capital expenditures).

Liquid BF ₃ -Methanol complex as catalyst for polymerization of isobutylene

One of the processes for the polymerization of olefins is described in U.S. Patent Nos. 6,525,149, 6,562,913, 6,683,138, 6,884,858 and 6,992,152, the disclosure of which is incorporated herein by reference in its entire entire entire entire entire disclosure get on. The reactor is designed to allow for very efficient and efficient removal of the heat of reaction so that a relatively high feed rate and a richer feed stream can be employed. The BF ₃ -methanol complex is used as a catalyst, and since the catalyst is particularly stable, a higher reaction temperature can be employed. The BF ₃ -methanol catalyst composite may be formed in advance, formed by injecting the methanol composite agent in situ, or in combination.

Taking into account the high isobutene polymerization temperature can not be used for other BF ₃ complex oxide, in particular higher alcohols, secondary alcohols, ethers and the like persons, the plurality of BF ₃ - methanol complex is very stable. Moreover, since a higher reaction temperature can be used, the reaction rate is thus increased.

However, in all of the patents cited above, the BF ₃ catalysts, or at least portions of the BF ₃ , are soluble in the polymeric products. The residual BF _{3 is} destructive to the quality of the product and must be removed as soon as possible. Therefore, these processes must perform some catalyst quenching and catalyst removal steps after the reaction. The quenched BF ₃ stream cannot be recovered and the BF _{3 is} thus wasted.

Solid isobutylene polymerization catalyst

The polymerization of isobutylene and butene can also be carried out using a solid catalyst, especially a Friedel-Crafts type catalyst such as AlCl ₃ . An advantage of these processes is that the catalyst is a solid and insoluble in the product. Compared to the plurality of BF ₃ catalyst from the reaction, the catalyst was removed by purification of the product and easier.

U.S. Patent No. 2,484,384 to California Research Corporation, U.S. Patent No. 2,677,002 to Standard Oil Co., U.S. Patent No. 2,957,930 to Cosden Petroleum Corporation, and U.S. Patent No. 3,119,884 to Cosden Petroleum Corporation. The bed reactor system performs a butene polymerization process catalyzed by AlCl ₃ .

U.S. Patent No. 4,306,105 to Cosden Petroleum Corporation describes the preparation of an alumina chloride catalyst by reacting pure alumina with pure chlorine. The fluidized bed reactor is used for the polymerization of butene.

Solid state catalysts are also used to produce olefin polymers having a high proportion of terminal vinylidene groups.

U.S. Patent No. 5,710,225 to Lubrizol claims the use of phosphotungstates to polymerize C ₂ -C ₃₀ olefins to produce polymers having molecular weights ranging from 300 to 20,000. The patent also describes the use of a phosphotungstic acid catalyst in a fixed bed reactor, but at a very low flow rate and typically operates as a plug flow reactor. The resulting polymer has an undesirably high degree of polymerization distribution. The fixed bed reactor described in this example is also not economically viable.

Let the Exxon Chemical Patents, Inc. Of U.S. Patent No. 5,770,539 discloses a porous polymeric substrate is fixed in the phase with a Lewis acid polymerization catalyst, such as BF _3. The BF ₃ system is complexed with an aromatic ring of a crosslinked polystyrene copolymer.

U.S. Patent No. 5,874,380 to Exxon Chemical Patents, Inc., which is incorporated herein by reference in its entirety in the the the the the the the the the A strong metal salt and a carbocation active transition metal catalyst selected from Groups IIIA, IVA, VA and VIA of the Periodic Table of the Elements.

U.S. Patent No. 6,384,154 to the disclosure of U.S. Patent No. 6,384,154, the disclosure of which is incorporated herein by reference. An oxide or element of a transition element or a main group element of Group I, II, III, IV, V, VI, VII or VIII. The polymerization is carried out in a fixed bed reactor.

The solid, hetero-phase butene polymerization catalysts cited above do solve the problem of catalyst residues in the reactor water outlet, thereby eliminating the need for post-reaction processing. However, the conversion rate is low, the space velocity is low, and the reaction temperature is also low.

In the prior art, metal oxides activated with BF _{3 are} not described as polymerization catalysts for the production of polybutene or polyisobutylene. In fact, U.S. Patent No. 6,710,140 to BASF Aktiengesellshaft claims the use of alumina as a solid state deactivator to adsorb residues of the BF ₃ catalyst from the polyisobutylene reactor outlet. Arising BF ₃ - alumina composite is described as a non-catalytic.

In accordance with the concepts and principles of the present invention, a process is provided for preparing an improved catalyst system that can be used in an acid catalyzed organic compound conversion reaction. The catalyst system desirably comprises a reaction product of one of BF ₃ /alcohol-metal oxides which is more active than the catalyst composition obtained by other processes and methods. The reaction products of the BF ₃ /alcohol-metal oxide of the present invention are stable under operating conditions, and the organic conversion products produced by the catalyst systems are free of catalyst residues and no boron or fluorine residues. . Since the conversion products do not contain catalyst residues, there is no need to carry out catalyst removal after the reaction. Therefore, the heterogeneous production process is greatly simplified by using the catalyst system of the present invention.

The catalyst systems of the present invention are particularly useful for heterogeneously catalyzed polymerization of isobutylene in a stream containing isobutylene to produce polyisobutylene or, more specifically, highly reactive polyisobutylene (HR PIB).

The catalyst systems of the present invention are particularly suitable for use in acid catalyzed reactions such as dimerization and oligomerization of olefins.

In accordance with the concepts and principles of the present invention, a highly stable catalyst system is provided for heterogeneous catalysis of the conversion of organic compounds. The system desirably may comprise a reaction product of (i) a BF ₃ /alcohol catalyst composite and (ii) an activated metal oxide support of the catalyst composite. The reaction product, which may be referred to as a BF ₃ /alcohol-metal oxide system, comprises an amount of the catalyst composite that is effective to catalyze the conversion reaction. In particular, the catalyst system of the present invention is useful for conversion reactions such as: Friedel-Crafts alkylation, phenol alkylation, olefin dimerization, olefin oligomerization, olefins Polymerization, propylene oligomerization, propylene polymerization, butene dimerization, butene oligomerization, isobutylene dimerization, isobutylene oligomerization, butene polymerization, isobutylene polymerization or isoalkane alkylation. The catalyst systems of the present invention are highly stable and are generally not consumed during the reaction. That is, the catalyst systems of the present invention do not require regeneration. Moreover, when the catalyst systems of the present invention are used in the form of a fixed bed, it is generally not necessary to treat the product in order to remove catalyst residues.

Preferably, the alcohol of the catalyst system does not have alpha-hydrogen. More preferably, the alcohol may include a C ₁ -C ₁₀ one-membered alcohol, a glycol or a polyol. Ideally, the alcohol can be methanol.

Preferably, the catalyst composite may have a weight percent concentration on the alumina ranging from about 10% to about 30%.

In a preferred embodiment of the invention, the catalyst system can be used in the form of a fixed bed, the activated metal oxide support can comprise gamma-alumina, and the conversion reaction can comprise polymerizing isobutylene to form a poly Isobutylene product.

It is desirable that the ratio of alcohol to BF ₃ in the catalyst composite can range from about 0.5 mole alcohol to 1 mole BF ₃ to about 2 mole alcohol to 1 mole BF ₃ . Ideally, for the composite catalyst, BF ₃ alcohol and the ratio may range from about 1 molar ratio of alcohol of 1 mole to 1 mole of the alcohol BF BF _{3. 3} to about 1.3 mole of.

In an excellent embodiment of the invention, a catalyst system is provided for heterogeneous catalysis of the polymerization of isobutylene, and the system comprises the reaction product of: (i) a BF ₃ /methanol catalyst composite and Ii) one of the catalyst composites, a gamma-alumina support. In this preferred form of the present invention, the range of the ratio of alcohol to BF ₃ in the catalyst composite of from about 0.5 molar to 1 molar ratio of alcohol to about 2 BF ₃ molar ratio of 1 mole of alcohol BF ₃ and the weight percent concentration of the catalyst composite on the alumina can range from about 10% to about 30%. Furthermore, the catalyst system is desirably used in the form of a fixed bed.

According to another aspect of the invention, a process is provided for the preparation of a catalyst system which is prepared for heterogeneous catalysis of an organic compound conversion reaction. The method comprises reacting (i) a BF ₃ /alcohol catalyst composite and (ii) one of the catalyst composites to activate a metal oxide support. The reaction product includes an amount of the catalyst composite that is effective to catalyze the conversion reaction.

It is desirable that the alcohol does not have alpha-hydrogen. More preferably, the alcohol may be methanol.

Preferably, the catalyst composite may have a weight percent concentration on the alumina ranging from about 10% to about 30%.

In a preferred form of the invention, the conversion reaction may comprise polymerizing isobutylene to form a polyisobutylene product, the activated metal oxide support may comprise gamma-alumina, and in the catalyst composite, the alcohol and BF ₃ The ratio can range from about 0.5 moles of alcohol to 1 mole of BF ₃ to about 2 moles of alcohol to 1 mole of BF ₃ .

In an excellent form of the invention, a process is provided for the preparation of a catalyst system which is prepared for heterogeneous catalysis of the polymerization of isobutylene. In accordance with this preferred form of the invention, the process comprises reacting (i) a BF ₃ /methanol catalyst composite and (ii) one of the catalyst composites, a gamma-alumina support. Ideally, in the catalyst composite, the ratio of alcohol to BF ₃ may range from about 0.5 moles of alcohol to 1 mole of BF ₃ to about 2 moles of alcohol to 1 mole of BF ₃ , and The weight percent concentration of the catalyst composite on the alumina can range from about 10% to about 30%.

The invention also provides a process for carrying out an organic compound conversion reaction in which one of the reactive organic compounds is selected for contact with a catalyst system as described above. In particular, the present invention provides a process for the polymerization of isobutylene comprising contacting isobutylene with a catalyst system comprising a reaction product of: (i) a BF ₃ /methanol catalyst composite and Ii) one of the catalyst composites, a gamma-alumina support. In this preferred form of the present invention, the range of the ratio of alcohol to BF ₃ in the catalyst composite of from about 0.5 molar to 1 molar ratio of alcohol to about 2 BF ₃ molar ratio of 1 mole of alcohol BF ₃ and the weight percent concentration of the catalyst composite on the alumina can range from about 10% to about 30%. Furthermore, the catalyst system is desirably used in the form of a fixed bed.

It is an object of the present invention to provide an activated metal oxide catalyst composition or system which can be widely used in the conversion of organic compounds which require an acid catalyst. Organic conversion reactions can include, but are not limited to, Friedel-Crafts alkylation, phenol alkylation, olefin dimerization and oligomerization, olefin polymerization, propylene oligomerization And polymerization, dimerization of butene and isobutylene and oligomerization, polymerization of butene and isobutylene, alkylation of isoalkanes and the like.

One preferred embodiment of the present invention is to provide a different system in the range of dimerization and oligomerization of more advanced α- olefins of C ₅ -C ₁₂ cooperate with the composition of the catalyst or phase system. These products are very useful as synthetic lubricant intermediates, especially for the production of poly-α-olefins (PAO) based on the dimerization and oligomerization of α-olefins having C ₁₀ -C ₁₂ carbon atoms. In terms of.

A preferred embodiment of the invention provides an efficient heterogeneous catalyst system for the polymerization of isobutylene to produce highly reactive polyisobutylene.

The activated metal oxide catalyst of the present invention is prepared by reacting a generally liquid BF ₃ /alcohol complex with anhydrous crystalline alumina. Γ-alumina and θ-alumina are preferred crystal structures.

Conventional techniques BF ₃ - alumina of certain organic conversion reactions are non-catalytic, as reported in U.S. Patent No. 6,710,140. Further, in some cases, when the content of BF ₃ may be catalytic, the BF ₃ will elute, and thus additional BF ₃ needs to be added along with the reactant feed. This is undoubtedly the loss of the use of a solid heterogeneous catalyst purposes, because the outlet pipe must be treated to remove the reactor, the BF ₃ of these residues.

According to the present invention, it has been surprisingly found that if a generally liquid BF ₃ /alcohol complex is used instead of BF ₃ gas, the resulting reaction products with crystalline alumina are highly catalytic, stable, long-lived, and not Loss of activity or consumption during the catalytic process. In addition, a problem of high content of BF ₃ without BF ₃ dissolved in the reaction mixture can be obtained.

Suitable crystalline alumina types include theta-alumina and gamma-alumina. Preferably, the crystal structure of [gamma] alumina, alumina as compared with θ-, [gamma] alumina has a higher ability to respond to the catalyst composite BF ₃ / alcohol ratio. The least suitable is alpha-alumina.

Prior to reaction with the BF ₃ / alcohol complex, the aluminum oxide must be substantially dry. This can be achieved by heating the alumina at a temperature of 200 ° C for 10 to 20 hours.

The BF ₃ /alcohol complex can be formed by passing a BF ₃ gas through a solution of one of the pure anhydrous alcohols at a rate that allows the BF _{3 to} be efficiently absorbed. In general, the ratio of alcohol to BF ₃ can range from about 0.5 moles of alcohol to 1 mole of BF ₃ to about 2 moles of alcohol to 1 mole of BF ₃ . A preferred range is from about 1 mole of alcohol to 1 mole of BF ₃ to about 2 moles of alcohol to 1 mole of BF ₃ . The preferred range is from about 1 mole of alcohol to 1 mole of BF ₃ to about 1.3 moles of alcohol to 1 mole of BF ₃ .

Alcohols having a carbon number in the range of C ₁ - C ₁₀ and no α-hydrogen are suitable for complexing with BF ₃ . Alcohols with alpha-hydrogen are readily desorbed by BF ₃ to form olefins. For example, even if the BF ₃ /alcohol complex can be formed at a low temperature, the obtained composites are not stable at the reaction temperature. Preferred alcohols are methanol and neoalcohols such as neopentyl alcohol. The most preferred alcohol is methanol.

Diols and polyols without α-hydrogen can also be used; for example, ethylene glycol.

The reaction of the BF ₃ /alcohol complex with alumina is a highly exothermic reaction and must be controlled to avoid wasting BF ₃ . The BF ₃ /alcohol complex can be added in any mechanical manner that allows the composite to be thoroughly mixed with alumina and with sufficient temperature control in mind. A preferred method is to add the alumina to a rotating biconical mixer and then meter the BF ₃ /alcohol complex to control the temperature within the desired range. The temperature during this mixing should not exceed 50 ° C to 60 ° C.

The concentration range of BF ₃ / alcohol complex on the alumina may be from about 10% to about 30%. A preferred weight percentage concentration ranges from about 20% to about 30%. The optimum weight percentage concentration ranges from about 25% to about 30%. In the BF ₃ /alcohol complex-alumina system, the actual concentration of fluorine or boron depends on the alcohol used.

The final catalyst composition (system), which is a product of the BF ₃ /alcohol-alumina reaction, can be used to catalyze the conversion of organic compounds. The catalyst composition can be contacted with the reactants in a batch or in a continuous process.

In a preferred embodiment of the invention, the reactor may be a shell and tube heat exchanger in which the catalyst composition may be filled in the tubes. This arrangement can be referred to as a fixed bed reactor. This is particularly suitable for highly exothermic reactions such as the polymerization of olefins, especially isobutylene polymerization.

The exchanger can be placed upright. The heat exchange media can be circulated through the shell side of the exchanger. The switch can be of a single process or a multi-process type. The better one is a pair of process exchangers. The exchanger can be equipped with a recirculation loop to accommodate a volumetric recycle stream. The feed containing olefins can be passed to the reactor from a location downstream of the pump via a recycle pump. The recycle pump pushes the olefin stream through the reactor tubes and allows the olefin to flow back to the suction side of the pump. In the dual process exchanger, the recycle stream can be passed from the bottom of the reactor, then passed through the tubes, and then from the bottom of the reactor and back to the pump. This process constitutes one of the commonly recognized loop reactors. The flow rate is controlled by the rate of the pump, or the pump itself is an internal recirculation loop. Preferably, the flow rate is sufficient to produce a rate of turbulence or to cause at least a non-laminar flow of the olefin feed stream above the fixed bed catalyst composition charged in the tubes.

A volumetric feed stream can enter the recycle loop at a location near the beginning of the first stream via a feed pump from a location between the discharge port of the recycle pump and the bottom of the reactor. At equilibrium, the concentration of the olefin monomer and the polymer products is constant throughout the reactor so that the location of the reaction effluent leaving the reactor can be selected. However, it may be convenient to have the effluent tube located at the top of the reactor after the first process. The effluent stream rate must be equal to the volumetric feed stream rate. The volumetric feed stream rate is independent of the volumetric recycle stream rate, and ideally, the volumetric feed stream rate can be adjusted to achieve the desired residence time and conversion.

The reactor can be equipped with suitable temperature, pressure and flow indicators and controls that must be operated under controlled conditions.

The size of the heat exchange reactor is arbitrary and will depend on the desired amount of product. A suitable size is 10 to 15 feet in length and 4 to 6 feet in diameter. The number of tubes and the diameter of the tubes in the reactor depend on the type, size, shape, and desired yield of the catalyst. For the above reactor size, a suitable number of tubes is from 150 to 200 tubes having an inner diameter of 1/2 to 1 inch per process. In a pair of process exchangers, the tubes extend longitudinally up to the full length of the reactor and are joined by end caps at the top and bottom of the reactor. The olefin reaction mixture is introduced to one side of the bottom end cap and then returned via the other side of the bottom end cap. The interior of the top end cap is open and has a discharge port for the reaction effluent.

In a preferred embodiment, the pressure of the reactor may preferably be at least 150 psig or at least one level sufficient to ensure that the liquid phase is maintained within the reactor. This pressure can be controlled using a back pressure regulator on the reactor effluent tube.

In the case of polyisobutylene, the temperature and conditions of operation of the reactor preferably produce a polymer product having a molecular weight in the range of from about 300 amps to about 5,000 amps. Other temperatures and conditions can be employed as desired for the particular organic conversion reaction.

The volumetric recycle flow rate can be adjusted to provide a heat transfer coefficient of about 40-60 BTU/min-ft ² - °F. The volumetric feed stream rate can be maintained at a rate that provides from 1 to 30 kilograms of isobutylene per kilogram of catalyst per hour of Liquid Hour Space Velocity (LHSV). More preferably, the LHSV can be controlled at 3 to 10 kg of isobutylene per kg of catalyst per hour.

The preferred a-olefin feed is a C ₄ raffinate oil, also known as raffinate-1 or raff-1. The actual composition of such a stream will vary depending on its source, but typically one of the raff-1 streams may contain about 0.5 wt% C ₃ , about 4.5 wt % isobutane, and about 16.5 wt % n-butane. , about 38.5 wt% of 1-butene, about 28.3 wt% of isobutylene, about 10.2 wt% of cis-2-butene and trans 2-butene, and less than 0.5 wt% of butadiene and less than 1.0 wt% oxygen compound. The presence of an oxygen compound may or may not affect the catalytic reaction. C ₃ and the plurality of the n-butane is inert, it does not change through the reactor after, and will be removed from the reaction mixture in the plurality of downstream stripping step. The isobutylene will react to a high degree depending on the reaction conditions and the desired final product. The 1-butene and 2-butene can be reacted to different extent depending on the type of catalyst and the reactor conditions. The unreacted olefins are also removed from the polymer product during the downstream stripping steps. The Raff-1 feed is especially suitable for the production of highly reactive, unimportant polymers. These products are referred to as ordinary PIB or PB.

Another preferred olefin feed is an effluent that dehydrogenates isobutane to isobutene, referred to simply as a dehydrogenation effluent or DHE. DHE is typically contain from about 42-45 wt% of isobutylene and from about 50-52 wt% of isobutane remaining in a small amount of C _3, n-butanes, n-butenes and butadiene. The feed is particularly suitable for the production of polyisobutylene where the inert isobutane can be used, for example in combination with one unit of isobutane dehydrogenation.

Yet another preferred olefin feed is a DHE in which a majority of the inert isobutane has been removed. This stream is referred isobutylene concentrate, typically comprising from about 88-90 wt% of isobutylene and from about 5-10 wt% of isobutane, the balance being trace amounts of C _3, n-butanes, n-butenes and butadiene Alkene. This feed is also suitable for the production of highly reactive polyisobutylene.

Still another preferred olefin feed is high purity isobutylene containing greater than 99 wt% isobutylene. This feed is very suitable for the production of highly reactive polyisobutylene. Unreacted olefins can be easily recovered.

After the reaction effluent leaves the reactor, it can be purified simply by atmospheric pressure gas extraction or vacuum stripping to remove light by-products and inert materials. The unreacted monomers can be recovered, but it must be specified to separate or rinse the inert materials in accordance with the type of olefin feed.

Since the reaction process discussed above takes into account the removal of the heat of reaction in an extremely efficient manner so that the conditions of the isothermal and CSTR (Continuous Stirred Tank Reactor) can be maintained, the volumetric efficiency is high. . That is, a large amount of product can be produced for a given reactor volume. Therefore, the capital cost per volume of the product is very low. This fact, without the need for downstream catalyst removal and/or catalyst regeneration equipment, has a further positive impact on total capital costs.

Table 1 presents the production of polyisobutylene previous and current commercial processes, / alcohol with the use of the novel BF ₃ - Comparison between the process of the present invention made of a metal oxide catalyst system. In Table 1, the column labeled "Soltex" represents the present invention. Further, the abbreviation "IB" stands for isobutylene.

Table 1:

Comparison of PIB process technology

The above description of one of the processes for the polymerization of isobutylene is useful for presenting the activated metal oxide catalyst system of the present invention. The description of the preferred embodiments is not intended to limit the scope of the invention. For the reaction of any organic product requiring an acidic catalyst, the reaction product of the BF ₃ /alcohol-metal oxide of the present invention can be used as a catalyst for the organic product. Such reactions include, but are not limited to, Friedel-Crafts alkylation, phenol alkylation, isoalkane alkylation, general olefin dimerization and polymerization, higher alpha olefins Dimerization, dimerization of isobutylene, and the like.

The above disclosure and description of the present invention are exemplary and illustrative. The details of the method can be varied in various ways without departing from the true spirit of the invention.

Claims (8)

a catalyst system heterogeneously catalyzed in a polymerization of isobutylene to form a polyisobutylene product comprising a reaction product of: (i) a BF ₃ /alcohol catalyst complex wherein the alcohol does not have alpha-hydrogen, (ii) an alumina support of one of the catalyst composites, the catalyst composition having a concentration percentage on the alumina support ranging from about 10% to about 30%, and the alcohol and BF ₃ in the catalyst composite The ratio ranges from 0.5 moles of alcohol to 1 mole of BF ₃ to 2 moles of alcohol to 1 mole of BF ₃ , which is composed essentially of alumina. The catalyst system of claim 1, wherein the isobutylene polymerization comprises Friedel-Crafts alkylation, phenol alkylation, olefin dimerization, olefin oligomerization, olefin polymerization, propylene oligomerization, propylene polymerization. Action, butene dimerization, butene oligomerization, isobutylene dimerization, isobutylene oligomerization, butene polymerization, isobutylene polymerization or isoalkane alkylation. The catalyst system of claim 1, wherein the catalyst composite has a weight percent concentration on the alumina support ranging from about 25% to about 30%. The catalyst system of claim 1, wherein the catalyst system is a fixed bed. The catalyst system of claim 1, wherein the alumina support comprises gamma-alumina. The catalyst system of claim 1, wherein the ratio of alcohol to BF ₃ in the catalyst composite ranges from about 1 mole of alcohol to 1 mole of BF ₃ to 1.3 mole of alcohol to 1 mole. BF ₃ . One kind of an isobutene polymerization heterogeneous catalysis in a method of forming a catalyst system for the preparation of a polyisobutylene product of the method comprising (i) a BF ₃ / alcohol catalyst composite, wherein the alcohol having no α- hydrogen, and (ii An alumina support reaction of one of the catalyst composites, wherein the concentration ratio of the catalyst composite on the alumina support ranges from about 10% to about 30%, and wherein the alcohol and BF ₃ are combined in the catalyst The ratio ranges from 0.5 moles of alcohol to 1 mole of BF ₃ to 2 moles of alcohol to 1 mole of BF ₃ , which is composed essentially of alumina. The method of claim 7, wherein the alumina support comprises gamma-alumina.