WO1992002298A1 - Hydrogenation catalyst and method for preparing tetrahydrofuran - Google Patents

Hydrogenation catalyst and method for preparing tetrahydrofuran Download PDF

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Publication number
WO1992002298A1
WO1992002298A1 PCT/US1991/005165 US9105165W WO9202298A1 WO 1992002298 A1 WO1992002298 A1 WO 1992002298A1 US 9105165 W US9105165 W US 9105165W WO 9202298 A1 WO9202298 A1 WO 9202298A1
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Prior art keywords
acid
tetrahydrofuran
catalyst
weight percent
palladium
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PCT/US1991/005165
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English (en)
French (fr)
Inventor
Richard Edward Ernst
John Byrne Michel
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E.I. Du Pont De Nemours Company
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Priority to JP3513090A priority Critical patent/JPH06501875A/ja
Publication of WO1992002298A1 publication Critical patent/WO1992002298A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/06—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
    • C07D307/08—Preparation of tetrahydrofuran
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/656—Manganese, technetium or rhenium
    • B01J23/6567—Rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8986—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with manganese, technetium or rhenium

Definitions

  • the present invention relates to the hydrogenation of hydrogenatable precursors to
  • a novel tri- or polymetallic catalytic composite consisting essentially of a combination of: (1) a catalytically effective amount of palladium (Pd); (2) a catalytically effective amount of rhenium (Re); and, (3) a catalytically effective amount of one or more metals selected from rhodium (Rh), cobalt (Co), platinum (Pt), ruthenium (Ru), iron (Fe), thulium (Tm), cerium (Ce), yttrium (Y), neodymium (Nd), aluminum (Al), praesodymium (Pr) holmium (Ho), copper (Cu), samarium (Sm), europium (Eu), hafnium (Hf), manganese (Mn), vanadium (V), chromium (Cr), gold (Au), terbium (Tb), lutetium
  • the present invention relates to an efficient aqueous process for the manufacture of high purity tetrahydrofuran comprising continuous hydrogenation of a hydrogenatable
  • THF tetrahydrofuran
  • BDO 1,4-butanediol
  • Patent 4,609,636 describes the use of a catalyst composite comprising palladium and rhenium on a carbon support for making THF, BDO or mixtures thereof from a variety of hydrogenatable precursors.
  • U.S. Patent 4,973,717 discloses the batchwise or continuous production of an alcohol and/or ether from a
  • carboxylic acid ester using, for example, a palladium based catalyst and further discloses the important effect of a metal capable alloying with palladium.
  • The.use of these alloyed catalysts for the direct, selective production of THF/BDO from precursors containing one or more carboxylic acid groups is not disclosed in U.S. Patent 4,973,717.
  • Patent 4,609,636 teaches that the relative ratio of THF to BDO can be increased by increasing one or more variables selected from operating temperature, contact time, and hydrogen spacetime. It is also known from numerous references, such as U.S. Patent 3,726,905, that the dehydration of BDO to give THF is catalyzed by acid and that increasing the acid concentration results in an increase in the relative ratio of THF to BDO. However, it is also known that rhenium
  • water and succinic acid may be considered as the chief inhibitor components of the step involving the reduction of the intermediate succinic anhydride to gamma-butyrolactone.
  • Selectivity is defined herein to refer to a measure of the percentage of the exit stream composed of THF/BDO/gammabutyrolactone ("GBL”) in a plug flow reactor or a back-mixed reactor.
  • Space time yield is defined herein to refer to the amount of grams of THF/kilogram catalyst/hour.
  • Activity is defined herein to refer to the percent acid converted at a given hold up time in a plug-flow reactor. Another important area subject to
  • tetrahydrofuran is a useful solvent for high polymers, such as polyvinyl chloride and as a monomer in
  • lutetium, nickel, scandium and niobium produces high space time yields of THF while maintaining high selectivity in a back mixed reactor or produces a high acid conversion in a plug flow reactor.
  • a hydrogenatable precursor such as maleic acid, maleic anhydride, fumaric acid, succinic acid, succinic anhydride, malic acid, or mixtures thereof, i.e., these precursors can be described as dicarboxylic acids, or anhydrides, or mixtures of said acids and/or anhydrides, is reacted with hydrogen in a back-mixed reactor or in a plug flow reactor at a temperature of about 150oC to 300oC at a pressure of about 1000 to 3000 psig in the presence of a novel tri- or
  • polymetallic catalytic composite comprising a
  • a catalytically effective amount of palladium, rhenium and one or more metals i.e., a metal component selected from rhodium, cobalt, platinum, ruthenium, iron, thulium, cerium, yttrium, neodymium, aluminum, praesodymium, holmium, copper, samarium, europium, hafnium, manganese, vanadium, chromium, gold, terbium, lutetium, nickel, scandium and niobium deposited on a support such as an
  • porous carbon carrier with a surface area m excess of about 650 m 2/g or a refractory oxide carrier, e.g., alumina, zirconia, titania, hafnium oxide, silica or barium carbonate and the like, to produce high space time yields of THF while a refractory oxide carrier, e.g., alumina, zirconia, titania, hafnium oxide, silica or barium carbonate and the like, to produce high space time yields of THF while
  • the polymetallic catalytic composites of this invention consist by total weight of: (1) from about 0.1 to 10 weight percent of a palladium
  • a hydrogenatable precursor is reacted on a continuous basis in an aqueous medium with hydrogen in a
  • One aspect of the invention relates to a novel tri- or polymetallic catalytic composite
  • Suitable supports include activated, porous carbons and
  • refractory oxide carriers e.g., alumina, zirconia, titania, hafnium oxide, silica or barium carbonate and the like.
  • the preferred carrier is an activated, porous carbon carrier.
  • Suitable carbon supports have a surface area in excess of about 650 m 2 /g (measured ising standard N 2 BET techniques), typically in excess of about 1000 m 2 /g, preferably m excess of about 1500 m 2 /g
  • the catalyst carbon support is fine powder particles for use in a slurry reactor or larger support granules for use in a fixed bed reactor.
  • the tri- or polymetallic catalytic composite of this invention can be prepared in any one of a number of different methods known in the art.
  • a preferred step in the method for preparing said catalyst involves sequential deposition of the palladium component and the rhenium component as described in greater detail in U.S. Patent 4,609,636, the teachings of which are incorporated herein by reference.
  • a method for preparing said catalyst includes, in sequence, the steps of:
  • impregnated carbon at a temperature in the range of from 100oC to 500oC, under reducing conditions for about 0.5 to 24 hours;
  • the solution containing the palladium compound is typically an aqueous medium containing an amount of palladium compound to yield a catalyst product with the requisite amount of palladium.
  • the palladium compound is typically PdCl 2 and can also be, but is not limited to, a palladium compound such as PdBr 2 , Pd(NO 3 ) 2 , Pd(C 2 H 3 O 2 ) 2 (wherein C 2 H 3 O 2 denotes acetate), Pd(C 5 H 7 O 2 ) 2 (wherein C 5 H 7 O 2 denotes
  • the solution containing the rhenium compound is typically an aqueous one containing an amount of rhenium compound to yield a catalyst product with the requisite amount of rhenium.
  • the rhenium compound is typically Re 2 O 7 but can be perrhenic acid or a perrhenate of ammonium or of an alkali metal, K 2 ReCl 6 , (C 2 H 3 O 2 ) 2 ReCl, or (NH 4 ) 2 Re 2 Cl 8 , etc.
  • the solution containing the metal compounds M are typically aqueous and contain an amount of metal sufficient to yield a catalyst product with the requisite metal loading.
  • the metal is rhodium
  • the rhodium compound is typically
  • RhCl 3 *xH 2 O but can also be a rhodium compound such as RhBr 3 *xH 2 O, Rh 2 (C 2 H 3 O 2 ) 4 , Rh 6 (CO) 16 , Rh 4 (CO) 12 ,
  • Rh(CO) 2 Cl) 2 Rh(C 5 H 7 C 2 ) 3 or Rh(NO 3 ) 3 *2H 2 O, Rh 2 (SO 4 ) 3 , as well as salts thereof exemplified by Na 3 RhCl 6 , and (C 4 H 9 ) 4 NRh(CO) 2 Cl 2 , and coordination compounds where Rh is ligated, for example by amines, halides,
  • compound is typically FeCl 3 *6H 2 O but can also be an iron compound such as FeCl 2 *xH 2 O, FeBr 2 , Fe(NO 3 ) 3 *9H 2 O, Fe(SO 4 )*7H 2 O, Fe 2 (SO 4 ) 3 , Fe(C 5 H 7 O 2 ) 3 , (C 5 H 5 ) 2 Fe (wherein C 5 H 5 denotes cyclopentadienyl), Fe(CO) 5 , Fe 2 (CO) 9 , as well as salts and coordination compounds thereof.
  • iron compound is typically FeCl 3 *6H 2 O but can also be an iron compound such as FeCl 2 *xH 2 O, FeBr 2 , Fe(NO 3 ) 3 *9H 2 O, Fe(SO 4 )*7H 2 O, Fe 2 (SO 4 ) 3 , Fe(C 5 H 7 O 2 ) 3 , (C 5 H 5 ) 2 Fe (wherein C 5 H 5 denotes cyclopentadieny
  • the cobalt compound is typically CoCl 2 *6H 2 O but can also be a cobalt compound such as CoBr 2 *xH 2 O, Co(OH) 2 , Co(NO 3 ) 2 *6H 2 O, CoSO 4 *7H 2 O, Co(C 2 H 3 O 2 ) 2 , Co 3 O 4 ,
  • Co(C 5 H 7 O 2 ) 2 Co(C 5 H 7 O 2 ) 3 , Co 2 (CO) 8 , coordination compounds such as Co(NH 3 ) 6 Cl 3 , and salts such as
  • the platinum compound is typically H 2 PtCl 6 *6H 2 O, but can also be a platinum compound such as PtCl 2 , Na 2 PtCl 4 , PtCl 4 , PtBr 2 , PtBr 4 , H 2 PtBr 6 , H 2 Pt(OH) 6 , Pt(C 5 H 7 O 2 ) 2 , coordination compounds such as (NH 4 ) 2 PtCl 4 ,
  • RuCl 3 *3H 2 O typically RuCl 3 *3H 2 O, but can also be a ruthenium compound such as RuBr 3 *xH 2 O, RuNO(NO 3 ) 3 , RuO 2 *xH 2 O, Ru(C 5 H 7 O 2 ) 3 , Ru 2 (C 2 H 3 O 2 ) 4 C1, coordination compounds such as Ru(NH 3 ) 5 Cl 3 and (NH 4 ) 2 Ru(H 2 O) Cl 5 , (NH 4 ) 2 RuCl 6 , and organometallic compounds such as Ru 3 (CO) 12 .
  • the metal is thulium
  • the thulium compound is a ruthenium compound such as RuBr 3 *xH 2 O, RuNO(NO 3 ) 3 , RuO 2 *xH 2 O, Ru(C 5 H 7 O 2 ) 3 , Ru 2 (C 2 H 3 O 2 ) 4 C1, coordination compounds such as Ru(NH 3 ) 5 Cl 3 and (NH 4 ) 2 Ru(H 2
  • TmCl 3 *7H 2 O typically TmCl 3 *7H 2 O, but can also be a thulium compound such as TmBr 3 *xH 2 O, TmF 3 , TmI 3 , Tm 2 O 3 ,
  • the cerium compound is typically CeCl 3 *xH 2 O, but can also be a cerium compound such as CeBr 3 *6H 2 O, CeF 3 , CeI 3 ,
  • the yttrium compound is typically YCl 3 *6H 2 O, but can also be a yttrium
  • the neodymium compound is typically
  • NdCl 3 *6H 2 O can also be a neodymium compound such as NdBr 3 *xH 2 O, NdF 3 , NdI 3 , Nd 2 O 3 , Nd(C 2 H 3 O 2 ) 3 *H 2 O, Nd(C 5 H 7 O 2 ) 3 , Nd(NO 3 ) 3 *6H 2 O and Nd 2 (CO 3 ) 3 *xH 2 O.
  • the aluminum compound is typically AlCl 3 *6H 2 O, but can also be an aluminum compound such as AlCl 3 , AlBr 3 and hydrates, AlF 3 and hydrates, AlI 3 , Al(OH) 3 , Al(C 3 H 7 O) 3 (wherein C 3 H 7 is isopropoxide), Al(C 5 H 7 O 2 ) 3 , and Al(NO 3 ) 3 *9H 2 O.
  • the praesodymium compound is typically PrCl 3 *7H 2 O, but can also be a
  • the holmium compound is typically HoCl 3 *6H 2 O, but can also be a holmium compound such as HoBr 3 and hydrates, HoF 3 , HoI 3 , Ho 2 O 3 , Ho(C 5 H 7 O 2 ) 3 ,
  • the M precursor can be any M compound with properties suitable for the catalyst preparation, e.g., soluble in the solvent of choice. Suitable compounds include oxides, carbonates, alkoxides, -diketonates, halides, nitrates, sulfates, hydroxides, carboxylates,
  • a preferred M compound is of the general formula
  • the preparation of the catalyst composite may be carried out in the presence of Group IA or IIA metals, which may be present in the carbon as obtained or may be added.
  • Group IA or IIA metals which may be present in the carbon as obtained or may be added.
  • the beneficial effect of the addition of potassium is shown in Example 70. It is believed that addition of potassium to the slurry catalyst of the present invention can be beneficially employed in a slurry reactor.
  • the fixed bed catalyst support carbon contains potassium as obtained.
  • Another aspect of the present invention involves the catalytic process for preparing THF, employing the tri- or polymetallic catalytic composite described above, in a back-mixed reactor to achieve a high space time yield, e.g., in excess of about 280 g THF/kg catalyst/hr in a back-mixed reactor while maintaining high selectivity, e.g., up to about 90%.
  • the process can be carried out in a plug flow reactor with a catalyst of the present invention exhibiting high activity, e.g., in excess of 58% acid conversion of a 5% by weight maleic acid feed at 250°C, 2000 psig total pressure and a contact time of 0.016 hour.
  • More preferred composites employed in the process are those wherein the metal component is selected from rhodium, cobalt, platinum, ruthenium, iron, thulium, cerium, yttrium, neodymium, aluminum, praesodymium and holmium.
  • the hydrogenatable precursors i.e.,
  • inventions are, for example, maleic acid, maleic anhydride, fumaric acid, succinic acid, succinic anhydride, malic acid, or mixtures thereof.
  • These precursors can be described as dicarboxylic acids, or anhydrides, or mixtures of said acids and/or
  • Preferred hydrogenatable precursors include maleic acid and maleic anhydride.
  • Suitable hydrogentable precursors to 3-methylTHF include, but are not limited to, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid, citric acid and aconitic acid. Itaconic acid is a preferred precursor due to cost and ease of reduction. It is further recognized that analogous precursors to other substituted THFs, such as 3-ethylTHF and
  • 3-propylTHF can be beneficially employed in the process of this invention.
  • Production bf THF includes the hydrogenation of the hydrogentable precursor in an aqueous or organic solvent medium, i.e., the precursor solution is reacted with hydrogen in a back-mixed reactor or in a plug flow reactor.
  • a preferred solvent for the process of this invention is water.
  • the hydrogenation conditions include a reaction temperature in the range of about 150°C to 300°C, preferably about 250oC and a hydrogen pressure of about 1000 to 3000 psig,
  • the hydrogenation of this invention can be run using conventional apparatus and techniques in a back-mixed or plug flow reactor. Hydrogen is fed continuously, generally i n considerable stoichiometric excess.
  • Unreacted hydrogen can be returned to the reactor as ⁇ recycled stream.
  • the precursor solution e.g., maleic acid-water solution, is fed continuously at
  • the catalyst carbon support is fine powder particles for use in a slurry reactor or larger support granules for use in a fixed bed reactor.
  • the amount of catalyst required will vary widely and is dependent upon a number of factors such as reactor size and design, contact time and the like.
  • One method for carrying out the invention is in a plug flow reactor as described in greater detail in the examples.
  • the selectivity was a measure of what percent of the exit stream is composed of THF, BDO and GBL.
  • the highly active catalysts of this invention when tested in a plug flow reactor, typically exhibit higher activity, and comparable selectivity, than a similarly prepared bimetallic Pd,Re/C catalyst. The loss of selectivity observed in some cases may be caused by over hydrogenation. If the catalyst is highly active but unselective at a certain temperature, decreasing its activity by lowering the temperature increases selectivity.
  • a preferred method of preparing THF is in a back-mixed reactor such as, for example, a continuous slurry reactor. It has been discovered in the present invention that the higher activity of the tri- or polymetallic catalytic composite described above can be most effectively utilized to give high STY and selectivity to THF in this type of reactor. while this reactor configuration results in a high
  • THF vapor take off of THF, i.e., the THF can be purged from the reactor shortly after being formed, thus minimizing "over-hydrogenation", i.e., further
  • a second advantage of the back-mixed reactor is that acid in the feed is distributed throughout the reaction mass, and is thus available to catalyze the last step in the maleic acid to THF sequence, i.e., the ring closing of BDO to THF. This is of critical importance since it has been found that the BDO is also subject to over hydrogenation and a rapid conversion of BDO to THF serves to minimize yield losses due to over reduction of the BDO. It will be appreciated by those skilled in the art that these two features of a back-mixed reactor contribute to the ability to use the catalyst of higher activity without loss in selectivity. Alternatively, a fixed bed reactor with adequate recycle such that it
  • Tetrahydrofuran and 1,4-butanediol are the products produced by the process of this invention in a plug flow reactor or in a back-mixed reactor.
  • the catalysts and processes of this invention are
  • Another aspect of the invention is the production of THF in an essentially back-mixed reactor using a continuous process which provides definite advantages for separation and recovery of THF, for example: (1) THF and over reduced by products are volatile and can be distilled out of a back mixed reactor as they are formed and, if necessary, the THF further purified using conventional procedures; (2) the maleic acid starting material and the intermediates (up to and including BDO) are less volatile and tend to remain behind in the reactor; and (3) small amounts of THF precursors or intermediates, such as GBL, which are swept out with the THF can be separated and recycled to the reactor.
  • the BDO and THF are the continuous hydrogenation process of this invention.
  • catalysts for use in this continuous process are comprised of, by total weight, from about 0.1 to 10 weight percent of palladium, about 1 to 20 weight percent of rhenium and optionally from about 0.01 to 1.0 weight percent of a component containing one or more of the metals selected from rhodium, cobalt, platinum, ruthenium, iron, thulium, cerium, yttrium, neodymium, aluminum, praesodymium, holmium, copper, samarium, europium, hafnium,
  • A-preferred hydrogenatable precursor for use in this continuous process is aqueous maleic acid.
  • the required acid is provided by maleic, succinic, and to a lesser extent, other acids distributed throughout the reaction mixture in the back-mixed reactor.
  • Suitable hydrogentable precursors to 3-methylTHF include, but are not limited to, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid, citric acid and aconitic acid. Itaconic acid is a preferred precursor due to cost and ease of reduction. It is further recognized that analogous precursors to other substituted THFs, such as 3-ethylTHF and 3-propylTHF can be beneficially employed in the continuous process of this invention. The following examples serve to illustrate the invention, but are not intended to limit the scope of the invention. EXAMPLE 1
  • This example describes the preparation of a Rh+Pd,Re/C trimetallic catalytic composite of the present invention, suitable for use in a slurry reactor (type).
  • the notation M+Pd,Re/C is meant to imply that M and Pd were codeposited and reduced followed by Re deposition and reduction.
  • the reduced powder was cooled to 50oC, purged with He, cooled to room temperature in flowing He, and then passivated 30 minutes in flowing 1% 02 in N 2 .
  • the Rh,Pd,Re/C sample was dried, reduced and
  • Nominal loadings are 0.2% Rh(% M) , 1.0% Pd(% Pd), and 2.8% Re(% Re). Nominal loading is defined as 100*wt metal/wt support
  • This example describes the preparation of a trimetallic Rh+Pd,Re/C catalytic composite of the present invention suitable for use in the fixed bed reactor. Note that the items in parentheses refer to the parameter headings in Table 1.
  • the preparations of fixed bed catalysts of Examples 5-12 were done in the same way; the parameters used in the preparation of Examples 5-12 are listed in Table l.
  • Rh+Pd,Re/C sample was dried, reduced and passivated as above. Nominal loadings are 0.3% Rh(% M), 1.0% Pd(% Pd), and 3.6% Re(% Re).
  • Example 13 The catalysts of Examples 13-29 were prepared similarly, but a slightly different reduction protocol was used. The preparation of Example 13 is described in detail to indicate these slight
  • the Tm,Pd/C powder was recovered and then reduced at 300'C in flowing H -He (3:97) for 5.8 hours.
  • the reduced powder was purged with He at 300oC for 0.5 hour, cooled to room temperature overnight (>5 hours) in flowing He.
  • Tm+Pd,Re/C sample was dried and reduced as above. Nominal loadings are 0.6% Tm(% M), ⁇ .98% Pd(% Pd), and 4.0% Re(% Re).
  • Rh,Pd,Re/C catalyst of Example 30 was prepared using a different sequence of metal
  • Rh was deposited on the carbon support and reduced.
  • Pd was next deposited and reduced, and then Re was deposited and reduced.
  • KCl KCl was dissolved in 230cc DI water and mixed well. This mixture was added to 100g Darco KBB ® carbon, commercially available, and stirred occasionally over a 3 hour period at room temperature. The slurry was dried overnight at 115oC. 5.4 ml
  • PdCl 2 -HCl stock solution containing 0.82 g Pd was added to 192cc water and mixed well. The solution was added to 85. lg K/C and the resulting slurry was stirred occasionally over a 3 hour period at room temperature. The slurry was dried overnight at 115oC. The K,Pd/C powder was recovered and then reduced at 300o C in flowing H 2 -He (1:1) for eight hours. The reduced powder was cooled to 50°C, purged with He, cooled to room temperature in flowing He, and then passivated 30 minutes in flowing 1% O 2 in N 2 . A solution was prepared by adding 36.2 ml of a Re 2 O 7 -H 2 O stock solution containing 2.84g Re to 200ml H 2 O.
  • the catalyst for a back-mixed reactor was tested by charging 7-15 g dry basis) of slurry catalyst in 150 ml water to a 300 ml Hastaloy C autoclave, equipped with an agitator, a thermocouple, feed lines for hydrogen and maleic acid, and an exit line through which the product was swept out with the excess hydrogen and water.
  • the catalyst was activated by heating at 250oC under a 1000 ml/min hydrogen flow at 2000 psig for one hour.
  • the maleic acid was fed as a 40% by weight aqeous solution at feed rates ranging from 18 to 36 ml/min, and the reactor was maintained at 2000 psig and 250oC.
  • the volatile products and water were swept out of the reactor at a rate
  • the hydrogen feed rate was adjusted so that the amount of water carried out with the exiting hydrogen gas balances the amount of water added with the maleic acid feed and the amount produced by the reaction; the reactor level was maintained at 100-200cc. Note that in all cases a very large excess of hydrogen was fed, compared to the amount consumed by the reaction; thus, the hydrogen feed rate does not affect catalyst performance.
  • a catalyst test was made up of several runs. Typically, each run lasts 8-12 hours, with the reactor in steady state operation for 6-10 hours.
  • composition data were measured in the following way. A portion of the volatilized products/water in the exit gas stream is condensed and collected as "liquid product". The volume of the liquid product collected each hour was measured, and its composition analyzed using a calibrated gas chromatograph (GC) equipped with a flame ionization detector. The remaining uncondensed product(THF and alkanes) still in the exit gas stream was analyzed by measuring the gas flow rate, then analyzing the gas stream every two hours, using procedures similar to the one used for liquid analysis. The reactor contents are sampled every four hours and analyzed by GC and titration. The GC analysis was carried out using a Supelcowax 10
  • THF STY for the 1%, 4% Pd,Re/C slurry catalyst of comparative example A was 280 g THF/kg catalyst/hr.
  • the trimetallic catalyst of this invention gave a THF STY in excess of 280 g THF/kg catalyst/hr.
  • the selectivity was a measure of what percentage of the exit stream was made up of THF, BDO and GBL.
  • the addition of rhodium greatly improved STY, while maintaining high selectivity.
  • the back-mixed run results are summarized in Table 2.
  • Another aspect of the invention is control of the acid concentration in the reaction mixture within the. range of about 1% and 10% by weight
  • Example A was run in several days in the backmixed reactor to demonstarate the beneficial effects of acid control.
  • the results, listed in Table A show the beneficial effects on STY and selectivity, e.g., increasing the acid concentration from about 3% to about 10% benefits STY and selectivity.
  • THF liquid phase hydrogenation using conventional apparatus and techniques in a plug flow reactor as described in greater detail in U.S. Patent 4,609,636, the teaching of which are incorporated herein by reference.
  • the catalyst for a plug flow reactor was tested by charging 3 g of catalyst to a 1/4 inch diameter Hastaloy U-tube reactor which was immersed in a heated sand bath for temperature control. The catalyst was activated by heating for one hour at 250oC in a 100 ml/min hydrogen flow at 2000 psig.
  • Hydrogen and maleic acid were co-fed to one end of the reactor, and the liquid/gas stream exited from the reactor through a pressure let-down valve which was set to control the pressure at the desired level.
  • the excess gas was disengaged from the liquid in a chilled separator held at 90 psig pressure.
  • the maleic acid was fed as a 5% aqueous solution at flow rates ranging from 6 to 300 ml/hr. Hydrogen flow was maintained in large excess at 100 to 200 ml/min. The temperature was maintained at 250oC and pressure at 2000 psig.
  • the fixed bed performance data are summarized in Table 3.
  • the percent of acid converted at a given hold up time is a measure of catalyst activity.
  • the selectivity to (THF + BDO + GBL) is the maximum observed in a fitted plot of selectivity vs contact time for the four different flow rates.
  • the THF STY(g THF/kg catalyst/hr) is the curve maximum from a fitted plot of STY vs contact time for the four different flow rates.
  • the catalyst of this invention exhibited higher activity, and comparable selectivity, than the bimetallic Pd,Re/C catalyst of comparative Example B.
  • the loss of selectivity observed in some cases was caused by "over-hydrogenation", i.e. reaction that goes beyond the desired THF product, to form alcohols and alkanes.
  • over-hydrogenation i.e. reaction that goes beyond the desired THF product
  • the catalyst was too active at this temperature, resulting in over-hydrogenation, decreasing its activity by lowering the temperature increased selectivity, as shown in Table 4. Operating at lower temperatures can be an advantage in itself.
  • Rh,Pd,Re/C EX.30 250 100 80 388 67 Rh,Pd,Re/C EX.30 200 76 84 142

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  • Furan Compounds (AREA)
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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996027436A1 (en) * 1995-03-03 1996-09-12 E.I. Du Pont De Nemours And Company IMPROVED Ru, Re/CARBON CATALYST FOR HYDROGENATION IN AQUEOUS SOLUTION
EP0848991A1 (en) * 1996-12-20 1998-06-24 The Standard Oil Company Improved catalysts for the hydrogenation of maleic acid to 1,4-butanediol
US5883266A (en) * 1998-01-16 1999-03-16 Battelle Memorial Institute Hydrogenated 5-carbon compound and method of making
EP1077080A1 (en) * 1999-08-18 2001-02-21 The Standard Oil Company Improved catalysts for the hydrogenation of maleic acid to 1,4-butanediol
EP1112776A1 (en) * 1999-12-28 2001-07-04 Tonen Chemical Corporation Pd-Re catalyst for hydrogenating dicarboxylic acids
US6486367B1 (en) 1997-12-01 2002-11-26 The Standard Oil Company Process for the hydrogenation of maleic acid to 1,4-butanediol
AU772779B2 (en) * 1999-08-09 2004-05-06 Ineos Usa Llc Improved catalysts for the hydrogenation of maleic acid to 1,4-butanediol
WO2005051875A1 (en) 2003-10-31 2005-06-09 Davy Process Technology Limited Homogeneous process for the hydrogenation of dicarboxylic acids and/or anhydrides thereof
RU2294240C2 (ru) * 2005-02-24 2007-02-27 Институт Катализа Имени Г.К. Борескова Сибирского Отделения Российской Академии Наук Способ приготовления нанесенных полиметаллических катализаторов (варианты)
WO2009129325A3 (en) * 2008-04-16 2010-03-18 Battelle Memorial Institute Hydrogenolysis processes and hydrogenolysis catalyst preparation methods
WO2010054976A1 (de) * 2008-11-17 2010-05-20 Basf Se Verfahren zur herstellung von tetrahydrofuran
WO2019103399A1 (ko) * 2017-11-21 2019-05-31 국민대학교 산학협력단 수소화 촉매 및 이를 이용한 이산화탄소의 수소화 방법
CN111057170A (zh) * 2019-12-06 2020-04-24 中玺新材料（安徽）有限公司 一种负载铬钕钴三金属催化剂及其制备方法和应用
CN115445623A (zh) * 2022-10-11 2022-12-09 宏业控股集团有限公司 一种呋喃连续加氢制四氢呋喃催化剂及其制备方法和应用
US11547984B2 (en) 2018-07-06 2023-01-10 Toyo Tire Corporation Production methods of catalyst for hydrogenation and diol

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US7019155B2 (en) * 2001-11-13 2006-03-28 Invista North America S.A.R.L. Hydrogenation of tetrahydroxybutane to tetrahydrofuran
CN105228991B (zh) * 2013-05-21 2017-12-29 株式会社大赛璐 四氢呋喃的制造方法
JP6318479B2 (ja) * 2013-06-21 2018-05-09 宇部興産株式会社 触媒及び触媒の製造方法、並びにそれを用いたポリオール化合物の製造方法
WO2022093489A1 (en) * 2020-10-30 2022-05-05 Dow Global Technologies Llc Processes for producing an ether

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2403824A1 (fr) * 1977-09-23 1979-04-20 Engelhard Min & Chem Compositions catalytiques, preparation et utilisation
US4243558A (en) * 1979-07-27 1981-01-06 Uop Inc. Nonacidic multimetallic catalytic composite
US4302359A (en) * 1980-05-23 1981-11-24 Exxon Research & Engineering Co. Process for preparing multimetallic reforming catalysts
EP0055512A1 (en) * 1980-12-22 1982-07-07 The Standard Oil Company Process for the manufacture of 1-4-butanediol and tetrahydrofuran
US4369129A (en) * 1980-06-25 1983-01-18 Exxon Research And Engineering Co. Production of rhenium-containing reforming catalysts
EP0147219A2 (en) * 1983-12-22 1985-07-03 E.I. Du Pont De Nemours And Company Pd/Re Hydrogenation catalyst and process for making tetrahydrofuran and 1,4-butanediol
US4795733A (en) * 1987-11-27 1989-01-03 Gaf Corporation Hydrogenation catalyst and process for its preparation

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2403824A1 (fr) * 1977-09-23 1979-04-20 Engelhard Min & Chem Compositions catalytiques, preparation et utilisation
US4243558A (en) * 1979-07-27 1981-01-06 Uop Inc. Nonacidic multimetallic catalytic composite
US4302359A (en) * 1980-05-23 1981-11-24 Exxon Research & Engineering Co. Process for preparing multimetallic reforming catalysts
US4369129A (en) * 1980-06-25 1983-01-18 Exxon Research And Engineering Co. Production of rhenium-containing reforming catalysts
EP0055512A1 (en) * 1980-12-22 1982-07-07 The Standard Oil Company Process for the manufacture of 1-4-butanediol and tetrahydrofuran
EP0147219A2 (en) * 1983-12-22 1985-07-03 E.I. Du Pont De Nemours And Company Pd/Re Hydrogenation catalyst and process for making tetrahydrofuran and 1,4-butanediol
US4795733A (en) * 1987-11-27 1989-01-03 Gaf Corporation Hydrogenation catalyst and process for its preparation

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996027436A1 (en) * 1995-03-03 1996-09-12 E.I. Du Pont De Nemours And Company IMPROVED Ru, Re/CARBON CATALYST FOR HYDROGENATION IN AQUEOUS SOLUTION
EP0848991A1 (en) * 1996-12-20 1998-06-24 The Standard Oil Company Improved catalysts for the hydrogenation of maleic acid to 1,4-butanediol
AU720496B2 (en) * 1996-12-20 2000-06-01 Standard Oil Company, The Improved catalysts for the hydrogenation of maleic acid to 1,4-butanediol
US6486367B1 (en) 1997-12-01 2002-11-26 The Standard Oil Company Process for the hydrogenation of maleic acid to 1,4-butanediol
US5883266A (en) * 1998-01-16 1999-03-16 Battelle Memorial Institute Hydrogenated 5-carbon compound and method of making
AU772779B2 (en) * 1999-08-09 2004-05-06 Ineos Usa Llc Improved catalysts for the hydrogenation of maleic acid to 1,4-butanediol
EP1077080A1 (en) * 1999-08-18 2001-02-21 The Standard Oil Company Improved catalysts for the hydrogenation of maleic acid to 1,4-butanediol
EP1112776A1 (en) * 1999-12-28 2001-07-04 Tonen Chemical Corporation Pd-Re catalyst for hydrogenating dicarboxylic acids
WO2005051875A1 (en) 2003-10-31 2005-06-09 Davy Process Technology Limited Homogeneous process for the hydrogenation of dicarboxylic acids and/or anhydrides thereof
US7498450B2 (en) 2003-10-31 2009-03-03 Davy Process Technology Limited Homogeneous process for the hydrogenation of dicarboxylic acids and/or anhydrides thereof
RU2294240C2 (ru) * 2005-02-24 2007-02-27 Институт Катализа Имени Г.К. Борескова Сибирского Отделения Российской Академии Наук Способ приготовления нанесенных полиметаллических катализаторов (варианты)
WO2009129325A3 (en) * 2008-04-16 2010-03-18 Battelle Memorial Institute Hydrogenolysis processes and hydrogenolysis catalyst preparation methods
WO2010054976A1 (de) * 2008-11-17 2010-05-20 Basf Se Verfahren zur herstellung von tetrahydrofuran
WO2019103399A1 (ko) * 2017-11-21 2019-05-31 국민대학교 산학협력단 수소화 촉매 및 이를 이용한 이산화탄소의 수소화 방법
US11547984B2 (en) 2018-07-06 2023-01-10 Toyo Tire Corporation Production methods of catalyst for hydrogenation and diol
CN111057170A (zh) * 2019-12-06 2020-04-24 中玺新材料（安徽）有限公司 一种负载铬钕钴三金属催化剂及其制备方法和应用
CN111057170B (zh) * 2019-12-06 2022-06-03 中玺新材料（安徽）有限公司 一种负载铬钕钴三金属催化剂及其制备方法和应用
CN115445623A (zh) * 2022-10-11 2022-12-09 宏业控股集团有限公司 一种呋喃连续加氢制四氢呋喃催化剂及其制备方法和应用

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