PROCESS FOR PREPARING A POLYETHERAMINE

Abstract

A process for producing a polyetheramine by reacting a polyether alcohol, previously synthesized in the presence of a basic potassium or sodium compound as catalyst, with ammonia in the presence of hydrogen and a catalyst in one reactor or a plurality of reactors, wherein the employed polyether alcohol when previously synthesized in the presence of a basic potassium compound as catalyst has a content of potassium ions of less than 50 wppm and when previously synthesized in the presence of a basic sodium compound as catalyst has a content of sodium ions of less than 50 wppm.

Claims

1.-26. (canceled)

27. A process for producing a polyetheramine by reacting a polyether alcohol, previously synthesized in the presence of a basic potassium compound as catalyst, with ammonia in the presence of hydrogen and a catalyst in one reactor or a plurality of reactors, wherein the employed polyether alcohol has a content of potassium ions of 20 wppm.

28. The process according to claim 27, wherein the employed polyether alcohol has a content of potassium ions of less than 10 wppm.

29. The process according to claim 27, wherein the reaction of the polyether alcohol to afford the polyetheramine is carried out in the liquid phase at an absolute pressure in the range of from 50 to 220 bar.

30. The process according to claim 27, wherein the reaction of the polyether alcohol to afford the polyetheramine is carried out at a temperature in the range of from 150° C. to 240° C.

31. The process according to claim 27, wherein the reaction of the polyether alcohol to afford the polyetheramine is carried out using ammonia in a molar ratio per mole of alcoholic hydroxyl group in the polyether alcohol in the range of from 1.5 to 500.

32. The process according to claim 27, wherein in the reaction of the polyether alcohol to afford the polyetheramine the catalyst is arranged in the reactor/in the reactors as a fixed bed.

33. The process according to claim 27, which is carried out continuously.

34. The process according to claim 27, wherein the reaction of the polyether alcohol to afford the polyetheramine is carried out in one or more tubular reactor(s) or tube bundle reactor(s).

35. The process according to claim 27, wherein the reaction is carried out in a fresh gas mode or a cycle gas mode.

36. The process according to claim 35, wherein the reaction is carried out with a cycle gas flow rate in the range of from 50 to 1000 normal cubic meters of cycle gas/(m.sup.3.sub.cat..Math.h) or a fresh gas flow rate in the range of from 1 to 200 normal cubic meters of fresh gas/(m.sup.3.sub.cat..Math.h).

37. The process according to claim 27, Wherein the reaction of the polyether alcohol to afford the polyetheramine is carried out at a catalyst space velocity in the range of from 0.01 to 10 kg of polyether alcohol/(l.sub.cat..Math.h).

38. The process according to claim 27, wherein the basic potassium compound is potassium hydroxide.

39. The process according to claim 27, wherein the polyether alcohol to be reacted is a secondary alcohol and the polyetheramine produced is a primary amine.

40. The process according to claim 27, for producing polyetheramine of the following formula by reaction of polyether alcohol of formula IIa with ammonia: ##STR00008## wherein the polyether alcohol and the polyetheramine are each in the form of a mixture of molecules where n is on average in the range of from 2.3 to 3.0 and the molar mass of the polyetheramine is on average in the range of from 210 to 250 g/mol.

41. The process according to claim 27 for producing polyetheramine of the following formula by reaction of polyether alcohol of formula IIb with ammonia: ##STR00009## wherein the polyether alcohol and the polyetheramine are each in the form of a mixture of molecules where n is on average in the range of from 31.5 to 35.0 and the molar mass of the polyetheramine is on average in the range of from 1900 to 2100 g/mol.

42. The process according to claim 27, wherein the catalyst for the reaction of the poly-ether alcohol to afford the polyetheramine comprises copper and/or cobalt and/or nickel.

43. The process according to claim 27, wherein prior to its reduction with hydrogen, for the reaction of the polyether alcohol to afford the polyetheramine, the catalytically active mass of the catalyst comprises oxygen-containing compounds of aluminum and/or zirconium and/or chromium and oxygen-containing compounds of copper.

44. The process according to claim 27, wherein prior to its reduction with hydrogen, for the reaction of the polyether alcohol to afford the polyetheramine, the catalytically active mass of the catalyst comprises oxygen-containing compounds of aluminum and/or zirconium and/or chromium and oxygen-containing compounds of copper and nickel.

45. The process according to claim 27, wherein prior to its reduction with hydrogen, for the reaction of the poly-ether alcohol to afford the polyetheramine, the catalytically active mass of the catalyst comprises oxygen-containing compounds of aluminum and/or zirconium and oxygen-containing compounds of copper and cobalt and nickel.

46. The process according to claim 27, wherein prior to its reduction with hydrogen, for the reaction of the polyether alcohol to afford the polyetheramine, the catalytically active mass of the catalyst comprises oxygen-containing compounds of aluminum, copper, nickel and cobalt and in the range of from 0.2 to 5.0 wt % of oxygen-containing compounds of tin calculated as SnO.

47. The process according to claim 27, wherein prior to its reduction with hydrogen, for the reaction of the polyether alcohol to afford the polyetheramine, the catalytically active mass of the catalyst comprises in the range of from 15 to 80 wt % of oxygen-containing compounds of aluminum, calculated as Al.sub.2O.sub.3, from 1 to 20 wt % of oxygen-containing compounds of copper, calculated as CuO, from 5 to 35 wt % of oxygen-containing compounds of nickel, calculated as NiO, from 5 to 35 wt % of oxygen-containing compounds of cobalt, calculated as CoO and from 0.2 to 5.0 wt % of oxygen-containing compounds of tin, calculated as SnO.

48. The process according to claim 27, wherein prior to its reduction with hydrogen, for the reaction of the polyether alcohol to afford the polyetheramine, the catalytically active mass of the catalyst comprises in the range of from 20 to 85 wt % of oxygen-containing compounds of zirconium, calculated as ZrO.sub.2, from 1 to 30 wt % of oxygen-containing compounds of copper, calculated as CuO, from 14 to 70 wt % of oxygen-containing compounds of nickel, calculated as NiO, and from 0 to 5 wt % of oxygen-containing compounds of molybdenum, calculated as MoO.sub.3.

49. The process according to claim 27, wherein for the reaction of the polyether alcohol to afford the polyetheramine the catalyst is a cobalt-containing catalyst comprising manganese and phosphorus.

50. The process according to claim 27, wherein for the reaction of the polyether alcohol to afford the polyetheramine the catalyst is a cobalt sponge catalyst or a nickel sponge catalyst.

51. The process according to claim 27, wherein from the reaction product of the reaction, by (i) initially any unconverted ammonia is removed overhead, (ii) water is removed overhead, (iii) any by-products present and having a lower boiling point than the process product are removed overhead together with any remaining water, (iv) the process product polyetheramine is removed as bottom product.

Description

EXAMPLES

1. Production of Catalyst A

[0121] Catalyst A was produced according to Example 5 of WO 2011/067199 A1 (BASF SE). The catalyst thus obtained had the composition shown in table I below.

TABLE-US-00001 TABLE I Ni Co Cu Sn BET**) Catalyst*) % % % % m.sup.2/g Support Catalyst A 18.6 17.3 10.6 1.1 187 Al.sub.2O.sub.3 *)Catalyst composition in wt %; remainder up to 100 wt % is the support **)ISO 9277: 1995
2. Reaction of Polyether Alcohol (Pluriol®) P230 with Ammonia to Afford PEA D230 in a Continuously Operated Tubular Reactor

[0122] A reproducible correlation between the potassium ion concentration in the polyether alcohol and the speed of catalyst deactivation was determined by simultaneously carrying out two tests using the same batch of the alcohol amination catalyst A (in the form of 1.0-1.6 mm spall produced from the reduced and passivated tablets), wherein Pluriol® P230 feeds having potassium ion contents of 5 ppm and 10-15 ppm were compared.

Example 2a (P230 Comprising 5 Ppm of K.SUP.+.)

[0123] A heated tubular reactor having an internal diameter of 14 mm, a centrally mounted thermocouple and a total volume of 89 ml was charged in the lower part with a layer of glass spheres (15 ml) and on top of that with 70 ml of the reduced amination catalyst A, and finally the remaining part was in turn charged with glass spheres. Prior to the reaction, the catalyst was activated at not more than 280° C. under hydrogen (25 NI/h) [NI=normal liter=volume converted to standard conditions (20° C., 1 bar abs.)] at atmospheric pressure for 12 hours. Passed through the reactor from bottom to top were 17.5 g/h of Pluriol® P230 comprising 5 ppm of K.sup.+, 28 g/h of liquid ammonia and 8 NI/h of hydrogen. The reactor was maintained at a temperature of 193° C. and a total pressure of 120 bar. Following sampling after 1145 hours the temperature was increased to 203° C. Following sampling after 1649 hours the plant was rinsed for 5 hours with 30 g/h of water, rinsed for five days with 30 g/h of ammonia and then started up again under the same conditions as before the rinsing.

[0124] The mixture exiting the reactor was in each case cooled down and decompressed to atmospheric pressure. Samples of the reaction mixture were taken and analyzed at various time points (cf. FIG. 1). The potassium ion content in the feed and in the output was determined regularly prior to the wet-chemistry analysis.

Example 2b (P230 Comprising 10-15 Ppm of K.SUP.+.)

[0125] The reaction was carried out analogously to Example 2a in an identically constructed parallel apparatus except that Pluriol® P230 comprising 10-15 ppm K.sup.+ was used. Following the water/ammonia rinsing after a run time of 1649 h, the plant was started up under the same conditions as before the rinsing except that Pluriol® P230 having a potassium ion content of 5 ppm was employed. The same catalyst batch was employed and reaction conditions identical to those in Example 2a were run.

TABLE-US-00002 TABLE II K+ in AN AC tert. AN Degree of feed/ Run [mg [mg [mg amination effluent time h Example KOH/g] KOH/g] KOH/g] [%] [ppm] 41 2a 464.8 497.5 0.60 93.43  5/0 2b 464.3 500.7 0.5 92.73 10/0 137 2a 460.0 497.5 0.94 92.47  5/0 2b 462.4 500.7 0.5 92.35 10/0 305 2a 442.5 501.4 0.7 88.25  5/0 2b 436.6 504.3 0.4 86.58 14/0 473 2a 432.8 503.1 0.5 86.03  5/0 2b 417.0 505.8 0.7 82.43 15/0 641 2a 414.3 498.4 0.4 83.13  5/0 2b 395.6 498.9 0.4 79.29 15/0 809 2a 396.3 504.0 0.8 78.63  5/0 2b 366.8 507.0 0.8 72.35 15/0 977 2a 374.1 504.5 0.8 74.15  5/0 2b 335.6 504.9 0.8 66.47 15/0 1145 2a 342.2 502.6 0.9 68.09  5/0 2b 304.0 503.9 0.6 60.33 15/0 1169 2a 414.0 502.6 0.9 82.37  5/0 2b 388.0 503.9 0.9 77.00 15/0 1337 2a 409.3 500.2 0.8 81.83  5/0 2b 387.1 498.5 1.0 77.65 15/0 1505 2a 401.1 500.0 0.9 80.22  5/0 2b 371.0 497.9 0.8 74.51 15/0 1649 2a 398.5 500.0 0.9 79.70  5/0 2b 362.0 494.3 0.7 73.23 15/0 1697 2a 453.6 500.0 0.9 90.72  5/0 2b 388.4 500.0 0.4 77.68  5/0 1745 2a 449.6 496.9 0.9 90.48  5/0 2b 386.7 502.4 0.4 76.97  5/0

Analyses:

Amine Number (AN) Determination:

[0126] A weighed sample of the polyetheramine is diluted with methanol and titrated with 1 N HCl.

[0127] The amine number (AN) is determined according to the formula

(consumption of 1 N HCl [ml].Math.56.1 [mg/ml])/weighed portion [g]=amine number [mg KOH/g]

Acetylation Number (AC) Determination:

[0128] A weighed sample of the polyetheramine is admixed with a weighed excess of acetylation mixture (pyridine, acetic anhydride, glacial acetic acid) and stirred for two hours at 110° C. The mixture is then admixed with water and stirred for a further 10 min. Once cooled down the mixture is titrated with 0.5 N aqueous sodium hydroxide solution. A blank test (acetylation mixture only, no PEA sample) is produced in analogous fashion.

[0129] The AC is determined according to the formula

(consumption of 0.5 N NaOH [ml] for blank−consumption of 0.5 N NaOH [ml] for sample.Math.56.1 [mg/ml]).Math.0.5/weighed portion [g]=acetylation number [mg KOH/g]

Tertiary Amine Number Determination (Tert. AN):

[0130] A weighed sample of the polyether amine is treated with an excess of acetic anhydride to mask the primary and secondary amine functions. The mixture is subsequently titrated with 0.1 N perchloric acid.

[0131] The tert. AN is determined according to the formula

(consumption of 0.1 N perchloric acid [ml].Math.5.61 [mg/ml])/weighed portion [g]=tertiary amine number [mg KOH/g]

[0132] The degree of amination is the quotient of AN and AC and is reported in percent.

[0133] The potassium ion content in the polyether alcohol and in the polyetheramine was determined using inductively coupled plasma atomic emission spectrometry. A Varian 720 ES instrument was used. The sample was pretreated with acid prior to analysis.

Results:

[0134] Under identical reaction conditions and subject to experimental error, at the start of the test identical amine numbers were initially obtained over the catalyst A of the same catalyst batch in the two simultaneously operated tubular reactors. The only difference between the two tests was the concentration of potassium ions in the polyether alcohol feed (Example 2a: 5 ppm, Example 2b: 10-15 ppm). The activity of the catalysts in the two reactors was identical at the start of the test. Over the further course of the test, the activity of both catalysts decreased (lower amine number and lower degree of amination), but the activity of the catalyst from Example 2b, which had the higher concentration of potassium ions in its feed, fell more severely. No potassium ions were detectable in the output of either reactor, i.e. the potassium ions remained on the amination catalyst. As the only difference between the two tests, the deposition of potassium ions on the catalyst was evidently responsible for the activity losses. A temperature increase of 10° C. to 203° C. after a test duration of 1169 h enhanced the degree of amination/the amine number in both tests but the activity of the two catalysts having different degrees of potassium ion contamination was different also at this higher temperature (203° C.).

[0135] Rinsing of the catalyst with, for example, water/ammonia after a run time of 1649 h almost fully restored the catalyst activity in test 2a, where Pluriol® P230 having a potassium ion content of 5 ppm had been employed, (amine number and degree of amination almost achieve the initial test values) while in test 2b, where Pluriol® P230 having a potassium ion content of 10-15 ppm had been employed, the catalyst activity did not achieve the original condition (amine number and degree of amination fell far short of the initial test values) because the rinsing duration was not yet long enough.

3. Production of Pluriol® P230 having a potassium ion content of 5 ppm/10-15 ppm

[0136] A mixture of monopropylene glycol and potassium hydroxide is admixed with about 2.5 mole equivalents of propylene oxide and the resulting mixture is stirred for five hours at 130-140° C. After cooling-down of the mixture, phosphoric acid is added until a pH of 7 is reached. The resuiting precipitate is filtered off. Depending on the quality of the precipitation and the filtration, residual potassium ion contents of 5/of 10-15 wppm in the polyether alcohol are determined in different batches.