Supported catalyst used for synthesizing polyether amine, and manufacturing method

Abstract

A supported catalyst used for synthesizing a polyether amine, and a manufacturing method of the catalyst. The catalyst comprises: a porous oxide as a support; Ni, Cu, Pd, and Rh as active components; and one or more of any of Zr, Cr, Mo, Fe, Zn, Sn, Bi, Ce, La, Hf, Sr, Sb, Mg, Be, Re, Ta, Ti, Sc, Ge and related metals as an auxiliary agent. The catalyst can be used in an amination reaction for a large molecular weight polyether polyol, and is particularly active and selective for an amination reaction of a low molecular weight polyether polyol. The catalyst has a simple and economic manufacturing technique and good potential for future applications.

Claims

1. A supported catalyst used for synthesizing polyether amines, comprising a support and active components, wherein the active components comprises: 1-15 wt % of Ni, 0.5-10 wt % of Cu, 0.1-1.0 wt % of Pd, and 0.05-0.5 wt % of Rh, based on the total weight of the catalyst.

2. The supported catalyst according to claim 1, wherein the active components of the catalyst comprises: 4-12 wt % of Ni, 1-8 wt % of Cu, 0.5-0.8 wt % of Pd, and 0.15-0.4 wt % Rh, based on the total weight of the catalyst.

3. The supported catalyst according to claim 2, wherein the active components of the catalyst comprises: 5-10 wt % of Ni, 3-5 wt % of Cu, 0.6-0.7 wt % of Pd, and 0.2-0.3 wt % of Rh, based on the total weight of the catalyst.

4. The supported catalyst according to claim 2, wherein the catalyst optionally comprises an auxiliary agent which is selected from the group consisting of Zr, Cr, Mo, Fe, Zn, Sn, Bi, Ce, La, Hf, Sr, Sb, Mg, Be, Re, Ta, Ti, Sc, Ge, and any combination thereof, preferably the group consisting of Zr, Ce, Mg, Mo, Ti, and any combination thereof, more preferably Zr and/or Mg.

5. The supported catalyst according to claim 1, wherein the catalyst optionally comprises an auxiliary agent which is selected from the group consisting of Zr, Cr, Mo, Fe, Zn, Sn, Bi, Ce, La, Hf, Sr, Sb, Mg, Be, Re, Ta, Ti, Sc, Ge, and any combination thereof, preferably the group consisting of Zr, Ce, Mg, Mo, Ti, and any combination thereof, more preferably Zr and/or Mg.

6. The supported catalyst according to claim 5, wherein the content of the auxiliary agent is 0-0.5 wt %, preferably 0.05-0.45 wt %, more preferably 0.1-0.3 wt %, based on the total weight of the catalyst.

7. The supported catalyst according to claim 5, wherein the total content of the active components is not less than 5 wt %, preferably not less than 10 wt %, based on the total weight of the catalyst.

8. The supported catalyst according to claim 5, wherein the support is selected from the group consisting of porous γ-Al.sub.2O.sub.3, SiO.sub.2, MgO, TiO.sub.2, ZrO.sub.2, and any combination thereof, preferably γ-Al.sub.2O.sub.3.

9. The supported catalyst according to claim 1, wherein the total content of the active components is not less than 5 wt %, preferably not less than 10 wt %, based on the total weight of the catalyst.

10. The supported catalyst according to claim 1, wherein the support is selected from the group consisting of porous γ-Al.sub.2O.sub.3, SiO.sub.2, MgO, TiO.sub.2, ZrO.sub.2, and any combination thereof, preferably γ-Al.sub.2O.sub.3.

11. A method of preparing the supported catalyst according to claim 1, wherein the method comprises the following steps: 1) Preparation of a metal salt solution: weighing metal salts proportionally, and adding deionized water to prepare a metal salt solution; wherein the metal salts are metal salts of the active components and the optional auxiliary agent; 2) Adsorption: adding the support to adsorb the metal salt complex solution obtained in step 1) to obtain an adsorbed wet support; 3) Drying, calcining, and reducing the wet support to obtain the supported catalyst.

12. The method according to claim 11, wherein the metal salt is one or more of metal halide, metal nitrate, organic acid metal salt, preferably one or more of metal nitrate, metal formate, metal acetate and metal oxalate, more preferably metal nitrate.

13. The method according to claim 12, wherein the method further comprises step 1a) preparation of a metal salt complex solution: forming a metal salt complex solution by reacting the metal salt solution with a ligand; preferably, the ligand is one or more of ammonia and organic amines, more preferably one or more of ammonia, EDTA and diethylamine.

14. The method according to claim 11, wherein the method further comprises step 1a) preparation of a metal salt complex solution: forming a metal salt complex solution by reacting the metal salt solution with a ligand; preferably, the ligand is one or more of ammonia and organic amines, more preferably one or more of ammonia, EDTA and diethylamine.

15. The method according to claim 14, wherein the method further comprises step 2a) in-situ precipitation of CO.sub.2: precipitating the metal salt complex on the adsorbed wet support obtained in the step 2) by using carbon dioxide gas; preferably, the reaction condition for in-situ precipitation of CO.sub.2 is: performing the precipitation reaction in an atmosphere containing carbon dioxide at a reaction temperature of 20° C.-50° C., preferably 30° C.-40° C. for 2 h-10 h, preferably 4 h-6 h.

16. A method for preparing a polyether amine by amination of a polyether polyol, wherein the method is as follow: subjecting the polyether polyol to a reductive amination reaction in the presence of hydrogen, an amination reagent and a supported catalyst to prepare a polyether amine; wherein the supported catalyst is prepared by the method according to claim 11.

17. A method for preparing a polyether amine by amination of a polyether polyol, wherein the method is as follow: subjecting the polyether polyol to a reductive amination reaction in the presence of hydrogen, an amination reagent and a supported catalyst to prepare a polyether amine; wherein the supported catalyst is the supported catalyst according to claim 1.

18. The method according to claim 17, wherein the polyether polyol contains an EO and/or PO skeleton and has a weight average molecular weight of 90-7,000, preferably a molecular weight of 100-5,000, more preferably a molecular weight of 200-600.

19. The method for preparing a polyether amine by amination of a polyether polyol according to claim 18, wherein the space velocity of the polyether polyol is 0.01-3 h.sup.−1, preferably 0.1-1.0 h.sup.−1.

20. The method according to claim 17, wherein the space velocity of the polyether polyol is 0.01-3 h.sup.−1, preferably 0.1-1.0 h.sup.−1.

Description

EXAMPLE 1

(1) Into 85 ml of formate solution containing 6.5 g of Ni, 7.5 g of Cu, 0.9 g of Pd and 0.2 g of Rh (based on the weight of the metal elements, the same as follows), ammonia water with a concentration of 25 wt % was added dropwise until the precipitate formed was completely dissolved, to obtain a mixed solution of metal ammonium salts. At room temperature, 84.9 g of dried strip-shaped alumina having a diameter of 3 mm was completely impregnated in the above solution, and the solution was allowed to stand for 5.5 hours and substantially completely adsorbed.

(2) The impregnated support was taken out and placed in a tubular reactor, and was treated with carbon dioxide gas introduced at 45° C. for 4 hours, which was then slowly heated to 80° C. to dry for 12 hours.

(3) Nitrogen gas was introduced to completely replace carbon dioxide in the tubular reactor, and part of the support was calcined at 450° C. for 4.5 h in nitrogen atmosphere. An excess barium hydroxide solution was used to absorb the CO.sub.2 produced by the decomposition of the carbonate, so that the carbon dioxide was completely converted into barium carbonate precipitate, and 2 drops of phenolphthalein indicator was added into the solution which was then titrated with an oxalic acid standard solution having a concentration of c (mol/ml) until the color of the solution changed from red to colorless, while the volume a (ml) of the consumed oxalic acid standard solution was recorded. At the same time, the barium hydroxide solution without absorbing any CO.sub.2 was used as a blank titration to record the volume b (ml) of the consumed oxalic acid standard solution. The mass of CO.sub.2 produced after calcination of the catalyst can be calculated according to the following formula.
m=M*(b−a)*c

(4) Wherein, m is the mass of carbon dioxide, g; M is the molecular weight of carbon dioxide, g/mol; a is the volume of the oxalic acid standard solution for sample titration, ml; b is the volume of the oxalic acid standard solution for blank titration, ml; c is the molar concentration of the oxalic acid standard solution, mol/ml.

(5) After calculation, the carbon dioxide produced by the decomposition of carbonate is about 96% of the theoretical consumption of carbon dioxide, indicating that the metal salt has been sufficiently precipitated in the in-situ precipitation step of carbon dioxide.

(6) The remaining support was reduced with a mixture of 5 vol % of hydrogen and 95 vol % of nitrogen at 200° C. for 12 h to obtain a supported catalyst A-1 containing 6.5 wt % of Ni, 7.5 wt % of Cu, 0.9 wt % of Pd and 0.2 wt % of Rh.

EXAMPLE 2

(7) Into 86 ml of nitrate solution containing 10.0 g of Ni, 3.0 g of Cu, 0.5 g of Pd, 0.3 g of Rh and 0.1 g of Zr, ammonia water with a concentration of 25 wt % was added dropwise until the precipitate formed was completely dissolved to obtain a mixed solution of metal ammonium salts. At room temperature, 86.1 g of dried strip-shaped alumina having a diameter of 3 mm was completely impregnated in the above solution, and the solution was allowed to stand for 6 hours and substantially completely adsorbed.

(8) The impregnated support was placed in a tubular reactor and heated to 35° C., and was treated with the introduced carbon dioxide for 6 h, which was then slowly heated to 80° C. to dry for 10 h, calcined at 400° C. for 4 h, cooled, and then reduced at 250° C. with a mixed gas of 50 vol % of hydrogen and 50 vol % of nitrogen for 8 hours to obtain a supported catalyst A-2 containing 10.0 wt % of Ni, 3.0 wt % of Cu, 0.5 wt % of Pd, 0.3 wt % of Rh and 0.1 wt % of Zr.

EXAMPLE 3

(9) Into 86 ml of nitrate solution containing 8.5 g of Ni, 4.5 g of Cu, 0.65 g of Pd, 0.5 g of Rh and 0.45 g of Mg, ammonia water with a concentration of 28 wt % was added dropwise until the precipitate formed was completely dissolved to obtain a mixed solution of metal ammonium salts. At room temperature, 85.4 g of dried spherical alumina having a diameter of 3 mm was completely impregnated in the above solution, and the solution was allowed to stand for 8 hours and substantially completely adsorbed.

(10) The impregnated support was placed in a tubular reactor and heated to 40° C., and was treated with the introduced carbon dioxide for 5 h, which was then slowly heated to 85° C. to dry for 8 h, calcined at 450° C. for 3 h, cooled, and then reduced at 100° C. with a mixed gas of 20 vol % of hydrogen and 80 vol % of nitrogen for 16 hours to obtain a supported catalyst A-3 containing 8.5 wt % of Ni, 4.5 wt % of Cu, 0.65 wt % of Pd, 0.5 wt % of Rh and 0.45 wt % of Mg.

EXAMPLE 4

(11) Into 84 ml of acetate solution containing 9.5 g of Ni, 5.0 g of Cu, 0.7 g of Pd, 0.4 g of Rh, 0.25 g of Ce, 0.15 g of Mo, 0.05 g of Ti and 0.05 g of Fe, ammonia water with a concentration of 30 wt % was added dropwise until the precipitate formed was completely dissolved to obtain a mixed solution of metal ammonium salts. At room temperature, 83.9 g of dried clover-type alumina having a diameter of 3 mm was completely impregnated in the above solution, and the solution was allowed to stand for 5 hours, and the solution was substantially completely adsorbed.

(12) The impregnated support was placed in a tubular reactor and heated to 30° C., and was treated with the introduced carbon dioxide for 4 h, which was then slowly heated to 90° C. to dry for 6 h, calcined at 300° C. for 8 h, cooled, and then reduced at 250° C. with a mixed gas of 5 vol % of hydrogen and 95 vol % of nitrogen for 24 hours to obtain a supported catalyst A-4 containing 9.5 wt % of Ni, 5.0 wt % of Cu, 0.7 wt % of Pd, 0.4 wt % of Rh, 0.24 wt % of Ce, 0.15 g of Mo, 0.05 g of Ti and 0.05 g of Fe.

EXAMPLE 5

(13) Into 86 ml of nitrate solution containing 12.0 g of Ni, 1.0 g of Cu, 0.8 g of Pd, 0.2 g of Rh, 0.1 g of Ce, 0.27 g of Mg, 0.03 g of Zn, and 0.1 g of Sn, ammonia water with a concentration of 25 wt % was added dropwise until the precipitate formed was completely dissolved to obtain a mixed solution of metal ammonium salts. At room temperature, 85.5 g of dried strip-shaped alumina having a diameter of 2 mm was completely impregnated in the above solution, and the solution was allowed to stand for 7 hours and substantially completely adsorbed.

(14) The impregnated support was placed in a tubular reactor and heated to 50° C., and was treated with the introduced carbon dioxide for 2 h, which was then slowly heated to 60° C. to dry for 12 h, calcined at 500° C. for 2 h, cooled, and then reduced at 300° C. with pure hydrogen for 4 hours to obtain a supported catalyst A-5 containing 12.0 wt % of Ni, 1.0 wt % of Cu, 0.8 wt % of Pd, 0.2 wt % of Rh, 0.1 wt % of Ce, 0.27 wt % of Mg, 0.03 wt % of Zn and 0.1 wt % of Sn.

EXAMPLE 6

(15) Into 88 ml of oxalate solution containing 5.0 g of Ni, 5.5 g of Cu, 1.0 g of Pd, 0.3 g of Rh, 0.05 g of Zr, 0.3 g of Mg, 0.07 g of Zn, 0.05 g of Fe and 0.03 g of Sn, ammonia water with a concentration of 25 wt % was added dropwise until the precipitate formed was completely dissolved to obtain a mixed solution of metal ammonium salts. At room temperature, 87.7 g of dried cylindrical alumina having a diameter of 3 mm was completely impregnated in the above solution, and the solution was allowed to stand for 6 hours and substantially completely adsorbed.

(16) The impregnated support was placed in a tubular reactor and heated to 20° C., and was treated with the introduced carbon dioxide for 10 h, which was then slowly heated to 85° C. to dry for 10 h, calcined at 400° C. for 4 h, cooled, and then reduced at 240° C. with pure hydrogen for 10 hours to obtain a supported catalyst A-6 containing 5.0 wt % of Ni, 5.5 wt % of Cu, 1.0 wt % of Pd, 0.3 wt % of Rh, 0.05 wt % of Zr, 0.3 wt % of Mg, 0.07 wt % of Zn, 0.05 wt % of Fe and 0.03 wt % of Sn.

EXAMPLE 7

(17) Into 87 ml of nitrate solution containing 4.0 g of Ni, 8.0 g of Cu, 0.6 g of Pd, 0.05 g of Rh, 0.1 g of Mg, 0.15 g of Ce, 0.08 g of Mo and 0.12 g of Fe, ammonia water with a concentration of 28 wt % was added dropwise until the precipitate formed was completely dissolved to obtain a mixed solution of metal ammonium salts. At room temperature, 86.9 g of dried strip-shaped alumina having a diameter of 3 mm was completely impregnated in the above solution, and the solution was allowed to stand for 6 hours and substantially completely adsorbed.

(18) The impregnated support was placed in a tubular reactor and heated to 35° C., and was treated with the introduced carbon dioxide for 7 h, slowly heated to 50° C. and dried for 24 h, calcined at 350° C. for 6 h, cooled, and then reduced at 220° C. with pure hydrogen for 10 hours to obtain a supported catalyst A-7 containing 7.5 wt % of Ni, 8.0 wt % of Cu, 0.6 wt % of Pd, 0.1 wt % of Rh, 0.1 wt % of Mg, 0.15 wt % of Ce, 0.08 wt % of Mo and 0.12 wt % of Fe.

EXAMPLE 8

(19) Into 88 ml of nitrate solution containing 1.0 g of Ni, 10.0 g of Cu, 0.3 g of Pd, 0.15 g of Rh, 0.2 g of Zr, 0.04 g of Ce, 0.05 g of Mo, 0.1 g of Ti and 0.06 g of Sn, ammonia water with a concentration of 25 wt % was added dropwise until the precipitate formed was completely dissolved to obtain a mixed solution of metal ammonium salts. At room temperature, 88.1 g of dried spherical alumina having a diameter of 2 mm was completely impregnated in the above solution, and the solution was allowed to stand for 7 hours and substantially completely adsorbed.

(20) The impregnated support was placed in a tubular reactor and heated to 35° C., and was treated with the introduced carbon dioxide for 6 h, which was then slowly heated to 120° C. to dry for 4 h, calcined at 600° C. for 5 h, cooled, and then reduced at 400° C. with pure hydrogen for 1 hours to obtain a supported catalyst A-8 containing 1.0 wt % of Ni, 10.0 wt % of Cu, 0.3 wt % of Pd, 0.15 wt % of Rh, 0.2 wt % of Zr, 0.04 wt % of Ce, 0.05 wt % of Mo, 0.1 wt % of Ti and 0.06 wt % of Sn.

EXAMPLE 9

(21) Into 84 ml of nitrate solution containing 15.0 g of Ni, 0.5 g of Cu, 0.1 g of Pd, 0.25 g of Rh, 0.3 g of Zr and 0.05 g of Mg, ammonia water with a concentration of 28 wt % was added dropwise until the precipitate formed was completely dissolved to obtain a mixed solution of metal ammonium salts. At room temperature, 83.8 g of dried spherical alumina having a diameter of 3 mm was completely impregnated in the above solution, and the solution was allowed to stand for 6 hours and substantially completely adsorbed.

(22) The impregnated support was placed in a tubular reactor and heated to 40° C., and was treated with the introduced carbon dioxide was introduced 8 h, which was then slowly heated to 85° C. to dry for 6 h, calcined at 200° C. for 12 h, cooled, and then reduced at 240° C. with a mixed gas of 10 vol % of hydrogen and 90 vol % of nitrogen for 12 hours to obtain a supported catalyst A-9 containing 15 wt % of Ni, 0.5 wt % of Cu, 0.1 wt % of Pd, 0.25 wt % of Rh, 0.3 wt % of Zr and 0.05 wt % of Mg.

EXAMPLE 10

(23) Into 84 ml of nitrate solution containing 6.0 g of Ni, 9.5 g of Cu, 0.4 g of Pd, 0.35 g of Rh and 0.05 Mg, ammonia water with a concentration of 25 wt % was added dropwise until the precipitate formed was completely dissolved to obtain a mixed solution of metal ammonium salts. At room temperature, 83.7 g of dried strip-shaped alumina having a diameter of 3 mm was completely impregnated in the above solution, and the solution was allowed to stand for 7 hours and substantially completely adsorbed.

(24) The impregnated support was placed in a tubular reactor and heated to 30° C., and was treated with the introduced carbon dioxide for 8 h, which was then slowly heated to 80° C. to dry for 6 h, calcined at 350° C. for 10 h, cooled, and then reduced at 200° C. with a mixed gas of 25 vol % of hydrogen and 75 vol % of nitrogen for 8 hours to obtain a supported catalyst A-10 containing 6 wt % of Ni, 9.5 wt % of Cu, 0.4 wt % of Pd, 0.35 wt % of Rh and 0.05 wt % of Mg.

EXAMPLE 11

(25) Into 86 ml of nitrate solution containing 7.0 g of Ni, 6.5 g of Cu, 0.75 g of Pd, 0.15 g of Rh, 0.15 g of Zr and 0.15 Mg, ammonia water with a concentration of 25 wt % was added dropwise until the precipitate formed was completely dissolved to obtain a mixed solution of metal ammonium salts. At room temperature, 85.3 g of dried clover-type alumina having a diameter of 3 mm was completely impregnated in the above solution, and the solution was allowed to stand for 5 hours and substantially completely adsorbed.

(26) The impregnated support was placed in a tubular reactor and heated to 35° C., and was treated with the introduced carbon dioxide for 7 h, slowly heated to 85° C. and dried for 6 h, calcined at 450° C. for 8 h, cooled, and then reduced at 300° C. with pure hydrogen for 4 hours to obtain a supported catalyst A-11 containing 7 wt % of Ni, 6.5 wt % of Cu, 0.75 wt % of Pd, 0.15 wt % of Rh, 0.15 wt % of Zr and 0.15 wt % of Mg.

EXAMPLE 12

(27) Into 85 ml of nitrate solution containing 8.0 g of Ni, 7.0 g of Cu, 0.25 g of Pd, 0.05 g of Rh, and 0.2 g of Zr, ammonia water with a concentration of 25 wt % was added dropwise until the precipitate formed was completely dissolved to obtain a mixed solution of metal ammonium salts. At room temperature, 84.5 g of dried cylindrical alumina having a diameter of 3 mm was completely impregnated in the above solution, and the solution was allowed to stand for 6 hours and substantially completely adsorbed.

(28) The impregnated support was placed in a tubular reactor and heated to 40° C., and was treated with the introduced carbon dioxide for 5 h, which was then slowly heated to 80° C. to dry for 12 h, calcined at 500° C. for 4 h, cooled, and then reduced at 350° C. with pure hydrogen for 5 hours to obtain a supported catalyst A-12 containing 8.0 wt % of Ni, 7.0 wt % of Cu, 0.25 wt % of Pd, 0.05 wt % of Rh and 0.2 wt % of Zr.

EXAMPLE 1-1

(29) The difference from Example 1 is that the metal salt solution was not further prepared into a metal ammonium salt solution but was directly used for adsorption of the support; in addition, the adsorbed wet support is directly subjected to drying, calcination and reduction treatment. The supported catalyst A-1-1 was obtained.

COMPARATIVE EXAMPLE 1

(30) The difference from Example 1 is that Rh is not contained in the mixed solution of the metal ammonium salts. The supported catalyst D-1 was obtained.

EXAMPLE 13

(31) Amination of Diethylene Glycol (M=106)

(32) A fixed-bed reactor was loaded with supported catalyst A-1 having a bulk volume of 30 ml. The reaction temperature was raised to 250° C. and the system pressure (absolute pressure, the same as follows) was raised to 10 MPa, then starting to feed the reactor. The space velocity of diethylene glycol was 0.3 h.sup.−1, the molar ratio of liquid ammonia/diethylene glycol was 60:1, and the molar ratio of hydrogen/diethylene glycol was 1:1. The reactants were distilled to remove excess ammonia and water, and analyzed by gas chromatography. The content of diaminodiethylene glycol was 99.6 wt %, the content of morpholine was 0.4 wt %, and monoaminodiethylene glycol and diethylene glycol were not detected. According to the sampling and analysis after 120 h, the result was unchanged. The conversion rate of the raw material was 100%, and the yield of the amination product was 99.6%.

EXAMPLE 14

(33) Amination of Dipropylene Glycol (M=134)

(34) A fixed-bed reactor was loaded with supported catalyst A-2 having a bulk volume of 30 ml. The reaction temperature was lowered to 210° C. and the system pressure was raised to 18 MPa, then starting to feed the reactor. The space velocity of dipropylene glycol was 0.75 h.sup.−1, the molar ratio of ammonia/dipropylene glycol was 30:1, and the molar ratio of hydrogen/dipropylene glycol was 0.05:1. The reactants were distilled to remove excess ammonia and water, and analyzed by gas chromatography. The content of diaminodipropylene glycol was 99.5 wt %, the content of dimethylmorpholine was 0.5 wt %, and monoaminodipropylene glycol and dipropylene glycol were not detected. According to the sampling and analysis after 150 h, the result was unchanged. The conversion rate of the raw material was 100%, and the yield of the amination product was 99.5%.

EXAMPLE 15

(35) Amination of Polyether Polyol PPG-230 (Difunctional, Molecular Weight of 230)

(36) A fixed-bed reactor was loaded with supported catalyst A-3 having a bulk volume of 30 ml. The reaction temperature was raised to 220° C. and the system pressure was raised to 15 MPa, then starting to feed the reactor. The space velocity of PPG-230 was 3 h.sup.−1, the molar ratio of liquid ammonia/PPG-230 was 6:1, and the molar ratio of hydrogen/PPG-230 was 0.5:1. The reactants were distilled to remove excess ammonia and water, and analyzed by gas chromatography. The content of diamination product was 99.8 wt %, the monoamination product and PPG-230 were not detected, and the content of dimethylmorpholine was 0.2 wt %. According to sampling and analysis after 200 h, the result was unchanged. The conversion rate of the raw material was 100%, and the yield of the amination product was 99.8%.

EXAMPLE 16

(37) Amination of Polyether Polyol T-2000 (Trifunctional, Molecular Weight of 2000)

(38) A fixed-bed reactor was loaded with supported catalyst A-4 having a bulk volume of 30 ml. The reaction temperature was lowered to 180° C., and the system pressure was raised to 12 MPa, then starting to feed the reactor. The space velocity of T-2000 was 0.5 h.sup.−1, the molar ratio of liquid ammonia/T-2000 was 20:1, and the molar ratio of hydrogen/T-2000 was 0.7:1. The reactants were distilled to remove excess ammonia and water, and analyzed by gas chromatography. The content of triamination product was 99.7 wt %, the diamination product, monoamination product and T-2000 were not detected, and the content of dimethylmorpholine was 0.3 wt %. According to the sampling and analysis after 200 h, the result was unchanged. The conversion rate of the raw material was 100%, and the yield of the amination product was 99.7%.

EXAMPLE 17

(39) Amination of Polyether Polyol D-5000 (Difunctional, Molecular Weight of 5000)

(40) A fixed-bed reactor was loaded with supported catalyst A-5 having a bulk volume of 30 ml. The reaction temperature was lowered to 150° C., and the system pressure was raised to 16 MPa, then starting to feed the reactor. The space velocity of D-5000 was 2.0 h.sup.−1, the molar ratio of liquid ammonia/D-5000 was 13:1, and the molar ratio of hydrogen/D-5000 was 0.2:1. The reactants were distilled to remove excess ammonia and water, and analyzed by gas chromatography. The content of diamination product was 99.9 wt %, the monoamination product and D-5000 were not detected, and the content of dimethylmorpholine was 0.1 wt %. According to the sampling and analysis after 150 h, the result was unchanged. The conversion rate of the raw material was 100%, and the yield of the amination product was 99.9%.

EXAMPLE 18

(41) Amination of Polyether Polyol T-403 (Trifunctional, Molecular Weight of 400)

(42) A fixed-bed reactor was loaded with supported catalyst A-6 having a bulk volume of 30 ml. The reaction temperature was raised to 225° C., and the system pressure was raised to 20 MPa, then starting to feed the reactor. The space velocity of T-403 was 1.5 h.sup.−1, the molar ratio of liquid ammonia/T-403 was 18:1, and the molar ratio of hydrogen/T-403 was 0.4:1. The reactants were distilled to remove excess ammonia and water, and analyzed by gas chromatography. The content of triamination product was 99.6 wt %, the diamination product, monoamination product and T-403 raw material were not detected, and the content of dimethylmorpholine was 0.4 wt %. According to the sampling and analysis after 150 h, the result was unchanged. The conversion rate of the raw material was 100%, and the yield of the amination product was 99.6%.

EXAMPLE 19

(43) Methylation of Polyether Polyol D-400 (Difunctional, Molecular Weight of 400)

(44) A fixed-bed reactor was loaded with supported catalyst A-7 having a bulk volume of 30 ml. The reaction temperature was lowered to 190° C., and the system pressure was raised to 15 MPa, then starting to feed the reactor. The space velocity of D-400 was 0.1 h.sup.−1, the molar ratio of methylamine/D-400 was 10:1, and the molar ratio of hydrogen/D-400 was 0.35:1. The reactants were distilled to remove excess methylamine and water, and analyzed by gas chromatography. The content of di(methylamination) product was 99.8 wt %, the mono(methylamination) product and D-400 raw material were not detected, and the content of others were 0.2 wt % totally. According to the sampling and analysis after 150 h, the result was unchanged. The conversion rate of the raw material was 100%, and the yield of the amination product was 99.8%.

EXAMPLE 20

(45) Dimethylation of Polyether Polyol D-2000 (Difunctional, Molecular Weight of 2000)

(46) A fixed-bed reactor was loaded with supported catalyst A-8 having a bulk volume of 30 ml. The reaction temperature was lowered to 230° C., and the system pressure was raised to 5 MPa, then starting to feed the reactor. The space velocity of D-2000 was 0.5 h.sup.−1, the molar ratio of dimethylamine/D-2000 was 15:1, and the molar ratio of hydrogen/D-2000 was 0.1:1. The reactants were distilled to remove excess dimethylamine and water, and analyzed by gas chromatography. The content of di(dimethylamination) product was 99.7 wt %, the mono(dimethylamination) product and D-2000 raw material were not detected, and the content of others were 0.3 wt % totally. According to the sampling and analysis after 150 h, the result was unchanged. The conversion rate of the raw material was 100%, and the yield of the amination product was 99.7%.

EXAMPLE 21

(47) Amination of Polyether Polyol D-600 (Difunctional, Molecular Weight of 600)

(48) A fixed-bed reactor was loaded with supported catalyst A-9 having a bulk volume of 30 ml. The reaction temperature was lowered to 165° C., and the system pressure was raised to 13 MPa, then starting to feed the reactor. The space velocity of D-600 was 0.6 If′, the molar ratio of liquid ammonia/D-600 was 16:1, and the molar ratio of hydrogen/D-600 was 0.25:1. The reactants were distilled to remove excess ammonia and water, and analyzed by gas chromatography. The content of diamination product was 99.9 wt %, the monoamination product and D-600 were not detected, and the content of dimethylmorpholine was 0.1 wt %. According to the sampling and analysis after 160 h, the result was unchanged. The conversion rate of the raw material was 100%, and the yield of the amination product was 99.9%.

EXAMPLE 22

(49) Methylation of Polyether Polyol D-600 (Difunctional, Molecular Weight of 600)

(50) A fixed-bed reactor was loaded with supported catalyst A-10 having a bulk volume of 30 ml. The reaction temperature was raised to 215° C., the system pressure was raised to 17 MPa, then starting to feed the reactor. The space velocity of D-600 was 0.6 h.sup.−1, the molar ratio of methylamine/D-600 was 19:1, and the molar ratio of hydrogen/D-600 was 0.15:1. The reactants were distilled to remove excess methylamine and water, and analyzed by gas chromatography. The content of di(methylamination) product was 99.8 wt %, the mono(methylamination) product and D-600 raw material were not detected, and the content of others were 0.2 wt % totally. According to the sampling and analysis after 180 h, the result was unchanged. The conversion rate of the raw material was 100%, and the yield of the amination product was 99.8%.

EXAMPLE 23

(51) Dimethylation of Polyether Polyol D-600 (Difunctional, Molecular Weight of 600)

(52) A fixed-bed reactor was loaded with supported catalyst A-11 having a bulk volume of 30 ml. The reaction temperature was lowered to 200° C., and the system pressure was raised to 18 MPa, then starting to feed the reactor. The space velocity of D-600 was 1.0 h.sup.−1, the molar ratio of dimethylamine/D-600 was 12:1, and the molar ratio of hydrogen/D-600 was 0.3:1. The reactant was distilled to remove excess dimethylamine and water, and analyzed by gas chromatography. The content of di(dimethylamination) product was 99.6 wt %, the mono(dimethylamination) product and D-600 raw material were not detected, and the content of others were 0.4 wt % totally. According to the sampling and analysis after 120 h, the result was unchanged. The conversion rate of the raw material was 100%, and the yield of the amination product was 99.6%.

EXAMPLE 24

(53) Amination of Polyether Polyol T-3000 (Trifunctional, Molecular Weight of 3000)

(54) A fixed-bed reactor was loaded with supported catalyst A-12 having a bulk volume of 30 ml. The reaction temperature was lowered to 180° C., and the system pressure was raised to 16 MPa, then starting to feed the reactor. The space velocity of T-3000 was 0.5 h.sup.−1, the molar ratio of liquid ammonia/T-3000 was 18:1, and the molar ratio of hydrogen/T-3000 was 0.35:1. The reactants were distilled to remove excess ammonia and water, and analyzed by gas chromatography. The content of diamination product was 99.7 wt %, the monoamination product and T-3000 raw material were not detected, and the content of dimethylmorpholine was 0.3 wt %. According to the sampling and analysis after 210 h, the result was unchanged. The conversion rate of the raw material was 100%, and the yield of the amination product was 99.7%.

EXAMPLE 25

(55) The difference from Example 13 was that the reaction was carried out using Catalyst A-1-1.

(56) Upon detection, the reaction results were as follows: the content of diaminodiglycol was 92.6 wt %, the content of morpholine was 2.1 wt %, the content of monoaminodiglycol was 5.3 wt %, and diglycol were not detected. According to the sampling and analysis after 120 h, the result was unchanged. The conversion rate of the raw material was 100%, and the yield of amination product was 90.6%.

COMPARATIVE EXAMPLE 2

(57) The difference from Example 13 was that the reaction was carried out using Catalyst D-1.

(58) Upon detection, the reaction results were as follows: the content of diaminodiglycol was 93.6 wt %, the content of morpholine was 1.4 wt %, the content of monoaminodiglycol was 5.0 wt %, and diglycol was not detected. According to the sampling and analysis after 120 h, the result was unchanged. The conversion rate of the raw material was 100%, and the yield of the amination product was 90.6%.

COMPARATIVE EXAMPLE 3

(59) The catalyst was prepared according to the method described in Example 1 of CN102336903A by reacting a NaOH solution with a Ni—Al alloy. By adjusting the amount of NaOH added, the prepared catalyst had a Ni content of 90 wt % and an Al content of 10 wt %. The catalyst was evaluated according to the amination of polyether polyol PPG-230 (difunctional, molecular weight of 230) in Example 15 of the present application. Using gas chromatography to analyze the reaction products: the content of diamination product was 90.5 wt %, the content of monoamination product was 2.0 wt %, the content of dimethylmorpholine was 2.5 wt %, and the content of raw material was 5.0 wt %. According to the sampling and analysis after 50 h, the result was unchanged. The conversion rate of the raw material was 95%, and the yield of the amination product was 92.5%.

COMPARATIVE EXAMPLE 4

(60) The catalyst was prepared according to the method described in Example 1 of CN102336903A by reacting a NaOH solution with a Ni—Al alloy. By adjusting the amount of NaOH added, the prepared catalyst had a Ni content of 95 wt % and an Al content of 5 wt %. The catalyst was evaluated according to the amination of polyether polyol T-403 (trifunctional, molecular weight of 400) in Example 18 of the present application. Using gas chromatography to analyze the reaction products: the content of triamination product was 85.6 wt %, the content of diamination product was 3.4 wt %, the content of monoamination product was 2.0 wt %, the content of dimethylmorpholine content was 1.0 wt %, and the content of raw material T-403 was 8.0 wt %. According to the sampling and analysis after 100 h, the result was unchanged. The conversion rate of the raw material was 92%, and the yield of the amination product was 91.0%.

(61) Conclusion: It can be seen from the above description that the specific combination of the active components of nickel, copper, palladium and rhodium in the catalyst of the present invention can greatly reduce by-products in the amination process of polyether polyol (eg, monoamino and/or bisamino by-products, dimethylmorpholine by-products generated by low molecular weight polyethers, etc.), especially under the conditions that the polyether polyol is completely converted, thereby greatly improving the selectivity and product yield of primary amines.