FIELD OF THE INVENTION

[0001] This invention pertains to a process for the preparation of a diol from the corresponding dione. In particular, this invention pertains a process for the preparation of a 2,2,4,4-tetraalkylcyclobutane-l,3-diol by hydrogenation of a 2,2,4,4-tetraalkylcyclobutane- 1,3-dione in the vapor phase in the presence of a supported catalyst.

BACKGROUND OF THE INVENTION

[0002] Tetraalkylcyclobutane-l,3-diols can be important intermediates for producing a variety of polymeric materials which possess advantageous properties. For example, polyesters derived from dicarboxylic acids and 2,2,4,4-tetramethylcyclobutane-l,3-diol possess higher glass transition temperatures, superior weatherability, and hydrolytic stability compared to polyesters prepared from other commonly-used diols. Tetraalkylcyclobutane-1,3- diols can be prepared by the catalytic hydrogenation of the corresponding 2,2,4,4- tetraalkylcyclobutane-l,3-dione (I) to the corresponding 2,2,4,4-tetraalkylcyclobutane-l,3- diol (I I), wherein R is an alkyl group, as illustrated in Figure 1.

[0003] The hydrogenation of the corresponding tetraalkylcyclobutanediones can be carried out using a variety of catalysts such as, for example, nickel, ruthenium, and cobalt. For example, the hydrogenation of 2,2,4,4-tetramethylcyclobutane-l,3-dione to 2,2,4,4- tetramethylcyclobutane-l,3-diol can be accomplished using nickel or ruthenium containing catalysts as described in U.S. Patents No.'s 3,000,906, 3,190,928; 5,169,994; 5,258,556; and 2,936,324. Cobalt containing catalysts also can be used. For example, U.S. Patent Nos.

5,528,556 and 5,169,994 disclose that Raney cobalt is effective for hydrogenation of 2,2,4,4- tetramethylcyclobutane-l,3-dione to 2,2,4,4-tetramethylcyclobutane-l,3-diol. These processes, however, can exhibit long reaction times. The reaction rate can be increased by raising the temperature and pressure, but these measures can be expensive and can result in the formation of by-products from the decomposition of the products and starting materials. [0004] In general, the hydrogenation of 2,2,4,4-tetramethylcyclobutane-l,3-dione produces the corresponding 2,2,4,4-tetramethylcyclobutane-l,3-diol as a mixture of cis and trans isomers. For example, U.S. Patent No. 3,190,928 discloses a process for hydrogenation of 2,2,4,4-tetramethylcyclobutane-l,3-dione to 2,2,4,4-tetramethylcyclobutane-l,3-diol using nickel- or ruthenium-based catalysts that produce cisitrans molar ratios ranging from about 0.5:1 to about 1.2:1 depending on reaction conditions. A wide variation in the cisitrans ratio, however, can result in polyesters with inconsistent and/or undesirable properties. I n addition, for some applications, a high cisitrans ratio is desirable, but catalysts that produce a high ratio of cisitrans isomers may not give the good yields or acceptable rates of hydrogenation.

[0005] There is a need in the art, therefore, for a process that can produce 2,2,4,4- tetramethylcyclobutanediol at good conversions and selectivities and with consistently high cisitrans isomer ratios, e.g., greater than 1:1. There is also a need for such a process that can be operated economically at modest pressures and temperatures.

SUMMARY OF THE INVENTION

[0006] We have discovered that 2,2,4,4-tetraalkylcyclobutane-l,3-diols having high cisitrans ratios can be prepared efficiently by vapor-phase hydrogenation the corresponding 2,2,4,4-tetraalkylcyclobutane-l,3-dione in the presence of nickel or ruthenium catalysts. A general embodiment of our invention, therefore, is a process for the preparation of a 2,2,4,4-tetraalkylcyclobutane-l,3-diol, comprising:

I . continuously feeding to a hydrogenation zone hydrogen and a hydrogenatable reac- tant comprising a 2,2,4,4-tetraalkylcyclobutane-l,3-dione having the formula (I):

wherein the hydrogen and hydrogenatable reactant a re in the gas phase and R is a alkyl radical containing 1 to 8 carbon atoms;

continuously contacting the hydrogen and hydrogenatable reactant of step (I) under hydrogenation conditions of temperature and pressure with a catalyst comprising nickel, ruthenium, or combination thereof, to form a hydrogenation product comprising a 2,2,4,4-tetraalkylcyclobutane-l,3-diol having the formula (I I):

wherein the temperature is greater than the dew point of the hydrogenation product; and

I II . continuously recovering from the reaction zone a gaseous effluent comprising the hydrogenation product.

I n general, our process can produce 2,2,4,4-tetraalkylcyclobutane-l,3-diols in high yields an can be operated with increased safety and operating economy at modest pressures and temperatures.

[0007] Our process may be used, in particular, for the preparation of 2,2,4,4- tetramethylcyclobutane-l,3-diol from 2,2,4,4-tetramethylcyclobutane-l,3-dione, and can be carried out under modest pressures and temperatures under continuous operating conditions. The process can give 2,2,4,4-tetramethylcyclobutane-l,3-diol product with an excess of the cis isomer. Thus, another aspect of the invention is a process for the preparation of 2,2,4,4-tetramethylcyclobutane-l,3-diol, comprising

I . continuously feeding to a hydrogenation zone hydrogen and a hydrogenatable reactant comprising2,2,4,4-tetramethylcyclobutane-l,3-dione

wherein the hydrogen and hydrogenatable reactant a re in the gas phase;

I I. continuously contacting the hydrogen and hydrogenatable reactant of step (I) at a temperature of about 100 to about 200 °C and a pressure of about 7 to about 28 bar with a catalyst comprising about 1 to about 8 weight percent ruthenium, based on the total weight of the catalyst, deposited on a support, to form a hydrogenation product comprising 2,2,4,4-tetramethylcyclobutane-l,3-diol having a cis:trans ratio of about 1:1 to about 1.6:1, wherein the temperature is greater than the dew point of the hydrogenation product;

III. continuously recovering from the reaction zone a gaseous effluent comprising the hydrogenation product; and

IV. continuously recycling a portion of the gaseous effluent to the hydrogenation zone.

[0008] We have found that ruthenium deposited on activated carbon, carbonized poly- sulfonated vinylaromatic polymer particles, graphitized carbon, or combinations thereof, are useful catalysts for our novel process. Therefore, another embodiment of our invention is a process for the preparation of2,2,4,4-tetramethylcyclobutane-l,3-diol, comprising:

I. continuously feeding to a hydrogenation zone hydrogen and a hydrogenatable reac- tant comprising 2,2,4,4-tetramethylcyclobutane-l,3-dione at a hydrogen: 2,2,4,4- tetramethylcyclobutane-l,3-dione molar ratio of about 100:1 to about 500:1, wherein the hydrogen and hydrogenatable reactant are in the gas phase;

II. continuously contacting the hydrogen and hydrogenatable reactant of step (I) at a temperature of about 100 to about 160 °C and a pressure of about 14 to about 21 bars with a catalyst comprising about 1 to about 8 weight percent ruthenium, based on the total weight of the catalyst, deposited on a support comprising activated carbon, carbonized polysulfonated vinylaromatic polymer particles, carbonized phenol formaldehyde resin particles, graphtized carbon, or combinations thereof, to form a hydrogenation product comprising 2,2,4,4-tetramethylcyclobutane-l,3-diol having a cis:trans ratio of about 1:1 to about 1.6:1, wherein the temperature is greater than the dew point of the hydrogenation product;

III. continuously recovering from the reaction zone a gaseous effluent comprising the hydrogenation product.

The vapor-phase hydrogenation process may be carried in the presence or absence of a solvent and in a variety of reactor types such as, tubular fixed bed, moving bed, or fluidized bed. DETAILED DESCRIPTION

[0009] The invention provides a process for the preparation of 2,2,4,4- tetraalkylcyclobutane-l,3-diols such as, for example, 2,2,4,4-tetramethylcyclobutane-l,3- diol, by hydrogenation of the corresponding 2,2,4,4-tetraalkylcyclobutane-l,3-dione in the vapor-phase in presence of ruthenium or nickel cata lysts. A general embodiment of our invention, therefore, is a process for the preparation of a 2,2,4,4-tetraalkylcyclobutane-l,3- diol, comprising:

I . continuously feeding to a hydrogenation zone hydrogen and a hydrogenatable reac- tant comprising a 2,2,4,4-tetraalk lcyclobutane-l,3-dione having the formula (I):

I wherein the hydrogen and hydrogenatable reactant a re in the gas phase and R is a alkyl radical containing 1 to 8 carbon atoms;

I I. continuously contacting the hydrogen and hydrogenatable reactant of step (I) under hydrogenation conditions of temperature and pressure with a catalyst comprising nickel, ruthenium, or combination thereof, to form a hydrogenation product comprising a 2,2,4,4-tetraalkylcyclobutane-l 3-diol having the formula (I I):

wherein the temperature is greater than the dew point of the hydrogenation product; and I II . continously recovering from the reaction zone a gaseous effluent comprising the hy- drogenation product.

[0010] Unless otherwise indicated, all numbers expressing quantities of ingredients, properties such as molecular weight, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about." Unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present invention. At the very least, each numerical parameter should be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Further, the ranges stated in this disclosure and the claims are intended to include the entire range specifically and not just the endpoint(s). For example, a range stated to be 0 to 10 is intended to disclose all whole numbers between 0 and 10 such as, for example 1, 2, 3, 4, etc., all fractional numbers between 0 and 10, for example 1.5, 2.3, 4.57, 6.1113, etc., and the endpoints 0 and 10. Also, a range associated with chemical substituent groups such as, for example, "CI to C5 hydrocarbons", is intended to specifically include and disclose CI and C5 hydroca rbons as well as C2, C3, and C4 hydrocarbons.

[0011] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in its respective testing measurements.

[0012] Also, it is to be understood that the mention of one or more process steps does not preclude the presence of additional process steps before or after the combined recited steps or intervening process steps between those steps expressly identified. Moreover, the lettering of process steps or ingredients is a convenient means for identifying discrete activities or ingredients and the recited lettering can be arranged in any sequence, unless otherwise indicated.

[0013] The term "hydrogenatable reactant," as used herein, is intended to mean a substance that is introduced into a hydrogenation reactor that is capable of undergoing a hy- drogenation reaction, that is the addition of hydrogen across a double or triple bond between two chemical elements, typically, a carbon-carbon double bond or carbon-oxygen double bond, in the presence of a catalyst. As used herein, the terms "tetraalkylcyclobu- tanediol," "tetraalkylcyclobutanedione," "tetramethylcyclobutanedione," and "tetramethyl- cyclobutanediol" are understood to be synonymous with the terms "2,2,4,4- tetraalkylcyclobutane-l,3-diol," "2,2,4,4-tetraalkylcyclobutane-l,3-dione," and "2,2,4,4- tetramethylcyclobutane-l,3-diol," respectively. The terms "ruthenium" and "nickel" are understood to encompass all the various forms of the metals including elemental ruthenium and nickel as well as any compounds of ruthenium and nickel such as, for example, those containing oxygen, halide, trivalent nitrogen, carbon monoxide, hydrogen, carboxylates, and diones, either alone or in any combination.

[0014] Our invention provides a process for the preparation of a 2,2,4,4-tetraalkyl- cyclobutane-l,3-diol having the formula (II) by continuously feeding to a hydrogenation zone hydrogen and a hydrogenatable reactant comprising a 2,2,4,4-tetraalkylcyclobutane- 1,3-dione having the formula (I) as shown in Figure 1 below:

Figure 1

Hydrogenation of 2,2,4,4-Tetraalkycyclobutane-l,3-dione

wherein the R groups are identical, alkyl radicals having 1 to 8 carbon atoms. For example, the alkyl radicals represented by R can comprise 1 to 6 carbon atoms, 1 to 4 carbon atoms, or 1 to 2 carbon atoms. The alkyl radicals may be linear, branched or a combination of linear and branched alkyl radicals. Representative alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isoamyl, hexyl, heptyl, and octyl. Some examples of 2,2,4,4- tetralkylcyclobutane-l,3-diones that can be hydrogenated in the pro- cess of the invention include 2,2,4,4-tetramethylcyclobutane-l,3-dione, 2,2,4,4-tetraethyl- cyclobutane-l,3-dione, 2,2,4,4- tetra-n-propylcyclobutane-l,3-dione, 2,2,4,4- tetrai- sopropylcyclobutane-l,3-dione, 2,2,4,4-tetra-n-butylcyclobutane-l,3-dione, 2,2,4,4- tetraisobutylcyclobutane-l,3-dione, 2,2,4,4-tetra-n-amylcyclobutane- 1,3-dione, 2,2,4,4- tetraisoamylcyclobutane-l,3-dione, 2,2,4,4-tetra-n-hexylcyclobutane-l,3-dione, 2,2,4,4- tetra-n-heptylcyclobutane-l,3-dione, and 2,2,4,4-tetra-n-octylcyclobutane-l,3-dione. In one embodiment of the invention, for example, the hydrogenatable reactant comprises 2,2,4,4- tetramethylcyclobutane-l,3-dione (R is methyl in Formula I) and produces a hydrogenation product comprising 2,2,4,4- tetramethylcyclobutane-l,3-diol (R is methyl in Formula II).

[0015] The hydrogenation process comprises continuously feeding to a hydrogenation zone hydrogen and a hydrogenatable reactant comprising a 2,2,4,4-tetraalkylcyclobutane- 1,3-dione. The source and purity of the hydrogen gas used in the processes of the present invention are not critical. The hydrogen gas may comprise fresh hydrogen or a mixture of fresh hydrogen and recycle hydrogen. The hydrogen gas can be a mixture of hydrogen, optionally minor amounts, typically less than about 30 mole %, of components such as CO and C0 ₂ , and inert gases, such as argon, nitrogen, or methane. Typically, the hydrogen gas can comprise at least 70 mole % of hydrogen. For example, the hydrogen gas can comprise at least 90 mole % or, in another example, at least 97 mole %, of hydrogen. The hydrogen gas can be obtained from any of the conventional sources well known in the art such as, for example, by partial oxidation or steam reforming of natural gas. Pressure swing absorption can be used if a high purity hydrogen gas is desired. If hydrogen gas recycle is utilized in the process, then the recycled hydrogen gas will normally contain minor amounts of one or more products of the hydrogenation reaction, i.e., 2,2,4,4-tetraalkylcyclobutane-l,3-diols, which have not been fully condensed in the product recovery stage downstream from the hydrogenation zone.

[0016] The hydrogenatable reactant and hydrogen can be contacted continuously under hydrogenation conditions of temperature and pressure with any catalyst capable of catalysing the hydrogenation of a ketone or carbonyl group to the corresponding alcohol or mixture of alcohols. Typical catalysts can include copper-containing catalysts and Group VIII metal-containing catalysts. For example, the catalyst can comprise copper chromite, nickel, ruthenium, palladium, platinum, cobalt, iridium, or combinations thereof. The term "copper chromite", as used herein, is intended have its commonly understood meaning in the art and includes copper chromite itself as represented by the general formula, CuCr ₂ Ox, non- stoichiometric mixed copper-chromium oxides, prepared by coprecipitation, and the various mixtures of copper chromite with copper metal, copper oxides, and chromium oxides that may be formed during the catalyst manufacturing process and its subsequent use as a hy- drogenation catalyst. For example, the copper chromite, as prepared, may comprise one or more of: copper (II) oxide, copper chromite (CuCr ₂ 0 ₄ ), chromium trioxide (Cr0 ₃ ), or chromic oxide (Cr ₂ 0 ₃ ). In one embodiment of the invention, for example, the copper chromite may comprise about 24-26 weight % copper(ll) oxide, about 65-67 weight % copper chromite, about 1 weight % chromium trioxide, about 1 weight % chromic oxide, and about 0-4 weight % graphite. During the hydrogenation process, a portion of the copper oxide may be reduced to copper metal. Thus, under hydrogenation conditions, the copper chromite of the invention can comprise mixtures of copper chromite, copper oxides, chromium oxides, and copper metal in various proportions. The copper chromite component of the catalysts can be prepared using conventional coprecipitation techniques well known in the art. In addition, the copper chromite may be further compounded with binders to aid in pellet formation or supported on additional support materials such as, for example, alumina, titania, carbon, graphite, zirconia, silica, silica-alumina, and the like.

[0017] Some additional examples of suitable copper-containing catalysts include reduced copper-on-alumina catalysts, reduced copper oxide/zinc oxide catalysts, with or without a promoter, and reduced manganese promoted copper catalysts. Suitable copper oxide/zinc oxide catalyst precursors include CuO/ZnO mixtures wherein the Cu:Zn weight ratio ranges from about 0.4:1 to about 2:1. Promoted copper oxide/zinc oxide precursors include CuO/ZnO mixtures wherein the Cu:Zn weight ratio ranges from about 0.4:1 to about 2:1 and which are promoted with about 0.1% by weight to about 15% by weight of barium, manganese or a mixture of barium and manganese. For example, manganese promoted copper catalyst precursors typically have a Cu:Mn weight ratio of from about 2:1 to about 10:1 and can include an alumina support, in which case the Cu:AI weight ratio typically can be from about 2:1 to about 4:1. Many of these catalysts are available commercially from Davy Research and Development Limited or BASF Catalysts.

[0018] The catalyst may comprise Group VIII metal catalysts such as, for example, cobalt, platinum, ruthenium, nickel, rhodium, iridium, and palladium catalysts. For example, various cobalt catalysts , such as metallic, alloy, and supported cobalt, may be used. An example of metallic and alloy cobalt is Raney ^® cobalt from W.R. Grace Co. The cobalt also may be deposited on the various support materials described herein. In one embodiment, for example, the catalyst can comprise metallic nickel or metallic ruthenium, i.e., as ruthenium or nickel powder, or in the form of a supported catalyst in which the ruthenium or nickel is deposited on a support material. The term "support," as used in the context of the present specification and claims is intended to have its commonly accepted meaning as would be well-understood by persons of ordinary skill in the art, that is, a nominally inert material on which a catalytically active material, e.g., typically a metal, is deposited on. The term, "deposited on," as used herein, is understood to mean any known method for adding the metal to the support including, but not limited to, depositing, adsorption, impregnation, ion-exchange, admixing, comprecipitation, and the like.

[0019] When deposited on a support, the amount of the ruthenium contained in the catalyst may range from about 0.01 to about 10 weight percent (abbreviated herein as "wt %") based upon the total weight of the catalyst. For example, the processes of the present invention may use a catalyst comprising about 0.01 to about 10 wt% ruthenium, based on the total weight of the catalyst. Other examples of ruthenium levels on the catalyst are 0.05 to about 7 wt% ruthenium and about 1 to about 5 wt % ruthenium. When, ruthenium metal is used as the catalyst in the absence of support, the weight percent of ruthenium in the catalyst is typically at least 95 to 100 weight percent, based on the total weight of the catalyst.

[0020] Similarly, the amount of the nickel compound that may be employed as the catalyst in our process may range from about 0.01 to about 100 weight percent based upon the total weight of the catalyst. For example, the processes of the present invention may use a catalyst comprising about 0.01 to about 80 wt% nickel, based on the total weight of the catalyst. Other examples of nickel levels on the catalyst are 0.05 to about 70 wt% nickel and about 1 to about 50 wt % nickel. For example, in one embodiment, the catalyst can comprise a Raney nickel.

[0021] The catalytic metals may be deposited on any recognized support material. For example, the support may comprise materials such as chromia, rare earth metal oxides, mixed metal oxides, zinc oxide, alumina, silica, silica-alumina, silicon carbide, zirconia, titania, carbon, graphite, graphitized carbon, carbon nanotubes, zeolites, carbonized polysulfonated vinylaromatic polymer particles, carbonized phenol-formaldehyde resin spheres, or combinations thereof. These support materials are well-known to persons skilled in the art and many are available commercially. For example, graphitized carbon supports are described in Rossetti et al. Catalysis Today, 2005, 102-103, pp. 219-224, and in U.S. Patent No. 7,115,239. The catalyst support may be further compounded with one or more binders to aid in pellet formation. The catalyst support along with any binder can be fabricated in any of the commonly used forms well-known in the art such as, for example, powders, extrudates, chips, granules, monoliths, pellets, cylinders, rings, saddles, spheres, stars, single lobe or multiple- lobe shapes, and the like. Depending on the particular support material employed and/or the method used to prepare a catalyst, ruthenium may be deposited primarily on the surface of the support or distributed throughout the support.

[0022] In one embodiment, the ruthenium and nickel may be deposited on a support comprising carbonized, phenol-formaldehyde resin particles or polysulfonated vinylaromatic polymer particles. As used herein, the term "carbonized, polysulfonated vinylaromatic polymer particles" is understood to mean macroporous copolymers and include macroporous or macroreticular copolymers that have been polysulfonated and then substantially transformed to carbon or a carbonaceous material by pyrolysis or the action of heat. The preparation of the carbonized polysulfonated vinylaromatic polymer particles is described in general in U.S. Patent No. 4,839,331. Similarly, the term "carbonized phenol-formaldehyde resin particles," is understood to mean polymers prepared by reacting a phenol with an aldehyde in the presence of an acid or a base and transformed into a carbonaceous material by the action of heat. These particles are typically obtained in the form of spheres or beads. The preparation of carbonized phenol-resin particles (beads) is described, for example, in U.S. Patent Application Publication No.'s 20070191571 and 20070191572. [0023] In another embodiment, the catalyst comprises ruthenium or nickel supported on carbon nanotubes. Carbon nanotubes (also known as fibrils) are well-known in the art as vermicular carbon deposits having diameters less than 1.0 μιη, preferably less than 0.5 μιη, and even more preferably less than 0.2 μιη. Carbon nanotubes can be either multi walled (i.e., have more than one graphene layer more or less parallel to the nanotube axis) or single walled (i.e., have only a single graphene layer parallel to the nanotube axis). Other types of carbon nanotubes are also known, such as fishbone fibrils (e.g., wherein the graphene sheets are disposed in a herringbone pattern with respect to the nanotube axis), etc. As produced, carbon nanotubes may be in the form of discrete nanotubes, aggregates of nanotubes (i.e., dense, microscopic particulate structure comprising entangled carbon nanotubes), or a mixture of both. Some representative examples of carbon nanotubes are described in U.S. Patent Application Publication No.'s 2009 0208391; 2008 0176069; 2008 0175787; 2006 0239893; 2006 0142149; 2006 0142148; and 2003 0039604.

[0024] It will be apparent to persons skilled in the art that any of the weight percentages of ruthenium or nickel described above can be used on any of the aforementioned supports. For example, the catalyst can comprise about 0.01 to about 10 weight percent ruthenium or about 0.01 to about 80 weight percent nickel, based on the total weight of the catalyst, deposited on a support comprising silica-alumina, titania, alumina-clay, clay, graphite, silicon carbide, zirconium, activated carbon, carbonized phenol formaldehyde resin particles, carbonized polysulfonated vinylaromatic polymer particles, carbon nanotubes, or combinations thereof.

[0025] The catalyst may be prepared by conventional techniques such as, for example, vapor deposition or impregnation of a ruthenium or nickel compound into the support material. Nickel or ruthenium may be provided as the metal itself or in the form of well-known ruthenium or nickel compounds such as, for example, salts of inorganic or organic acids, oxides, and organometallic complexes. The support material may be impregnated with ruthenium or nickel metal by immersing the support material in a solution of ruthenium or nickel compound in a suitable solvent or by spraying the support material with the solution. The support material typically is dried and the catalyst exposed to a reducing environment, e.g., hydrogen, in order to reduce the ruthenium or nickel compounds to the corresponding zero- valent metals.

[0026] The hydrogenation conditions of pressure and temperature may be varied depending on the activity of the catalyst, the mode of operation, selectivity considerations, and the desired rate of conversion. Our hydrogenation process typically is conducted at temperatures in the range of about 75 °C to about 250 °C. Other suitable temperature ranges include about 100 to about 200 °C, about 100 to about 180 °C, and about 120 to about 160 °C. The process can be conducted at pressures in the range of about 689 kPa (100 psi, 7 bar) to about 4134 kPa (600 psi, 42 bar). Further examples of temperatures and pressures at which the process of the invention may be operated are about 120 °C to about 200° C at a pressure of about 689 kPa (100 psi, 7 bar) to about 2756 kPa (400 psi, 28 bar)and about 130 °C to about 140 °C at a pressure ranging of about 1378 kPa (200 psi, 14 bar) to about 2067 kPa (300 psi, 21 bar).

[0027] The temperature and pressure of the reaction are chosen such that the hydroge- natable reactants enter and the products and unconverted reactants leave the hydrogenation zone in the vapor phase. Throughout the present invention, the terms "vapor phase", "gaseous", "vapor state", "vaporous", "gaseous state", and "gas phase" are used interchangeably and are intended to be synonymous. The process of the invention is operated at temperatures above the dew point of the hydrogenation feed and product mixtures. Because the dew point is a complex function of dilution (particularly with respect to non- condensable gases such as hydrogen or inert diluent gases), product composition, and pressure, the process may be operated over a wide range of temperatures, provided the temperature exceeds the dew point of the hydrogenation feed mixtures and product effluent. The term "dew point", as used herein, means the temperature, at a given pressure, at which a gas is saturated with respect to its condensable components and at which condensation occurs. The dew point of the hydrogenation reactants and products of the present invention may be calculated by methods well known to those skilled in the art, for example, as described in Perry's Chemical Engineer's Handbook, 6th ed, (McGraw-Hill), pp. 13-25 through 13-126. Dew points for single product or complex mixtures may be calculated using commercially available engineering computer programs, such as Aspen ^® , also well-known to those skilled in the art. In practice, as described previously, the process typically operates at a temperature range of about 75 to about 250 °C. Other examples of temperature ranges in which our process may operate include about 100 to about 200 °C, about 120 to about 200 °C, about 100 to about 180 °C, about 120 to about 160 °C, and about 130 to about 140 °C.

[0028] A convenient method of forming a gas phase mixture for use in a vapor phase process is to spray liquid 2,2,4,4-tetraalkylcyclobutane-l,3-dione or a 2,2,4,4-tetraalkyl- cyclobutane-l,3-dione solution into a stream of hot, hydrogen-containing gas to form a saturated or partially saturated vaporous mixture. Alternatively, a vapor mixture can be obtained by bubbling a hot hydrogen-containing gas through the liquid 2,2,4,4-tetraalkyl- cyclobutane-l,3-dione or 2,2,4,4-tetraalkylcyclobutane-l,3-dione solution. If a saturated vapor mixture is formed it can then be heated further or diluted with more hot gas to produce a partially saturated gaseous mixture prior to contact with the catalyst. To maintain the gaseous feed stream above its dew point at the inlet end of a catalyst bed at the operating pressure, the molar ratio of hydrogen and hydrogenatable reactant fed to the hydrogenation zone may be fed to the hydrogenation zone at a ratio of about 10:1 to about 8000:1. Other molar ratios of hydrogen:hydrogenatable reactant include about 100:1 to about 1000:1, about 100:1 to about 800:1, about 100:1 to about 700:1, and about 100:1 to about 600:1. Typically the feed temperature of the vaporous feed mixture to the hydrogenation zone is at least about 5 °C to about 10 °C above its dew point at the operating pressure.

[0029] Although the process of the invention is operated with the feed stream in the gas phase, it is convenient to express the feed rate of the 2,2,4,4-tetraalkylcyclobutane-l,3- dione to the hydrogenation zone as a liquid-hourly space velocity through the hydrogenation catalyst. The liquid-hourly space velocity is expressed as the ratio of the liquid feed rate of the hydrogenatable reactant to the hydrogenation zone to the volume of the hydrogenation catalyst. For example, the process can be operated at a liquid-hourly space velocity of the hydrogenatable reactant through the hydrogenation catalyst can range from about 0.05 to about 4.0 h ^"1 . Thus, the hydrogenatable reactant can be fed to the hydrogenation zone at a rate which is equivalent to, per unit volume of catalyst, of about 0.05 to about 4.0 unit volumes of hydrogenarable material per hour (i.e. about 0.05 to about 4.0 m ³ h ¹ per m ³ of catalyst). Other examples feed rates expressed as liquid-hourly space velocities are from about 0.1 h ¹ to about 2.0 h ¹ and about 0.1 to about 2.0 h ^"1 . In one embodiment of the invention, for example, the process is operated at a temperature of about 100 to about 180 °C, a pressure of about 7 to about 28 bars absolute, and a liquid-hourly space velocity of about 0.05 to about 4 hr Persons of skill in the art will recognize that other combinations of the temperatures, pressures, and feed rates described hereinabove are possible.

[0030] Our process forms a hydrogenation product comprising a 2,2,4,4-tetraalkyl- cyclobutane-l,3-diol. The 2,2,4,4-tetraalkylcyclobutane-l,3-diol hydrogenation product can have a range of cis to trans isomers 0:1 to about 2:1. Other examples of cis:trans ratios are about 0.7:1 to about 1.8:1, about 0.7:1 to about 1.7:1, about 0.7:1 to about 1.6:1, about 0.7:1 to about 1.5:1, about 0.7:1 to about 1.4:l,about 0.7:1 to about 1.3:l,about 0.7:1 to about 1.2:l,about 0.7:1 to about 1.1:1, about 0.7:1 to about 1.0:1, about 0.7:1 to about 0.9:1, and about 0.7:1 to about 0.8:1. For example, in one embodiment of the invention, hy- drogenatable reactant can comprise 2,2,4,4-tetramethylcyclobutane-l,3-dione and the hydrogenation product comprises 2,2,4,4-tetramethylcyclobutane-l,3-diol having a cis:trans isomer ratio of about 0.7:1 to about 1.7:1. Some other representative examples of ranges of cis:trans ratios of the product 2,2,4,4-tetramethylcyclobutane-l,3-diol are about 0.7:1 to about 1.6:1, about 0.7:1 to about 1.4:1, about 0.7:1 to about 1.2:1, about 0.7:1 to about 1.0:1, and about 0.7:1 to about 0.8:1.

[0031] The hydrogenatable reactant may further comprise a solvent. The solvent may be selected from a wide variety of compounds or mixture of compounds provided that they do not affect adversely the hydrogenation process and are substantially inert or show limited reactivity (e.g., typically less than 1% conversion under process conditions) with respect to the catalyst, hydrogen, the tetraalkylcyclobutanedione starting material, and tetraalkylcy- clobutanediol product. The starting 2,2,4,4-tetraalkylcyclobutane-l,3-dione, for example, can be dissolved or partially dissolved in a solvent selected from water, alcohols, ethers, glycols, glycol ethers, alkanes, esters, and mixtures thereof. Some specific examples of solvents that may used in the isomerization process include, but are not limited to, water, methanol, ethanol, propanol, 1-butanol, 2-butanol, 2-ethylhexanol, 2,2-dimethyl-l,3-propanediol, ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol, 2,2,4,4- tetramethylcyclobutane-l,3-diol, hexane, heptane, cyclohexane, octane, decane, diethyl ether, diisopropyl ether, tetrahydrofuran, methyl tert-butyl ether, ethylene glycol mono- butyl ether, diethylene glycol monobutyl ether, ethyl acetate, n-propyl acetate, isopropyl isobutyrate, isobutyl propionate, octyl acetate, isobutyl isobutyrate, isobutyl acetate, methyl butyrate, and mixtures thereof. In one embodiment, for example, the solvent comprises isobutyl isobutyrate. In another example, the solvent comprises tetrahydrofuran. Typically, the 2,2,4,4-tetraalkylcyclobutane-l,3-dione can be dissolved in the solvent at a concentration of about 1 to about 60 weight percent, based on the total weight of the tetraalkylcyclo- butanedione solution. Some other examples of tetraalkylcyclobutanedione concentrations are about 5 to about 50 weight percent, about 3 to about 25 weight percent, and about 10 to about 25 weight percent. In another example, the tetraalkylcyclobutanedione comprises 2,2,4,4-tetraalkylcyclobutanedione and is dissolved in a solvent comprising isobutyl isobutyrate or tetrahydrofuran at a concentration of about 1 to about 60 weight percent, about 5 to about 50 weight percent, about 3 to about 25 weight percent, or about 10 to about 25 weight percent. Also, it can be economically advantageous to conduct the hydrogenation in the absence of solvent and use the neat, molten 2,2,4,4-tetraalkylcyclobutane-l,3-dione alone or as a mixture with the 2,2,4,4-tetraalkylcyclobutane-l,3-diol as the feed to the process.

[0032] For economic and operability reasons, the process can be operated as a continuous process. Continuous operation may utilize a tubular fixed bed with a larger particle size of catalyst such as, for example, granules, pellets, various multilobal shaped pellets, rings, and saddles, or a fluidized bed reactor with smaller particle sizes that can be readily suspended on a column of moving gas. These reactor types are well known to persons skilled in the art. As an example of a continuous process, the catalyst bed may be fixed in a high pressure, tubular or columnar reactor, the vaporous tetraalkylcyclobutanedione fed continuously into the top of the bed at elevated pressure and temperature, and the crude hydrogenation product effluent continuously removed from the base of the reactor. Alternatively, it is possible to feed the tetraalkylcyclobutanedione into the bottom of the bed and continously remove the hydrogenated product effluent from the top of the reactor. It is also possible to use 2 or more catalyst beds connected in parallel or in series to improve conversion, to reduce the quantity of catalyst, or to by pass a catalyst bed for periodic maintenance or cata- lyst removal. For example, the process may be carried in a similar manner, for example, as in the hydrogenation process disclosed in U.S. Patent No. 5,395,987.

[0033] Our process comprises continously recovering a gaseous effluent comprising the hydrogenation product. The gaseous effluent, for example, can be recovered using methods well-known to persons skilled in the art. The process of the invention may further comprise continuously recycling a portion of the product effluent to the hydrogenation zone. For example, the product effluent can be cooled, the tetraalkylcyclobutanediol and any solvent present can be condensed and purified, and any unreacted tetraalkylcyclobutanedione and hydrogen gas recycled to the hydrogenation zone. Purification of the tetraalkylcyclobutanediol hydrogenation product typically can be accomplished by conventional distillation or crystallization procedures. For example, where the hydrogenation product comprises 2,2,4,4-tetramethylcyclobutanediol, the solvent may be removed as a vapor in a first distillation and then low boiling by-products such as 2,2,4-trimethyl-3-oxo-l-pentanol may be vaporized from the diol product in a second distillation. Finally, the product diol may be distilled, optionally under reduced pressure, to obtain substantially pure 2,2,4,4- tetramethylcyclobutanediol.

[0034] Our process can be illustrated with particular reference to the preparation of 2,2,4,4-tetramethylcyclobutanediol by hydrogenation of 2,2,4,4-tetramethylcyclo- butanedione in the gas phase. Another embodiment of our invention, therefore, is a process for the preparation of 2,2,4,4-tetramethylcyclobutane-l,3-diol, comprising:

I. continuously feeding to a hydrogenation zone hydrogen and a hydrogenatable reac- tant comprising 2,2,4,4-tetramethylcyclobutane-l,3-dione

wherein the hydrogen and hydrogenatable reactant are in the gas phase;

II. continuously contacting the hydrogen and hydrogenatable reactant of step (I) at a temperature of about 100 to about 200 °C and a pressure of about 7 to about 28 bar with a catalyst comprising about 1 to about 8 weight percent ruthenium, based on the total weight of the catalyst, deposited on a support, to form a hydrogenation product comprising 2,2,4,4-tetramethylcyclobutane-l,3-diol having a cis:trans ratio of about 1:1 to about 1.6:1, wherein the temperature is greater than the dew point of the hydrogenation product; III. continously recovering from the reaction zone a gaseous effluent comprising the hy- drogenation product; and

IV. continuously recycling a portion of the gaseous effluent to the hydrogenation zone. It will be apparent to persons skilled in the art that the various embodiments of cis:trans isomer ratios, dew points, catalyst metal, catalyst support, reaction conditions of temperature and pressure, feed ratios, purification and recycling of product effluent, and solvents described hereinabove are also application to the above process.

[0035] For example, the hydrogenatable reactant may further comprise at least one non- protic solvent. In another example, the support can comprise activated carbon, alumina, carbon nanotubes, or graphitized carbon and the non-protic solvent can be selected from hexane, heptane, cyclohexane, octane, diethyl ether, diisopropyl ether, tetrahydrofuran, methyl tert-butyl ether, ethyl acetate, n-propyl acetate, isopropyl isobutyrate, isobutyl propionate, octyl acetate, methyl butyrate, isobutyl isobutyrate, and isobutyl acetate. In one embodiment, for example, the solvent can comprise tetrahydrofuran.

[0036] In another embodiment, the catalyst can comprise ruthenium deposited on activated carbon, carbonized phenol formaldehyde resin particles, carbonized polysulfonated vinylaromatic polymer particles, graphtized carbon, or combinations thereof. Thus, another embodiment of our invention is a process for the preparation of 2,2,4,4- tetramethylcyclobutane-l,3-diol, comprising:

I. continuously feeding to a hydrogenation zone hydrogen and a hydrogenatable reactant comprising 2,2,4,4-tetramethylcyclobutane-l,3-dione at a hydrogen: 2,2,4,4- tetramethylcyclobutane-l,3-dione molar ratio of about 100:1 to about 500:1, wherein the hydrogen and hydrogenatable reactant are in the gas phase;

II. continuously contacting the hydrogen and hydrogenatable reactant of step (I) at a temperature of about 100 to about 160 °C and a pressure of about 14 to about 21 bars with a catalyst comprising about 1 to about 8 weight percent ruthenium, based on the total weight of the catalyst, deposited on a support comprising activated carbon, carbonized phenol formaldehyde resin particles, carbonized polysulfonated vinylaromatic polymer particles, graphtized carbon, or combinations thereof, to form a hydrogenation product comprising 2,2,4,4-tetramethylcyclobutane-l,3-diol having a cis:trans ratio of about 1:1 to about 1.6:1, wherein the temperature is greater than the dew point of the hydrogenation product; and

III. continously recovering from the reaction zone a gaseous effluent comprising the hydrogenation product.

The above process is understood to include the various embodiments of cis:trans isomer ratios, dew points, catalyst metal, catalyst support, reaction conditions of temperature and pressure, feed ratios, purification and recycling product effluent, and solvents described above. For example, the hydrogenatable reactant may further comprise at least one non- protic solvent selected from hexane, heptane, cyclohexane, octane, diethyl ether, diisopro- pyl ether, tetrahydrofuran, methyl tert-butyl ether, ethyl acetate, n-propyl acetate, isopro- pyl isobutyrate, isobutyl propionate, octyl acetate, methyl butyrate, isobutyl isobutyrate, and isobutyl acetate. In one embodiment, for example, the solvent can comprise tetrahydrofuran.

[0037] The invention also includes the following embodiments that are set forth below and in paragraphs [0038]-[0051]: a process for the preparation of a 2,2,4,4- tetraalkylcyclobutane-l,3-diol, comprising:

I. continuously feeding to a hydrogenation zone hydrogen and a hydrogenatable reactant comprising a 2,2,4,4-tetraalk lcyclobutane-l,3-dione having the formula (I):

I wherein the hydrogen and hydrogenatable reactant are in the gas phase and R is a alkyl radical containing 1 to 8 carbon atoms;

II. continuously contacting the hydrogen and hydrogenatable reactant of step (I) under hydrogenation conditions of temperature and pressure with a catalyst comprising nickel, ruthenium, or combination thereof, to form a hydrogenation product comprising a 2,2,4,4-tetraalkylcyclobutane-l 3-diol having the formula (I I):

wherein the temperature is greater than the dew point of the hydrogenation product; and

I II . continously recovering from the hydrogenation zone a gaseous effluent comprising the hydrogenation product.

[0038] A process that includes the embodiments of paragraph [0037] in which R is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isoamyl, hexyl, heptyl, or octyl.

[0039] A process that includes the embodiments of any one of paragraphs [0037]-[0038] in which R is methyl.

[0040] A process that includes the embodiments of any one of paragraphs [0037]-[0039] in which the catalyst comprises metallic nickel or metallic ruthenium.

[0041] A process that includes the embodiments of any one of paragraphs [0037]-[0039] in which the catalyst comprises about 0.01 to about 10 weight percent ruthenium or about

0.01 to about 80 weight percent nickel, based on the total weight of the catalyst, deposited on a support comprising silica-alumina, titania, alumina-clay, clay, graphite, silicon carbide, zirconium, activated carbon, carbonized phenol formaldehyde resin particles, carbonized polysulfonated vinylaromatic polymer particles, or combinations thereof.

[0042] A process that includes the embodiments of paragraph [0041] in which the support comprises carbon nanotubes or graphitized carbon.

[0043] A process that includes the embodiments of any one of paragraphs [0037]-[0042] in which the hydrogen and hydrogenatable reactant a re fed to the hydrogenation zone in a ratio of about 100:1 to about 1000:1 [0044] A process that includes the embodiments of any one of paragraphs [0037]-[0043] in which the hydrogenatable reactant is fed to the hydrogenation zone at a liquid-hourly space velocity of about 0.05 to about 4 hr ^"1 , the temperature is about 100 to about 180 °C, and the pressure is about 7 to about 28 bars absolute.

[0045] A process that includes the embodiments of any one of paragraphs [0037]-[0044] in which the hydrogenatable reactant further comprises at least one solvent selected from water, alcohols, ethers, glycols, glycol ethers, alkanes, esters and mixtures thereof.

[0046] A process that includes the embodiments of any one of paragraphs [0037]-[0045] in which the solvent is selected from water methanol, ethanol, propanol, 1-butanol, 2- butanol, 2-ethylhexanol, 2,2-dimethyl-l,3-propanediol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,4-butanediol, 2,2,4,4-tetramethylcyclobutane-l,3- diol, cyclohexanol, diethylene glycol, hexane, heptane, cyclohexane, octane, decane, diethyl ether, diisopropyl ether, tetrahydrofuran, methyl tert-butyl ether, ethylene glycol mono- butyl ether, diethylene glycol monobutyl ether, ethyl acetate, n-propyl acetate, isopropyl isobutyrate, isobutyl propionate, octyl acetate, isobutyl isobutyrate, methyl butyrate, and isobutyl acetate.

[0047] A process that includes the embodiments of any one of paragraphs [0037]-[0046] in which the 2,2,4,4-tetraalkylcyclobutane-l,3-diol comprises 2,2,4,4- tetramethylcyclobutane-l,3-diol having a cis:trans molar ratio of about 0.7:1 to about 1.7:1.

[0048] A process that includes the embodiments of any one of paragraphs [0037]-[0047] in which the reaction zone comprises a tubular or fluidized bed reactor.

[0049] A process that includes the embodiments of any one of paragraphs [0037]-[0048] further comprising (IV) continuously recycling a portion of the gaseous effluent to the hydrogenation zone.

[0050] A process that includes the embodiments of paragraph [0037] in which the hydrogenatable reactant comprises 2,2,4,4-tetramethylcyclobutane-l,3-dione, the hydrogen and hydrogenatable reactant of step (I) are contacted at a temperature of about 100 to about 200 °C and a pressure of about 7 to about 28 bar with a catalyst comprising about 1 to about 8 weight percent ruthenium, based on the total weight of the catalyst, deposited on a support comprising activated carbon, alumina, carbon nanotubes, or graphitized carbon, to form a hydrogenation product comprising 2,2,4,4-tetramethylcyclobutane-l,3-diol having a cis:trans ratio of about 1:1 to about 1.6:1.

[0051] A process that includes the embodiments of paragraph [0050] in which the hydro- genatable reactant is fed into the hydrogenation zone at a hydrogen: 2,2,4,4-tetramethyl- cyclobutane-l,3-dione molar ratio of about 100:1 to about 500:1 at temperature is about 100 to about 160 °C and a pressure of about 14 to about 21 bars, and further comprising continously recovering from the hydrogenation zone a gaseous effluent comprising the hydrogenation product.

[0052] The process of the invention are further described and illustrated by the following examples.

EXAMPLES

[0053] General - The following is a general description of the reactor system and analytical methods used henceforward in Examples 1-5 unless otherwise specified. The reactor was constructed entirely of HASTELLOY™ C alloy. Reactants entered the base of the reactor via a 0.375 inch (9.5 mm) outer diameter (O.D.) inlet tube having a wall thickness of 0.065 inch (1.65 mm). The portion above the inlet tube expanded as a collar piece as a cone into a cylindrical section having a 0.625-inch (1.6 cm) inner diameter (I.D.) and a wall thickness of 0.1875 inch (4.8 mm) with overall length of 2.00 inches (5.1 cm). The top 0.38-inch (9.7 mm) portion of the collar was machined to a diameter of 0.750 inch (1.9 cm). The machined portion of the collar contained a 0.735-inch (1.87 cm) diameter by 0.0625-inch (1.65 mm) thick HASTELLOY™ C alloy 5 micron metal filter, which acted as a gas dispersion device and support for the catalyst. The filter and the collar containing the filter were welded to a 6.25-inch (15.9 cm) long by 0.625-inch (1.6 cm) I.D./0.750-inch (1.9 cm) O.D. HASTELLOY™ C alloy reaction tube. The reaction tube was welded to an expanded zone increasing in a conical fashion at 45 degrees to an outer diameter of 1.50 inches (3.81 cm), continuing in a cylindrical fashion for another 1.83 inches (4.65 cm) and then decreasing at a 45-degree angle and welded to a 4.50 inch (11.4 cm) long by 0.375-inch (9.5 mm) O.D. loading and sensing tube. The vertical loading and sensing tube contained a 0.375-inch (9.5 mm) O.D. pressure transducer side arm located 2.0 inches (5.1 cm) above the expanded zone and positioned at 45 degrees from vertical of the loading and sensing tube. Vapor product was removed from the expanded zone through a 0.250 inch (6.36 mm) O.D. product removal line connected approximately half the vertical distance of the expanded zone. The product removal line exited the reactor horizontally and then bent downward.

[0054] Metered gas flows were maintained by Brooks 5850 Series E mass flow controllers interfaced with a CAMILE™ 3300 Process Monitoring and Control System. Temperature control was also provided by the CAMILE™ 3300 Process Monitoring and Control System. Liquid feed was provided by an Alltech 301 HPLC pump. Liquid and gas feeds were vaporized by feeding to a heated HASTELLOY™ C alloy vaporizer maintained at 150 °C and transported in the vapor phase through a transfer line at 150 °C to the base of the reactor inlet tube. Heat to the reactor was provided by three separate split aluminum blocks with each split aluminum block surrounded by band heaters. Each split aluminum block heating unit had its own temperature control provided by the CAMILE™ 3300 Process Monitoring and Control System. The bottom heater provided heat to the reactor inlet tube and collar piece. The central heater provided heat to the reaction tube section. The top heated provided heat to the expansion zone.

[0055] The end of the product removal line was connected to a 50 micron filter attached to a HASTELLOY™ C alloy condenser, which was attached to a HASTELLOY™ C alloy product collection tank with a working capacity of one liter. The pressure was maintained using a Tescom Model 44-2300 backpressure regulator attached to a vent line on the top of product collection tank. Liquid samples were collected from a valve at the base of the liquid collection tank. Liquid products from the collection tank were weighed and analyzed by gas chromatography using a Hewlett Packard Model 5890A gas chromatograph fitted with a 30 m x 0.25 mm DB-17 capillary column (0.25 micron film thickness) programmed at 90 °C for 2 minutes, 8 °C/minute to 140 °C and holding at 140 °C for 5 minutes, 40 °C/minute to 250 °C and holding at 250 °C for 5 minutes using a FID detector held at 250 °C (injector temperature = 250 °C). The conversion, selectivity, yield, and the cis:trans ratio of the 2,2,4,4- tetramethylcyclobutane-l,3-diol product were calculated on the basis of GC area percentages. The percent 2,2,4,4-tetramethylcyclobutane-l,3-dione ("Dione") conversion was determined by the following formula: , . (moles Dione fed into the reactor - moles unreacted Dione) % Dione conversion =100 X ⁵

moles Dione fed into the reactor

[0056] The following abbreviations are used in the Tables. "TMCB" is 2,2,4,4- tetramethylcyclobutane-l,3-dione. "Ring-opened Ketol" is l-hydroxy-2,2,4-trimethyl-3- pentanone, a product of the partial hydrogenation and ring opening of 2,2,4,4- tetramethylcyclobutane-l,3-dione. "Cyclic Ketol" is 3-hydroxy-2,2,4,4- tetramethylcyclobutanone, a product of the partial hydrogenation of 2,2,4,4- tetramethylcyclobutane-l,3-dione. "TMPD" is 2,2,4-trimethyl-l,3-pentanediol, a production of hydrogenation of l-hydroxy-2,2,4-trimethyl-3-pentanone. "Cis-Diol" is cis-2,2,4,4- tetramethylcyclobutane-l,3-diol. "Trans-Diol" is trans-2,2,4,4-tetramethylcyclobutane-l,3- diol. "DIPK" is diisopropyl ketone. "DIPA" is diisopropyl carbinol.

[0057] The sample time shown in the tables, in hours, is the liquid sample collection time either from the start of the reaction, as in sample 1, or from the end of the previous sample. Pressures are reported in bars gauge (barg) unless otherwise indicated. Catalyst surface areas were measured volumetrically using the Brunauer-Emmett-Teller (BET) method.

[0058] Example 1 - This example illustrates the hydrogenation of 2,2,4,4- tetramethylcyclobutane-l,3-dione in the presence of a catalyst containing 43 weight percent Ni on an alumina support (surface area = 175 m ² /g, purchased from Engelhard, now BASF Catalysts, under the designation "E-235TR") at elevated pressure utilizing the process of the invention. The reactor was loaded with the 8.565 g of 20-40 mesh Ni/Al ₂ 0 ₃ catalyst through the top of the reactor with hydrogen flowing at 500 standard cubic centimeters per minute (SCCM) through the base of the reactor. Hydrogen flows were maintained until the catalyst was removed from the reactor. A HASTELLOY™ C alloy thermowell extending from the top of the reactor to the bottom 5-micron sintered HASTELLOY™ C alloy filter was attached to the top of the vertical loading and sensing tube, and a pressure transducer was attached to the pressure transducer side arm. The system was pressurized to 20.7 bar gauge (300 psig) with 500 SCCM H ₂ . The three reactor heaters were set for 150 °C. A solution consisting of 2,2,4,4-tetramethylcyclobutane-l,3-dione /THF in a weight ratio of 25/534.5 was fed to the reactor system at 0.479 ml/minute. The result is reported as El-1 in Table 1. The hydrogenation of 2,2,4,4-tetramethylcyclobutane-l,3-dione over a range of flow rates, pressures and temperatures are reported as El-2 to El-24 in Tables 1A-1C.

Table 1A

Table IB

Table 1C

[0059] Example 2 - This example illustrates the hydrogenation of 2,2,4,4- tetramethylcyclobutane-l,3-dione in the presence of prereduced Ru on carbon at elevated pressure utilizing the process of the invention. The reactor was loaded with 3.609 g of a prereduced, 20-40 mesh, 7 wt% Ru on graphitized carbon (surface area=528 m ² /g, purchased from Engelhard, now BASF Catalysts, under the designation "C3610") through the top of the reactor. The in-situ prereduction with hydrogen was carried as follows: the catalyst was swept with nitrogen at a flow rate of 500 SCCM at room temperature for 2 hours. The catalyst was then reduced with 50 volume % hydrogen in nitrogen at 150 °C for 2.5 hours and then 180 °C for 2 hours. The prereduced catalyst was cooled overnight under nitrogen. The following morning, the three reactor heaters were set for 130-140 °C with hydrogen flowing at 1135 standard cubic centimeters per minute (SCCM) through the base of the reactor. The system was pressurized to 20.7 barg (300 psig) with 1135 SCCM H ₂ . A solution consisting of 2,2,4,4-tetramethylcyclobutane-l,3-dione /methanol in a weight ratio of 25/534.5 was fed to the reactor system at 0.479 ml/minute. The results are reported in Table 2.

Table 2

[0060] Example 3 - This example illustrates the hydrogenation of 2,2,4,4- tetramethylcyclobutane-l,3-dione in the presence of a prereduced Ni on Al ₂ 0 ₃ catalyst at elevated pressure utilizing the process of the invention. The reactor was loaded with 8.983 g of a pre-reduced, 20-40 mesh, 60 wt% nickel on alumina catalyst (surface area = 190-240 m ² /g, purchased from Sud-chemie under the designation "NiSAT-H") through the top of the reactor. The prereduction with hydrogen was carried out in-situ by sweeping the catalyst with nitrogen at a flow rate of 500 SCCM at room temperature for 2 hours. The catalyst was then reduced with 50 volume % hydrogen in nitrogen at 150 °C overnight and then 180 °C for 2 hours. The prereduced catalyst was cooled down under nitrogen. The three reactor heaters were then set for 130-140 °C with hydrogen flowing at 1135 standard cubic centimeters per minute (SCCM) through the base of the reactor. The system was pressurized to 300 psig (20.78 bars) with 1135 SCCM H ₂ . A solution consisting of 2,2,4,4- tetramethylcyclobutane-l,3-dione /THF in a weight ratio of 25/534.5 was fed to the reactor system at 0.479 ml/minute. The results are reported in Table 3.

Table 3

[0061] Example 4 - This example illustrates the hydrogenation of 2,2,4,4- tetramethylcyclobutane-l,3-dione in the presence of a prereduced nickel on alumina catalyst at elevated pressure utilizing the process of the invention. The reactor was loaded with 8.264 g of a pre-reduced, 20-40 mesh catalyst containing 60 weight percent Ni on an alumina support (surface area = 160 m ² /g, purchased from Engelhard, now BASF Catalysts, under the designation "ΝΪ3288") through the top of the reactor. The in-situ prereduction with hydrogen was done as following: sweep the catalyst with nitrogen at a flow rate of 500 SCCM at room temperature for 2 hours. Then the catalyst was reduced with 50 volume % hydrogen in nitrogen at 150 °C for 2 hours and then 180 °C for 2 hours. The prereduced catalyst was cooled down under nitrogen. Then the three reactor heaters were set for 120-135°C with hydrogen flowing at 1135 standard cubic centimeters per minute (SCCM) through the base of the reactor. The system was pressurized to 20.7 barg (300 psig) with 1135 SCCM H ₂ . A solution consisting of 2,2,4,4-tetramethylcyclobutane-l,3-dione /THF in a weight ratio of 25/534.5 was fed to the reactor system at 0.479 ml/minute. The results are reported in Table 4.

Table 4

[0062] Example 5 -Steam-activated carbononized phenol-formaldehyde resin spheres (20 g) were placed in an evaporating dish and combined with a solution prepared from ruthenium nitrosyl nitrate containing 36.1 wt % Ru (3.88g) and water (20 ml). The mixture was stirred until uniform and was evaporated on the steam bath with occasional stirring until the solids became free flowing. The Ru-impregnated, steam-activated catalyst was transferred to a quartz tube containing a quartz wool support plug. The quartz tube was placed into a LINDBERG™ electric furnace and heated in an upward flow of nitrogen (100 SCCM) over a 2 hour period to 300 °C and held at 300 °C for 2 hours before cooling back to ambient temperature. The dried catalyst had a BET surface area of 1183 m ² /g- [0063] This example illustrates the hydrogenation of 2,2,4,4-tetramethylcyclobutane-l,3- dione in the presence of the prereduced Ru on carbonized phenol-formaldehyde resin spheres described above at elevated pressure utilizing the process of the invention. The reactor was loaded with 6.60 g of the 7 wt% Ru/C catalyst made above (20-40 mesh) through the top of the reactor. The prereduction with hydrogen was carried out in-situ by sweeping the catalyst with helium at a flow rate of 500 SCCM at room temperature overnight. The catalyst was then reduced with 50 volume % hydrogen in helium at 150 °C for 2 hours and at 180 °C for 2 hours. The prereduced catalyst was cooled under helium. The three reactor heaters were set for 130-140 °C with hydrogen flowing at 1135 standard cubic centimeters per minute (SCCM) through the base of the reactor. The system was pressurized to 20.7 barg (300 psig) with 1135 SCCM H ₂ anda solution of 2,2,4,4-tetramethylcyclobutane-l,3- dione in THF in a weight ratio of 25/534.5 was fed to the reactor system at 0.479 ml/minute. The results are reported in Table 5.

Table 5

[0064] Preparation of Ru/carbon nanotube catalysts - This example illustrates a procedure for the preparation of a ruthenium on carbon nanotube catalyst by using a wet impregnation method. Carbon nanotube extrudates (20 g, 1/16", surface area = 244 m ² /g, available from Hyperion Catalyst International, Inc) were charged to a 100 mL glass bottle, cooled in a dry ice batch, followed by 44 g of a 2% ruthenium acetoacetate solution in acetone added dropwise. The impregnated carbon nanotube extrudates were dried at ambient temperature for 4 hours and then in an oven at 120 °C for 2 hours. The dried extrudates were then loaded in a ½" stainless steel tube and exposed to 200 standard cubic centimeters per minute (SCCM) of 10% hydrogen in nitrogen at 180 °C for 2 hours. The nominal Ru loading was 3%.

[0065] Comparative Example 1 - A mixture of 18 g of 2,2,4,4-tetramethylcyclobutane-l,3- dione, 160 g of isobutyl isobutyrate (IBIB), and 15 g of a catalyst containing 2 weight percent Ru on an a-alumina support and having a surface area of 40 m ² /g (obtained from BASF Catalysts), was charged to a 300 mL stainless steel autoclave. The catalyst was placed in a stainless steel catalyst basket within the autoclave. The autoclave was agitated and purged twice with nitrogen (0.069 MPa,10 psig) at an ambient temperature and then purged with hydrogen (0.069 MPa, 10 psig). The autoclave was then heated to 130 °C and pressurized with hydrogen (2.76 MPa, 400 psig). After 2 hours, a product sample was taken and analyzed by gas chromatography (GC). The conversion of dione was 94% and the selectivity to diol was 41%. The cis:trans isomer ratio of the diol was 1.02.

[0066] Comparative Example 2 - A pre-reduced catalyst (2.5 g) containing 7 weight percent Ru on a graphitized carbon support (purchased from Engelhard, now BASF Catalysts, under the designation "C3610") and having a surface area of 589 m ² /g was loaded in a 300 mL stainless steel autoclave in a stainless steel catalyst basket with 18 g of 2,2,4,4- tetramethylcyclobutane-l,3-dione and 160 g of isobutyl butyrate (IBIB). The autoclave was agitated and purged twice with nitrogen (0.069 MPa, 10 psig) at an ambient temperature and then purged with hydrogen (0.069 MPa, 10 psig). The autoclave was heated to 130 °C and pressurized with hydrogen (2.76 MPa, 400 psig). After 1 hour, a product sample was taken and analyzed by GC. The conversion of dione was 55% and the selectivity to diol was 29%. The cis:trans isomer ratio of the diol was 1.06. [0067] Comparative Example 3 - A 2 wt% Ru on silica catalyst (2.5 g, surface area = 300 m ² /g, obtained from BASF Catalysts) was charged to a 300 mL stainless steel autoclave in a stainless steel catalyst basket, followed by 18 g of 2,2,4,4-tetramethylcyclobutane-l,3-dione and 160 g of IBIB. The autoclave was agitated and purged twice with nitrogen (0.069 MPa, 10 psig) at ambient temperature and then purged with hydrogen (0.069 MPa, 10 psig). The autoclave was heated to 130 °C and pressurized with hydrogen (2.76 MPa, 400 psig). After 1 hour, a product sample was taken and analyzed by GC. The conversion of dione was 52% and the selectivity to diol was 30%. The cis:trans isomer ratio of the diol was 1.06.

[0068] Comparative Example 4 - A 3 wt% Ru on carbon nanotube catalyst (0.5 g, surface area = 244 m ² /g) was loaded in a 100 mL stainless steel autoclave in a stainless steel catalyst basket with 6 g of 2,2,4,4-tetramethylcyclobutane-l,3-dione and 54 g of IBIB. The autoclave was agitated and purged twice with helium (0.69 MPa, 100 psig) at ambient temperature and then purged with hydrogen (0.69 MPa, 100 psig). The autoclave then was heated to 130 °C and pressurized with hydrogen (2.76 MPa, 400 psig). After 1 hour, a product sample was taken and analyzed by GC. The conversion of dione was 99.9% and the selectivity to diol was 91%. The cis:trans isomer ratio of the diol was 1.04.

[0069] Comparative Example 5 - A 3 wt% Ru on carbon nanotube catalyst (0.5 g, surface area = 244 m ² /g) was loaded in a 100 mL stainless steel autoclave in a stainless steel catalyst basket with 6 g of 2,2,4,4-tetramethylcyclobutane-l,3-dione and 54 g of IBIB. The autoclave was agitated and purged twice with helium (0.69 MPa, 100 psig) at ambient temperature and then purged with hydrogen (0.69 MPa, 100 psig). The autoclave was then heated to 140 °C and pressurized with hydrogen (2.76 MPa, 400 psig). After 1 hour, a product sample was taken and analyzed by GC. The conversion of dione was 100% and the selectivity to diol was 87%. The cis:trans isomer ratio of the diol was 1.08.

[0070] Comparative Example 6 - A 3 wt% Ru on carbon nanotube catalyst (0.5 g, surface area = 244 m ² /g) was loaded in a 100 mL stainless steel autoclave in a stainless steel catalyst basket with 6 g of 2,2,4,4-tetramethylcyclobutane-l,3-dione and 54 g of IBIB. The autoclave was agitated and purged twice with helium (0.69 MPa, 100 psig) at ambient temperature and then purged with hydrogen (0.69 MPa, 100 psig). The autoclave was then heated to 120 °C and pressurized with hydrogen (2.76 MPa, 400 psig). After 1 hour, a product sample was taken and analyzed by GC. The conversion of dione was 99.9% and selectivity to diol was 94%. The cis:trans isomer ratio of the diol was 1.07.

[0071] Comparative Example 7 - This example followed a similar procedure to Example 1 of U.S. Patent No. 2,936,324 using 5 weight percent Ru on activated carbon catalyst, except that a higher temperature and lower pressure was used. A 5 wt% Ru on carbon powder catalyst (obtained from Engelhard, now BASF Catalysts, surface area = 881 m ² /g) was dried in a conventional oven at 105 °C overnight. The dried catalyst (1.33 g) was loaded in a 100 mL stainless steel autoclave reactor. The autoclave was purged twice with helium (0.69 MPa, 100 psig) and then with hydrogen at ambient temperature. After the autoclave was heated to 150 °C and the reactor pressure was increased to 2.76 MPa (400 psig) with hydrogen. After 1 hour, the reactor was cooled to about 50 °C and 26.7 g of 2,2,4,4- tetramethylcyclobutane-l,3-dione and 66.7 g of methanol were added. The autoclave was agitated and purged twice with helium (0.69 MPa, 100 psig) and then with hydrogen (0.69 MPa, 100 psig). The autoclave was then heated to 140 °C and pressurized to 2.76 MPa (400 psig). After 1 hour, a product sample was taken and analyzed by GC. The conversion of dione was 99.7% and the selectivity to diol was 85.8%. The cis:trans isomer ratio of the diol was 0.84.

[0072] Comparative Example 8 - Ru powder (0.1 g, purchased from Aldrich Chemical Co.) was loaded in a 100 mL stainless steel autoclave reactor with 64 g of IBIB. the autoclave was agitated and purged twice with helium (0.69 MPa, 100 psig) and then with hydrogen at ambient temperature. The autoclave was heated to 150 °C and the reactor pressure was increased to (2.76 MPa, 400 psig) with hydrogen. After the 1 hour, the reactor was cooled down to approximately 50 °C, and 6 g of 2,2,4,4-tetramethylcyclobutane-l,3-dione were added to the autoclave reactor. The autoclave was agitated and purged twice with helium (0.69 MPa, 100 psig) followed by hydrogen. The autoclave was then heated to 140 °C and pressurized to 2.76 MPa (400 psig). After 1 hour, a product sample was taken and analyzed. The conversion of dione was 99.8% and the yield of diol was 59.5%. The cis:trans isomer ratio of the diol was 1.11.

[0073] Comparative Example 9 - A catalyst (2.5 g) containing 7 weight percent Ru on a graphitized carbon support (purchased from Engelhard, now BASF Catalysts, under the designation "C3610") and having a surface area of 589 m ² /g was loaded in a 300 mL stainless steel autoclave in a stainless steel catalyst basket with 28 g of 2,2,4,4- tetramethylcyclobutane-l,3-dione and 160 g of THF. The autoclave was agitated and purged twice with nitrogen (3.45 MPa,500 psig) at an ambient temperature and then purged with hydrogen (0.69 MPa,100 psig). Then, the autoclave was heated to 130 °C and pressurized with hydrogen (2.76 MPa,400 psig). After 1 hour, a product sample was taken and analyzed by GC. The conversion of dione was 99% and the selectivity to diol was 58%. The cis:trans isomer ratio of the diol was 1.06.

[0074] Comparative Example 10 - A catalyst (701.3 g) containing 60 weight percent Ni on an alumina support (purchased from Engelhard, now BASF Catalysts, under the designation "ΝΪ3288") and having a surface area of 160 m ² /g was loaded in a trickle bed reactor. The reactor was pressurized to 1000 psig (6.90 MPa) with H ₂ and heated up to 170 °C. A solution consisting of 20 wt% of 2,2,4,4-tetramethylcyclobutane-l,3-dione in isobutyl acetate was fed to the reactor at 93 g/minute. After 3 hours, three product samples were taken with increment of 0.5 hr and analyzed by GC. The average conversion of dione was 100% and selectivity to diol was 80%. The average of cis:trans isomer ratio of the diol was 1.16.

[0075] Comparative Example 11- A catalyst (759.7 g) containing 43 weight percent Ni on an alumina support (purchased from Engelhard, now BASF Catalysts, under the designation "E-235TR") and having a surface area of 175 m2/g was loaded in a trickle bed reactor. The reactor was pressurized to 500 psig (3.45 MPa) with H2 and heated up to 170 °C. A solution consisting of 25 wt% of 2,2,4,4-tetramethylcyclobutane-l,3-dione in isobutyl acetate was fed to the reactor at 96 g/minute. After 1.5 hours, three product samples were taken with increment of 0.5 hr and analyzed by GC. The average conversion of dione was 100% and selectivity to diol was 84%. The average of cis:trans isomer ratio of the diol was 0.98.