Preparation method of 1, 2, 4-butantriol

Abstract

The invention discloses a preparation method of 1, 2, 4-butantriol. The preparation method comprises the following steps: carrying out epoxidation reaction on 2-butene-1, 4-diol to generate 2, 3-epoxy-1, 4-butanediol, and carrying out catalytic hydrogenolysis on the 2, 3-epoxy-1, 4-butanediol to obtain 1, 2, 4-butantriol, and is characterized in that a catalyst for the epoxidation reaction is supported heteropolytungstate, and a catalyst for hydrogenolysis is carbon-supported palladium hydroxide. Compared with the prior art, the method has the advantages that the catalyst can be efficiently separated and reused, the production cost is reduced, and the catalytic hydrogenolysis condition is milder.

Description

Technical Field

[0001] The present invention relates to a method for preparing 1,2,4 - butanetriol. Background Art

[0002] 1,2,4 - butanetriol is an important chemical and chemical intermediate, which is widely used in the fields of military industry, medicine, agriculture, cosmetics, papermaking, polymer materials, tobacco, etc.

[0003] Currently, the chemical synthesis method of 1,2,4 - butanetriol is mainly to obtain 2,3 - epoxy - 1,4 - butanediol through the epoxidation reaction of 2 - butene - 1,4 - diol, and then the product 2,3 - epoxy - 1,4 - butanediol is catalytically hydrogenolyzed to obtain the target product. The reaction is as follows: .

[0004] Dalian Institute of Chemical Physics (CN1803747A) reported the use of phosphotungstic heteropolyacid as the catalyst for the above epoxidation reaction, and the combination of Ranny Ni and Pd / C as the catalyst for the above hydrogenolysis reaction, so as to obtain higher epoxidation catalytic efficiency and milder hydrogenolysis conditions. The homogeneous catalyst system has problems such as difficult product separation, and difficult separation and reuse of the catalyst. Summary of the Invention

[0005] The present invention improves the above - mentioned existing method for preparing 1,2,4 - butanetriol to achieve the efficient recycling of heteropolyacid and milder hydrogenolysis conditions.

[0006] To achieve the above object, the present invention adopts the following technical solutions: A method for preparing 1,2,4 - butanetriol, including the epoxidation reaction of 2 - butene - 1,4 - diol to generate 2,3 - epoxy - 1,4 - butanediol, and then the catalytic hydrogenolysis of 2,3 - epoxy - 1,4 - butanediol to obtain 1,2,4 - butanetriol, characterized in that: the catalyst for the epoxidation reaction is a supported tungsten heteropolyacid salt, and the catalyst for the hydrogenolysis is palladium hydroxide supported on carbon.

[0007] Preferably, the tungsten heteropolyacid salt is [π - C5H5NC 16 H 33 3[P(W3O 10 )4], [π - C5H5NC 16 H 33 4[Si(W3O 10 )4], [π - C5H5NC 16 H 33 3[PO4(WO3)4], [(C 18 H 37)2N(CH3)2]3[P(W3O 10 )4], [(C 18 H 37 )2N(CH3)2]4[Si(W3O 10 )4] or [(C 18 H 37 )2N(CH3)2]3[PO4(WO3)4].

[0008] Preferably, the carrier is alumina, silica or titanium silicalite.

[0009] A method for preparing 2,3-epoxy-1,4-butanediol, comprising reacting 2-butene-1,4-diol with an oxidant in the presence of a catalytic amount of a supported tungsten heteropolyacid salt to produce 2,3-epoxy-1,4-butanediol.

[0010] Preferably, the tungsten heteropolyacid salt is [π-C5H5NC 16 H 33 3[P(W3O 10 )4], [π-C5H5NC 16 H 33 4[Si(W3O 10 )4], [π-C5H5NC 16 H 33 3[PO4(WO3)4], [(C 18 H 37 )2N(CH3)2]3[P(W3O 10 )4], [(C 18 H 37 )2N(CH3)2]4[Si(W3O 10 )4] or [(C 18 H 37 )2N(CH3)2]3[PO4(WO3)4].

[0011] Preferably, the carrier is alumina, silica or titanium silicalite.

[0012] Preferably, the amount of the supported tungsten heteropolyacid salt used is 5-25 wt.% of the total feed amount, more preferably 8-20 wt.%.

[0013] Preferably, the oxidant is hydrogen peroxide or oxygen.

[0014] Preferably, an organic tertiary amine is added as a co-catalyst to the reaction.

[0015] More preferably, the organic tertiary amine is N-methylmorpholine, N-methyldiethanolamine, pyridine or triethylamine.

[0016] Preferably, the mass ratio of the supported tungstophosphoric acid salt to the cocatalyst is 1:0.1 - 0.3.

[0017] Preferably, the solvent for the reaction is dichloromethane, 1,2-dichloroethane, isopropanol or ethanol.

[0018] Preferably, the reaction temperature is 30 - 60 °C.

[0019] Preferably, the reaction time is 3 - 5 h.

[0020] A method for preparing 1,2,4-butanetriol, comprising reacting 2,3-epoxy-1,4-butanediol with hydrogen under the catalysis of a catalytic amount of palladium hydroxide on carbon to obtain 1,2,4-butanetriol.

[0021] Preferably, the reaction temperature is 40 - 160 °C and the reaction pressure is 4 - 8 MPa.

[0022] Preferably, the amount of palladium hydroxide on carbon used is 1 - 6 wt.% of the total feed amount, and more preferably 2 - 5 wt.%.

[0023] Preferably, the solvent for the reaction is 1,2-dichloroethane, methanol, ethanol or isopropanol.

[0024] Preferably, the reaction time is 2 - 8 h.

[0025] Compared with the prior art, the method of the present invention can enable efficient separation and reuse of the catalyst, reduce production costs, and the catalytic hydrogenolysis conditions are milder. Detailed implementation mode

[0026] The technical solution of the present invention will be further described in detail below in conjunction with the embodiments.

[0027] Example 1 Preparation process of supported heteropolyacid salt [π-C5H5NC 16 H 33 3[P(W3O 10 )4]@Al2O3: Add phosphotungstic acid (36 g, 12.5 mmol) to 150 ml of deionized water, dropwise add a dichloromethane solution (200 ml) of cetylpyridinium chloride (9.42 g, 25 mmol), react at room temperature for 1 hour, then add mesoporous Al2O3 (37.5 g, 0.368 mol) and react at room temperature for another 4 hours. After filtration, dry to obtain a light yellow solid.

[0028] Comparative Example 1 Supported heteropolyacid salt [π-C5H5NC 16 H 33 3[P(W3O 10 )4]@SiO2 was prepared in the same manner as in Example 1, except that mesoporous Al2O3 was replaced with SiO2.

[0029] Example 2 Supported heteropolyacid salt [(C 18 H 37 )2N(CH3)2]3[P(W3O 10 )4]@Al2O3 was prepared in the same manner as in Example 1, except that cetylpyridinium chloride was replaced with dioctadecyldimethylammonium chloride.

[0030] Example 3 Preparation process of supported heteropolyacid salt [π-C5H5NC 16 H 33 3[PO4(WO3)4]@Al2O3: Add tungstic acid (12.5 g, 50 mmol) to 30% aqueous hydrogen peroxide solution (50 ml), heat to 60 °C with vigorous stirring until tungstic acid is completely dissolved to obtain a pale yellow solution; after the solution is cooled to room temperature, add 15 ml of 80% H3PO4 (1.6 g, 12.5 mmol) aqueous solution, and dilute to 150 ml with deionized water. At the same time, add mesoporous Al2O3 (37.5 g, 0.368 mol) and react at room temperature for 30 minutes; add a dichloromethane solution (200 ml) of cetylpyridinium chloride (9.42 g, 25 mmol), and react at room temperature for another 4 hours. After filtration and drying, a pale yellow solid is obtained.

[0031] Example 4 In a 250 mL three-necked flask, successively add [π-C5H5NC 16 H 33 3[P(W3O 10 )4]@Al2O3 (10.9 g), 2-butene-1,4-diol (24 g, 0.272 mol), N-methylmorpholine (2.0 g) and dichloromethane (50 ml), start stirring, and heat to 40 °C. Add 44.8 g of 30% hydrogen peroxide dropwise, react at 40 °C for 4 h, and analyze the reaction solution by gas chromatography. The conversion rate of 2-butene-1,4-diol is 91%, and the selectivity of 2,3-epoxy-1,4-butanediol is 90%.

[0032] Comparative Example 2 The reaction conditions were the same as in Example 4, except that [π-C5H5NC 16 H 33 3[P(W3O 10)4]@SiO2 was used as the catalyst, the conversion rate of 2-butene-1,4-diol was 68%, and the selectivity of 2,3-epoxy-1,4-butanediol was 80%.

[0033] Example 5 The reaction conditions were the same as those in Example 4. The difference was that [(C 18 H 37 )2N(CH3)2]3[P(W3O 10 )4]@Al2O3 was used as the catalyst, the conversion rate of 2-butene-1,4-diol was 95%, and the selectivity of 2,3-epoxy-1,4-butanediol was 88%.

[0034] Example 6 The reaction conditions were the same as those in Example 4. The difference was that [π-C5H5NC 16 H 33 3[PO4(WO3)4]@Al2O3 was used as the catalyst, the conversion rate of 2-butene-1,4-diol was 94%, and the selectivity of 2,3-epoxy-1,4-butanediol was 88%.

[0035] Examples 7 to 22 The operation procedures of Examples 7 to 22 were the same as those in Example 4, and the reaction conditions were adjusted according to Table 1. The reaction results are shown in Table 2.

[0036] Table 1 [π-C5H5NC 16 H 33 3[P(W3O 10 )4]@Al2O3 catalytic epoxidation reaction conditions Example Catalyst (g) Reaction Temperature (°C) Oxidizing Agent Reaction Time (h) Additive Solvent 7 12.5 40 30% Hydrogen Peroxide 4 NMM <![CDATA[CH2Cl2]]> 8 18 40 30% Hydrogen Peroxide 4 NMM <![CDATA[CH2Cl2]]> 9 25 40 30% Hydrogen Peroxide 4 NMM <![CDATA[CH2Cl2]]> 10 18 30 30% Hydrogen Peroxide 4 NMM <![CDATA[CH2Cl2]]> 11 18 50 30% Hydrogen Peroxide 4 NMM <![CDATA[CH2Cl2]]> 12 18 40 50% Hydrogen Peroxide 4 NMM <![CDATA[CH2Cl2]]> 13 18 40 <![CDATA[O2 (atmospheric pressure)]]> 4 NMM <![CDATA[CH2Cl2]]> 14 18 40 <![CDATA[O2 (1 MPa)]]> 4 NMM <![CDATA[CH2Cl2]]> 15 18 40 30% Hydrogen Peroxide 3 NMM <![CDATA[CH2Cl2]]> 16 18 40 30% Hydrogen Peroxide 5 NMM <![CDATA[CH2Cl2]]> 17 18 40 30% Hydrogen Peroxide 4 MEDA <![CDATA[CH2Cl2]]> 18 18 40 30% Hydrogen Peroxide 4 Py <![CDATA[CH2Cl2]]> 19 18 40 30% Hydrogen Peroxide 4 <![CDATA[Et3N]]> <![CDATA[CH2Cl2]]> 20 18 40 30% Hydrogen Peroxide 4 NMM DCE 21 18 40 30% Hydrogen Peroxide 4 NMM Isopropanol 22 18 40 30% Hydrogen Peroxide 4 NMM <![CDATA[C2H5OH]]>

[0037] Note: NMM is N-methylmorpholine, MEDA is N-methyldiethanolamine, Py is pyridine, Et3N is triethylamine, and DCE is 1,2-dichloroethane.

[0037] Table 2 [π-C5H5NC 16 H 33 3[P(W3O 10 )4]@Al2O3 catalytic epoxidation reaction results Example Conversion of 2-Butene-1,4-diol Selectivity of 2,3-Epoxy-1,4-butanediol 7 93% 90% 8 97% 91% 9 97% 90% 10 85% 88% 11 98% 85% 12 97% 86% 13 88% 90% 14 90% 90% 15 87% 88% 16 98% 86% 17 97% 88% 18 96% 85% 19 94% 87% 20 94% 88% 21 93% 89% 22 89% 90%

[0039] Example 23 After the reaction in Example 8 was completed, the mixture was allowed to stand and separate. The upper layer was the product phase, and the lower layer catalyst phase was left in the reaction kettle for repeated use. The reaction conditions for repeated use were the same as those in Example 8, and the reaction effects are shown in Table 3.

[0038] Table 3 [π-C5H5NC 16 H 33 3[P(W3O10 )4]@Recycling effect of Al2O3 Number of Uses Conversion of 2-Butene-1,4-diol Selectivity of 2,3-Epoxy-1,4-butanediol 1 time 97% 91% 2 times 97% 90% 3 times 98% 90% 4 times 96% 90% 5 times 95% 89%

[0039] Example 24 Add 2,3-epoxy-1,4-butanediol (5.2 g, 0.05 mol), 5% Pd(OH)2 / C (1.32 g) and isopropanol (50 ml) into a 100 ml high-pressure reactor. Replace with H2 three times. The pressure of the system under equilibrium state is 6 MPa. React at 80 °C for 8 h and then cool. Filter off the catalyst. Distill the filtrate under reduced pressure to obtain 1,2,4-butanetriol. The conversion rate of 2,3-epoxy-1,4-butanediol is 88%, and the selectivity of 1,2,4-butanetriol is 90%.

[0040] Examples 25 - 36 The operation procedures of Examples 25 - 36 are the same as that of Example 24. The specific reaction conditions are adjusted according to Table 4, and the reaction results are shown in Table 5.

[0041] Table 4 Reaction conditions for catalytic hydrogenolysis with Pd(OH)2 / C Example Catalyst, Dosage Reaction Temperature (°C) Reaction Pressure (MPa) Reaction Time (h) Solvent 25 <![CDATA[5% Pd(OH)2 / C, 0.66 g]]> 100 6 8 Isopropanol 26 <![CDATA[10% Pd(OH)2 / C, 0.66 g]]> 100 6 8 Isopropanol 27 <![CDATA[5% Pd(OH)2 / C, 2.64 g]]> 100 6 8 Isopropanol 28 <![CDATA[5% Pd(OH)2 / C, 2.64 g]]> 80 6 8 Isopropanol 29 <![CDATA[5% Pd(OH)2 / C, 2.64 g]]> 120 6 8 Isopropanol 30 <![CDATA[5% Pd(OH)2 / C, 2.64 g]]> 140 6 8 Isopropanol 31 <![CDATA[5% Pd(OH)2 / C, 2.64 g]]> 100 8 8 Isopropanol 32 <![CDATA[5% Pd(OH)2 / C, 2.64 g]]> 100 6 4 Isopropanol 33 <![CDATA[5% Pd(OH)2 / C, 2.64 g]]> 100 6 10 Isopropanol 34 <![CDATA[5% Pd(OH)2 / C, 2.64 g]]> 100 6 12 Isopropanol 35 <![CDATA[5% Pd(OH)2 / C, 2.64 g]]> 100 6 8 Ethanol 36 <![CDATA[5% Pd(OH)2 / C, 2.64 g]]> 100 6 8 DCE

[0042] Table 5 Reaction results for catalytic hydrogenolysis with Pd(OH)2 / C Example Conversion of 2,3-Epoxy-1,4-butanediol Selectivity of 1,2,4-Butanetriol 25 85% 90% 26 90% 92% 27 95% 90% 28 84% 91% 29 90% 88% 30 92% 89% 31 92% 90% 32 85% 90% 33 92% 92% 34 92% 88% 35 90% 90% 36 88% 88%

[0043] Example 37 After the reaction in Example 33 is completed, press out the reaction solution from the dip tube through the filter. The catalyst remains in the reactor for repeated use. The repeated use conditions are the same as those in Example 33, and the reaction results are shown in Table 6.

[0044] Table 6 Recycling effect of Pd(OH)2 / C Number of Uses Conversion of 2,3-Epoxy-1,4-butanediol Selectivity of 1,2,4-Butanetriol 1 time 92% 92% 2 times 92% 91% 3 times 92% 92% 4 times 92% 92% 5 times 90% 90% 6 times 87% 90% .

[0045] Finally, it should be noted that the above are only the preferred embodiments of the present invention and are not used to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements for some of the technical features. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A method for preparing 1,2,4 - butanetriol, which includes the epoxidation reaction of 2 - butene - 1,4 - diol to generate 2,3 - epoxy - 1,4 - butanediol, and then the catalytic hydrogenolysis of 2,3 - epoxy - 1,4 - butanediol to obtain 1,2,4 - butanetriol, characterized in that: The catalyst for the epoxidation reaction is a supported tungstophosphoric acid salt, and the catalyst for the hydrogenolysis is palladium hydroxide supported on carbon.

2. The preparation method according to claim 1, characterized in that: The tungstophosphoric acid salt is [π-C5H5NC 16 H 33 3[P(W3O 10 )4], [π-C5H5NC 16 H 33 4[Si(W3O 10 )4], [π-C5H5NC 16 H 33 3[PO4(WO3)4], [(C 18 H 37 )2N(CH3)2]3[P(W3O 10 )4], [(C 18 H 37 )2N(CH3)2]4[Si(W3O 10 )4] or [(C 18 H 37 )2N(CH3)2]3[PO4(WO3)4].

3. The preparation method according to claim 1, characterized in that: The carrier belongs to alumina, silica or titanium silicalite.

4. A method for preparing 2,3-epoxy-1,4-butanediol, which comprises reacting 2-butene-1,4-diol with an oxidant under the catalysis of a catalytic amount of supported tungstophosphoric acid salt to produce 2,3-epoxy-1,4-butanediol.

5. The preparation method according to claim 4, characterized in that: The tungstophosphoric acid salt is [π-C5H5NC 16 H 33 3[P(W3O 10 )4], [π-C5H5NC 16 H 33 4[Si(W3O 10 )4], [π-C5H5NC 16 H 33 3[PO4(WO3)4], [(C 18 H 37 )2N(CH3)2]3[P(W3O 10 )4], [(C 18 H 37 )2N(CH3)2]4[Si(W3O 10 )4] or [(C 18 H 37 )2N(CH3)2]3[PO4(WO3)4].

6. The preparation method according to claim 4, characterized in that: The carrier belongs to alumina, silica or titanium silicalite.

7. The preparation method according to claim 4, characterized in that: The oxidant is hydrogen peroxide or oxygen.

8. The preparation method according to claim 4, characterized in that: An organic tertiary amine is added as a co-catalyst to the reaction. Preferably, the organic tertiary amine is N-methylmorpholine, N-methyldiethanolamine, pyridine or triethylamine.

9. A method for preparing 1,2,4-butanetriol, which comprises reacting 2,3-epoxy-1,4-butanediol with hydrogen under the catalysis of a catalytic amount of palladium hydroxide supported on carbon to obtain 1,2,4-butanetriol.

10. The preparation method according to claim 9, characterized in that: The reaction temperature is 40~160 °C, and the reaction pressure is 4~8 MPa.