Method for producing hydride using unsaturated compound having carbon number of 4 as raw material

Abstract

The present invention relates to a method for producing a hydride having a carbon number of 4, comprising contacting, in liquid phase, an unsaturated compound having a carbon number of 4 as a raw material with a solid catalyst obtained by loading a metal element belonging to Groups 9 to 11 of the long periodic table on a support, thereby performing hydrogenation to produce a corresponding hydride having a carbon number of 4, wherein hydrogenation is performed in the presence of, as a solvent, a 1,4-butanediol having a nitrogen component concentration of 1 ppm by weight to 1 wt % in terms of nitrogen atom.

Claims

1. A method for producing a hydride having a carbon number of 4, comprising contacting, in liquid phase, an unsaturated compound having a total carbon number of 4 as a raw material with a solid catalyst obtained by loading a metal element belonging to Groups 9 to 11 of the long periodic table on a support, and performing hydrogenation to continuously produce a corresponding hydride having a carbon number of 4, wherein the hydrogenation is performed in the presence of a solvent comprising 1,4-butanediol having a nitrogen component concentration of 1 ppm by weight to 1 wt % in terms of nitrogen atom.

2. The method for producing a hydride having a carbon number of 4 according to claim 1, wherein the support is at least one member of silica and diatomaceous earth.

3. The method for producing a hydride having a carbon number of 4 according to claim 1, wherein the unsaturated compound having a carbon number of 4 is 1,4-dihydroxy-2-butene and the corresponding hydride having a carbon number of 4 is at least one member of 2, -hydroxytetrahydrofuran and 1,4-butanediol.

4. A method for producing 1,4-butanediol comprising flowing crude 1,4-butanediol containing an unsaturated compound having a total carbon number of 4 into a packed bed filled with a solid catalyst obtained by loading a metal element belonging to Groups 9 to 11 of the long periodic table on a support, and converting the unsaturated compound having a carbon number of 4 into a corresponding hydride having a carbon number of 4 to obtain 1,4-butanediol reduced in the concentration of an unsaturated compound having a carbon number of 4, wherein the concentration of a nitrogen component contained in the crude 1,4-butanediol in the packed bed is from 1 ppm by weight to 1 wt % in terms of nitrogen atom.

5. The method for producing a hydride having a carbon number of 4 according to claim 1, wherein the metal element belonging to Groups 9 to 11 of the long periodic table is a metal element belonging to Group 10 of the long periodic table.

6. The method according to claim 4, wherein the metal element belonging to Groups 9 to 11 of the long periodic table is a metal element belonging to Group 10 of the long periodic table.

7. The method for producing a hydride having a carbon number of 4 according to claim 5, wherein the metal element is nickel or palladium.

8. The method according to claim 6, wherein the metal element is nickel or palladium.

9. The method for producing a hydride having a carbon number of 4 according to claim 1, wherein the nitrogen component is an eluate of an anionic exchange resin having a primary amine polyethylene diamine skeleton having an NH bond.

10. The method according to claim 4, wherein the nitrogen component is an eluate of an anionic exchange resin having a primary amine polyethylene diamine skeleton having an NH bond.

11. The method for producing a hydride having a carbon number of 4 according to claim 1, wherein the unsaturated compound having a total carbon number of 4 is present in an amount of 0.1 to 30 wt %.

12. The method for producing a hydride having a carbon number of 4 according to claim 1, wherein the unsaturated compound having a total carbon number of 4 is present in an amount of 0.5 to 20 wt %.

13. The method for producing a hydride having a carbon number of 4 according to claim 1, wherein the solvent comprises from 50 to 99.99 wt % of 1,4 butanediol.

14. The method for producing a hydride having a carbon number of 4 according to claim 1, wherein the nitrogen component concentration is 3 to 500 ppm by weight in terms of nitrogen atom.

15. The method according to claim 4, wherein the nitrogen component concentration is 3 to 500 ppm by weight in terms of nitrogen atom.

16. The method for producing a hydride having a carbon number of 4 according to claim 1, wherein the nitrogen component is tributylamine.

17. The method according to claim 4, wherein the nitrogen component is tributylamine.

18. The method for producing a hydride having a carbon number of 4 according to claim 1, wherein the method is a continuous method.

Description

EXAMPLES

(1) The present invention is described in greater detail below by referring to Examples, but the present invention is not limited to these Examples as long as the gist of the present invention is observed. Incidentally, the analysis was performed by gas chromatography according to an internal standard method. At this time, n-dodecane was used as the internal standard, and GC-14A (column: DB-WAX) manufactured by Shimadzu Corporation was used for the gas chromatography.

Example 1

(2) A 500 cc-volume glass-made chromatograph tube with a jacket capable of flowing warm water and thereby heating the tube was filled with 300 cc of an anion exchange resin (Diaion (registered trademark), model: WA20, produced by Mitsubishi Chemical Corporation), and 1,4-butanediol containing 1,4-dihydroxy-2-butene was flowed from the top of the glass-made chromatograph tube at 215 g/hr. At this time, the temperature on contacting 1,4-butanediol with the anion exchange resin was 55 C., and the pressure was atmospheric pressure. Incidentally, the liquid after flowing contained a nitrogen component in an amount of 12 ppm by weight in terms of nitrogen atom, and both the chloride ion concentration and the sulfur concentration were below the detection limit.

(3) This 1,4-butanediol containing 10.65 wt % of 1,4-dihydroxy-2-butene after the anion exchange resin treatment was subjected to a hydrogenation reaction by using a flow reaction apparatus having a reactor volume of 120 cc. For the catalyst, 100 cc of a pellet-shaped diatomaceous earth-supported nickel-chromium catalyst (amount supported: 12 wt % of nickel, 1.5 wt % of chromium) was used. Here, the reactor of the flow reaction apparatus was filled with the solid catalyst by providing a filter manufactured by SUS, a glass bead bed, a solid catalyst bed, a glass bead bed, and a filter manufactured by SUS in this order.

(4) The reaction conditions of the hydrogenation reaction were set to a reaction temperature of 100 C. and a reaction pressure of 3.5 MPaG. Also, the flow rate of the reaction solution was set to 50 cc/h. The results are shown in Table 1.

Example 2

(5) 10 g of an anion exchange resin (Diaion (registered trademark), model: WA20, produced by Mitsubishi Chemical Corporation) was added to 100 g of 1,4-butanediol containing 10.0 wt % of 1,4-dihydroxy-2-butene (chloride ion concentration: 70 ppm, sulfur concentration: below detection limit, nitrogen concentration: below detection limit), and the mixture was stirred at room temperature for 2 hours.

(6) After separating the anion exchange resin by filtration, 4.0 g of the resulting solution (nitrogen concentration: 14 ppm) and 1.0 g of a pellet-shaped diatomaceous earth-supported nickel-chromium catalyst (amount supported: 12 wt % of nickel, 1.5 wt % of chromium) were put in a 50 cc glass vessel and heated in an oil bath at 140 C. for 5 hours.

(7) A 100 cc stainless steel-made autoclave was charged with 1 g of the heat-treated catalyst and 40.0 g of the 1,4-butanediol (nitrogen concentration: 14 ppm) containing 10.0 wt % of 1,4-dihydroxy-2-butene and after nitrogen purging, the hydrogen pressure was set to 0.99 MPaG. This autoclave was shaken in an oil bath at 140 C. for 4 hours.

(8) The solution after the completion of reaction was analyzed, as a result, the conversion rate of 1,4-dihydroxy-2-butene was 94.2%.

Example 3

(9) Tributylamine was added to 100 g of 1,4-butanediol containing 10.0 wt % of 1,4-dihydroxy-2-butene (chloride ion concentration: 70 ppm, sulfur concentration: below detection limit, nitrogen concentration: below detection limit) to have a concentration of 1 ppm in terms of nitrogen atom, and 4.0 g of this solution (nitrogen concentration: 1 ppm) and 1.0 g of a pellet-shaped diatomaceous earth-supported nickel-chromium catalyst (amount supported: 12 wt % of nickel, 1.5 wt % of chromium) were put in a 50 cc glass vessel and heated in an oil bath at 140 C. for 5 hours.

(10) A 100 cc stainless steel-made autoclave was charged with 1 g of the heat-treated catalyst and 40.0 g of the 1,4-butanediol containing tributylamine at a concentration of 1 ppm in terms of nitrogen atom and 10.0 wt % of 1,4-dihydroxy-2-butene and after nitrogen purging, the hydrogen pressure was set to 0.99 MPaG. This autoclave was shaken in an oil bath at 140 C. for 4 hours.

(11) The solution after the completion of reaction was analyzed, as a result, the conversion rate of 1,4-dihydroxy-2-butene was 97.6%.

Example 4

(12) The reaction was performed entirely in the same manner as in Example 3 except that 1,4-butanediol containing tributylamine at a concentration of 700 ppm in terms of nitrogen atom and 10.0 wt % of 1,4-dihydroxy-2-butene was used in place of 1,4-butanediol containing tributylamine at a concentration of 1 ppm in terms of nitrogen atom and 10.0 wt % of 1,4-dihydroxy-2-butene.

(13) The solution after the completion of reaction was analyzed, as a result, the conversion rate of 1,4-dihydroxy-2-butene was 98.2%.

Example 5

(14) Tributylamine was added to 100 g of 1,4-butanediol containing 10.0 wt % of 1,4-dihydroxy-2-butene (chloride ion concentration: 70 ppm, sulfur concentration: 2 ppm, nitrogen concentration: below detection limit) to have a concentration of 5 ppm in terms of nitrogen atom, and 4.0 g of this solution (nitrogen concentration: 1 ppm) and 1.0 g of a pellet-shaped silica-supported nickel catalyst (amount supported: 17 wt % of nickel, 55 wt % of nickel oxide) were put in a 50 cc glass vessel and heated in an oil bath at 140 C. for 5 hours.

(15) A 100 cc stainless steel-made autoclave was charged with 1 g of the heat-treated catalyst and 40.0 g of the 1,4-butanediol containing tributylamine at a concentration of 5 ppm in terms of nitrogen atom and 10.0 wt % of 1,4-dihydroxy-2-butene and after nitrogen purging, the hydrogen pressure was set to 0.99 MPaG. This autoclave was shaken in an oil bath at 140 C. for 1 hour.

(16) The solution after the completion of reaction was analyzed, as a result, the conversion rate of 1,4-dihydroxy-2-butene was 90.3%.

Example 6

(17) Tributylamine was added to 100 g of 1,4-butanediol containing 10.0 wt % of 1,4-dihydroxy-2-butene (chloride ion concentration: 70 ppm, sulfur concentration: 2 ppm, nitrogen concentration: below detection limit) to have a concentration of 5 ppm in terms of nitrogen atom, and 4.0 g of this solution (nitrogen concentration: 1 ppm) and 1.0 g of a pellet-shaped silica-supported palladium catalyst (amount supported: 2 wt % of palladium) were put in a 50 cc glass vessel and heated in an oil bath at 140 C. for 5 hours.

(18) A 100 cc stainless steel-made autoclave was charged with 1 g of the heat-treated catalyst and 40.0 g of the 1,4-butanediol containing tributylamine at a concentration of 5 ppm in terms of nitrogen atom and 10.0 wt % of 1,4-dihydroxy-2-butene and after nitrogen purging, the hydrogen pressure was set to 0.99 MPaG. This autoclave was shaken in an oil bath at 100 C. for 1 hour.

(19) The solution after the completion of reaction was analyzed, as a result, the conversion rate of 1,4-dihydroxy-2-butene was 36.8%.

Example 7

(20) Tributylamine was added to 100 g of 1,4-butanediol containing 10.0 wt % of methyl vinyl ketone (chloride ion concentration: below detection limit, sulfur concentration: 2 ppm, nitrogen concentration: below detection limit) to have a concentration of 5 ppm in terms of nitrogen atom, and 4.0 g of this solution (nitrogen concentration: 1 ppm) and 1.0 g of a pellet-shaped diatomaceous earth-supported nickel-chromium catalyst (amount supported: 12 wt % of nickel, 1.5 wt % of chromium)) were put in a 50 cc glass vessel and heated in an oil bath at 140 C. for 5 hours.

(21) A 100 cc stainless steel-made autoclave was charged with 1 g of the heat-treated catalyst and 40.0 g of the 1,4-butanediol containing tributylamine at a concentration of 5 ppm in terms of nitrogen atom and 2.0 wt % of methyl vinyl ketone and after nitrogen purging, the hydrogen pressure was set to 0.99 MPaG. This autoclave was shaken in an oil bath at 100 C. for 1 hour.

(22) The solution after the completion of reaction was analyzed, as a result, the conversion rate of 1,4-dihydroxy-2-butene was 38.6%.

Example 8

(23) Tributylamine was added to 100 g of 1,4-butanediol containing 10.0 wt % of crotonaldehyde (chloride ion concentration: below detection limit, sulfur concentration: 2 ppm, nitrogen concentration: below detection limit) to have a concentration of 5 ppm in terms of nitrogen atom, and 4.0 g of this solution (nitrogen concentration: 1 ppm) and 1.0 g of a pellet-shaped diatomaceous earth-supported nickel-chromium catalyst (amount supported: 12 wt % of nickel, 1.5 wt % of chromium)) were put in a 50 cc glass vessel and heated in an oil bath at 140 C. for 5 hours.

(24) A 100 cc stainless steel-made autoclave was charged with 1 g of the heat-treated catalyst and 40.0 g of the 1,4-butanediol containing tributylamine at a concentration of 5 ppm in terms of nitrogen atom and 2.0 wt % of crotonaldehyde and after nitrogen purging, the hydrogen pressure was set to 0.99 MPaG. This autoclave was shaken in an oil bath at 60 C. for 1 hour.

(25) The solution after the completion of reaction was analyzed, as a result, the conversion rate of 1,4-dihydroxy-2-butene was 63.4%.

Comparative Example 1

(26) The hydrogenation reaction was performed entirely under the same conditions as in Example 1 except that the raw material solution of 1,4-butanediol containing 1,4-dihydroxy-2-butene (chloride ion concentration: 70 ppm, sulfur concentration: below detection limit) was not flowed to the anion exchange resin. The results are shown in Table 1.

Comparative Example 2

(27) The reaction was performed entirely in the same manner as in Example 3 except that tributylamine was not added to 1,4-butanediol containing 10.0 wt % of 1,4-dihydroxy-2-butene (chloride ion concentration: 70 ppm, sulfur concentration: below detection limit, nitrogen concentration: below detection limit).

(28) The solution after the completion of reaction was analyzed, as a result, the conversion rate of 1,4-dihydroxy-2-butene was 90.2%.

Comparative Example 3

(29) The reaction was performed entirely in the same manner as in Example 5 except that tributylamine was not added to 1,4-butanediol containing 10.0 wt % of 1,4-dihydroxy-2-butene (chloride ion concentration: 70 ppm, sulfur concentration: 2 ppm, nitrogen concentration: below detection limit).

(30) The solution after the completion of reaction was analyzed, as a result, the conversion rate of 1,4-dihydroxy-2-butene was 88.2%.

Comparative Example 4

(31) The reaction was performed entirely in the same manner as in Example 6 except that tributylamine was not added to 1,4-butanediol containing 10.0 wt % of 1,4-dihydroxy-2-butene (chloride ion concentration: 70 ppm, sulfur concentration: 2 ppm, nitrogen concentration: below detection limit).

(32) The solution after the completion of reaction was analyzed, as a result, the conversion rate of 1,4-dihydroxy-2-butene was 30.5%.

Comparative Example 5

(33) The reaction was performed entirely in the same manner as in Example 7 except that tributylamine was not added to 1,4-butanediol containing methyl vinyl ketone (chloride ion concentration: below detection limit, sulfur concentration: 2 ppm, nitrogen concentration: below detection limit).

(34) The solution after the completion of reaction was analyzed, as a result, the conversion rate of methyl vinyl ketone was 34.1%.

Comparative Example 6

(35) The reaction was performed entirely in the same manner as in Example 8 except that tributylamine was not added to 1,4-butanediol containing crotonaldehyde (chloride ion concentration: below detection limit, sulfur concentration: 2 ppm, nitrogen concentration: below detection limit).

(36) The solution after the completion of reaction was analyzed, as a result, the conversion rate of crotonaldehyde was 56.5%.

Reference Example 1

(37) A 100 cc stainless steel-made autoclave was charged with 1 g of a pellet-shaped diatomaceous earth-supported nickel-chromium catalyst (amount supported: 12 wt % of nickel, 1.5 wt % of chromium) and 40.0 g of the 1,4-butanediol containing 10.0 wt % of 1,4-dihydroxy-2-butene (chloride ion concentration: 70 ppm, sulfur concentration: below detection limit, nitrogen concentration: below detection limit) and after nitrogen purging, the hydrogen pressure was set to 0.99 MPaG. This autoclave was shaken in an oil bath at 140 C. for 4 hours.

(38) The solution after the completion of reaction was analyzed, as a result, the conversion rate of 1,4-dihydroxy-2-butene was 98.2%.

Reference Example 2

(39) A 100 cc stainless steel-made autoclave was charged with 1.0 g of a pellet-shaped silica-supported nickel catalyst (amount supported: 17 wt % of nickel, 55 wt % of nickel oxide) and 40.0 g of 1,4-butanediol containing 10.0 wt % of 1,4-dihydroxy-2-butene (chloride ion concentration: 70 ppm, sulfur concentration: below detection limit, nitrogen concentration: below detection limit) and after nitrogen purging, the hydrogen pressure was set to 0.99 MPaG. This autoclave was shaken in an oil bath at 140 C. for 1 hour.

(40) The solution after the completion of reaction was analyzed, as a result, the conversion rate of 1,4-dihydroxy-2-butene was 97.6%.

Reference Example 3

(41) A 100 cc stainless steel-made autoclave was charged with 1.0 g of a pellet-shaped silica-supported palladium catalyst (amount supported: 2 wt % of palladium) and 40.0 g of 1,4-butanediol containing 10.0 wt % of 1,4-dihydroxy-2-butene (chloride ion concentration: 70 ppm, sulfur concentration: below detection limit, nitrogen concentration: below detection limit) and after nitrogen purging, the hydrogen pressure was set to 0.99 MPaG. This autoclave was shaken in an oil bath at 100 C. for 1 hour.

(42) The solution after the completion of reaction was analyzed, as a result, the conversion rate of 1,4-dihydroxy-2-butene was 42.7%.

Reference Example 4

(43) A 100 cc stainless steel-made autoclave was charged with 1 g of a pellet-shaped diatomaceous earth-supported nickel-chromium catalyst (amount supported: 12 wt % of nickel, 1.5 wt % of chromium) and 40.0 g of 1,4-butanediol containing 2.0 wt % of methyl vinyl ketone (chloride ion concentration: 70 ppm, sulfur concentration: 2 ppm, nitrogen concentration: below detection limit) and after nitrogen purging, the hydrogen pressure was set to 0.99 MPaG. This autoclave was shaken in an oil bath at 100 C. for 1 hour.

(44) The solution after the completion of reaction was analyzed, as a result, the conversion rate of methyl vinyl ketone was 41.1%.

Reference Example 5

(45) A 100 cc stainless steel-made autoclave was charged with 1 g of a pellet-shaped diatomaceous earth-supported nickel-chromium catalyst (amount supported: 12 wt % of nickel, 1.5 wt % of chromium) and 40.0 g of 1,4-butanediol containing 2.0 wt % of crotonaldehyde (chloride ion concentration: 70 ppm, sulfur concentration: 2 ppm, nitrogen concentration: below detection limit) and after nitrogen purging, the hydrogen pressure was set to 0.99 MPaG. This autoclave was shaken in an oil bath at 60 C. for 1 hour.

(46) The solution after the completion of reaction was analyzed, as a result, the conversion rate of crotonaldehyde was 65.5%.

(47) TABLE-US-00001 TABLE 1 Raw Material/14BG Solution Treatment of Raw Material Raw Material Cl Raw Material S N Concentration Concentration Concentration after Treatment Unsaturated Compound ppm ppm N Compound ppm Heat Treatment of Catalyst Example 1 1,4-butenediol 70 below DT WA20 12 100 C., 300 hour Example 2 1,4-butenediol 70 below DT WA20 14 140 C., 5 h heating Example 3 1,4-butenediol 70 below DT tributylamine 1 140 C., 5 h heating Example 4 1,4-butenediol 70 below DT tributylamine 700 140 C., 5 h heating Example 5 1,4-butenediol 70 2 tributylamine 5 140 C., 5 h heating Example 6 1,4-butenediol 70 2 tributylamine 5 140 C., 5 h heating Example 7 methyl vinyl ketone 2 tributylamine 5 140 C., 5 h heating Example 8 crotonaldehyde 2 tributylamine 5 140 C., 5 h heating Comparative 1,4-butenediol 70 below DT below DT 100 C., 300 hours Example 1 Comparative 1,4-butenediol 70 below DT below DT 140 C., 5 h heating Example 2 Comparative 1,4-butenediol 70 2 below DT 140 C., 5 h heating Example 3 Comparative 1,4-butenediol 70 2 below DT 140 C., 5 h heating Example 4 Comparative methyl vinyl ketone 2 below DT 140 C., 5 h heating Example 5 Comparative crotonaldehyde 2 below DT 140 C., 5 h heating Example 6 Reference 1,4-butenediol 70 below DT below DT none (fresh catalyst) Example 1 Reference 1,4-butenediol 70 2 below DT none (fresh catalyst) Example 2 Reference 1,4-butenediol 70 2 below DT none (fresh catalyst) Example 3 Reference methyl vinyl ketone 2 below DT none (fresh catalyst) Example 4 Reference crotonaldehyde 2 below DT none (fresh catalyst) Example 5 Evaluation Conditions Concentration of Reaction Reaction Reaction Conversion Raw Material Temperature Pressure Time Rate Catalyst Reaction Mode (BG solvent) C. MPaG hr (%) Example 1 Ni/diatomaceous earth flow 10 wt % 100 3.5 2 98.3 Example 2 Ni/diatomaceous earth batch 10 wt % 140 0.99 4 94.2 Example 3 Ni/diatomaceous earth batch 10 wt % 140 0.99 4 97.6 Example 4 Ni/diatomaceous earth batch 10 wt % 140 0.99 4 98.2 Example 5 Ni/SiO2 batch 10 wt % 140 0.99 1 90.3 Example 6 2% Pd/SiO2 batch 10 wt % 100 0.99 1 36.8 Example 7 Ni/diatomaceous earth batch 2 wt % 100 0.99 1 38.6 Example 8 Ni/diatomaceous earth batch 2 wt % 60 0.99 1 63.4 Comparative Ni/diatomaceous earth flow 10 wt % 100 3.5 2 76.3 Example 1 Comparative Ni/diatomaceous earth batch 10 wt % 140 0.99 4 90.2 Example 2 Comparative Ni/SiO2 batch 10 wt % 140 0.99 1 88.2 Example 3 Comparative 2% Pd/SiO2 batch 10 wt % 100 0.99 1 30.5 Example 4 Comparative Ni/diatomaceous earth batch 2 wt % 100 0.99 1 34.1 Example 5 Comparative Ni/diatomaceous earth batch 2 wt % 60 0.99 1 56.5 Example 6 Reference Ni/diatomaceous earth batch 10 wt % 140 0.99 4 98.2 Example 1 Reference Ni/SiO2 batch 10 wt % 140 0.99 1 97.6 Example 2 Reference 2% Pd/SiO2 batch 10 wt % 100 0.99 1 42.7 Example 3 Reference Ni/diatomaceous earth batch 2 wt % 100 0.99 1 41.1 Example 4 Reference Ni/diatomaceous earth batch 2 wt % 60 0.99 1 65.5 Example 5 *DT: detection limit

(48) According to the present invention, the catalyst life can be improved when a nitrogen-containing component exists, as compared with the case where a nitrogen-containing component is not present.

(49) While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof. This application is based on a Japanese patent application filed on Jul. 20, 2011 (Application No. 2011-159105), a Japanese patent application filed on Jul. 28, 2011 (Application No. 2011-165937) and a Japanese patent application filed on Nov. 2, 2011 (Application No. 2011-241574), the content thereof being incorporated herein by reference.