METHOD FOR PREPARING 1,3-PROPANEDIOL BY COUPLING ETHYLENE OXIDE WITH SYNGAS

Abstract

A catalytic reaction of ethylene oxide (EO) coupling with syngas to produce 1,3-propanediol (1,3-PDO) is disclosed. The catalytic reaction of EO, carbon monoxide and the alcohol uses a N,O-ligand coordinated metal complex catalyst. The reaction is carried out in an organic solvent in the presence of an additive at the temperature of 30-190 C. and the CO pressure of 1-150 atm for 0.1-200 h to prepare 3-hydroxypropinate (3HP). The catalytic reaction of 3HP with dihydrogen uses a copper-containing mixed metal silicon oxide catalyst with a molecular formula of M.sub.uCu.sub.vSi.sub.yO.sub.z. The reaction is carried out at 80-400 C. and 20-150 atm for 0.1-200 h to prepare the 1,3-PDO. The yield of the 1,3-PDO can reach to 73%. The alcohol byproduct generated in the second step catalytic hydrogenation reaction can be recycled to use for the first step catalytic reaction by the ring opening-carbonylation-esterification.

Claims

1. A method for preparing 1,3-propanediol (1,3-PDO) by coupling ethylene oxide (EO) with syngas, comprising: S1: subjecting EO, carbon monoxide and an alcohol molecule to ring opening-carbonylation-esterification to prepare 3-hydroxypropionate (3HP); S2: hydrogenating the obtained 3HP to produce 1,3-PDO; wherein the two steps use different catalysts, and an alcohol molecule byproduct generated in the second step can be used for the first step reaction.

2. The method according to claim 1, wherein S1 specifically comprises: a) subjecting EO, carbon monoxide and alcohol to reaction in an organic solvent in the presence of a catalyst and an additive under required reaction conditions as settled temperature and pressure and controlled time; b) conducting phase separation of the species obtained from the reaction system after reaction is completed, where an aqueous phase, an organic phase and a precipitate phase are formed and the 3HP product is maximally retained in the organic phase; c) collecting the organic phase, from which the 3HP product is further subject to separation for use, or alternatively the 3HP-containing organic solution is for direct use in the subsequent reaction.

3. The method according to claim 1, wherein S2 specifically comprises: d) subjecting the 3HP separated from 2-c) to reaction with dihydrogen in an organic solvent in the presence of a catalyst at settled temperature and pressure within controlled time; or subjecting the 3HP-containing organic solution obtained in 2-c) to reaction with dihydrogen in the presence of a catalyst at settled temperature and pressure in controlled time; and e) separating the species obtained from the reaction system, wherein 1,3-PDO, the alcohol byproduct and the other organic components are obtained respectively, and the alcohol byproduct can be recycled for 2-a).

4. The method according to claim 1, wherein in 2-a), the catalyst is a metal ligand complex, specifically, a N,O-ligand coordinated metal complex with the following structure character: ##STR00023## wherein, a metal M represents one of nickel, cobalt, ruthenium, rhodium, palladium, platinum, osmium, iridium, iron, copper and chromium, preferably one of cobalt, ruthenium, rhodium and iridium; a N,O ligand represents an organic group with N and O as the coordinating atom; N and O both have a -bond interaction with the metal M; B represents a bridging organic group connecting two N,O ligands by bonding to the nitrogen atom in the two ligands; X represents an anionic group or an atom or a neutral group; n represents a number of X; X and n fit to ensure the reliable oxidation state and coordination number of the central M after coordination by the N,O ligand; X is preferably one selected from H, CO, halogen, pseudohalogen, alkyl, alkoxyl, alkyl sulfydryl, aryl, benzyl, amino, hydroxyl and carboxylic group.

5. The method according to claim 1, wherein in 2-a), the additive is one selected from a basic metal oxide, a main group metal alkoxyl compound, a main group metal carboxyl compound, a metal carbonyl compound and a Lewis basic nitrogen-containing compound.

6. The method according to claim 1, wherein in 2-a), during the reaction of EO, carbon monoxide and the alcohol molecule in the organic solvent, the alcohol molecule is one selected from a C.sub.1-C.sub.20 alcohol, and preferably one selected from methanol, ethanol, propanol, butanol and pentanol; the organic solvent is one selected from alcohol, ether, saturated alkane and saturated aromatic hydrocarbons.

7. The method according to claim 1, wherein in 2-a), the reaction of EO, carbon monoxide and the alcohol molecule in the organic solvent is carried out at the temperature of 30-190 C. and the CO pressure of 1-150 atm for 0.1-200 h.

8. The method according to claim 1, wherein in 2-b), the reaction product system is separated by adding distilled water to generate the aqueous phase, adding an organic solvent to generate the organic phase, and adding a precipitating agent to generate the precipitate phase; the organic solvent is one selected from alcohol, ether, saturated alkane, saturated aromatic hydrocarbons, ester, C.sub.5 and above long-chain olefin and C.sub.4 and above long-chain alkyne; the precipitating agent is one selected from Bronsted acid, Bronsted base, Lewis acid, Lewis base, silica gel, molecular sieve, alumina, kaolin, hydrotalcite and ion exchange resin; the phase separation method is one selected from extraction, standing, centrifuge separation, filtration, distillation, column chromatography separation and vacuum extraction.

9. The method according to claim 1, wherein in 2-c), the 3HP product in the organic phase needs to be separated from the organic solvent by a method selected from distillation, rectification, column chromatography separation and vacuum extraction.

10. The method according to claim 1, wherein in the catalytic hydrogenation reaction of the 3HP in 3-d), the catalyst is a copper-containing mixed metal silicon oxide, and specifically, a copper-containing mixed metal silicon oxide having a general formula of M.sub.uCu.sub.vSi.sub.yO.sub.z, wherein u, v, y and z ensure to maintain a reliable M.sub.uCu.sub.vSi.sub.yO.sub.z formula molecule; M is one or two or three metals selected from zinc, manganese, barium, lanthanide series metal, cobalt, silver, gold, nickel and potassium.

11. The method according to claim 1, wherein in the catalytic hydrogenation reaction of the 3HP with dihydrogen in the organic solvent in 3-d), the organic solvent is one selected from ether, saturated alkane and saturated aromatic hydrocarbons; the reaction is carried out at the temperature of 80-400 C. and the H.sub.2 pressure of 20-150 atm for 0.1-200 h.

12. The method according to claim 1, wherein after the catalytic hydrogenation reaction in 3-e), the product system is separated by a method selected from distillation, rectification, column chromatography separation and vacuum extraction; the alcohol byproduct obtained by the separation is recovered for the reaction according to claim 7.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0025] FIGURE shows a gas chromatographic spectrum of product yielded in Example 9.

DETAILED DESCRIPTION

[0026] The present invention is described in detail below for practice. Those skilled in the art should understand that the present invention is not limited to the following content disclosed.

[0027] The catalytic reaction of ethylene oxide (EO), carbon monoxide and alcohol in organic solvent was generally operated as follows.

[0028] To a 2000 mL reactor, flushed with N.sub.2 for at least three times, was added a N,O-ligand coordinated metal complex, an additive, EO, an alcohol and an organic solvent in sequence, where the catalyst has a concentration of 1 mmol/L, the additive has a concentration of 2 mmol/L, the EO has a concentration of 400 mmol/L, and the alcohol has a concentration of 400 mmol/L. The reactor was closed, and the temperature, the stirring rate and the reaction time were set. After reaching to the settled temperature, the carbon monoxide was switched on to the reactor with the settled pressure to start the reaction. By the settled reaction time, the carbon monoxide was switched off. The reactor was cooled to 0 C., and then the excess unreacted carbon monoxide was slowly released through the vent valve collected to the reactor. The reaction solution was poured out for treatment.

[0029] The quantitative and qualitative analysis of the reaction products was analyzed by means of the GC and GC-MS spectra. The reaction sample for analysis obtained by Gas chromatographic analyses of the product mixture were made on a gas chromatograph. The analysis data and the calculation data thereof were recorded in Table 1.

[0030] The treatment process for separation was described as follows.

[0031] To the solution was added a double volume of H.sub.2O and then an equivalent volume of CH.sub.2Cl.sub.2. A two-phase mixture solution was formed, which was subjected to the separation by using the separating funnel. The organic component was collected and dried with Na.sub.2SO.sub.4. The rectification allowed separation of 3-HP, methanol, and CH.sub.2Cl.sub.2, respectively, as the main component.

Examples 1 to 19

[0032] These examples select a catalyst with a structure shown in the following.

##STR00003##

[0033] In order to fully evaluate the reactivity of this catalyst in combining the sodium methoxide as the additive in methanol solvent, the experiments were carried out by adopting varied conditions. First, the reactions were carried out at the CO pressure of 50 atm within 4 h by varying the temperatures from 40 to 60, 80, 100, 120 and finally 140 C., and the results are recorded in Table 1 (Examples 1 to 6). Second, the reactions were carried out at the temperature of 80 C. within 4 h by varying the CO pressure from 5 to 10, 30, 50, 70, 90, 100 and finally 120 atm, and the results are recorded in Examples 7 to 13 in Table 1. Third, the reactions were carried out at the temperature of 80 C. and the CO pressure of 30 atm by varying the reaction time from 1 to 2, 3, 5 and 6 h, respectively, and the results are recorded in Examples 14 to 18 in Table 1.

[0034] Table 1 Summary of the reaction results

TABLE-US-00001 Selectivity Reaction EO of Temperature Pressure time Conversion 3-HMP Example ( C.) (atm) (h) Rate (%) (%) 1 40 50 4 22.3 84.3 2 60 50 4 59.0 86.2 3 80 50 4 96.9 96.5 4 100 50 4 95.4 69.5 5 120 50 4 96.4 56.7 6 140 50 4 98.3 26.8 7 80 5 4 23.4 76.8 8 80 10 4 66.7 80.1 9 80 30 4 96.3 95.5 10 80 70 4 94.5 78.2 11 80 90 4 96.2 96.1 12 80 100 4 97.8 97.3 13 80 120 4 98.9 98.8 14 80 30 1 26.3 86.5 15 80 30 2 43.8 89.9 16 80 30 3 56.2 87.1 17 80 30 5 98.8 95.2 18 80 30 6 99.6 98.6

Examples 19 to 48

[0035] By using the catalyst shown in the above, reactions were carried out in methanol as a solvent in the presence of different additives by setting the temperature at 80 C., the CO pressure of 30 atm, and the reaction time for 4 h. The results obtained are recorded in Examples 19 to 32 of Table 2.

[0036] By using the catalyst shown in the above, reactions were carried out in the presence of pyridine as an additive in different solvents by setting the temperature at 80 C., the CO pressure of 30 atm, and the reaction time for 4 h, where methanol was used as a reactant with the concentration of 400 mmol/L. The results are recorded in Examples 33 to 41 of Table 2.

[0037] By using the catalyst shown in the above and introducing different alcohols, reactions were carried out in methyl tert-butyl ether as a solvent in the presence of pyridine as an additive at the temperature of 80 C. and the CO pressure of 30 atm within 4 h. The results are recorded in Examples 42 to 48 of Table 2

[0038] Table 2 Summary of the reaction results

TABLE-US-00002 EO Selectivity Conversion of 3HP Example Alcohol Additive Solvent Rate (%) (%) 19 Sodium ethoxide Methanol 56.8 78.9 20 Magnesium ethoxide Methanol 46.5 86.4 21 Lithium Methanol 52.3 88.6 diisopropylamide 22 Sodium acetate Methanol 31.1 91.2 23 Sodium carbonate Methanol 48.5 52.6 24 Triethylamine Methanol 47.9 90.1 25 Lithium Methanol 56.2 76.2 dimethylphenylamine 26 Pyridine Methanol 68.9 93.5 27 Pyrrole Methanol 70.2 91.6 28 2-hydroxypyridine Methanol 68.5 90.1 29 3-hydroxypyridine Methanol 96.2 98.6 30 4-hydroxypyridine Methanol 86.8 96.8 31 Imidazole Methanol 78.5 90.2 32 Indole Methanol 50.6 80.1 33 Methanol Pyridine Diethyl ether 86.5 90.2 34 Methanol Pyridine Tetrahydrofuran 90.1 88.2 35 Methanol Pyridine Methyl 80.6 84.9 tert-butyl ether 36 Methanol Pyridine Pentane 85.3 90.2 37 Methanol Pyridine Hexane 86.2 87.6 38 Methanol Pyridine Benzene 86.9 67.5 39 Methanol Pyridine Methylbenzene 90.6 56.8 40 Methanol Pyridine 1-hexene 78.9 60.8 41 Methanol Pyridine 1-octene 70.6 68.1 42 Ethanol Pyridine Methyl 74.6 80.5 tert-butyl ether 43 N-propanol Pyridine Methyl 86.2 86.9 tert-butyl ether 44 Isopropanol Pyridine Methyl 47.5 43.6 tert-butyl ether 45 N-butanol Pyridine Methyl 72.3 79.8 tert-butyl ether 46 Isobutanol Pyridine Methyl 45.8 32.9 tert-butyl ether 47 Tert-butanol Pyridine Methyl 42.1 43.0 tert-butyl ether 48 N-pentanol Pyridine Methyl 86.7 90.7 tert-butyl ether

Examples 49 to 55

[0039] In this section, the examples are designed to study the reactivity of the different metal complex catalysts incorporated with the N,O-ligand shown in forming catalyst. Reactions were carried out by using methanol as a reactant, pyridine as an additive, and methyl tert-butyl ether as a solvent at the temperature of 80 C. and the CO pressure of 30 atm for 4 h. The results are recorded in Examples 49 to 32 of Table 3.

[0040] Table 3 Summary of the reaction results

TABLE-US-00003 EO Conversion Selectivity of Example Metal Rate (%) 3-HMP (%) 49 Ruthenium 76.9 50.8 50 Rhodium 60.6 61.3 51 Palladium 33.5 43.4 52 Platinum 45.3 56.1 53 Osmium 30.6 39.7 54 Iridium 20.9 16.9 55 Iron 13.8 7.9

Examples 49 to 55

[0041] In this section, the examples are designed to study the reactivity of different cobalt complex catalysts coordinated with different N,O-ligands. Reactions were carried out at the temperature of 80 C. and the CO pressure of 30 atm for 4 h by using methanol as a reactant, pyridine as an additive, methyl tert-butyl ether as a solvent. The results are recorded in Examples 49 to 55 of Table 4.

[0042] Catalyst II with a structure shown in the following is selected.

##STR00004##

[0043] Catalyst III with a structure shown in the following is selected.

##STR00005##

[0044] Catalyst IV with a structure shown in the following is selected.

##STR00006##

[0045] Catalyst V with a structure shown in the following is selected.

##STR00007##

[0046] Catalyst VI with a structure shown in the following is selected.

##STR00008##

[0047] Catalyst VII with a structure shown in the following is selected.

##STR00009##

[0048] Catalyst VIII with a structure shown in the following is selected.

##STR00010##

[0049] Catalyst IX with a structure shown in the following is selected.

##STR00011##

[0050] Catalyst X with a structure shown in the following is selected.

##STR00012##

[0051] Catalyst XI with a structure shown in the following is selected.

##STR00013##

[0052] Catalyst XII with a structure shown in the following is selected.

##STR00014##

[0053] Catalyst XIII with a structure shown in the following is selected.

##STR00015##

[0054] Catalyst XIV with a structure shown in the following is selected.

##STR00016##

[0055] Catalyst XV with a structure shown in the following is selected.

##STR00017##

[0056] Catalyst XVI with a structure shown in the following is selected.

##STR00018##

[0057] Catalyst XVII with a structure shown in the following is selected.

##STR00019##

[0058] Catalyst XVIII with a structure shown in the following is selected.

##STR00020##

[0059] Catalyst XIX with a structure shown in the following is selected.

##STR00021##

[0060] Catalyst XX with a structure shown in the following is selected.

##STR00022##

[0061] Table 4 Summary of reaction results

TABLE-US-00004 EO Conversion Selectivity of Example Catalyst Rate (%) 3-HMP (%) 56 II 80.3 94.7 57 III 71.1 87.1 58 IV 83.9 75.4 59 V 91.1 79.5 60 VI 66.4 80.9 61 VII 43.6 72.8 62 VIII 79.4 86.1 63 IX 56.1 91.6 64 X 60.3 87.6 65 XI 86.9 73.9 66 XII 93.5 47.2 67 XIII 59.5 86.4 68 XIV 81.3 68.1 69 XV 92.4 81.5 70 XVI 40.5 76.4 71 XVII 76.9 73.8 72 XVIII 63.1 91.8 73 XIX 40.3 56.4 74 XX 83.6 49.8

[0062] The following is on the catalytic reaction of 3HP and dihydrogen.

[0063] The preparation procedure of the copper-containing mixed metal silicon oxide catalyst is described as follows.

[0064] A mixture of Cu(NO.sub.3).sub.2.3H.sub.2O and M(NO.sub.3).sub.m.n H.sub.2O was dissolved in distilled water, and to it was added a silica sol solution when stirring. The mixture was allowed to heat to 60-95 C., and then to it was added a Na.sub.2CO.sub.3 solution. The solid precipitate was formed which reached to a maximum amount by aging for 4-8 h. The solid precipitate was collected by filtration, and washed thoroughly with deionized water till the Na.sup.+ and other metal ions was reduced in a maximum amount. The solid precipitate was dried at 120 C. for 24 h, and then calcined at 350-600 C. for 4-10 h to give a copper-containing mixed metal silicon oxide catalyst. On the basis of the original amount of reactants used as well as the amount of metal ions washed away, the formulas of the catalysts obtained are Zn.sub.0.1Cu.sub.2.1SiO.sub.3.3, Mn.sub.0.15Cu.sub.1.8SiO.sub.3.5, La.sub.0.3Cu.sub.2.2SiO.sub.3.6, Zn.sub.0.1Mn.sub.0.1Cu.sub.1.7SiO.sub.3.4, Zn.sub.0.1La.sub.0.2Cu.sub.2.4SiO.sub.3.5, and Mn.sub.0.15La.sub.0.2Cu.sub.2.2SiO.sub.3.6, respectively.

[0065] The H.sub.2-reduction activation of the copper-containing mixed metal silicon oxide catalyst is described as follows.

[0066] The catalyst was granulated into 40-70 meshes prior to use. 5 g catalyst was filled in the middle of a reaction tube, where the front and the end part of the tube were filled with the inert quartz sand or a ceramic circle. This filling should be compact to ensure a smooth and stable passing of the gas and the liquid species under a setting pressure during the reaction. To this catalyst-filled tube was pressurized with the reducing gas, H.sub.2 (5% vol)/N.sub.2, and the tube was subject to heat treatment. The first process was conducted by heating the tube from room temperature to 50 C. at a rate of 0.833 C./min. This step needed ca. 30 min. The second process was the further heating from 50 C. to 300 C. at a rate of 0.625 C./min. This step required ca. 400 min. At this temperature, the reducing gas was introduced, and this step treatment lasted for 550 min. After this, under the input of the forming reducing gas, the temperature was decreased to a settled temperature within 60 min for further use.

[0067] The H.sub.2-hydrogenation process of 3-HP by using the forming activated copper-containing mixed metal silicon oxide catalyst is described as follows.

[0068] The forming reducing gas was switched to H.sub.2 at the above settled temperature. The H.sub.2 flow rate was set to 30-48 mL/min with the pressure in the range of 40-68 atm. A solution containing 3HP and an organic solvent with a volume ratio of 1:10 was pumped into the tube by using a metering pump at the flow rate of 0.02-0.10 mL/min. In the proceeding of the reaction, the reaction aliquot was picked up for analysis at the regular intervals. The results obtained are recorded in the table.

Examples 75 to 111

[0069] These example results are obtained by selecting the catalyst Mn.sub.0.15Cu.sub.1.8SiO.sub.3.5.

[0070] In order to fully evaluate the reactivity of the catalyst Mn.sub.0.15Cu.sub.1.8SiO.sub.3.5, experiments were carried out by adopting varied conditions. Firstly, reactions were carried out by using 3-HMP as a reactant in hexane as a solvent at the H.sub.2 pressure of 60 atm, where the flow rate of H.sub.2 was set by 34 mL/min and that of 3-HMP by 0.06 mL/min and meanwhile the reaction temperature was settled at 140, 145, 150, 155, 160, 165, 170, 180, 190 and 200 C., respectively. The results obtained are recorded in Examples 75 to 84 in Table 5. Secondly, under the forming conditions, the reaction temperature was kept at 160 C. while the H.sub.2 pressure was settled by varying from 40, 45, 50, 55, 58, 62, 64, 66, and finally to 68 atm. The results produced are recorded in Examples 85 to 93 in Table 5. Thirdly, by means of the reaction conditions applied in the first cases, the reaction temperature was kept at 160 C. while the H.sub.2 flow rate was settled by 30, 32, 36, 38, 42, 45, and finally 48 mL/min. The results yielded are recorded in Examples 94 to 100 in Table 5. Fourthly, by means of the reaction conditions applied in the first cases, the reaction temperature was kept at 160 C. while the 3-HMP flow rate was settled by 0.02, 0.03, 0.04, 0.05, 0.08, and finally 0.10 mL/min. The results obtained are recorded in Examples 101 to 106 in Table 5. Fifthly, under the reaction conditions applied in the first cases, the reaction temperature was kept at 160 C. Meanwhile, the solvents such as pentane, benzene, methylbenzene, methanol and tetrahydrofuran were used instead of hexane. The results generated are recorded in Examples 107 to 111 in Table 5.

[0071] Table 5 Summary of the reaction results

TABLE-US-00005 H.sub.2 Flow 3-HMP 3-HMP Selectivity Temperature Pressure Rate Flow Rate Conversion of 1,3-PDO Example Solvent ( C.) (atm) (mL/min) (mL/min) Rate (%) (%) 75 Hexane 140 60 34 0.06 36.1 56.2 76 Hexane 145 60 34 0.06 40.6 61.5 77 Hexane 150 60 34 0.06 56.2 50.2 78 Hexane 155 60 34 0.06 78.5 69.5 79 Hexane 160 60 34 0.06 95.6 81.3 80 Hexane 165 60 34 0.06 96.8 68.1 81 Hexane 170 60 34 0.06 97.2 60.4 82 Hexane 180 60 34 0.06 98.2 50.3 83 Hexane 190 60 34 0.06 99.1 40.2 84 Hexane 200 60 34 0.06 99.3 30.1 85 Hexane 160 40 34 0.06 23.1 10.5 86 Hexane 160 45 34 0.06 30.1 20.6 87 Hexane 160 50 34 0.06 42.3 67.1 88 Hexane 160 55 34 0.06 65.8 72.8 89 Hexane 160 58 34 0.06 92.1 80.3 90 Hexane 160 62 34 0.06 93.2 83.1 91 Hexane 160 64 34 0.06 94.0 85.4 92 Hexane 160 66 34 0.06 93.8 79.8 93 Hexane 160 68 34 0.06 96.5 76.9 94 Hexane 160 60 30 0.06 86.5 40.6 95 Hexane 160 60 32 0.06 83.9 80.4 96 Hexane 160 60 36 0.06 90.5 82.6 97 Hexane 160 60 38 0.06 87.6 62.8 98 Hexane 160 60 42 0.06 92.6 54.3 99 Hexane 160 60 45 0.06 82.6 50.9 100 Hexane 160 60 48 0.06 86.7 49.7 101 Hexane 160 60 34 0.02 43.6 53.2 102 Hexane 160 60 34 0.03 50.1 57.8 103 Hexane 160 60 34 0.04 60.4 60.2 104 Hexane 160 60 34 0.05 71.8 85.1 105 Hexane 160 60 34 0.08 86.2 80.3 106 Hexane 160 60 34 0.10 76.3 81.6 107 Pentane 160 60 34 0.06 86.4 81.7 108 Benzene 160 60 34 0.06 67.8 65.4 109 Methylbenzene 160 60 34 0.06 80.9 76.5 110 Methanol 160 60 34 0.06 89.2 78.9 111 Tetrahydrofuran 160 60 34 0.06 78.7 82.4

Examples 112 to 118

[0072] In this section, the experiments are designed to study the catalytic hydrogenation reactivity of the catalyst Mn.sub.0.15Cu.sub.1.8SiO.sub.3.5 on different 3HP. Reactions were carried out in hexane as a solvent at the temperature of 160 C., the H.sub.2 pressure of 60 atm, the H.sub.2 flow rate of 34 mL/min and the 3HP flow rate of 0.06 mL/min. The results are recorded in Examples 112 to 118 in Table 6.

[0073] Table 6 Summary of the reaction results

TABLE-US-00006 3HP Selectivity of Conversion 1,3-PDO Example Selectivity of 3HP Rate (%) (%) 112 Ethyl 3-hydroxypropionate 80.6 76.9 113 N-propyl 3-hydroxypropionate 75.9 83.1 114 Isopropyl 3-hydroxypropionate 62.9 66.8 115 N-butyl 3-hydroxypropionate 76.4 70.1 116 Isobutyl 3-hydroxypropionate 43.2 58.2 117 Tert-butyl 3-hydroxypropionate 30.1 46.2 118 N-pentyl 3-hydroxypropionate 56.2 43.1

Examples 119 to 123

[0074] In this section, the experiments are designed to study the catalytic reactivity of the catalysts such as Zn.sub.0.1Cu.sub.2.1SiO.sub.3.3, La.sub.0.3Cu.sub.2.2SiO.sub.3.6, Zn.sub.0.1Mn.sub.0.1Cu.sub.1.7SiO.sub.3.4, Zn.sub.0.1La.sub.0.2Cu.sub.2.4SiO.sub.3.5 and Mn.sub.0.15La.sub.0.2Cu.sub.2.2SiO.sub.3.6 on the 3-HMP H.sub.2-hydrogenation. Reactions were carried out in hexane as a solvent at the temperature of 160 C., the H.sub.2 pressure of 60 atm, the H.sub.2 flow rate of 34 mL/min and the 3-HMP flow rate of 0.06 mL/min. The results are recorded in Examples 119 to 123 of Table 7.

[0075] Table 7 Summary of the reaction results

TABLE-US-00007 3-HMP Selectivity of Conversion 1,3-PDO Example Catalyst Rate (%) (%) 119 Zn.sub.0.1Cu.sub.2.1SiO.sub.3.3 52.1 62.0 120 La.sub.0.3Cu.sub.2.2SiO.sub.3.6 23.4 13.5 121 Zn.sub.0.1Mn.sub.0.1Cu.sub.1.7SiO.sub.3.4 86.3 89.8 122 Zn.sub.0.1La.sub.0.2Cu.sub.2.4SiO.sub.3.5 41.6 25.9 123 Mn.sub.0.15La.sub.0.2Cu.sub.2.2SiO.sub.3.6 39.2 8.9

[0076] In the present invention, the catalytic reaction examples of EO, carbon monoxide and alcohol revealed the guaranty for the preparation of the 3HP by using the related catalyst invented. Also guarantied is the H.sub.2-hydrogenation of the 3HP to prepare the 1,3-PDO target. In the first step catalytic reaction, the 3HP product can be separated from the product system for the use in the subsequent catalytic hydrogenation reaction. In view of the whole combined two-step reaction, if the 3HP product was not separated, the production of the 1,3-PDO would not be effective. Especially noted is that the 1,3-PDO is not able to produce directly from the catalytic reaction of EO, carbon monoxide and alcohol. Moreover, these results show that it is necessary to use different catalyst system for each reaction in the process of the two-step reactions above-mentioned. Therefore, the invented technique is different from the hydroformylation on the reaction system of EO, carbon monoxide, and H.sub.2, by means of whether the one-step or two-step method. The key point herein is the introduction of the alcohol and then the procedures and the catalysts are remarkably differed.

[0077] The results of the examples in Table 6 show that the series of the hydrogenation reactions of the 3HP produced the 1,3-PDO and the alcohol byproduct. The results of the examples in Table 2 show that the alcohol byproduct can be recycled to the reaction of EO and carbon monoxide to produce the 3HP.