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CN-122010703-A - Method for carrying out olefin hydroformylation by utilizing crude hydrogen, olefin hydroformylation reaction system and application thereof

CN122010703ACN 122010703 ACN122010703 ACN 122010703ACN-122010703-A

Abstract

The invention relates to the technical field of olefin hydroformylation, and discloses a method for carrying out olefin hydroformylation by utilizing crude hydrogen, an olefin hydroformylation reaction system and application thereof, wherein the method comprises the steps of carrying out contact reaction on olefin, crude hydrogen and a catalytic material in the presence of an ester compound to obtain an olefin hydroformylation product, wherein the catalytic material comprises a first active component and a second active component, the first active component is Cu, the second active component is Rh, and the volume ratio of H 2 to CO in the crude hydrogen is 0.1-10. The method can directly utilize crude hydrogen to carry out olefin formylation reaction, simultaneously realize olefin hydroformylation and ester hydrogenation, remove surplus hydrogen components through ester capture, and use the rest of optimized composition gas for olefin hydroformylation, thereby realizing the production of high-value chemicals.

Inventors

  • ZHU YIFENG
  • CHEN YUE
  • GAO GE
  • KONG XIAO
  • BAO XINHE

Assignees

  • 复旦大学

Dates

Publication Date
20260512
Application Date
20241108

Claims (10)

  1. 1. A method for carrying out olefin hydroformylation by utilizing crude hydrogen is characterized by comprising the steps of contacting olefin, crude hydrogen and a catalytic material in the presence of an ester compound for reaction to obtain an olefin hydroformylation product, wherein the catalytic material comprises a first active component and a second active component, the first active component is Cu, and the second active component is Rh; Wherein, in the crude hydrogen, the volume ratio of H 2 to CO is 0.1-10.
  2. 2. The method of claim 1, wherein the mass ratio of the ester compound to the olefin is P1, the volume ratio of H 2 to CO is P2, the ratio of P1 to P2 is 0.5-5; Preferably, the mass ratio P1 of the ester compound to the olefin is 1-10; preferably, the volume ratio P2 of H 2 to CO is 0.5-5.
  3. 3. A method according to claim 1 or 2, wherein the mass ratio of the first active component Cu to the second active component Rh in the catalytic material is 100 (0.5-10), preferably 100 (1-5).
  4. 4. A method according to any one of claims 1 to 3, wherein the catalytic material comprises a support and first and second active components supported on the support; preferably, the carrier is present in an amount of 5 to 90 wt.%, based on the total amount of the catalytic material, the first active component is present in an amount of 10 to 90 wt.%, based on the element, and the second active component is present in an amount of 0.01 to 5 wt.%, based on the element.
  5. 5.A method according to any one of claims 1 to 3, wherein the catalytic material comprises a first catalyst comprising a first support and a first active component supported on the first support and a second catalyst comprising a second support and a second active component supported on the second support; Preferably, the content of the first carrier is 1 to 95wt% based on the total amount of the first catalyst, and the content of the first active component is 5 to 99wt% in terms of elements; preferably, the content of the second carrier is 95 to 99.99wt% based on the total amount of the second catalyst, and the content of the second active component is 0.01 to 5wt% in terms of elements; preferably, the contact mode comprises the steps of sequentially contacting olefin and crude hydrogen with a first catalyst and a second catalyst in the presence of an ester compound, or contacting olefin and crude hydrogen with a mixture of the first catalyst and the second catalyst in the presence of the ester compound; preferably, the mass ratio of the first catalyst to the second catalyst is 1 (0.01-5), preferably 1 (0.2-2).
  6. 6. The method of claim 4 or 5, wherein the carrier, the first carrier and the second carrier are each independently selected from at least one of a metal or non-metal oxide, preferably at least one of SiO 2 、ZnO、ZrO 2 and Al 2 O 3 , a carbon material.
  7. 7. The method according to any one of claims 1 to 6, wherein the ester compound has a structure represented by formula (1), Wherein R 1 and R 2 are each independently selected from C1-C4 hydrocarbyl groups, or R 1 and R 2 together with the attached carbon and oxygen atoms form a five-to eight-membered saturated or unsaturated heterocyclic ring; preferably, the ester compound is selected from at least one of formate, butyrate, propionate, butyrolactone and valerolactone; Preferably, the olefin is selected from C6-C20 olefins, preferably at least one of hexene, octene, 1-hexadecene, styrene, para-vinyl toluene, 1-naphthalene ethylene and 1-benzyl ethylene.
  8. 8. The process of any one of claims 1-7, wherein the reaction comprises an olefin hydroformylation reaction and an ester hydrogenation reaction; Preferably, the temperature of the reaction is from 100 to 200 ℃, preferably from 140 to 180 ℃; preferably, the pressure of the reaction is 0.1-10MPa, preferably 1-5MPa; Preferably, the contacting is carried out in a tank reactor, the mass ratio of the catalytic material to the olefin being 1 (5-50), preferably 1 (10-20), or the contacting is carried out in a continuous reactor, preferably a fixed bed reactor, the mass space velocity of the olefin being 0.01-10h -1 , preferably 0.1-5h -1 , relative to the total mass of the catalytic material.
  9. 9. An olefin hydroformylation reaction system comprises a raw material supply unit, a coupling reaction unit and a product separation unit which are sequentially communicated in the direction of flow; Wherein the raw material supply unit comprises an olefin storage tank, an ester compound storage tank and a crude hydrogen supply device, and is used for supplying olefin, ester compound and crude hydrogen to the coupling reaction unit; the coupling reaction unit comprises at least one reactor, and is used for contacting olefin, ester compounds and crude hydrogen from the raw material supply unit with catalytic materials to carry out olefin hydroformylation reaction and ester compound hydrogenation reaction; the product separation unit is used for separating the reaction products from the coupling reaction unit to obtain a hydroformylation product and an ester hydrogenation product; Preferably, the reaction system further comprises a dehydrogenation reactor, wherein the dehydrogenation reactor is respectively communicated with the product separation unit and the raw material supply unit and is used for carrying out dehydrogenation reaction on the separated ester hydrogenation product, and the ester compound obtained by dehydrogenation returns to the raw material supply unit.
  10. 10. Use of the process for the hydroformylation of olefins according to any of claims 1 to 8 or the olefin hydroformylation reaction system according to claim 9 in a hydrogen production process and/or an olefin hydroformylation process.

Description

Method for carrying out olefin hydroformylation by utilizing crude hydrogen, olefin hydroformylation reaction system and application thereof Technical Field The invention relates to the technical field of olefin hydroformylation, in particular to a method for carrying out olefin hydroformylation by utilizing crude hydrogen, an olefin hydroformylation reaction system and application thereof. Background Crude hydrogen is an unavoidable by-product of the hydrogenation process involved. Because of the large difference of different reaction processes, the method generally has the characteristics of complex components and large fluctuation of physical parameters, and takes the metallurgical industry as an example, the byproduct gas rich in synthesis is an important waste generated in the production process, and because the byproduct gas contains CO, CO 2、CH4, a certain content of H 2 and other components, the direct emission not only causes pollution to the environment, but also wastes a large amount of energy sources, the recovery cost is higher, the operation process is more complicated, and the effective recovery of economic value components has a great challenge. The energy of coal used in the metallurgical process is about 34% converted into byproduct gas, and the annual yield is huge, so that the recovery treatment of crude hydrogen has considerable utilization value and huge yield scale, and is one of key industries for realizing the double-carbon target. The synthesis gas is an important product obtained by hydrogen production and waste hydrogen recovery, is an important building unit for high-value chemical production, and can be used for synthesizing high-value chemicals through hydroformylation of olefins. The hydrogen-to-carbon ratio (typically H 2/co=1) of the synthesis gas required for olefin hydroformylation is significantly different from the composition of the raw hydrogen obtained in the conventional hydrogen production industry and the purge gas containing synthesis gas produced in the hydrogen industry (typically the hydrogen component content is higher than the CO content). Therefore, a special adjustment process is needed to remove redundant hydrogen in a gas source to obtain the raw gas meeting the requirements so as to avoid side reactions such as product hydrogenolysis and the like. CN113735060a discloses a system for adjusting the hydrogen-carbon ratio of synthesis gas and simultaneously producing hydrogen as a byproduct through coupling of membrane separation and pressure swing adsorption, thereby realizing adjustment of the hydrogen-carbon ratio of the gas and producing hydrogen with high concentration as a byproduct, but the required process equipment is more, the production investment is higher, and the method is not suitable for crude/waste hydrogen as a byproduct in medium and small chemical enterprises. And the Pd membrane used for membrane separation has higher cost and low space-time yield. CN211111788U proposes a process for adjusting the hydrogen-to-carbon ratio of the hydrogen-rich synthesis gas purge gas by using low temperature methanol to wash enriched CO 2, which has the problems that the single pass conversion of CO 2 hydrogenation to methanol is low, more unconverted CO 2 is introduced, and more CO is hydrogenated under the condition of CO 2 hydrogenation (typically at a temperature of >230 ℃) to obtain methanol with lower added value, the irrelevant loss of the obtained gas is larger, new impurities are introduced, and the influence on the hydroformylation catalyst is larger. CN103289769a proposes to regulate the product gas by means of methanation of the synthesis gas, involving higher operating temperatures, in the range 300-500 ℃. Therefore, the related separation process is generally needed before the hydroformylation reaction, so that the removal of the surplus hydrogen is realized, the cost is high, and the energy consumption is high. Disclosure of Invention The invention aims to solve the problems of the prior art that the olefin hydroformylation reaction has severe requirement on the composition of synthesis gas, requires an additional gas separation step and has high process cost, and provides a method for directly carrying out olefin hydroformylation by using crude hydrogen, an olefin hydroformylation reaction system and application thereof. In order to achieve the aim, the invention provides a method for carrying out olefin hydroformylation by using crude hydrogen, which comprises the steps of contacting and reacting olefin, crude hydrogen and a catalytic material in the presence of an ester compound to obtain an olefin hydroformylation product, wherein the catalytic material comprises a first active component and a second active component, the first active component is Rh, and the second active component is Cu; Wherein, in the crude hydrogen, the volume ratio of H 2 to CO is 0.1-10. Preferably, the mass ratio of the ester compound to the olefin is P1, the v