Method for olefin hydroformylation by using crude hydrogen, olefin hydroformylation reaction system and application of olefin hydroformylation reaction system

Abstract

The invention relates to the technical field of olefin hydroformylation, and discloses a method for olefin hydroformylation by using crude hydrogen, an olefin hydroformylation reaction system and application thereof, the method comprises the following steps: in the presence of an ester compound, olefin, crude hydrogen and a catalytic material are contacted for reaction to obtain an olefin hydroformylation product; 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 H2 to CO is 0.1 to 10. According to the method, crude hydrogen can be directly used for olefin formylation reaction, olefin hydroformylation and ester hydrogenation are realized at the same time, redundant hydrogen components are captured and removed through esters, and residual optimized composition gas is used for olefin hydroformylation, so that production of high-value chemicals is realized.

Description

Technical Field

[0001] This invention relates to the field of olefin hydroformylation technology, specifically to a method for olefin hydroformylation using crude hydrogen, an olefin hydroformylation reaction system, and its applications. Background Technology

[0002] Crude hydrogen is an unavoidable byproduct of hydrogen-related chemical processes. Due to significant differences in various reaction processes, it generally exhibits complex composition and highly volatile physical properties. Taking the metallurgical industry as an example, the byproduct coal gas rich in synthesis is a significant waste generated during its production process. Containing components such as CO, CO2, CH4, and a certain amount of H2, direct emission not only pollutes the environment but also wastes a large amount of energy. Recovery costs are high, and the operational processes are complex, making the effective recovery of economically valuable components a significant challenge. Approximately 34% of the energy from coal used in metallurgical processes is converted into byproduct coal gas, with a huge annual output. Therefore, the recovery and treatment of crude hydrogen has considerable utilization value and a large production scale, making it a key industry for achieving dual-carbon goals.

[0003] Syngas is an important product from hydrogen production and waste hydrogen recovery, and a crucial building block in the production of high-value chemicals. It can be used in the hydroformylation of olefins to synthesize high-value chemicals. However, the hydrogen-to-carbon ratio (typically H2 / CO = 1) of the syngas required for olefin hydroformylation differs significantly from the composition of crude hydrogen obtained from conventional hydrogen production industries and the purge gas containing syngas produced by hydrogen-using industries (usually, the hydrogen content is higher than the CO content). Therefore, a specialized adjustment process is needed to remove excess hydrogen from the gas source to obtain a feed gas that meets the requirements, thereby avoiding side reactions such as product hydrogenolysis.

[0004] CN113735060A discloses a system for adjusting the hydrogen-to-carbon ratio of syngas while simultaneously producing hydrogen as a byproduct through membrane separation and pressure swing adsorption coupling. This system aims to adjust the hydrogen-to-carbon ratio of the gas and produce high-concentration hydrogen as a byproduct. However, it requires a large amount of equipment and involves high investment, making it unsuitable for the crude / waste hydrogen produced as a byproduct in small and medium-sized chemical enterprises. Furthermore, the Pd membranes used in membrane separation are expensive, and the space-time yield is low. CN211111788U proposes a process for adjusting the hydrogen-to-carbon ratio of hydrogen-rich syngas purge gas by using CO2 enriched through low-temperature methanol washing. This process suffers from low single-pass conversion of CO2 to methanol, introducing a significant amount of unconverted CO2. Additionally, a large amount of CO will undergo hydrogenation under CO2 hydrogenation conditions (typically at temperatures >230°C), resulting in methanol with low added value. The resulting gas exhibits significant irrelevant losses and introduces new impurities, which have a substantial impact on the hydroformylation catalyst. CN103289769A proposes a method of adjusting the product gas by methanation of syngas, which involves a relatively high operating temperature of 300-500℃.

[0005] Therefore, it is evident that a related separation process is generally required before the hydroformylation reaction to remove excess hydrogen, which is costly and energy-intensive. Summary of the Invention

[0006] The purpose of this invention is to overcome the problems of existing technologies, such as stringent requirements on the composition of syngas for olefin hydroformylation, the need for additional gas separation steps, and high process costs. This invention provides a method for direct olefin hydroformylation using crude hydrogen, an olefin hydroformylation reaction system, and its applications. This method can utilize crude hydrogen for olefin hydroformylation without the need for additional separation processes to optimize the gas composition, thus simplifying the process flow and significantly reducing process costs.

[0007] To achieve the above objectives, the present invention provides a method for hydroformylation of olefins using crude hydrogen, the method comprising: reacting an olefin, crude hydrogen, and a catalyst in the presence of an ester compound to obtain a hydroformylation product of the olefin; wherein the catalyst comprises a first active component and a second active component, the first active component being Rh and the second active component being Cu.

[0008] In the crude hydrogen, the volume ratio of H2 to CO is 0.1-10.

[0009] Preferably, the mass ratio of the ester compound to the olefin is P1, the volume ratio of H2 to CO is P2, and P1 and P2 satisfy the condition that the ratio of P1 to P2 is 0.5-5.

[0010] A second aspect of the present invention provides an olefin hydroformylation reaction system, comprising a raw material supply unit, a coupling reaction unit and a product separation unit connected sequentially along the flow direction;

[0011] The raw material supply unit includes an olefin storage tank, an ester compound storage tank, and a crude hydrogen supply device, which are used to supply olefins, ester compounds, and crude hydrogen to the coupled reaction unit.

[0012] The coupled reaction unit includes at least one reactor for contacting olefins, esters and crude hydrogen from the feedstock unit with a catalytic material to carry out olefin hydroformylation and ester hydrogenation reactions.

[0013] The product separation unit is used to separate the reaction products from the coupled reaction unit to obtain hydroformylation products and ester hydrogenation products.

[0014] Preferably, the reaction system further includes a dehydrogenation reactor, which is connected to the product separation unit and the raw material supply unit respectively, and is used to dehydrogenate the separated ester hydrogenation product, and the dehydrogenated ester compound is returned to the raw material supply unit.

[0015] The third aspect of the present invention provides the application of the above-described method for olefin hydroformylation or the above-described olefin hydroformylation reaction system in hydrogen production processes and / or olefin hydroformylation processes.

[0016] The technical solution provided by this invention, in the presence of a two-component catalytic material including active component Cu and active component Rh, introduces ester compounds into the olefin hydroformylation reaction, reducing the requirement for the C-H ratio in the feed gas. This allows for the direct use of crude hydrogen in the olefin hydroformylation reaction without the need for additional production or separation equipment. The inventors discovered that active component Rh has weak activation of ester compounds, and active component Cu has weak affinity for CO and olefins, exhibiting poor double bond activation ability. This allows for the simultaneous realization of olefin hydroformylation and ester hydrogenation during the reaction. Excess hydrogen is removed by ester capture, and the remaining optimized gas composition is used for olefin hydroformylation, thereby achieving the production of high-value chemicals.

[0017] The method provided by this invention can be flexibly adjusted according to the needs of the gaseous and liquid products of the process, and does not require special gas materials to adjust the production line or additional high-purity single-component gas, which helps to reduce production costs. Attached Figure Description

[0018] Figure 1 This is a schematic diagram of a reaction system according to a specific embodiment of the present invention.

[0019] Explanation of reference numerals in the attached figures

[0020] 1. Crude hydrogen supply unit; 2. Gas compressor; 3. Heater A

[0021] 4. Ester hydrogenation reactor; 5. Olefin hydroformylation reactor; 6. Tail gas recovery unit; 7. Separator; 8. Olefin hydroformylation product storage tank; 9. Constant flow pump A; 10. Heater B; 11. Dehydrogenation reactor; 12. Hydrogen storage tank; 13. Ester compound storage tank; 14. Olefin storage tank; 15. Liquid phase mixer; 16. Constant flow pump B Detailed Implementation

[0022] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0023] This invention provides a method for direct hydroformylation of olefins using crude hydrogen. The method includes: reacting an olefin, crude hydrogen, and a catalyst in the presence of an ester compound to obtain a hydroformylation product of the olefin; the catalyst includes a first active component and a second active component, wherein the first active component is Cu and the second active component is Rh.

[0024] In the crude hydrogen, the volume ratio of H2 to CO is 0.1-10.

[0025] The syngas required for olefin hydroformylation has stringent hydrogen-to-carbon ratio requirements (typically H2 / CO = 1), which differs significantly from the composition of crude hydrogen obtained in conventional hydrogen production and the purge gas containing syngas produced in hydrogen-using industries. Therefore, existing technologies typically require specialized syngas preparation or gas composition adjustment processes to obtain feedstock gas that meets the requirements and to avoid side reactions such as product hydrogenolysis.

[0026] The inventors of this invention discovered in their research that the active component Rh has weak activation of ester compounds, and the active component Cu has weak affinity for CO and olefins, resulting in poor activation of double bonds. In the presence of a two-component catalytic material including the active component Cu and the active component Rh, by introducing ester compounds into the olefin hydroformylation reaction, olefin hydroformylation and ester hydrogenation can be achieved simultaneously. By capturing and removing excess hydrogen components through esters, the crude hydrogen can be directly used for the olefin formylation reaction, significantly relaxing the requirements on the composition range of H2 and CO in the crude hydrogen, and eliminating the need for additional production or separation equipment.

[0027] The method provided by this invention can be flexibly adjusted according to the requirements of the gas phase products and liquid phase products of the process. For example, the ratio of olefins / esters can be adjusted according to the ratio of H2 / CO in the gas source to obtain the desired product distribution and enrich the tail gas distribution.

[0028] According to some preferred embodiments of the present invention, the mass ratio of the ester compound to the olefin is P1, and the volume ratio of H2 to CO is P2. P1 and P2 satisfy the condition that the ratio of P1 to P2 is 0.5-5, for example, it can be a specific but not limiting ratio such as 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, etc. Using the above preferred embodiments is beneficial for high selectivity of the hydroformylation product.

[0029] Preferably, the mass ratio P1 of the ester compound to the olefin is 1-10, more preferably 1.5-5.

[0030] Preferably, the volume ratio of H2 to CO, P2, is 0.5-5.

[0031] In this invention, the content range of the first active component and the second active component in the catalytic material is relatively wide. As long as the catalytic material contains the above two active components, olefin hydroformylation and ester hydrogenation can be achieved simultaneously during the reaction process.

[0032] According to some preferred embodiments of the present invention, in the catalytic material, the mass ratio of the first active component Cu to the second active component Rh is 100:(0.5-10), for example, it can be a specific but not limiting mass ratio or any range between the two, such as 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10. Preferably, the mass ratio of the first active component Cu to the second active component Rh is 100:(1-5). In the above preferred cases, it is beneficial to further improve the selectivity of the hydroformylation product.

[0033] In this invention, there are no special requirements for the specific structure of the catalytic material. The catalytic material can be a single catalyst or a composition of two or more catalysts, as long as it contains the first active component and the second active component mentioned above.

[0034] According to some preferred embodiments of the present invention, the catalytic material is a single catalyst, comprising a support and a first active component and a second active component supported on the support. Preferably, based on the total amount of the catalytic material, the content of the support is 5-90 wt%, more preferably 10-80 wt%; the content of the first active component (based on elemental composition) is 10-90 wt%, more preferably 20-80 wt%; and the content of the second active component (based on elemental composition) is 0.01-5 wt%, more preferably 0.2-2 wt%.

[0035] According to some preferred embodiments of the present invention, the catalytic material includes a first catalyst and a second catalyst, the first catalyst including a first support and a first active component supported on the first support, and the second catalyst including a second support and a second active component supported on the second support.

[0036] Preferably, based on the total amount of the first catalyst, the content of the first support is 1-95 wt%, more preferably 30-90 wt%; and the content of the first active component, calculated by element, is 5-99 wt%, more preferably 10-70 wt%.

[0037] Preferably, based on the total amount of the second catalyst, the content of the second support is 95-99.99 wt%, more preferably 98-99.9 wt%; and the content of the second active component, calculated by element, is 0.01-5 wt%, more preferably 0.1-2 wt%.

[0038] When the catalytic material comprises a first catalyst and a second catalyst, the present invention does not particularly limit the contact method. The contact method may be: in the presence of an ester compound, contacting the olefin and crude hydrogen sequentially with the first catalyst and the second catalyst. Alternatively, the contact method may be: in the presence of an ester compound, contacting the olefin and crude hydrogen with a mixture of the first catalyst and the second catalyst.

[0039] In this invention, there are no particular requirements regarding the types of the carrier, the first carrier, and the second carrier mentioned above; conventional choices in the art can be used. Preferably, the carrier, the first carrier, and the second carrier are each independently selected from at least one of metal or non-metal oxides and carbon materials, and the metal or non-metal oxide is preferably at least one of SiO2, ZnO, ZrO2, and Al2O3.

[0040] According to the present invention, there is no particular limitation on the source of the catalytic material, and it can be prepared by any preparation method known in the art, as long as the composition of the catalytic material is satisfied.

[0041] According to the present invention, preferably, the method further includes: reducing and activating the catalytic material in the presence of hydrogen. The reduction and activation can be performed using methods conventional in the art, well known to those skilled in the art, as long as at least a portion of the first active component and at least a portion of the second active component can be reduced to elemental form. When the catalytic material comprises a first catalyst and a second catalyst, the first catalyst and the second catalyst can be reduced and activated separately, or they can be mixed before reduction and activation; the present invention does not particularly limit this.

[0042] According to some preferred embodiments of the present invention, the conditions for reduction activation include: a reduction temperature of 200-300°C, a reduction time of 0.5-2 h, and a hydrogen pressure of 0.02-0.5 MPa.

[0043] The present invention allows for a wide range of specific types of ester compounds. To further improve hydrogen capture efficiency and hydroformylation efficiency, preferably, the ester compound has the structure shown in formula (1).

[0044]

[0045] R1 and R2 may be the same or different, and each is independently selected from C1-C4 hydrocarbon groups, such as at least one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and pentyl; or R1 and R2 together with the attached carbon and oxygen atoms form a five- to eight-membered saturated or unsaturated heterocycle.

[0046] In a further preferred embodiment, the ester compound is selected from at least one of formate, butyrate, propionate, butyrolactone, and valerolactone. The hydrogenation product obtained using the above-preferred ester compounds is relatively easy to dehydrogenate, thereby achieving the function of producing high-purity hydrogen as a byproduct. The butyrate ester may be, for example, butyl butyrate, and the propionate ester may be, for example, propyl propionate. Preferably, the ester compound is selected from at least one of butyrolactone, valerolactone, and butyl butyrate.

[0047] According to the present invention, there are no particular requirements for the type of olefin, and those skilled in the art can select it according to actual production needs. Preferably, the olefin is selected from C6-C20 olefins, and more preferably at least one of hexene, octene, 1-hexadecene, styrene, p-vinyltoluene, 1-naphthylethylene, and 1-benzylethylene.

[0048] According to the present invention, the reaction includes olefin hydroformylation and ester hydrogenation. The present invention does not have special requirements for the conditions of the reaction, as long as the conditions are sufficient to enable the above two reactions to proceed.

[0049] According to some preferred embodiments of the present invention, the temperature of the reaction is 100-200°C, preferably 140-180°C.

[0050] Preferably, the reaction pressure is 0.1-10 MPa, more preferably 1-5 MPa.

[0051] By adopting the above-mentioned preferred embodiments, olefin hydroformylation and ester hydrogenation reactions can be achieved in the same temperature range without the need for material heating and cooling, which helps to further reduce heat loss and extend the service life of the catalyst.

[0052] The present invention does not have any special requirements for the reactor used in the reaction, and can be carried out in any conventional reaction apparatus in the art.

[0053] According to some preferred embodiments of the present invention, the contact is carried out in a batch reactor, such as a batch reactor, and the mass ratio of the catalyst to the olefin is 1:(5-50), preferably (10-20):1.

[0054] According to some other preferred embodiments of the invention, the contact is carried out in a continuous reactor, preferably in a fixed-bed reactor, and the mass hourly space velocity of the olefin is 0.01-10 h⁻¹ relative to the total mass of the catalyst material. -1 Preferably 0.1-5h -1 .

[0055] According to some preferred embodiments of the present invention, the method further includes: separating the products obtained from the reaction to obtain an olefin hydroformylation product and an ester hydrogenation product. The separation can be carried out using any conventional method in the art, as long as product separation is achieved, such as fractional distillation.

[0056] Preferably, the method further includes: subjecting the ester hydrogenation product to a dehydrogenation reaction to obtain hydrogen gas and a dehydrogenation product, wherein the dehydrogenation product is used to provide at least a portion of the ester compound. By employing the above preferred embodiments, the ester compound can be recycled while supplying high-purity hydrogen gas, thereby achieving the co-production of high-purity hydrogen in the olefin hydroformylation process, which is beneficial for further improving the economics of the process.

[0057] The present invention does not impose any particular limitations on the conditions for the dehydrogenation reaction, and it can be carried out using conventional methods and conditions in the art.

[0058] According to some preferred embodiments of the present invention, the dehydrogenation reaction is carried out in a batch reactor, and the conditions of the dehydrogenation reaction include: a temperature of 100-200°C, a reaction pressure of 0.01-1 MPa, and a mass ratio of the total amount of liquid phase stream to the dehydrogenation catalyst of 1:(0.02-0.5).

[0059] Alternatively, the dehydrogenation reaction may be carried out in a continuous reactor under the following conditions: a temperature of 100-240°C, a reaction pressure of 0.01-1 MPa, and a total liquid hourly space velocity (LLHSV) of 0.01-10 mL / g. cat. / h.

[0060] This invention does not impose any particular limitation on the dehydrogenation catalyst, and those skilled in the art can select one according to actual needs. Preferably, the dehydrogenation catalyst comprises a support and an active metal component Cu, wherein the support is selected from at least one of Al2O3, Cr2O3, MnO2, ZnO, and ZrO2. Based on the total amount of the dehydrogenation catalyst, the content of Cu element is 20-80 wt%, and the content of the support is 20-80 wt%.

[0061] In this invention, the dehydrogenation catalyst can be reduced before use. This invention does not have any particular limitations on the conditions of the reduction treatment, as long as some of the active metal components can be reduced to elemental form, which is well known to those skilled in the art.

[0062] The second invention provides an olefin hydroformylation reaction system, such as... Figure 1 As shown, the reaction system includes a raw material supply unit, a coupled reaction unit, and a product separation unit that are connected sequentially along the material flow direction;

[0063] The raw material supply unit includes an olefin storage tank 14, an ester compound storage tank 13, and a crude hydrogen supply device 1, which are used to supply olefins, ester compounds, and crude hydrogen to the coupled reaction unit.

[0064] Preferably, a gas compressor 2 is also provided on the pipeline between the crude hydrogen supply device 1 and the coupling reaction unit.

[0065] Preferably, the raw material supply unit further includes a liquid phase mixer 15 and an optional constant flow pump B16, for mixing olefins and esters from the olefin storage tank 14 and the ester compound storage tank 13, and then sending them into the coupling reaction unit.

[0066] According to the present invention, the coupled reaction unit includes at least one reactor for contacting olefins, esters, and crude hydrogen from the feedstock unit with a catalyst to carry out olefin hydroformylation and ester hydrogenation reactions. Preferably, the coupled reaction unit includes an ester hydrogenation reactor 4 and an olefin hydroformylation reactor 5 connected in series. Preferably, the coupled reaction unit further includes a heater A 3 for heating the feedstock from the feedstock unit before feeding it into the reactor.

[0067] Preferably, the reaction system further includes a tail gas recovery device 6 for collecting the reaction tail gas of the coupled reaction unit.

[0068] According to the present invention, the product separation unit is used to separate the reaction products from the coupled reaction unit to obtain a hydroformylation product and an ester hydrogenation product. Preferably, the product separation unit includes a separator 7. The present invention does not have a particular limitation on the device structure of the separator, as long as it can realize the above separation process.

[0069] Preferably, the reaction system further includes a hydroformylation product storage tank 8 connected to the separator for recovering the hydroformylation product.

[0070] Preferably, the reaction system further includes a dehydrogenation reactor 11, which is connected to both the product separation unit and the raw material supply unit. This reactor is used to dehydrogenate the separated ester hydrogenation product, and the resulting ester compounds are returned to the raw material supply unit. Using this preferred embodiment, high-purity hydrogen can be supplied simultaneously with the formylation reaction, and the ester compounds obtained from the dehydrogenation reaction can be reused, which helps reduce raw material costs and improves the overall economic efficiency of the reaction system. Preferably, a heater B10 and an optional constant-flow pump A9 are provided on the pipeline between the dehydrogenation reactor and the product separation unit to heat the ester hydrogenation product from the product separation unit before feeding it into the dehydrogenation reactor.

[0071] According to the present invention, the reaction system further includes a hydrogen storage tank 12, which is connected to the gas phase outlet of the dehydrogenation reactor 11, for recovering the hydrogen obtained from the dehydrogenation reaction.

[0072] The third aspect of the present invention provides the application of the above-described method for olefin hydroformylation or the above-described olefin hydroformylation reaction system in hydrogen production processes and / or olefin hydroformylation processes.

[0073] This method can be coupled with dehydrogenation steps, etc., to supply high-purity hydrogen while ester compounds can be recycled, thereby realizing the co-production of high-purity hydrogen in the olefin hydroformylation process, which is conducive to further improving the economics of the process.

[0074] The present invention will be described in detail below through embodiments.

[0075] Unless otherwise specified, all raw materials used in the following embodiments are commercially available.

[0076] Example 1

[0077] A Rh-Cu / SiO2 catalyst was used, with Cu comprising 30% by mass, Rh comprising 1% by mass, and the remainder being SiO2. The Rh-Cu / SiO2 catalyst was placed in a fixed-bed reaction tube, and the voids on both sides were filled with quartz sand. The catalyst was activated for 2 hours under H2 atmosphere, 250℃, and 0.1MPa.

[0078] Crude hydrogen (containing 16.7 vol% CO, 43.3 vol% H2, and the remainder N2) and a styrene-butyrolactone mixed liquid (styrene: 20 wt.%, butyrolactone: 80 wt.%) were simultaneously introduced into a fixed-bed reactor. The mass hourly space velocity (MSV) of styrene was 1 h⁻¹ relative to the mass of the catalyst. -1 The reaction was carried out at 170℃ and 3MPa for more than 5 hours.

[0079] The obtained liquid products were analyzed by gas chromatography. The results showed that the hydroformylation product of styrene accounted for 16.3 wt.%, the hydrogenation product of butyrolactone accounted for 13.3 wt.%, and the remainder was unconverted raw material.

[0080] Example 2

[0081] The catalysts used include Rh / Al2O3 catalyst (Rh mass fraction of 0.1%, the remainder being Al2O3) and Cu / ZrO2 catalyst (Cu mass fraction of 10%, the remainder being ZrO2).

[0082] 1 g of Cu / ZrO2 and 2 g of Rh / Al2O3 catalyst were respectively placed in the upper and lower layers of a fixed-bed reaction tube, and the voids on both sides were filled with quartz sand. The catalysts were activated for 2 h under H2 atmosphere, 250 °C, and 0.1 MPa.

[0083] Crude hydrogen (containing 10.7 vol.% CO and 75.1 vol.% H2) and a mixed liquid of p-vinyltoluene and propyl propionate (p-vinyltoluene: 20 wt.% and propyl propionate: 80 wt.%) were simultaneously fed into a fixed-bed reactor. The mass hourly space velocity (MSV) of p-vinyltoluene was 5 h⁻¹ relative to the total mass of Cu / ZrO₂ and Rh / Al₂O₃ catalysts. -1 The reaction was carried out at 140℃ and 3MPa for more than 5 hours.

[0084] The obtained liquid products were analyzed by gas chromatography, in which the hydroformylation product corresponding to vinyltoluene accounted for 4.1 wt.%, the hydrogenation product of propyl propionate accounted for 32.2 wt.%, and the remainder was unconverted raw material.

[0085] Example 3

[0086] The catalysts used include Rh / SiO2 catalyst (Rh mass fraction of 0.1%, the remainder being SiO2) and Cu / ZnO catalyst (Cu mass fraction of 10%, the remainder being ZnO).

[0087] 1 g of Cu / ZnO and 2 g of Rh / SiO2 catalyst were simultaneously placed in a fixed-bed reactor. The catalyst was activated for 2 h under H2 atmosphere, 250 °C, and 0.1 MPa.

[0088] Crude hydrogen (containing 40 vol.% CO and 60 vol.% H2) and a mixture of octene and ethyl butyrate (octene: 25 wt.% and ethyl butyrate: 75 wt.%) were simultaneously introduced into a fixed-bed reactor. The mass hourly space velocity (MSV) of octene was 2 h⁻¹. -1 The reaction was carried out at 140℃ and 0.1MPa for more than 5 hours.

[0089] The obtained liquid products were analyzed by gas chromatography, in which the hydroformylation product of octene accounted for 15 wt.%, the hydrogenation product of ethyl butyrate accounted for 10 wt.%, and the remainder was unconverted raw material.

[0090] Example 4

[0091] The method is the same as in Example 1, except that methyl formate is used instead of butyrolactone in equal mass.

[0092] The obtained liquid products were analyzed by gas chromatography. The hydroformylation product corresponding to styrene accounted for 10.3 wt.%, the hydrogenation product of methyl formate accounted for 7.9 wt.%, and the remainder was unconverted raw material.

[0093] Example 5

[0094] The method is the same as in Example 3, except that the amount of Cu / ZnO catalyst used is 1g and the amount of Rh / SiO2 catalyst used is 0.005g.

[0095] The obtained liquid products were analyzed by gas chromatography, in which the hydroformylation product of vinyltoluene accounted for 2.1 wt.%, the hydrogenation product of ethyl butyrate accounted for 8.5 wt.%, and the remainder was unconverted raw material.

[0096] Example 6

[0097] The method is the same as in Example 1, except that the reaction temperature is 100°C.

[0098] The obtained liquid products were analyzed by gas chromatography, in which the hydroformylation product corresponding to styrene accounted for 4.4 wt.%, the butyrolactone hydrogenation product accounted for 3.2 wt.%, and the remainder was unconverted raw material.

[0099] Comparative Example 1

[0100] The method is the same as in Example 6, except that crude hydrogen (containing 16.7 vol% CO, 43.3 vol% H2, and the remainder N2) and styrene are simultaneously introduced into the fixed-bed reactor.

[0101] The obtained liquid product was analyzed by gas chromatography, in which styrene hydroformylation product accounted for 1.4 wt.%, and the remainder was unconverted raw material.

[0102] Comparative Example 2

[0103] The method is the same as in Example 3, except that no Cu / ZnO catalyst is added.

[0104] The obtained liquid product was analyzed by gas chromatography, in which 2.1 wt.% of the styrene hydroformylation product was found, and the remainder was unconverted raw material.

[0105] Example 7

[0106] The mixture obtained from the hydroformylation and ester hydrogenation of the coupled system in Example 1, and the fractionated ester hydrogenation product, were pumped into a fixed-bed reactor using a constant flow pump. Hydrogen gas at a specific flow rate was used as the carrier gas, and a conventional Cu-based catalyst after reduction and activation was used. The reaction temperature was set at 170°C. The condensed gas was then analyzed by gas chromatography, revealing a hydrogen purity >99.99%. The ratio of butyrolactone to butanediol in the liquid phase could be adjusted by regulating the liquid hourly space velocity (LHSV).

[0107] The comparison of the above examples and comparative examples shows that by introducing ester compounds into the olefin hydroformylation reaction, crude hydrogen can be directly used to carry out the olefin formylation reaction, thereby improving the yield of the olefin formylation reaction.

[0108] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A method for hydroformylation of olefins using crude hydrogen, characterized in that, The method includes: reacting an olefin, crude hydrogen, and a catalyst in the presence of an ester compound to obtain an olefin hydroformylation product; the catalyst includes a first active component and a second active component, the first active component being Cu and the second active component being Rh; In the crude hydrogen, the volume ratio of H2 to CO is 0.1-10.

2. The method according to claim 1, wherein, The mass ratio of the ester compound to the olefin is P1, and the volume ratio of H2 to CO is P2. P1 and P2 satisfy the condition that 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 of H2 to CO, P2, is 0.5-5.

3. The method according to claim 1 or 2, wherein, In the catalytic material, the mass ratio of the first active component Cu to the second active component Rh is 100:(0.5-10), preferably 100:(1-5).

4. The method according to any one of claims 1-3, wherein, The catalytic material includes a support and a first active component and a second active component loaded on the support; Preferably, based on the total amount of the catalytic material, the content of the support is 5-90 wt%, the content of the first active component (based on elements) is 10-90 wt%, and the content of the second active component (based on elements) is 0.01-5 wt%.

5. The method according to any one of claims 1-3, wherein, The catalytic material includes a first catalyst and a second catalyst. The first catalyst includes a first support and a first active component supported on the first support. The second catalyst includes a second support and a second active component supported on the second support. Preferably, based on the total amount of the first catalyst, the content of the first support is 1-95 wt%, and the content of the first active component, calculated by element, is 5-99 wt%. Preferably, based on the total amount of the second catalyst, the content of the second support is 95-99.99 wt%, and the content of the second active component, calculated by element, is 0.01-5 wt%. Preferably, the contact method includes: contacting the olefin and crude hydrogen sequentially with the first catalyst and the second catalyst in the presence of an ester compound; or, contacting the olefin and crude hydrogen with a mixture of the first catalyst and the second catalyst in the presence of an ester compound. Preferably, the mass ratio of the first catalyst to the second catalyst is 1:(0.01-5), and more preferably 1:(0.2-2).

6. The method according to claim 4 or 5, wherein, The carrier, the first carrier, and the second carrier are each independently selected from at least one of metal or non-metal oxides and carbon materials, and the metal or non-metal oxides are preferably at least one of SiO2, ZnO, ZrO2, and Al2O3.

7. The method according to any one of claims 1-6, wherein, The ester compound has the structure shown in formula (1). R1 and R2 are each independently selected from C1-C4 hydrocarbon groups, or R1 and R2 together with the attached carbon and oxygen atoms form a five- to eight-membered saturated or unsaturated heterocycle. Preferably, the ester compound is selected from at least one of formate, butyrate, propionate, butyrolactone, and valproic acid. Preferably, the olefin is selected from C6-C20 olefins, and more preferably at least one of hexene, octene, 1-hexadecene, styrene, p-vinyltoluene, 1-naphthylethylene and 1-benzylethylene.

8. The method according to any one of claims 1-7, wherein, The reactions include olefin hydroformylation and ester hydrogenation. Preferably, the reaction temperature is 100-200℃, more preferably 140-180℃; Preferably, the reaction pressure is 0.1-10 MPa, more preferably 1-5 MPa; Preferably, the contact is carried out in a batch reactor, and the mass ratio of the catalyst to the olefin is 1:(5-50), more preferably 1:(10-20); or, the contact is carried out in a continuous reactor, preferably a fixed-bed reactor, and the mass hourly space velocity of the olefin is 0.01-10 h⁻¹ relative to the total mass of the catalyst. -1 Preferably 0.1-5h -1 .

9. An olefin hydroformylation reaction system, comprising a raw material supply unit, a coupled reaction unit, and a product separation unit connected sequentially along the flow direction; in, The raw material supply unit includes an olefin storage tank, an ester compound storage tank, and a crude hydrogen supply device, which are used to supply olefins, ester compounds, and crude hydrogen to the coupled reaction unit. The coupled reaction unit includes at least one reactor for contacting olefins, esters and crude hydrogen from the feedstock unit with a catalytic material to carry out olefin hydroformylation and ester hydrogenation reactions. The product separation unit is used to separate the reaction products from the coupled reaction unit to obtain hydroformylation products and ester hydrogenation products. Preferably, the reaction system further includes a dehydrogenation reactor, which is connected to the product separation unit and the raw material supply unit respectively, and is used to dehydrogenate the separated ester hydrogenation product, and the dehydrogenated ester compound is returned to the raw material supply unit.

10. The method for olefin hydroformylation according to any one of claims 1-8 or the olefin hydroformylation reaction system according to claim 9, in hydrogen production processes and / or olefin hydroformylation processes.

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