Products obtained by the conversion of glycolaldehyde derivatives and aminating agents and their conversion to ethyleneamines and ethanolamines

Abstract

A process for the manufacture of ethyleneamines and ethanolamines, comprising the steps of (i) converting a glycolaldehyde derivative of formula (II), in which R.sup.2, R.sup.3 arethe same or differenthydrogen, alkyl, such as C.sub.1-6-alkyl, or cycloalkyl such as Cs-e-cycloalkyl; and an animating agent of formula (III); in which R1 is hydrogen (H), alkyl, such as C.sub.1-6-alkyl, or cycloalkyl such as C.sub.3-6-cycloalkyl, in the gas or liquid phase; (ii) feeding the reaction products obtained in step (i) into a hydrogenation reactor, where the reaction products are converted with hydrogen in the presence of a hydrogenation catalyst. ##STR00001##

Claims

1. A process for the manufacture of ethyleneamines and ethanolamines, comprising the steps of (i) converting a glycolaldehyde derivative of formula (II) ##STR00007## in which R.sup.2, R.sup.3 arethe same or differenthydrogen, alkyl, or cycloalkyl; and an aminating agent of formula (III);
R1-NH.sub.2(III) in which R.sup.1 is C.sub.1-6-alkyl and C.sub.3-6-cycloalkyl, in the gas or liquid phase; (ii) feeding the reaction products obtained in step (i) into a hydrogenation reactor, where the reaction products are converted with hydrogen in the presence of a hydrogenation catalyst; wherein the hydrogenation catalyst is a Raney copper, Raney nickel, or Raney cobalt catalyst, or a catalyst obtained from the reduction of an oxide of nickel or cobalt; wherein prior to feeding the reaction products into step (ii), the reaction products obtained in step (i) are separated from the gas or liquid phase or the solutions or the dispersions obtained in step (i) are concentrated by evaporating at least part of the solvent comprised in such solutions.

2. A process according to claim 1, wherein the glycolaldehyde derivative of formula (II) is glycolaldehyde.

3. A process according to claim 1, wherein the molar ratio of aminating agents to glycolaldehyde derivates is in the range of 1:1 to 100:1.

4. A process according to claim 1, wherein step (i) is carried out under conditions in which hydrogenation or reductive amination of the glycolaldehyde derivative, the aminating agents and their reaction products are substantially impeded.

5. A process according to claim 1, wherein the glycolaldehyde derivative of formula (II) is provided to step (ii) in the gas or liquid form and is obtained from the hydrous thermolysis of sugars or the pyrolysis of wood.

6. A process according to claim 1, wherein the glycolaldehyde derivative of formula (II) and an aminating agent of formula (III) are provided in a gaseous form and step (i) is carried out in the gas phase.

7. A process according to claim 1, wherein step (ii) is conducted in the presence of ammonia.

8. A process according to claim 1, wherein step (ii) is conducted in the presence of one or more acids; wherein the one or more acids is at least one of an inorganic acid or an organic acid.

9. A process according to claim 1, wherein step (i) or step (ii) is carried out in the presence of one or more solvents; wherein the one or more solvents is at least one of water, alcohols, non-cyclic or cyclic ethers, polyalkylethers, and alkoxypolyalkylethers.

10. A process according to claim 9, wherein the one or more solvents are selected from the group consisting of water, methanol, ethanol, methyl tert-butyl ether, ethyl tert-butyl ether, dioxane, tetrahydrofuran, tetraethylene glycol dimethyl ether (tetraglyme), dipropylene glycol dimethyl ether (proglyme), bis(2-methoxyethyl) ether (diglyme) and polyethyleneoxide dimethyl ether (polyglyme).

11. A process according to claim 1, wherein the reaction products of step (i) are a triazinane derivative of formula I ##STR00008## in which R.sup.1, R.sup.2, R.sup.3 arethe same or differenthydrogen (H), alkyl, or cycloalkyl; or a diaminodioxane derivative formula (IV) ##STR00009## in which R.sup.1, R.sup.2, R.sup.3 arethe same or differenthydrogen (H), alkyl, or cycloalkyl.

12. A triazinane derivative of formula I ##STR00010## in which R.sup.1, R.sup.2, R.sup.3 arethe same or differenthydrogen (H), alkyl, or cycloalkyl.

13. A process for the manufacture of ethyleneamines and ethanolamines by converting a triazinane derivative of formula (I): ##STR00011## in which R.sup.1, R.sup.2, R.sup.3 arethe same or differenthydrogen (H), alkyl, or cycloalkyl: and/or a diaminodioxane derivative of formula (IV): ##STR00012## in which R.sup.1, R.sup.2, R.sup.3 arethe same or differenthydrogen (H), alkyl; with hydrogen in a hydrogenation reactor in the presence of a hydrogenation catalyst; wherein the hydrogenation catalyst is a Raney copper, Raney nickel, or Raney cobalt catalyst, or a catalyst obtained from the reduction of an oxide of nickel or cobalt.

14. The process according to claim 1, wherein R.sup.2, R.sup.3 arethe same or differentC.sub.1-6-alkyl, or C.sub.3-6-cycloalkyl.

15. The process according to claim 1, wherein R.sup.1 is a C.sub.1-6-alkyl or C.sub.3-6-cycloalkyl.

16. The process according to claim 11, wherein the reaction products of step (i) are a triazinane derivative of formula I.

17. The triazinane of claim 12, wherein R.sup.1, R.sup.2, R.sup.3 arethe same or differentC.sub.1-6-alkyl, or C.sub.3-6-cycloalkyl.

18. A process for the manufacture of ethyleneamines and ethanolamines, comprising the steps of: (i) converting a glycolaldehyde derivative of formula (II) ##STR00013## in which R.sup.2, R.sup.3 arethe same or differenthydrogen, alkyl, or cycloalkyl; and an aminating agent of formula (III);
R1-NH.sub.2(III) in which R.sup.1 is C.sub.1-6-alkyl and C.sub.3-6-cycloalkyl, in the gas or liquid phase; (ii) feeding the reaction products obtained in step (i) into a hydrogenation reactor, where the reaction products are converted with hydrogen in the presence of a hydrogenation catalyst; wherein the hydrogenation catalyst is a Raney copper, Raney nickel, or Raney cobalt catalyst, or a catalyst obtained from the reduction of an oxide of nickel or cobalt; wherein prior to feeding the reaction products into step (ii), the reaction products obtained in step (i) are separated from the gas or liquid phase or the solutions or the dispersions obtained in step (i) are concentrated by evaporating at least part of the solvent comprised in such solutions ##STR00014## in which R.sup.1, R.sup.2, R.sup.3 arethe same or differentC.sub.1-6-alkyl or C.sub.3-6-cycloalkyl or a diaminodioxane derivative formula (IV) ##STR00015## in which R.sup.1, R.sup.2, R.sup.3 arethe same or different C.sub.1-6-alkyl, or C.sub.3-6-cycloalkyl.

Description

EXAMPLES

Example 1: Conversion of Glycolaldehyde and Ammonia in the Gas Phase (Step (i))

(1) Gaseous glycolaldehyde was provided by evaporation of an aqueous solution of the glycolaldehyde dimer in THF (7.5 wt.-% glycolaldehyde dimer, 11.5 wt.-% THF, 80 wt.-% water and 1 wt.-% tetraglyme) by heating the solution to 160 C. in a tube evaporator comprising Raschig-rings. The gaseous feed was fed into an unheated reaction chamber operated at ambient pressure.

(2) Gaseous ammonia at room temperature was also fed to the reaction chamber through a separate inlet.

(3) It was observed that colorless crystals desublimated at the cooler parts of the reaction chamber.

(4) The crystals were analyzed by gas chromatography and yielded a distinct peak. The .sup.1H-NMR (see FIG. 1) and .sup.13C-NMR (see FIG. 2) confirmed the crystals had the following structure:

(5) ##STR00006##

(6) .sup.1H-NMR (500 MHz, D.sub.2O): 3.65 (d, 6H), 3.86 (t, 3H) ppm.

(7) .sup.13C-NMR (125 MHz, D.sub.2O): 4.3, 69.7 ppm.

(8) At the cooler, bottom of the reaction chamber, a yellow-brownish clear solution condensed from the gas phase. The product solution was drawn-off from the bottom of the reaction chamber through a valve.

(9) The product solution was analyzed with GC and yielded a distinct product peak, which was identical to the peak obtained by performing a GC on the crystals. The other substances in the product solutions were identified to be the solvents (THF, water, tetraglyme) from which the glycolaldehyde was evaporated from and excess ammonia.

(10) The total yield of conversion products of glycolaldehyde and ammonia, including the triazinane, was about 73%.

Example 2: Hydrogenation of the Reaction Products Obtained from Example 1 (Step (ii))

(11) 35 g of the product solution obtained from Example 1 were transferred to an autoclave. The autoclave was pressurized to 20 bar and was heated to 80 C.

(12) At 80 C., the autoclave was pressurized with hydrogen to a pressure of 100 bar.

(13) Hydrogenation was carried out in the presence of 0.5 g of a Raney cobalt catalyst.

(14) After a reaction time of 12 hours, the autoclave was depressurized and cooled to ambient temperature.

(15) The composition of the product solution was analyzed by gas chromatography.

(16) Following composition was obtained (in area percent):

(17) EDA: 10%

(18) MEOA: 36%

(19) DEOA: 8%

(20) MEG (monoethylene glycol): 3%

Example 3: Hydrogenation of the Reaction Products Obtained from Example 1 (Step (ii))

(21) Example 3 was identical to Example 2, with the exception that an additional 10 g of ammonia was added to the autoclave at 20 C. and the solution was stirred for 1 h at 80 C. before the autoclave was pressurized to 100 bar with hydrogen gas

(22) The composition of the product solution was analyzed by gas chromatography.

(23) Following composition was obtained (in area percent):

(24) EDA: 6%

(25) MEOA: 38%

(26) DEOA: 5%

(27) MEG (monoethylene glycol): 1%

Example 4: Conversion of Glycolaldehyde and Ammonia in the Liquid Phase (Step (i))

(28) 10 g of glycolaldehyde dimer and 11.32 g of ammonia in form of an aqueous solution of ammonia (25 wt.-%) were mixed in a reaction flask.

(29) The reaction mixture was subjected to an evaporation step in a rotary evaporator to obtain a brownish solid residue which was isolated, washed with cold water and dried again.

Example 5: Hydrogenation of the Reaction Products Obtained from Example 4 (Step (ii))

(30) The solid residue obtained in Example 4 was dissolved in 50 ml of methanol.

(31) The solution was transferred into an autoclave

(32) The autoclave was pressurized to 20 bar and was heated to 80 C.

(33) At 80 C., the autoclave was pressurized with hydrogen to a pressure of 100 bar.

(34) Hydrogenation was carried out in the presence of 0.5 g of a Raney cobalt catalyst.

(35) The composition of the product solution was analyzed by gas chromatography.

(36) Following composition was obtained (in area percent):

(37) EDA: 4%

(38) MEOA: 0%

(39) DEOA: 21%

(40) MEG (monoethylene glycol): 29%

Example 6: Hydrogenation of the Reaction Products Obtained from Example 4 (Step (ii))

(41) Example 6 was identical to Example 5, with the exception that an additional 15 g of ammonia were added to the autoclave at 20 C. and the solution was stirred for 1 h at 80 C. before the autoclave was pressurized to 100 bar with hydrogen gas.

(42) The composition of the product solution was analyzed by gas chromatography.

(43) Following composition was obtained (in area percent):

(44) EDA: 6%

(45) MEOA: 60%

(46) DEOA: 3%

(47) MEG (monoethylene glycol): 0%

Example 7: Conversion of Glycolaldehyde and Ammonia in the Liquid Phase (Step (i))

(48) Glycolaldehyde was converted with aqueous ammonia as described in Example 1 of U.S. Pat. No. 4,667,213.

(49) A white crystalline precipitate was obtained which was washed with cold water and dried.

Example 8: Hydrogenation of the Reaction Products Obtained from Example 7 (Step (ii))

(50) 5 g of the precipitate from Example 7 were dissolved in 60 ml of methanol.

(51) The solution was then transferred to an autoclave and was pressurized with hydrogen to a pressure of 20 bar at 20 C.

(52) The autoclave was heated to 100 C.

(53) At 100 C., the autoclave was pressurized with hydrogen to a pressure of 100 bar.

(54) Hydrogenation was carried out in the presence of 1 g of a Raney cobalt catalyst.

(55) After a reaction time of 21 hours, the autoclave was depressurized and cooled to ambient temperature.

(56) The composition of the product solution was analyzed by gas chromatography.

(57) Following composition was obtained (in area percent):

(58) EDA: 0%

(59) MEOA: 25%

(60) DEOA: 51%

(61) MEG (monoethylene glycol): 3%

Example 9: Hydrogenation of the Reaction Products Obtained from Example 7 (Step (ii))

(62) Example 9 was identical to Example 8, with the exception that an additional 14 g of ammonia were added to the autoclave.

(63) The composition of the product solution was analyzed by gas chromatography.

(64) Following composition was obtained (in area percent):

(65) EDA: 1%

(66) MEOA: 76%

(67) DEOA: 2%

(68) MEG (monoethylene glycol): 0%

Example 10: Hydrogenation of the Reaction Products Obtained from Example 7 (Step (ii))

(69) Example 10 was identical to Example 9, with the exception that only 2.7 g of the precipitate from Example 7 were dissolved in 60 ml of methanol and 7.6 g of ammonia were charged to the autoclave. In addition, the hydrogenation catalyst was a mixture of 0.5 g of a Raney cobalt catalyst and 1 g of a catalyst consisting of TiO.sub.2.

(70) The composition of the product solution was analyzed by gas chromatography.

(71) Following composition was obtained (in area percent):

(72) EDA: 0%

(73) MEOA: 59%

(74) DEOA: 1%

(75) MEG (monoethylene glycol): 0%

Example 11: Hydrogenation of the Reaction Products Obtained from Example 7 (Step (ii)) in the Presence of an Acid

(76) Example 11 was identical with example 9, with the exception that 0.34 g acetic acid were additionally added to the autoclave.

(77) The composition of the product solution was analyzed by gas chromatography.

(78) Following composition was obtained (in area percent):

(79) EDA: 0%

(80) MEOA: 82%

(81) DEOA: 6%

(82) MEG (monoethylene glycol): 0%