Hydrogenation of 3,4-tetrahydrofurandiol to tetrahydrofuran

Details Hydrogenation of 3,4-tetrahydrofurandiol to tetrahydrofuran Hydrogenation of 3,4-tetrahydrofurandiol to tetrahydrofuran

2002-11-12

2003-07-15

Owens, Amelia (Department: 1625)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

C549S505000, C549S507000

Reexamination Certificate

active

06593481

ABSTRACT:

FIELD OF INVENTION
3,4-Tetrahydrofurandiol is hydrogenated in the presence of metal catalysts to form tetrahydrofuran and precursors.
BACKGROUND
Tetrahydrofuran is an industrially important solvent and monomer. Commercially it is prepared from nonrenewable petrochemical feedstocks. With the potential depletion of the world's oil reserves, a need exists to develop a source of tetrahydrofuran from renewable sources such as biomass. Biomass comprises primarily a carbohydrate containing material. Biomass can also mean as comprising a polysaccharide material. It can also mean comprising cellulose, hemicellulose, or lignocellulose materials: for example, the biomass as obtained from wood, plants, residue from agriculture or forestry, organic component of municipal and industrial wastes, primary sludges from paper manufacture, waste paper, waste wood (e.g., sawdust), agricultural residues such as corn husks, corn cobs, rice hulls, straw, bagasse, starch from corn, wheat oats, and barley, waste plant material from hard wood or beech bark, fiberboard industry waste water, bagasse pity, bagasse, molasses, post-fermentation liquor, furfural still residues, aqueous oak wood extracts, rice hull, oats residues, wood sugar slops, fir sawdust, naphtha, corncob furfural residue, cotton balls, rice, straw, soybean skin, soybean oil residue, corn husks, cotton stems, cottonseed hulls, starch, potatoes, sweet potatoes, lactose, waste wood pulping residues, sunflower seed husks, hexose sugars, pentose sugars, sucrose from sugar cane and sugar beets, corn syrup, hemp, and combinations of the above. Carbohydrates offer a convenient starting material, with their multiple reactive hydroxyl groups, but a drawback of using most carbohydrates is the need to remove the unwanted hydroxyls.
1,2,3,4-Tetrahydroxybutane is a 4-carbon sugar alcohol, or tetritol, and can have three isomeric forms: erythritol, the meso form; D-threitol and L-threitol. Erythritol is used as a low calorie sweetener and sugar substitute and is typically produced commercially via the fermentation of corn starch. Threitol has limited commercial manufacture or use, but can be produced via modification of the equivalent isomer of tartaric acid. All the isomeric forms of 1,2,3,4-tetrahydroxybutane are easily cyclodehydrated to form anhydroerythritol or anhydrothreitol, which are isomeric forms of 3,4-tetrahydrofurandiol.
Much work has been done on the dehydration of erythritol to various products including anhydroerythritol (U.S. Pat. No. 4,939,277, Hudson et al. (
J. Org. Chem
. (1967), 32(11), p3650), Montassier, et al., (
J. Mol. Catal
. (1991), 70(1), p65), Braca, et al, (
J. Organomet Chem
. (1991), 417(1-2), p41)), but little or no tetrahydrofuran was prepared.
U.S. Pat. No. 6,013,812 describes a process for the cyclodehydration of a 4-carbon polyol in the presence of a supported metal catalyst, an acid catalyst and added water, producing a mixture of various hydroxylated cyclic ethers. U.S. Pat. No. 4,401,823 uses carbonaceous pyropolymer impregnated with a transition metal to hydrogenate polyols to produce a large variety of compounds. U.S. Pat. No. 4,313,884 prepares anhydropolyols from the corresponding polypls using various metal ions as catalysts; however no examples are described using erythritol.
SUMMARY OF THE INVENTION
The invention is directed towards a process to prepare tetrahydrofuran and precursors to tetrahydrofuran comprising: contacting 3,4-tetrahydrofurandiol with a catalytic amount of at least one metal catalyst. In a preferred embodiment, the process comprises contacting anhydroerythritol with a catalytic amount of one or more metals selected from Periodic Group 8, where the metal is optionally supported on a solid support. Preferably the metal is selected from the group consisting Rh, Re, Pd, Ru and Ni. A preferred support is carbon and a preferred metal is Re.
The invention may additionally comprise a metal promoter, preferably selected from Periodic Groups 8, 11, and 12 metals, and Sn and Pb. More preferably, the promoter is selected from the group consisting of Zn, Cd, Sn, Pb, Cu, Ag, Au, and Pt, most preferably Pt, Au, or Ru.
In one embodiment, the invention further comprises the conversion to tetrahydrofuran of the precursors. In another embodiment, the unsaturated precursors are recycled back into the said process.
The invention is also directed towards a process to prepare tetrahydrofuran and unsaturated precursors of tetrahydrofuran comprising the steps of:
a) converting 1,2,3,4-tetrahydroxybutane to 3,4-tetrahydrofurandiol;
b) optionally separating the 3,4-tetrahydrofurandiol; and
c) contacting 3,4-tetrahydrofurandiol with a catalytic amount of at least one metal catalyst.
DETAILED DESCRIPTION OF THE INVENTION
The invention is a process to prepare tetrahydrofuran and its precursors by contacting 3,4-tetrahydrofurandiol with a catalytic amount of one or more metals. Preferably the metals are from Periodic Group 8; more preferably the metals are selected from the group consisting Rh, Re, Pd, Ru and Ni. By “3,4-tetrahydrofurandiol” is meant any optical isomer, or mixture thereof of the compound shown below:
Various isomers of 3,4-tetrahydrofurandiol include anhydroerythritol and anhydrothreitol. A preferred isomer is erythritol.
By “precursors” herein is meant butanediol, unsaturated furans, and hydroxylated forms of tetrahydrofuran and unsaturated furans, as represented by Formulae I, II, and III below wherein each R is independently hydrogen and OH, and their isomeric forms. Preferred precursors are furan and 1,4-dihydrofuran.
The process of the instant invention may further comprise the conversion of the precursors of tetrahydrofuran. This may be done by any of the methods known in the art. See Ullmann's Encyclopedia of Industrial Chemistry, 5
th
Ed., Vol. A26, pp. 222-223 for a description of many of these methods. The instant process may also comprise the recycling of the precursors back into the process for further conversion to tetrahydrofuran.
The process of the instant invention may additionally comprise converting 1,2,3,4-tetrahydrobutane to 3,4-tetrahydrofurandiol; optionally separating the 3,4-tetrahydrofurandiol; and then contacting the 3,4-tetrahydrofurandiol with a catalytic amount of one or more metals from Periodic Group 8 to prepare tetrahydrofuran and unsaturated precursors of tetrahydrofuran. A preferred process comprises the conversion of erythritol to anhydroerythritol. Preferred metals are selected from the group consisting of Rh, Re, Pd, Ru and Ni. The conversion of erythritol to 3,4-tetrahydrofurandiol may be done by any method known in the art. See Advances in Carbohydrate Chemistry, S. Soltzberg, Vol. 25, pg. 229-231, 1970 for a description of many of these methods. The anhydroerythritol may be isolated before contact with the metal catalyst. This can be done by any method known in the art, such as distillation, decantation, recrystallization, or extraction.
The metal catalyst can optionally contain a promoter, preferably a metal selected from the group consisting of Periodic Group 8, 11, and 12 metals, and Sn and Pb. By “promoter” herein is meant a metal that is present at levels less than 50% by weight of the major metal.
Preferred are Au, Zn, Cd, Sn, Pb, Cu, Ag, Pt, and Au. More preferred are Pt and Au. A preferred metal catalyst is Re; more preferred is Re with a metal promoter being Ru, Rh, Pd, Ni, Pt, Au.
Suitable preferred solid supports include SiO
2
(silica), Al
2
O
3
(alumina), TiO
2
(titania), MgO (magnesia) or ZrO
2
(zirconia), zeolites, carbon, clays, or mixtures thereof. Preferred solid supports are those which are neutral and have low surface areas. Commonly used techniques for treatment of supports with metal catalysts can be found in B. C. Gates,
Heterogeneous Catalysis
, Vol. 2, pp. 1-29, Ed. B. L. Shapiro, Texas A & M University Press, College Station, Tex., 1984. Preferred solid supports include carbon, Al
2
O
3
, and SiO
2
. A more preferred solid support is carbon. More preferred carbons are those with a surface area>200 m
2
/gm. The

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