阅读说明：本技术 用于醛和/或醇的大规模制备的氢甲酰化方法 (Hydroformylation process for large scale production of aldehydes and/or alcohols ) 是由 S·祖德 R·帕普 B·布莱特沙伊德 A·朗格德奥利韦拉 于 2018-05-14 设计创作，主要内容包括：一种由底部馏分制备C<Sub>4</Sub>-C<Sub>13</Sub>单羟基化合物的方法,所述馏分在来自钴催化或铑催化的氢甲酰化的C<Sub>4</Sub>-C<Sub>13</Sub>羰基合成法醛的粗混合物的蒸馏中产生,或在C<Sub>4</Sub>-C<Sub>13</Sub>羰基合成法醇的粗混合物的蒸馏中产生。所述方法的特征在于,在氢气存在下使底部馏分与包含氧化铜及氧化铝的催化剂在150-300℃的温度及20-300巴的压力下接触,且将所得氢化粗产物蒸馏,且在氢化之后存在于氢化粗产物中的C<Sub>4</Sub>-C<Sub>13</Sub>单羟基化合物的量超过底部馏分中存在的酯及醛化合物的氢化化学计量给出的C<Sub>4</Sub>-C<Sub>13</Sub>单羟基化合物的量,包括在氢化之前仍存在于该底部馏分中的C<Sub>4</Sub>-C<Sub>13</Sub>单羟基化合物。(Preparation of C from bottom fraction 4 ‑C 13 Method for producing monohydroxy compounds, the fraction being at C from cobalt-or rhodium-catalysed hydroformylation 4 ‑C 13 Produced in the distillation of the crude mixture of aldehydes from the oxo process, or in C 4 ‑C 13 In the distillation of a crude mixture of oxo alcohols. Said method is characterized in that the bottom fraction is contacted with a catalyst comprising copper oxide and aluminum oxide in the presence of hydrogen at a temperature of 150-300 ℃ and a pressure of 20-300 bar, and the resulting hydrogenation crude is distilled and the C present in the hydrogenation crude after hydrogenation is 4 ‑C 13 Amount of monohydroxy compoundC given in excess of the hydrogenation stoichiometry of the ester and aldehyde compounds present in the bottom fraction 4 ‑C 13 The amount of monohydroxy compounds, including C, still present in the bottom fraction prior to hydrogenation 4 ‑C 13 A monohydroxy compound.)

1. Preparation of C from bottom fraction₄-C₁₃Method for producing monohydroxy compounds in C from cobalt-or rhodium-catalyzed hydroformylation₄-C₁₃Produced in the distillation of the crude mixture of aldehydes from the oxo process, or in C₄-C₁₃Produced in the distillation of a crude mixture of oxo-alcohols, which comprises contacting the bottom fraction with a catalyst comprising copper oxide (CuO) and aluminum oxide in the presence of hydrogen at a temperature of 150-300 ℃ and a pressure of 20-300 bar, and distilling the resulting hydrogenated crude product, and the C present in the hydrogenated crude product after hydrogenation₄-C₁₃The amount of monohydroxy compounds being greater than C given by the stoichiometry of the hydrogenation of the ester and aldehyde compounds present in the bottom fraction₄-C₁₃The amount of monohydroxy compounds, including C, still present in the bottom fraction prior to hydrogenation₄-C₁₃A monohydroxy compound.

2. The process of claim 1, wherein the catalyst comprises a fraction of 40 to 80 wt.% copper oxide (CuO), a fraction of 5 to 60 wt.% aluminum oxide, and 0 to 30 wt.% manganese oxide (MnO), lanthanum oxide, or zinc oxide, the weight percentages being based on the total weight of oxide materials present in the catalyst after calcination, the sum of the weight fractions adding up to 90 to 100%, and the fraction of oxide materials in the catalyst after calcination being at least 80 wt.%, based on the total weight of the catalyst after calcination.

3. The process as claimed in claim 1 or 2, wherein the bottom fraction is contacted with the catalyst in the presence of hydrogen at a temperature of 180 ℃ and 260 ℃ and a pressure of 150 bar and 280 bar.

4. The process as claimed in any of claims 1 to 3, for preparing C from the bottom fraction₄-C₉Monohydroxy compounds, the fraction being in a reaction vessel from cobalt-or rhodium-catalysed hydroformylation C₄-C₉Produced in the distillation of the crude mixture of aldehydes from the oxo process, or in C₄-C₉In the distillation of a crude mixture of oxo alcohols.

5. The process of claim 4 for the production of n-butanol and/or isobutanol from a bottoms fraction at C from rhodium catalysed hydroformylation₄Produced in the distillation of the crude mixture of aldehydes from the oxo process, or in C₄In the distillation of a crude mixture of oxo alcohols.

6. The process of any one of claims 1-5, wherein the bottom fraction is extracted, distilled, or stripped prior to contacting with hydrogen and the catalyst.

7. The process of any one of claims 1-5, wherein the bottom fraction is extracted and distilled prior to contacting with hydrogen and the catalyst.

8. The process of any one of claims 1-7, wherein a portion of the hydrogenated crude product obtained from hydrogenation is returned to the disclosed process and a portion of the hydrogenated crude product obtained from hydrogenation is distilled.

9. Use of a catalyst according to claim 1 or 2 for the preparation of C from a bottom fraction₄-C₁₃Monohydroxy compounds, the fraction being in a reaction vessel from cobalt-or rhodium-catalysed hydroformylation C₄-C₁₃Produced in the distillation of the crude mixture of aldehydes from the oxo process, or in C₄-C₁₃In the distillation of a crude mixture of oxo alcohols.

10. Use of the catalyst of claim 9 for the preparation of C from the bottom fraction₄Monohydroxy compound, said fraction being in C from rhodium-catalyzed hydroformylation₄Produced in the distillation of the crude mixture of aldehydes from the oxo process, or in C₄In the distillation of a crude mixture of oxo alcohols.

11. Use of a catalyst according to claim 10 for the preparation of n-butanol and/or isobutanol.

12. Use of the bottom fraction of claim 1 for the preparation of C₄-C₁₃A monohydroxy compound.

13. Use of the bottom fraction of claim 12 for the preparation of n-butanol, isobutanol or mixtures thereof, wherein the bottom fraction is at C from rhodium catalyzed hydroformylation₄Produced in the distillation of the crude mixture of aldehydes from the oxo process, or in C₄In the distillation of a crude mixture of oxo alcohols.

14. By hydrogenolysis of C₈Diol preparation C₄A method of making a monohydroxy compound comprising reacting C₈The glycol is contacted with a catalyst comprising copper oxide and aluminum oxide in the presence of hydrogen at a temperature of 150-300 ℃ and a pressure of 20-300 bar₈The diol is at least partially reacted to obtain C₄Monohydroxy compoundAnd for the obtained crude C₈The diol hydrogenation product is distilled.

15. Preparation of C from bottom fraction₄Method for producing monohydroxy compounds, the fraction being at C from rhodium-catalysed hydroformylation₄Produced in the distillation of the crude mixture of aldehydes from the oxo process, or in C₄Produced in the distillation of a crude mixture of oxo alcohols, which comprises contacting the bottom fraction with a catalyst comprising copper oxide and aluminum oxide in the presence of hydrogen at a temperature of 150-300 ℃ and a pressure of 20-300 bar, and distilling the resulting hydrogenated crude product, and the amount of n-butanol, isobutanol or a mixture thereof present in the hydrogenated crude product after the hydrogenation is greater than the amount of n-butanol, isobutanol or a mixture thereof stoichiometrically given by the hydrogenation of the ester and aldehyde compounds present in the bottom fraction, including the C still present in the bottom fraction before the hydrogenation₄A monohydroxy compound.

Examples