CONVERSION OF GLYCOLALDEHYDE WITH AN AMINATING AGENT

Abstract

A process for the conversion of glycolaldehyde with an aminating agent in the presence of hydrogen and of a catalyst in a glycolaldehyde conversion reactor, wherein one or more organic carboxylic acids are fed into the glycolaldehyde conversion reactor.

Claims

1.-15. (canceled)

16. A process for the conversion of glycolaldehyde with an aminating agent in the presence of hydrogen and of a catalyst in a glycolaldehyde conversion reactor, wherein one or more organic carboxylic acids are fed into the glycolaldehyde conversion reactor.

17. The process according to claim 16, wherein the one or more organic carboxylic organic acids are selected from the group consisting of saturated aliphatic monocarboxylic acids, unsaturated aliphatic monocarboxylic acids, saturated aliphatic dicarboxylic acids unsaturated aliphatic dicarboxylic acids, aryl carboxylic acids, and hydroxy carboxylic acids.

18. The process according to claim 16, wherein the one or more organic carboxylic acids are selected from the group consisting of formic acid, acetic acid, propionic acid, acrylic acid, levulic acid, lactic acid, glycolic acid and pyruvic acid.

19. The process according to claim 16, wherein the molar ratio of glycolaldehyde to each selected organic carboxylic acid fed into the glycol conversion reactor is in the range of 1:1 to 100:1.

20. The process according to claim 16, wherein the molar ratio of glycolaldehyde to the total amount of organic carboxylic acids fed into the glycol conversion reactor is in the range of 1:1 to 300:1.

21. The process according to claim 16, wherein one or more solvents are fed into the glycolaldehyde conversion reactor.

22. The process according to claim 16, wherein one or more solvents are selected from the group consisting of methanol, tetrahydrofuran and water.

23. The process according to claim 16, wherein the glycolaldehyde, the aminating agent, the organic carboxylic acid and optionally one or more solvents are fed separately to the glycolaldehyde conversion reactor or wherein at least two of the aforementioned components are mixed to obtain mixed feed streams comprising two or more components.

24. Process according to claim 16, wherein the mixed feed stream comprises 5 to 50 percent by weight of glycolaldehyde, 0.1 to 25 percent by weight of organic carboxylic acids, 0.1 to 25 percent by weight of other organic components, rest water.

25. The process according to claim 16, wherein the mixed feed stream is obtained by the hydrous thermolysis of sugars or from the pyrolysis of wood.

26. The process according to claim 16, wherein the aminating agent is a compound of formula (I) ##STR00002## in which R.sup.1, R.sup.2 are hydrogen (H), alkyl such as C.sub.1-20-alkyl, cycloalkyl such as C.sub.3-12-cycloalkyl, alkoxyalkyl such as C.sub.2-30-alkoxyalkyl, dialkylaminoalkyl such as C.sub.3-30-dialkylaminoalkyl, aryl, aralkyl such as C.sub.7-20-aralkyl, and alkylaryl such as C.sub.7-20-alkylaryl, or together are —(CH.sub.2).sub.j—X—(CH.sub.2).sub.k—, X is CH.sub.2, CHR.sup.3, oxygen (O), sulfur (S) or NR.sup.3, R.sup.3 is hydrogen (H), alkyl such as C.sub.1-4-alkyl, alkylphenyl such as C.sub.7-40-alkylphenyl, j, k are each integers from 1 to 4.

27. The process according to claim 16, wherein the aminating agent of formula (I) is (i) an alkylamine in which R.sup.1 is H and R.sup.2 is C.sub.1-20-alkyl or (ii) a dialkylamine in which R.sup.1 and R.sup.2 are each—the same or different—C.sub.1-20-alkyl.

28. The process according to claim 16, wherein the molar ratio of glycolaldehyde to aminating agents is in the range of 1:100 to 100:1.

29. The process according to claim 16, wherein the catalyst comprises one or more metals selected from groups 7, 8, 9, 10 and 11 of the periodic table of elements.

30. The process according to claim 16, in wherein the effluent from the glycolaldehyde conversion reactor is refined by performing at least one of the following steps: (i) Contacting the effluent with a base; (ii) Contacting the effluent with an anion exchanger; (iii) Distillation.

Description

EXAMPLES

[0199] The process according to the invention is illustrated in detail with reference to the examples adduced below.

Example 1 (Reference Example)

[0200] 25 mmol of glycolaldehyde dimer (corresponds to 50 mmol of monomeric glycolaldehyde), 141 mmol of dimethylamine, 60 g of THF and 3 g of a nickel catalyst were transferred to an autoclave under a nitrogen atmosphere.

[0201] The nickel catalyst used in the reaction was a powder of nickel supported on silica, commercially available as Ni-5249P.

[0202] At room temperature, the pressure was increased to 10 bar by injecting hydrogen into the autoclave.

[0203] Then, the autoclave was heated to 130° C.

[0204] Upon reaching 130° C., the pressure was increased to 175 bar by injecting further hydrogen into the autoclave.

[0205] Upon reaching 175 bar, the reaction mixture was stirred for one hour.

[0206] Thereafter, the reaction mixture was cooled to room temperature and the autoclave was depressurized and flushed with nitrogen gas.

[0207] The reaction mixture was analyzed by gas chromatography.

[0208] The composition of the reaction mixture (without solvents) is given in area percent and was as follows:

[0209] TMEDA: 55%

[0210] DMEOA: 26%

[0211] MEG: 1%

Example 2 (Reference Example)

[0212] Example 2 was identical to Example 1, with the exception, that the nickel catalyst used in Example 1 was reused in Example 2 and maintaining the catalyst under inert conditions (nitrogen atmosphere) when charging and discharging the autoclave. In this way, the glycolaldehyde in Example 2 is contacted with an activated catalyst, because activation of the catalyst occurred in-situ in Example 1.

[0213] The composition of the reaction mixture (without solvents) is given in area percent and was as follows:

[0214] TMEDA: 26%

[0215] DMEOA: 76%

[0216] MEG: 2%

Example 3: Conversion in the Presence of Organic Carboxylic Acid

[0217] Example 3 was identical to Example 1, with the exception that a carboxylic organic acid in an amount indicated in Table 1 was charged to the autoclave together with the other reactants.

[0218] The composition of the reaction mixture (without solvents) is given in area percent and is also depicted in Table 1.

[0219] After discharging the reaction mixture obtained during a first run under inert conditions, the reaction was repeated (second run) by charging the reactor with the same amount of components as in the first run and carrying out the reaction in the same way the reaction was carried out in the first run. The only difference between the first run and the second run was that the catalyst used in the second run is an activated catalyst which was activated in situ during the first run.

TABLE-US-00001 TABLE 1 Organic carboxylic Run Amount acid No. of acid Solvent TMEDA DMEOA MEG None (Ex- 1 — THF 55 32 1 ample 1) 2 26 76 2 Lactic acid 1  1 mmol THF 56 34 1 2 67 22 0 Lactic acid 1 10 mmol THF 66 20 0 2 63 23 0 Acetic acid 1 10 mmol THF 69 5 0 2 59 5 0 Glycolic acid 1 10 mmol THF 73 11 0 2 39 4 0 Lactic acid 1 10 mmol THF/water 18 22 3 2 10 mmol 65 14 1 Formic acid 1 10 mmol THF 60 12 0 Formic acid 2 10 mmol 65 7 0

[0220] Without the addition of organic carboxylic acids, the selectivity of the reaction drastically changes from TMEDA to DMEOA when the catalyst is reused. The catalyst is activated during the first run. Therefore, after the first run, the selectivity will shift from TMEDA to DMEOA.

[0221] Such a shift in selectivity can be prevented when adding an organic carboxylic acid according to the invention. Accordingly, it can be shown that the organic carboxylic acid acts as selectivity modifier and maintains a strong selectivity for conversion products of glycolaldehyde in which the terminal hydroxyl group of glycolaldehyde is converted.

Example 4: Conversion Over Cu-Catalyst in the Presence and Absence of an Organic Acid

[0222] 8.3 mmol of of glycolaldehyde dimer (16.6 mmol of monomeric glycolaldehyde), 50 mL of a 2.0 molar solution of DMA in THF (100 mmol) were put into a 160 mL steel autoclave and 5 g of a reduced copper catalyst (containing 68% Cu-oxide prior to reduction) soaked in THF was placed in a steel mesh basket that was fixed to the head of the autoclave. The autoclave was closed, flushed with argon, and a hydrogen pressure of 20 bar was applied. Then it was heated under stirring (mechanical stirrer with pitched blades) to 130° C. and the pressure was adjusted to 125 bar with hydrogen. Upon reaching this pressure the reaction mixture was stirred for 2 hours. Thereafter, the reaction mixture was cooled to room temperature and the autoclave was depressurized. The reaction mixture was analyzed by gas chromatography.

[0223] In two further experiments, 0.1 mL formic and 0.1 mL lactic acid were added to the mixture of DMA and glycolaldehyde dimer in THF. All results are listed in Table 2. The composition of the reaction mixture (calculated without solvents and DMA) is given in area-%:

TABLE-US-00002 TABLE 2 Organic carboxylic Amount acid of acid Solvent TMEDA DMEOA None — THF 71 23 Formic acid 2.6 mmol 75 4 Lactic acid 1.3 mmol THF 86 4