HK1179565B - Activated inorganic metal oxides - Google Patents

Description

Activated inorganic metal oxides

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is based on and claims priority from 35u.s.c. § 119(e) to currently pending U.S. provisional application serial No. 61/312,869 filed on 11/3/2010, the entire contents of which are incorporated herein by reference.

Technical Field

The present invention relates to catalysts for use in organic compound conversion reactions. More particularly, the present invention relates to activated metal oxide catalysts for use in organic compound conversion reactions.

Background

In order to carry out the conversion of organic compounds, a large number of different types of catalyst systems have been proposed in the past. These systems include the use of: (1) metal oxide BF₃A complex of (a); (2) BF (BF) generator₃And liquid BF₃As catalysts for the polymerization of isobutene; (3) liquid BF₃Methanol complex as catalyst for isobutylene polymerization; and (4) a solid isobutylene polymerization catalyst. The prior art associated with these prior art systems is described below.

Metal oxide BF₃Complex compounds

In the past, inorganic metal oxides such as alumina have been made by reaction with BF, usually in gaseous form₃The catalyst is activated by the contact. The contacting is typically followed by hydrolysis and calcination or some other post-treatment. These catalysts generally have limited activity, are unstable and release free BF to the reaction product₃Post-reaction is required to remove these residues.

U.S. patent 2,804,411 assigned to American oil company discloses the use of gaseous BF₃The Si-stabilized gelled alumina is treated. Free BF is required₃Added to the reaction mixture.

U.S. patent 2,976,338 assigned to Esso describes a BF containing solid support adsorbed on a solid carrier₃-H₃PO₄Complex olefin polymerization catalysts.

U.S. patent 3,114,785 assigned to UOP describes an olefin isomerization catalyst prepared by reacting anhydrous gamma or theta alumina with gaseous BF at a temperature of about 100 ℃ to 150 ℃₃Contact and hold for 10 hours or until alumina saturation. Advocate the use of BF₃-a process for the isomerization of olefins over an alumina catalyst; the composition of the catalyst is not claimed.

TransferU.S. patent 4,407,731 to UOP claims the subject catalytic composition prepared by pre-treating a metal oxide such as alumina with an aqueous acid and base, followed by calcination. Then, BF is utilized under high pressure at a temperature of 308 to 348 ℃₃The gas treats the treated gamma alumina to yield the final catalyst useful for oligomerization and alkylation reactions.

U.S. patent 4,427,791 assigned to mobiloilco discloses a method of using NH₄F or BF₃A process for treating alumina, contacting the fluoride containing product with an ammonium exchange solution and then calcining the final product to increase the activity of a metal oxide such as alumina.

U.S. patent 4,918,255 assigned to mobiloilco describes an isoparaffin alkylation catalyst that utilizes BF-containing catalysts in the presence of controlled amounts of water or water-producing materials₃Based on metal oxides and aluminosilicate zeolites treated with lewis acids. Using excess BF₃The need to carry out a post-reaction to convert the BF to₃Removal of the BF₃Is required to saturate the metal oxide.

U.S. patent 4,935,577 assigned to mobiloilco describes the use of BF₃A process for the catalytic distillation of a gas-activated non-zeolitic metal oxide. Using excess BF over that required to saturate the metal oxide₃The need to carry out a post-reaction to convert the BF to₃And (4) removing.

BF as catalyst for polymerization of isobutene₃And liquid BF₃Complex compounds

Using gaseous BF₃And liquid BF₃Homogeneous catalytic polymerization of olefins of complexes is well known. The polymers produced therefrom are generally of the highly reactive type, in which the majority of the polymers contain terminal double bonds or have a high vinylidene content. All of these processes require post-reaction to remove BF₃A catalyst.

U.S. patent to Boerzel et alDescribed in U.S. Pat. No. 4,152,499, using BF₃The gas serves as a catalyst to synthesize polyisobutylene having a degree of polymerization of 10 to 100 units. The polyisobutylene product was then reacted with maleic anhydride in yields of 60 to 90% showing a majority of terminal vinylidene groups.

U.S. Pat. No. 4,605,808 to Samson describes the production of polyisobutenes having at least 70% unsaturation at the terminal positions. Using BF₃The alcohol complex of (1) as a catalyst. For BF₃Performing the complexation appears to allow better control of the reaction and provide a higher vinylidene content.

Us patent 7,411,104 assigned to daelim industrialco describes the use of liquid BF₃A process for making highly reactive polyisobutylene from a raffinate-1 stream with a secondary alkyl ether-tertiary alcohol complex. The process requires low reaction temperatures and the catalyst complex is unstable and must be prepared in situ. The catalyst must be removed from the reactor effluent by a post-reaction treatment process.

U.S. Pat. No. 5,191,044 to Rath et al discloses a process for preparing polyisobutene using a net make BF₃The catalyst is completely complexed so that no free BF is present in the reactor or in the reaction zone₃. An excess of alcohol complexing agent is required to ensure that no free BF is present₃. At reaction temperatures below 0 ℃, the reaction times are in the order of 10 minutes.

Rath in us patent 5,408,018 describes a multistage process for preparing highly reactive polyisobutenes having a terminal vinylidene content of more than 80mol% and having an average molecular weight of from 500 to 5000 dalton by cationic polymerization of isobutene or isobutene-containing hydrocarbon feeds in the liquid phase at from 0 ℃ to-60 ℃ with the aid of boron trifluoride as catalyst, which comprises polymerization in the presence of secondary alcohols having from 3 to 20 carbon atoms and/or ethers having from 2 to 20 carbon atoms.

Olefin polymerization, especially the polymerization of isobutylene, is an exothermic process. Control of the reaction temperature is critical to product quality, catalyst life, degree of polymerization, and to achieve desired preselected properties. In the above patents, the reaction temperature is controlled by diluting the concentration of the olefin monomer, the complexed catalyst, the multistage reaction and/or the long reaction time and low reaction temperature. Low reaction temperatures increase energy requirements; long reaction times or dilute feed streams increase equipment size and equipment investment (capital expenditure).

Liquid BF as catalyst for polymerization of isobutene₃Methanol complex

U.S. patents 6,525149, 6,562,913, 6,683,138, 6,884,858 and 6,992,152 to Baxter et al describe an olefin polymerization process in which polymerization is carried out in the tube side of a heat exchanger under turbulent flow conditions. The design of the reactor allows for very efficient and effective removal of the heat of reaction, enabling the use of relatively high feed rates and concentrated feed streams. BF mixing₃The methanol complex is used as a catalyst and since the complex is particularly stable, higher reaction temperatures can be used. The in situ formation of BF can be carried out by injecting the methanol complexing agent alone or in combination₃-a methanol catalyst complex.

BF₃The methanol complex is very stable, so that higher isobutene polymerization temperatures can be used, which is the case for other BF' s₃Oxygenate complexes, especially higher alcohols, secondary alcohols and ethers, etc. are not possible. In addition, since a higher reaction temperature can be used, the reaction rate can be increased.

However, in all of the above patents, BF₃Or BF₃At least a portion of the catalyst is soluble in the polymer product. Residual BF₃Is disadvantageous for the product quality and must be removed as quickly as possible. Therefore, these processes must employ some type of catalyst quenching and catalyst removal step after the reaction. Quenched BF₃Stream not circulating and loss of BF₃。

Solid isobutylene polymerization catalyst

In addition, solid catalysis has been usedAgents, especially catalysts of the Fischer-Tropsch type, such as AlCl₃Polymerization of isobutylene and butene was carried out. The advantage of these processes is that the catalyst is solid and insoluble in the product. Catalyst removal and product purification ratio BF₃The catalyzed reaction is easier.

U.S. patent 2,484,384 assigned to California research corporation, U.S. patent 2,677,002 assigned to StandardOilCo, U.S. patent 2,957,930 assigned to Cosden Petroleum corporation, and U.S. patent 3,119,884 assigned to Cosden Petroleum corporation all describe AlCl using a fluidized bed reactor system₃Catalytic butene polymerization process.

U.S. patent 4,306,105 assigned to cosden petroleum corporation describes a chlorinated alumina catalyst prepared by reacting pure alumina with pure chlorine. A fluidized bed reactor was used for the polymerization of butene.

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

U.S. patent 5,710,225 assigned to Lubrizol claims the use of phosphotungstate for C₂To C₃₀Olefins are polymerized to produce polymers having molecular weights in the range of 300 to 20000. The use of phosphotungstic catalysts in fixed bed reactors is also described, but the flow rates are low and are typically run as plug flow reactors. The resulting polymers have an undesirably very high polydispersity. The fixed bed reactor described in the examples is economically unfeasible.

U.S. patent 5,770,539 assigned to Exxon chemical Patents, Inc. discloses heterogeneous Lewis acid polymerization catalysts such as BF immobilized in a porous polymeric substrate₃. BF mixing₃Complexed with the aromatic rings of the crosslinked polystyrene copolymer.

U.S. patent 5,874,380 assigned to exxon chemical patents, inc. claims a solid, insoluble salt catalyst system for the polymerization of carbocations of olefin monomers in the presence of a polar or non-polar reaction medium comprising an active transition metal catalyst of a strong acid and a carbocation selected from groups IIIA, IVA, VA and VIA of the periodic table of elements.

U.S. patent 6,384,154 assigned to BASFAktiengesellshaft discloses a process for preparing halogen-free, reactive polyisobutenes by cationic polymerization over acidic, halogen-free heterogeneous catalysts comprising oxides and elements from transition or main groups I, II, III, IV, V, VI, VII or VIII of the periodic table of the elements. The polymerization is carried out in a fixed bed reactor.

The above solid, heterogeneous butene polymerization catalysts do solve the problem of catalyst residues in the reactor effluent, thereby eliminating the need for post-reaction treatment. However, the conversion is low, the space velocity is low and the reaction temperature is low.

BF has not been dealt with in the prior art as a polymerization catalyst for producing polybutene or polyisobutene₃Activated metal oxides are described. In fact, U.S. Pat. No. 6,710,140 assigned to BASFAktiengesellshaft claims the use of alumina as a solid deactivator for the absorption of BF from polyisobutylene reactor effluent₃Catalyst residue. Prepared BF₃The alumina complex is described as not catalytic.

Summary of The Invention

In accordance with the concepts and principles of the invention of the present application, a method is provided for preparing an improved catalyst system that may be used in conjunction with acid-catalyzed organic compound conversion reactions. The catalyst system desirably comprises BF having a higher activity than catalyst compositions obtained using other processes and methods₃Alcohol-metal oxide reaction products. BF of the invention₃The alcohol-metal oxide reaction products are stable at operating conditions and the organic conversion products produced using these catalyst systems are free of catalyst residues and free of boron and fluorine residues. Since the conversion product contains no catalyst residues, removal of the catalyst after the reaction is not necessaryAnd (4) removing. Thus, by using the catalyst system of the invention of the present application, the heterogeneous production process can be greatly simplified.

The catalyst system of the invention is particularly suitable for the heterogeneously catalyzed polymerization of isobutene in an isobutene-containing stream, whereby polyisobutenes, still more particularly Highly Reactive Polyisobutenes (HRPIBs) are produced.

The catalyst system of the present invention is particularly well suited for use in combination with the implementation of 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 organic compound conversion reactions. The system desirably comprises (i) BF₃An alcohol catalyst complex and (ii) an activated metal oxide support for the catalyst complex. May be referred to as BF₃The reaction product of the alcohol-metal oxide system includes an amount of the catalyst complex effective to catalyze the conversion reaction. In particular, the catalyst system of the present invention may be used in conjunction with a conversion reaction such as fischer-tropsch alkylation, alkylation of phenols, dimerization of olefins, oligomerization of olefins, polymerization of olefins, oligomerization of propylene, polymerization of propylene, dimerization of butenes, oligomerization of butenes, dimerization of isobutene, oligomerization of isobutene, polymerization of butenes, polymerization of isobutene or alkylation of isoparaffins. The catalyst system of the present invention is highly stable and is not normally consumed during the reaction. That is, the catalyst system of the present invention does not require regeneration. Furthermore, when the catalyst system of the invention is used in the form of a fixed bed, it is generally not necessary to work up the product in order to remove catalyst residues.

Preferably, the alcohol of the catalyst system does not have an alpha hydrogen. Even more preferably, the alcohol may comprise C₁To C₁₀Monohydric alcohols, diols or polyols. Desirably, the alcohol may be methanol.

Preferably, the concentration of the catalyst complex on the alumina may be from about 10 to about 30 weight percent. Desirably, the concentration of the catalyst complex on the alumina can be from about 25 to about 30 weight percent.

In a preferred embodiment of the invention, the catalyst system may be used in the form of a fixed bed, the activated metal oxide support may comprise gamma alumina, and the conversion reaction may comprise the polymerization of isobutylene to form a polyisobutylene product.

Desirably, the alcohol in the catalyst complex is para BF₃The ratio of (A) to (B) may be in the range of one mole of BF to another₃About 0.5 moles of alcohol to every mole of BF₃About 2 moles of alcohol. Desirably, the alcohol pair BF in the catalyst complex₃The ratio of (A) to (B) may be in the range of one mole of BF to another₃About 1 mole of alcohol to per mole of BF₃About 1.3 moles of alcohol.

In a highly preferred embodiment of the present invention, a catalyst system is provided for the heterogeneous catalysis of isobutene polymerization and comprises (i) BF₃A reaction product of (i) an alcohol catalyst complex and (ii) a gamma alumina support for said catalyst complex. In this highly preferred form of the invention, the alcohol in the catalyst complex is para-BF₃The ratio of (A) to (B) may be in the range of one mole of BF to another₃About 0.5 moles of alcohol to each mole of BF₃About 2 moles of alcohol, and the concentration of the catalyst complex on the alumina can be from about 10 to about 30 weight percent. Furthermore, it is desirable to use the catalyst system in the form of a fixed bed.

According to another aspect of the present invention, a process is provided for preparing a catalyst system for heterogeneous catalysis of organic compound conversion reactions. The process comprises reacting (i) BF₃An alcohol catalyst complex and (ii) an activated metal oxide support for the catalyst complex. The reaction product includes an amount of the catalyst complex effective to catalyze the conversion reaction.

Desirably, the alcohol does not have an alpha hydrogen. Still more desirably, the alcohol may be methanol.

Preferably, the concentration of the catalyst complex on the alumina may be from about 10 to about 30 wt%.

In a preferred form of the invention, the conversion reaction may comprise polymerization of isobutylene to form a polyisobutylene product, the activated metal oxide support may comprise gamma alumina, and the alcohol in the catalyst complex is towards BF₃The ratio of (A) to (B) may be in the range of one mole of BF to another₃About 0.5 moles of alcohol to every mole of BF₃About 2 moles of alcohol.

In a highly preferred form of the invention, a process is provided for preparing a catalyst system for heterogeneous catalysis of isobutylene polymerization reactions. According to this highly preferred form of the invention, the process comprises reacting (i) BF₃A/methanol catalyst complex and (ii) a gamma alumina support for said catalyst complex. Desirably, the alcohol pair BF in the catalyst complex₃The ratio of (A) to (B) may be in the range of one mole of BF to another₃About 0.5 moles of alcohol to every mole of BF₃About 2 moles of alcohol, and the concentration of the catalyst complex on the alumina can be from about 10 to about 30 weight percent.

The present invention also provides a process for carrying out an organic compound conversion reaction wherein a selected reactive organic compound is contacted with the above-described catalyst system. In particular, the present invention provides a process for carrying out isobutylene polymerization reaction comprising contacting isobutylene with a catalyst system comprising (i) BF₃A reaction product of (i) a methanol catalyst complex and (ii) a gamma alumina support for said catalyst complex. In this highly preferred form of the invention, the alcohol in the catalyst complex is para-BF₃The ratio of (A) to (B) may be in the range of one mole of BF to another₃About 0.5 moles of alcohol to every mole of BF₃About 2 moles of alcohol, and the concentration of the catalyst complex on the alumina can be from about 10 to about 30 weight percent. Furthermore, it is desirable to use the catalyst system in the form of a fixed bed.

Detailed Description

It is an object of the present invention to provide an activated metal oxide catalyst composition or system that can be used in a wide range of organic compound conversion reactions requiring an acid catalyst. Organic conversion reactions include, but are not limited to, Fischer-Tropsch alkylation, alkylation of phenols, dimerization and oligomerization of olefins, polymerization of olefins, oligomerization and polymerization of propylene, dimerization and oligomerization of butenes and isobutenes, polymerization of butenes and isobutenes, alkylation of isoparaffins, and the like.

A preferred embodiment of the present invention provides a method for the preparation of C₅To C₁₂Heterogeneous catalyst compositions or systems for dimerization and oligomerization of a range of higher alpha olefins. The product is useful as an intermediate in synthetic lubricants, especially based on C₁₀To C₁₂Dimerization and oligomerization of alpha olefins to produce Polyalphaolefins (PAO).

A particularly preferred embodiment of the present invention is to provide a heterogeneous catalyst system which is highly efficient for the polymerization of isobutene to produce highly reactive polyisobutenes.

By liquid BF₃The general reaction of the alcohol complex with anhydrous crystalline aluminum oxide (alumina) can produce the activated metal oxide catalyst of the invention of the present application. Gamma and theta alumina are preferred crystalline structures.

BF of the prior art₃Alumina compositions are not catalytic for certain organic conversion reactions, as reported in U.S. Pat. No. 6,710,140. And, in BF₃In some cases, the content may be catalytic, BF₃Will leach out and require the addition of additional BF along with the reactant feed₃. This, of course, destroys the utility of the solid heterogeneous catalyst, since it requires a work-up of the reactor effluent for the removal of BF₃And (4) residue.

According to the invention of the present application, it was unexpectedly found that if ordinary BF is used₃Alcohol complex instead of BF₃The reaction product of the gas, with crystalline alumina, is highly catalytic, stable, long-lived, and does not deactivate or become consumed during the catalytic process. Moreover, BF can be realized₃High loading without causing BF₃Adding into a reaction mixerProblems in the composition.

Suitable crystalline alumina types include theta alumina and gamma alumina. The more preferred crystal structure is gamma alumina because it is higher for BF than theta alumina₃Volume of alcohol catalyst complex. Alpha alumina is least preferred.

In the presence of BF₃Before the reaction of the alcohol complex, the alumina must be substantially dried. This can be done by heating it at 200 ℃ for 10 to 20 hours.

In making BF₃At a rate of adequate absorption of BF₃The gas is passed through a solution of pure anhydrous alcohol to form BF₃Alcohol complex. Alcohol pair BF₃The ratio of (A) to (B) is usually such that every mole of BF₃About 0.5 moles of alcohol to each mole of BF₃About 2 moles of alcohol. A more preferred range is about per mole BF₃About 1 mole of alcohol to per mole of BF₃About 2 moles of alcohol. The most preferred range is about per mole BF₃About 1 mole of alcohol to per mole of BF₃About 1.3 moles of alcohol.

C free of alpha hydrogen₁To C₁₀Alcohols in the range are suitable for reacting with BF₃And (4) complexing. Alcohols with alpha hydrogen are readily BF bound₃Dehydration forms olefins. For example, BF can be formed even at low temperatures₃In the case of the alcohol complexes, the complexes obtained are not stable at the reaction temperature. More preferred alcohols are methanol and neo-alcohols such as neopentyl alcohol. The most preferred alcohol is methanol.

Diols and polyols which do not contain alpha hydrogen, such as ethylene glycol, may also be used.

BF₃The reaction of the alcohol complex with alumina is highly exothermic and must be controlled to avoid BF₃Is lost. The addition of BF can be carried out by any mechanical means which allows good mixing of the complex with the alumina and also allows sufficient temperature control₃Alcohol complex. The preferred method is to add alumina to a rotating double cone mixer and meter in BF₃Alcohol complex, thereby controlling the temperature within a desired range. The temperature during mixing should beNot exceeding 50 to 60 ℃.

BF₃The concentration of the/alcohol complex on the alumina may be from about 10 to about 30 wt.%. A preferred range is from about 20 to about 30 weight percent. The most preferred range is about 25 to 30 weight percent. In BF₃The actual concentration of F or B in the/alcohol complex-alumina system depends on the alcohol used.

Can be used as BF₃The final catalyst composition (system) of the alcohol-alumina reaction product is used to catalyze the conversion of organic compounds. The catalyst composition may be contacted with the reactants in a batch or continuous process.

In a preferred embodiment of the present invention, the reactor may be a shell-and-tube heat exchanger in which the catalyst composition is packed in tubes. This arrangement may be referred to as a fixed bed reactor. This applies in particular to highly exothermic reactions such as the polymerization of olefins, in particular of isobutene.

The heat exchanger may be placed vertically. The heat exchange medium may be circulated through the shell side of the heat exchanger. The heat exchanger may be of the single-pass or multi-pass type. A dual pass heat exchanger is particularly desirable. The heat exchanger may be fitted with a recirculation loop to accommodate a large volume of the recirculation flow. The olefin-containing feedstock enters the reactor through a recirculation pump located downstream of the pump. The recycle pump pushes the olefin stream through the reactor tubes and returns the stream to the suction side of the pump. In the case of a two-pass heat exchanger, the recycle stream may enter through the bottom of the reactor and then exit the reactor through a pipe from the bottom and return to the pump. This flow scheme constitutes what is commonly referred to as a loop reactor. The flow rate is controlled using the pump speed or an internal recirculation loop on the pump itself. The flow rate is preferably a velocity sufficient to create a turbulent or at least non-laminar flow of the olefin feed stream over the fixed bed catalyst composition packed in the tubes.

The bulk feed stream may enter the recirculation loop through a feed pump located between the outlet of the recirculation pump and the bottom of the reactor at the beginning of the first pass. At equilibrium, the concentration of olefin monomer and polymer product is constant throughout the reactor, so the point at which the reaction effluent leaves the reactor is a matter of choice. However, it is convenient for the effluent line to be located at the top of the reactor after the first pass. The effluent flow rate must be equal to the volumetric feed flow rate. The volumetric feed flow rate is independent of the volumetric recycle flow rate and can desirably be adjusted to achieve the desired residence time and conversion.

The reactor may be equipped with appropriate temperature, pressure and flow indicators and controllers as required to operate under controlled conditions.

The size of the heat exchanger reactor can be chosen at will and is based on the desired product volume. Convenient dimensions are a length of 10 to 15 feet and a diameter of 4 to 6 feet. The number of tubes and the diameter of the tubes in the reactor depend on the type, size and shape of the catalyst and on the desired output. For the reactor sizes described above, a convenient number of tubes is 150 to 200 tubes per pass, and an internal diameter of 1/2 to 1 inch. In a two-pass heat exchanger, the tubes extend vertically over the entire length of the reactor and are connected by end caps at the top and bottom of the reactor. The olefin reaction mixture is directed to one side of the bottom head cover and returned through the other side of the bottom head cover. The top end cap interior is open to the outlet for reaction effluent.

In a preferred embodiment, the pressure of the reactor may preferably be at least 150psig or at least at a sufficient level to ensure maintenance of a liquid phase in the reactor. The pressure may be controlled by a backpressure regulator on the reactor effluent line.

The reactor, in the case of polyisobutylene, is desirably operated at temperatures and conditions that produce a polymer product having a molecular weight range of about 300 to about 5000 daltons. Other temperatures and conditions may be used as desired for a particular organic conversion reaction.

The volumetric recirculation flow rate can be adjusted to provide about 40 to 60BTU/min-ft²Heat transfer coefficient of-. degree.F. The volumetric feed flow rate can be maintained at a liquid hourly space velocity to provide from 1 to 30kg of isobutylene per kg of catalyst (LHSV). More preferably, the LHSV can be controlled at about 3 to 10kg of isobutylene per kg of catalyst.

The preferred olefin feed is C4 raffinate, also known as raffinate-1 or raffinate-1. The actual composition of such streams will vary from source to source, but a typical raffinate-1 stream may contain about 0.5 wt% C₃About 4.5 wt% isobutane, about 16.5 wt% n-butane, about 38.5 wt% 1-butene, about 28.3 wt% isobutene, about 10.2 wt% cis-2-butene and trans-2-butene and less than 0.5 wt% butadiene and less than 1.0 wt% oxygenates. The presence of oxygenates may or may not affect the catalytic reaction. C₃The specie and n-butane are inert and pass through the reactor without modification and are removed from the reaction mixture in a downstream stripping step. Isobutene is highly reactive with the reaction conditions and the desired end product. The extent of reaction of 1-butene and 2-butene varies depending on the type of catalyst and the conditions of the reactor. Unreacted olefins are also removed from the polymer product in a downstream stripping step. The raffinate-1 feed is particularly preferred for making polymers where high activity is not important. These products are referred to as conventional PIB or PB.

Another preferred olefin feed is the effluent from the dehydrogenation of isobutane to isobutene, referred to as dehydrogenation effluent or DHE for short. DHE typically contains about 42 to 45 weight percent isobutylene and about 50 to 52 weight percent isobutane with the balance being a small amount of C₃N-butane and butene, and butadiene. The feedstock is particularly suitable for the manufacture of polyisobutylene in locations where inert isobutane may be utilized, such as in a manner that is co-operable with an isobutane dehydrogenation unit.

Another preferred olefin feed is DHE in which most of the inert isobutane has been removed. This stream is referred to as an isobutene concentrate and typically contains about 88 to 90 wt.% isobutene and about 5 to 10 wt.% isobutane, the balance being small amounts of C₃N-butane and butene, and butadiene. The feedstock is also suitable for the production of highly reactive polyisobutenes.

Yet another preferred olefin feed is high purity isobutylene, which contains more than 99 weight percent isobutylene. This feedstock is highly suitable for the production of highly reactive polyisobutenes. The unreacted olefin is easily recycled.

After leaving the reactor, the reaction effluent is simply purified by atmospheric and/or vacuum stripping to remove light hydrocarbons and inert components. Unreacted monomer can be recycled, but provided that the inert components must be separated or purged depending on the type of olefin feed.

The volumetric efficiency is very high because the above reaction scheme can remove the reaction heat very efficiently so that isothermal and CSTR (continuous stirred tank reactor) conditions can be maintained. That is, a large amount of product can be produced for a given reactor volume. Thus, the capital cost per volume of product is very low. The fact that no downstream catalyst removal and/or catalyst regeneration equipment is required further impacts the overall capital cost in a positive manner.

Table 1 below shows a comparison between the existing and current commercial processes for the preparation of polyisobutene and the inventive process of the present invention using the novel BF of the present invention₃Alcohol-metal oxide catalyst system. In table 1. The column labeled "Soltex" refers to the invention of the present application. In addition, the term IB refers to isobutylene.

The above description of the isobutylene polymer process has been used to demonstrate the efficacy of the activated metal oxide catalyst system of the invention of the present application. This description of the preferred embodiments is not intended to limit the scope of the invention. BF of the invention₃The alcohol-metal oxide reaction product can be used as a catalyst for all organic product reactions requiring an acid catalyst. These reactions include, but are not limited to, Fischer-Tropsch alkylation, alkylation of phenols, alkylation of isoparaffinsDimerization and polymerization in a broad sense of olefins, dimerization of higher alpha olefins and dimerization of isobutene, and the like.

The foregoing disclosure and description of the invention are illustrative and explanatory thereof. Various changes may be made in the details of the method described without departing from the true scope of the invention.

Claims (7)

1. A catalyst system for heterogeneously catalyzing the polymerization of isobutylene to form a polyisobutylene product, the catalyst system comprising (i) BF₃An alcohol catalyst complex and (ii) an alumina support for said catalyst complex, said alumina support consisting essentially of alumina, said catalyst complex having a concentration of 10 to 30 weight percent on said alumina support, said catalyst complex having an alcohol pair BF in said catalyst complex₃In a ratio of BF per mole₃0.5 mol of alcohol to every mole of BF₃2 moles of alcohol.

2. The catalyst system of claim 1, wherein the isobutylene polymerization reaction comprises oligomerization of isobutylene.

3. The catalyst system of claim 1, wherein the isobutylene polymerization reaction comprises dimerization of isobutylene.

4. The catalyst system of claim 1, wherein the concentration of the catalyst complex on the alumina support is from 25 to 30 wt.%.

5. The catalyst system of claim 1, wherein the catalyst system is in the form of a fixed bed.

6. The catalyst system of claim 1, wherein the alumina support comprises gamma-alumina.

7. The catalyst system of claim 1, wherein the alcohol pair BF in the catalyst complex₃In a ratio of BF per mole₃1 mol of alcohol to every mole of BF₃1.3 moles of alcohol.