A system and method for the production of a butyraldehyde-butanol mixture

Abstract

The application provides a preparation system and method of butyraldehyde-butanol mixture, which comprises a high-pressure reactor, wherein a partition plate is arranged in the middle of the high-pressure reactor; a first reaction zone is arranged above the partition plate, and a second reaction zone is arranged below the partition plate; a catalyst inlet is arranged on the side wall of the first reaction zone and the second reaction zone; a propylene inlet and a carbon monoxide inlet are arranged on the side wall of the first reaction zone; a first bubble breaker set is arranged in the first reaction zone; a mixed gas inlet is arranged on the side wall of the second reaction zone; and a second bubble breaker set is arranged in the second reaction zone. The system has a simple overall structure, butyraldehyde-butanol is prepared through the arrangement of two reaction zones, and the reaction efficiency is improved; meanwhile, the bubble breaker set is arranged in the high-pressure reactor, the phase interface mass transfer area of gas-liquid two phases is improved, the gas utilization rate and the reaction efficiency are improved, the energy consumption and the raw material loss are reduced, and the operation process is simplified.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of butyraldehyde and butanol preparation, and in particular to a system and method for preparing a butyraldehyde-butanol mixture. BACKGROUND

[0002] In the chemical industry, butanol and butyraldehyde are very important chemicals and are widely used in the manufacture of plastics, solvents and various chemical products. Butanol is usually obtained by the hydrogenation reduction of butyraldehyde, and the production of butyraldehyde mainly relies on the hydroformylation reaction of propylene and carbon monoxide. In the prior art, metal rhodium is usually used as a catalyst in the hydroformylation reaction process, and although various rhodium-based catalysts have been developed, these methods still face the problems of low conversion rate and complicated reaction steps. First, the butyraldehyde generated by the reaction needs to undergo a complex separation process to obtain high-purity butyraldehyde, and then the hydrogenation reduction can be carried out to produce butanol. This not only increases the production cost, but also reduces the overall production efficiency.

[0003] Moreover, the current butyraldehyde and butanol production process is limited due to its multi-step operation, high energy consumption and complex separation process. In particular, in the process of directly preparing a butyraldehyde-butanol mixture from propylene and carbon monoxide, the existing technology cannot effectively simplify the production steps and the conversion of propylene and carbon monoxide gas in the reaction process is not complete, resulting in low gas utilization rate. In addition, traditional methods require expensive catalysts and high-investment equipment, further increasing production costs.

[0004] Therefore, the present application is proposed. SUMMARY

[0005] The purpose of the present application is to provide a system and method for preparing a butyraldehyde-butanol mixture, which has a simple overall structure, improves the reaction efficiency by setting two reaction zones for the preparation of butyraldehyde-butanol, and at the same time, sets a gas bubble breaker set in the high-pressure reactor to increase the phase boundary mass transfer area of the gas-liquid two-phase, improve the gas utilization rate and reaction efficiency, reduce energy consumption and raw material loss, and simplify the operation process.

[0006] In order to achieve the above-mentioned purpose of the present application, the following technical solutions are adopted:

[0007] The present application provides a system for preparing a butyraldehyde-butanol mixture, comprising:

[0008] A high-pressure reactor is provided, and a partition plate is arranged in the middle of the high-pressure reactor; the first reaction zone is above the partition plate, and the second reaction zone is below the partition plate; a catalyst inlet is arranged on the side wall of the first reaction zone and the second reaction zone;

[0009] A propylene inlet and a carbon monoxide inlet are arranged on the side wall of the first reaction zone; a first gas bubble breaker set is arranged in the first reaction zone;

[0010] The second reaction zone side wall is configured with a mixed gas inlet; and the second reaction zone is provided with a second bubble breaker unit.

[0011] In the prior art, butyraldehyde generated by reaction needs to undergo a complex separation process to obtain high-purity butyraldehyde, and then hydrogenation reduction is performed to produce butanol. The current butyraldehyde and butanol production process is limited due to its multi-step operation, high energy consumption and complex separation process. In particular, in the process of directly preparing butyraldehyde-butanol mixture from propylene and carbon monoxide, the existing technology cannot effectively simplify the production steps and the conversion of propylene and carbon monoxide gas is not complete in the reaction process, and the utilization rate of gas is low.

[0012] The present application simplifies the preparation process of butyraldehyde-butanol mixture, does not require complex and tedious devices, and prepares butyraldehyde-butanol mixture by one-step method. In the device selection, a high-pressure reactor is used as the reaction device, and the high-pressure reactor is divided into two reaction zones by a partition plate to realize the function of two-stage reaction in the same reaction zone. The first reaction zone is a pre-reaction zone for preparing butyraldehyde by hydroformylation of propylene and carbon monoxide; the second reaction zone is a main reaction zone for further reacting the butyraldehyde generated in the first reaction zone and the butyraldehyde not completely reacted to generate butyraldehyde-butanol mixture; and a first bubble breaker unit and a second bubble breaker unit are respectively arranged in the first reaction zone and the second reaction zone to break and disperse the reaction raw materials in the reactor into micron-sized bubbles, improve the solubility of the gas, and at the same time, improve the contact area of the gas-liquid two phases, thereby improving the utilization rate of the raw materials.

[0013] Preferably, the first bubble breaker unit comprises a first bubble breaker arranged at the bottom of the first reaction zone and a plurality of diffusion discs arranged above the first bubble breaker, and there is an empty layer between adjacent two diffusion discs. The first bubble breaker can break and disperse propylene and carbon monoxide gas, and the diffusion discs are arranged above the first bubble breaker. The first bubble breaker and the diffusion discs are used in combination to further refine the bubbles coming out of the first bubble breaker, increase the surface area of gas-liquid contact, and improve the mass transfer efficiency. At the same time, the diffusion discs can make the gas-liquid distribution more uniform and reduce gas aggregation. By arranging the empty layer, the gas flow path is optimized to avoid excessive aggregation of bubbles during the rising process, thereby maintaining the minimum size of the bubbles coming out of the first bubble breaker and the diffusion discs, and further improving the efficiency of gas-liquid reaction and the utilization rate of gas.

[0014] Preferably, a plurality of beams are connected between adjacent diffusion discs to support the diffusion discs, and the plurality of beams divide the empty layer into a plurality of independent areas. By dividing the empty layer into a plurality of independent areas through the beams, the path of the gas from the first bubble breaker through the diffusion discs can be effectively controlled, thereby uniformly distributing the gas and increasing the opportunity for gas-liquid contact, enhancing the uniformity and efficiency of the reaction. By optimizing the distribution and mass transfer process of the gas, the efficiency of the reaction is improved, and the yield of butyraldehyde and butanol is increased. Meanwhile, the support of the beams can enhance the overall structural stability of the diffusion discs.

[0015] Preferably, the second bubble breaker set comprises a second bubble breaker and a third bubble breaker, the second bubble breaker is arranged above the third bubble breaker and the second bubble breaker and the third bubble breaker are arranged in the same straight line, a communication pipeline is arranged between the second bubble breaker and the third bubble breaker, and an output hole for outputting internal materials is arranged at a middle part of the communication pipeline. By arranging two bubble breakers in an up-down direction, the raw materials from the two bubble breakers can be counteracted, the bubble size is further refined, the surface area of gas-liquid contact is increased, and the reaction uniformity is improved, thereby improving the reaction speed and efficiency.

[0016] Moreover, the second reaction zone as the main reaction zone needs to further generate butyraldehyde-butanol mixture through hydrogenation reaction of butyraldehyde and incompletely reacted raw materials overflowing from the first reaction zone, therefore, the second bubble breaker set not only needs to continue to provide good bubble breaking and dispersion effect, but also needs to consider the effective dispersion and utilization of hydrogenation gas to ensure sufficient reaction of butyraldehyde. The present application arranges two oppositely arranged bubble breakers in the second bubble breaker set, which can generate smaller and uniformly distributed bubbles, reduce the occurrence of local over-reaction or unreacted areas, and improve product quality.

[0017] Preferably, a plurality of throttle discs are arranged in the communication pipeline, and the distance between adjacent two throttle discs is equal. By arranging the throttle discs in the communication pipeline, the local pressure drop generated by the throttle discs in the communication pipeline increases the shear force of the fluid, which can further refine the passing bubbles, so that the bubbles reach a smaller size before entering the second reaction zone, thereby increasing the surface area of gas-liquid contact and improving the solubility of the gas. Meanwhile, by uniformly arranging the throttle discs, the gas will experience a pressure drop and speed adjustment when flowing through each layer of throttle discs, which on the one hand prolongs the reaction time, and on the other hand makes the gas distribution more uniform, which is beneficial to improve the reaction efficiency of the whole reaction system and the conversion rate of the reactants.

[0018] Preferably, a stirring assembly is arranged below the second bubble breaker group, which comprises a stirring shaft and stirring blades installed at the end of the stirring shaft. When the micro-bubbles generated by the second bubble breaker group pass through the stirring zone, the movement of the stirring blades further disperses the bubbles, increases the gas-liquid contact area, and thus improves the gas dissolution rate and mass transfer efficiency. The stirring assembly ensures the continuous flow of the entire reaction liquid, so that the reactants in the reaction zone can be continuously updated, ensuring the uniform progress of the reaction.

[0019] Those skilled in the art can understand that the bubble breaker used in the present application has been embodied in the prior patents of the present inventor, such as the patents with the application numbers CN201610641119.6, CN201610641251.7, CN201710766435.0, CN106187660, CN105903425A, CN109437390A, CN205833127U and CN207581700U. The specific product structure and working principle of the micron bubble generator (i.e. bubble breaker) are introduced in detail in the prior patent CN201610641119.6, which records in the application file that "the micron bubble generator comprises a body and a secondary breaking piece, the body has a cavity, the body is provided with an inlet communicating with the cavity, the opposite first end and the second end of the cavity are open, wherein the cross-sectional area of the cavity decreases from the middle of the cavity to the first end and the second end of the cavity; the secondary breaking piece is arranged at least one of the first end and the second end of the cavity, a part of the secondary breaking piece is arranged in the cavity, and an annular channel is formed between the secondary breaking piece and the open through hole at both ends of the cavity. The micron bubble generator further comprises a gas inlet pipe and a liquid inlet pipe." From the specific structure disclosed in the application file, the specific working principle can be known: the liquid enters the micron bubble generator tangentially through the liquid inlet pipe, rotates at a high speed and cuts the gas, so that the gas bubbles are broken into micron-sized micro-bubbles, thereby increasing the mass transfer area between the liquid phase and the gas phase, and the micron bubble generator in the patent belongs to a pneumatic bubble breaker.

[0020] In addition, the prior patent 201610641251.7 discloses that a primary bubble breaker has a circulating liquid inlet, a circulating gas inlet and a gas-liquid mixture outlet, and a secondary bubble breaker is connected with the feed inlet and the gas-liquid mixture outlet, which indicates that the bubble breaker needs gas-liquid mixture to enter. In addition, from the following drawings, it can be seen that the primary bubble breaker mainly uses circulating liquid as power, so the primary bubble breaker actually belongs to a liquid-driven enhanced reactor. The secondary bubble breaker is connected with the gas-liquid mixture to rotate in the elliptical rotating ball, so as to realize bubble breaking in the rotating process. Therefore, the secondary bubble breaker actually belongs to a gas-liquid linkage type bubble breaker. Actually, whether the liquid-driven bubble breaker or the gas-liquid linkage type bubble breaker belongs to a specific form of bubble breaker, but the bubble breaker adopted in the present application is not limited to the above-mentioned forms. The specific structure of the bubble breaker disclosed in the prior patent is only one form that can be adopted in the present application.

[0021] In addition, the prior patent 201710766435.0 discloses that the principle of the bubble breaker is high-speed jet flow to achieve mutual collision of gas. In addition, the prior patent CN106187660 also discloses the specific structure of the bubble breaker, specifically see paragraphs

[0031] -

[0041] in the specification and the drawing part, which has a detailed description of the specific working principle of the bubble breaker S-2. The top of the bubble breaker is a liquid phase inlet, and the side is a gas phase inlet. The liquid phase from the top provides the entrainment power, so as to achieve the effect of crushing into ultra-fine bubbles. It can be seen from the drawing that the bubble breaker has a conical structure, and the diameter of the upper part is larger than that of the lower part, so that the liquid phase can provide better entrainment power.

[0022] In the early stage of the prior patent application, the bubble breaker was just developed, so it was named as a micron bubble generator (CN201610641119.6) in the early stage. With continuous technical improvement, it was renamed as a bubble breaker in the later stage. The bubble breaker in the present application is equivalent to the previous micron bubble generator and micro-interface generator, only the name is different. In summary, the bubble breaker of the present application belongs to the prior art.

[0023] Preferably, the first reaction zone is provided with an overflow pipe penetrating the partition plate to communicate the first reaction zone and the second reaction zone; and the product generated in the first reaction zone enters the second reaction zone through the overflow pipe. The overflow pipe enables the unreacted raw materials and intermediate products in the first reaction zone to directly enter the second reaction zone for continuous reaction, thereby reducing the waste of raw materials and improving the utilization rate of raw materials.

[0024] Preferably, a gas collecting chamber is provided at the top of the first reaction zone, the gas collecting chamber being higher than the liquid level in the first reaction zone. The gas outlet of the gas collecting chamber is connected to the first crushing unit to recover unreacted gas from the first reaction zone. By setting up the gas collecting chamber, unreacted gas can be recovered. The gas collecting chamber can effectively collect unreacted or partially reacted gaseous raw materials (such as propylene and carbon monoxide) in the first reaction zone, and reintroduce them into the first bubble crushing unit for reuse through the gas outlet. This recycling process reduces raw material loss, improves raw material utilization efficiency, and reduces environmental pollution.

[0025] Preferably, a demister is provided below the gas collecting chamber, the demister being located above the first bubble breaker unit and below the liquid surface in the first reaction zone. By providing the demister, large bubbles generated during the reaction can be broken up, improving gas recovery efficiency.

[0026] Preferably, the system for preparing the butyraldehyde-butanol mixture further includes:

[0027] The system includes a propylene storage tank, a carbon monoxide storage tank, and a hydrogen storage tank. The propylene storage tank and the carbon monoxide storage tank are respectively connected to the propylene inlet and the carbon monoxide inlet on the side wall of the first reaction zone. The hydrogen storage tank and the carbon monoxide storage tank are mixed in a mixed gas storage tank and then connected to the mixed gas inlet on the side wall of the second reaction zone.

[0028] A gas-liquid separator, wherein the gas-liquid separator is connected to the outlet at the bottom end of the high-pressure reactor;

[0029] A condenser is connected to the bottom of the gas-liquid separator.

[0030] Preferably, the outlet of the condenser is connected to a mixture separator to separate butyraldehyde and butanol.

[0031] In addition, the present invention also provides a method for preparing a butyraldehyde-butanol mixture, comprising the following steps: replacing the catalyst system with hydrogen, and after the replacement is completed, adding propylene, carbon monoxide and hydrogen in sequence to carry out a catalytic reaction to directly obtain a butyraldehyde-butanol mixture.

[0032] Preferably, the catalyst system is a catalytic system composed of organophosphorus-rhodium and organophosphorus-ruthenium in a certain proportion.

[0033] Preferably, the organophosphine ligand includes one or more of triphenylphosphine, 1,2-bis(diphenylphosphine)ethane, 1,8-bis(diphenylphosphine)naphthalene, 4,5-bisdiphenylphosphine-9,9-dimethyloxanthracene monophosphine or bisphosphine ligands.

[0034] Preferably, the mass ratio of the organophosphorus-rhodium and organophosphorus-ruthenium is (0-200):100.

[0035] The amount of the catalyst added is 0.005-2.0% of the solvent, calculated by mass percentage.

[0036] Preferably, the total pressure of the propylene, carbon monoxide and hydrogen is 0.5-3.0 MPa.

[0037] Preferably, the partial pressure ratio of the propylene to hydrogen is 10:1-1:10.

[0038] Preferably, the reaction temperature of the catalytic reaction is 80-160℃.

[0039] The catalyst system of the present application can be used in the process of preparing butyraldehyde from propylene and carbon monoxide, and also can be used in the process of preparing butanol from butyraldehyde hydrogenation, thus, the catalyst system of the present application can prepare a mixture of butyraldehyde-butanol in one step when propylene, carbon monoxide and hydrogen are all present. And under the condition of high temperature and high pressure and sufficient hydrogen, butyraldehyde in the mixture can be completely reduced to obtain butanol liquid. This is because the catalyst system of the present application combines organic phosphorus ligand with metal rhodium and cooperates with other metal catalysts, and the rhodium in the catalyst system is more resistant to high temperature and high pressure environment than the rhodium in the single metal rhodium-based catalyst in the prior art, thus, in the process of butyraldehyde hydrogenation, butyraldehyde can be catalyzed to generate butanol in one step without replacing the catalyst.

[0040] Compared with the prior art method of first preparing butyraldehyde from propylene hydroformylation and then preparing butanol from butyraldehyde reduction, the method adopted by the present application significantly simplifies the reaction process and effectively improves the reaction efficiency.

[0041] Compared with the prior art, the present application has the following advantages:

[0042] (1) By setting a partition plate in the high-pressure reactor, a staged reaction is realized, and by cooperating with the gas bubble breaker set, the solubility of the gas and the gas-liquid two-phase contact area are improved, thereby improving the reaction efficiency and the conversion rate of the raw materials.

[0043] (2) By setting a communication pipeline and a throttling disc in the second gas bubble breaker set, the local pressure drop generated in the communication pipeline increases the shear force of the fluid, which can further refine the passing bubbles, so that the bubbles reach a smaller size before entering the second reaction zone, thereby increasing the surface area of the gas-liquid contact and improving the solubility of the gas.

[0044] (3) By setting an overflow pipe to realize the continuous transmission of substances between the first reaction zone and the second reaction zone, and by designing the gas collection chamber and the defoaming disc, the system can more effectively control the reaction conditions, reduce the loss of unreacted gas, and prevent the excessive generation of reactant foam. BRIEF DESCRIPTION OF DRAWINGS

[0045] Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The accompanying drawings are included to provide a better understanding of the preferred embodiments, and are not intended to be limiting of the application. Moreover, in the drawings, like reference numerals denote similar parts throughout the several views. In the drawings:

[0046] Figure 1 A flow chart of a system for preparing a butyraldehyde-butanol mixture for use in Example 1 of the present application.

[0047] wherein:

[0048] 1 - high-pressure reactor; 101 - catalyst inlet;

[0049] 2 - partition plate; 3 - first reaction zone;

[0050] 301 - propylene inlet; 302 - carbon monoxide inlet;

[0051] 303 - gas collection chamber; 304 - demister tray;

[0052] 4 - second reaction zone; 401 - mixed gas inlet;

[0053] 402 - stirring assembly; 4021 - stirring shaft;

[0054] 4022 - stirring blade; 5 - overflow pipe;

[0055] 6 - first bubble breaker assembly; 601 - first bubble breaker;

[0056] 602 - diffusion disc; 603 - empty layer;

[0057] 604 - crossbeam; 7 - second bubble breaker assembly;

[0058] 701 - second bubble breaker; 702 - third bubble breaker;

[0059] 703 - communication pipe; 704 - throttling disc;

[0060] 8 - propylene storage tank; 9 - carbon monoxide storage tank;

[0061] 10 - hydrogen storage tank; 11 - gas-liquid separator;

[0062] 12 - condenser; 13 - mixed gas storage tank;

[0063] 14 - mixed liquid separator. DETAILED DESCRIPTION

[0064] The technical solutions of the present application will be described clearly and completely in the following description in combination with the drawings and specific embodiments, but those skilled in the art will understand that the following described embodiments are part of the embodiments of the present application, not all the embodiments, and are only used to illustrate the present application, and should not be regarded as limiting the scope of the present application. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application. If the specific conditions are not specified in the embodiments, the conventional conditions or the conditions recommended by the manufacturer are used. If the reagents or instruments used are not specified by the manufacturer, they are all conventional products that can be purchased on the market.

[0065] In the description of the present application, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer" and the like indicate the orientation or positional relationship shown in the drawings, which are only for the convenience of describing the present application and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a particular orientation, be constructed and operated in a particular orientation, and therefore cannot be understood as limiting the present application. In addition, the terms "first", "second", "third" are only for descriptive purposes and cannot be understood as indicating or implying relative importance.

[0066] In the description of the present application, it should be noted that unless otherwise explicitly specified and limited, the terms "mounting", "connecting", "connecting" should be understood broadly, for example, it can be fixedly connected, or it can be detachably connected, or integrally connected; it can be mechanically connected, or it can be electrically connected; it can be directly connected, or it can be indirectly connected through an intermediate medium; it can be the communication inside two elements. For those skilled in the art, the specific meaning of the above terms in the present application can be understood according to the specific circumstances.

[0067] In order to more clearly describe the technical solutions in the present application, the following will be described in the form of specific embodiments.

[0068] Embodiment 1

[0069] Referring to Figure 1 As shown in the figure, the preparation system of butyraldehyde-butanol mixture of the embodiment of the present application includes a high-pressure reactor 1, wherein a partition plate 2 is arranged in the middle of the high-pressure reactor 1, the partition plate 2 divides the upper part of the high-pressure reactor 1 into a first reaction zone 3 and divides the lower part of the high-pressure reactor 1 into a second reaction zone 4, and the side walls of the first reaction zone 3 and the second reaction zone 4 are provided with a catalyst inlet 101.

[0070] Preferably, an overflow pipe 5 is arranged in the first reaction zone 3, the overflow pipe 5 penetrates the partition plate 2 to communicate the first reaction zone 3 and the second reaction zone 4, and the products generated in the first reaction zone 3 enter the second reaction zone 4 through the overflow pipe 5.

[0071] Preferably, the first reaction zone 3 is provided with a propylene inlet 301 and a carbon monoxide inlet 302 on the side wall; and a first bubble breaker set 6 is arranged in the first reaction zone 3; wherein the first bubble breaker set 6 comprises a first bubble breaker 601 arranged at the bottom of the first reaction zone 3 and a plurality of diffusion discs 602 arranged above the first bubble breaker 601, and there is an empty layer 603 between adjacent two diffusion discs 602; specifically, a plurality of crossbeams 604 for supporting the diffusion discs 602 are connected between adjacent diffusion discs 602, and the empty layer 603 is divided into a plurality of independent areas by the plurality of crossbeams 604.

[0072] A gas collection chamber 303 is arranged at the top of the first reaction zone 3, the gas collection chamber 303 is higher than the liquid level in the first reaction zone 3, and the gas outlet of the gas collection chamber 303 is connected with the first bubble breaker set for recycling the unreacted gas in the first reaction zone 3.

[0073] Preferably, a defoaming disc 304 is arranged below the gas collection chamber 303, the defoaming disc 304 is arranged above the first bubble breaker set 6 and below the liquid level of the first reaction zone 3.

[0074] Preferably, the second reaction zone 4 is provided with a mixed gas inlet 401 on the side wall; and a second bubble breaker set 7 is arranged in the second reaction zone 4. Wherein the second bubble breaker set 7 comprises a second bubble breaker 701 and a third bubble breaker 702, the second bubble breaker 701 is arranged above the third bubble breaker 702 and the second bubble breaker 701 and the third bubble breaker 702 are arranged on the same straight line, and a communication pipeline 703 is arranged between the second bubble breaker 701 and the third bubble breaker 702. A plurality of throttle discs 704 are arranged in the communication pipeline 703, and the distance between adjacent two throttle discs 704 is equal.

[0075] Preferably, a stirring assembly 402 is arranged below the second bubble breaker set 7, the stirring assembly 402 comprises a stirring shaft 4021 and stirring blades 4022 mounted on the end of the stirring shaft 4021.

[0076] The butyraldehyde-butanol mixture preparation system of the embodiment further comprises:

[0077] A propylene storage tank 8, a carbon monoxide storage tank 9 and a hydrogen storage tank 10, the propylene storage tank 8 and the carbon monoxide storage tank 9 are connected with the propylene inlet 301 and the carbon monoxide inlet 302 on the side wall of the first reaction zone 3 respectively, and the hydrogen storage tank 10 is connected with the mixed gas inlet 401 on the side wall of the second reaction zone 4 after being mixed with the carbon monoxide storage tank 9 through the mixed gas storage tank 13.

[0078] A gas-liquid separator 11 is connected with the outlet at the bottom end of the high-pressure reactor 1.

[0079] A condenser 12 is connected to the bottom end of the gas-liquid separator 11.

[0080] The mixed liquid separator 14 is connected to the outlet of the condenser 12.

[0081] Example 2

[0082] Example 2 differs from Example 1 in that the first bubble breaker is disposed in the upper portion of the first reaction zone.

[0083] Example 3

[0084] Example 3 differs from Example 1 only in that the second bubble breaker and the third bubble breaker are not disposed on the same straight line.

[0085] Comparative Example 1

[0086] Comparative Example 1 differs from Example 1 only in that the first bubble breaker set is not provided.

[0087] Comparative Example 2

[0088] Comparative Example 2 differs from Example 1 only in that the second bubble breaker set is not provided.

[0089] Comparative Example 3

[0090] Comparative Example 3 differs from Example 1 only in that the first bubble breaker is not provided.

[0091] Comparative Example 4

[0092] Comparative Example 4 differs from Example 1 only in that the diffusion plate is not provided.

[0093] Comparative Example 5

[0094] Comparative Example 5 differs from Example 1 only in that the communication pipe is not provided.

[0095] Comparative Example 6

[0096] Comparative Example 6 differs from Example 1 only in that the throttle plate is not provided inside the communication pipe.

[0097] Comparative Example 7

[0098] Comparative Example 7 uses a related art to prepare a butyraldehyde-butanol mixture.

[0099] Experimental Example 1

[0100] The reaction system of the examples 1-3 and the comparative examples 1-7 was used to carry out the preparation reaction of butyl aldehyde-butyl alcohol mixture. The specific experimental conditions were as follows: triphenyl phosphine-ruthenium, triphenyl phosphine-rhodium, toluene were selected as catalysts, and the mass ratio of triphenyl phosphine-rhodium and triphenyl phosphine-ruthenium was 10:100. The reaction results are shown in Table 1 below.

[0101] Propylene conversion (%) Butanol fraction (%) Butyraldehyde fraction (%) Example 1 99.9 94 5 Example 2 98.2 92 6 Example 3 96.6 88 7 Comparative Example 1 91.6 83 7 Comparative Example 2 94.5 82 9 Comparative Example 3 93.3 84 8 Comparative Example 4 89.9 75 12 Comparative Example 5 88.3 72 15 Comparative Example 6 86.6 70 16 Comparative Example 7 80.5 60 20

[0102] Experimental example 2

[0103] The reaction system of the examples 1-3 and the comparative examples 1-7 was used to carry out the preparation reaction of butyl aldehyde-butyl alcohol mixture. The specific experimental conditions were as follows: triphenyl phosphine-ruthenium, toluene were selected as catalysts, and the reaction results are shown in Table 2 below.

[0104]

[0105]

[0106] Experimental example 3

[0107] The reaction system of the examples 1-3 and the comparative examples 1-7 was used to carry out the preparation reaction of butyl aldehyde-butyl alcohol mixture. The specific experimental conditions were as follows: triphenyl phosphine-ruthenium, triphenyl phosphine-rhodium, toluene were selected as catalysts, and the mass ratio of triphenyl phosphine-rhodium and triphenyl phosphine-ruthenium was 200:100. The reaction results are shown in Table 3 below.

[0108] Propylene conversion (%) Butanol fraction (%) Butyraldehyde fraction (%) Example 1 99.3 92 7 Example 2 97.5 90 7 Example 3 95.9 86 9 Comparative Example 1 90.9 81 9 Comparative Example 2 93.8 80 11 Comparative Example 3 92.7 82 10 Comparative Example 4 89.1 73 14 Comparative Example 5 87.6 70 17 Comparative Example 6 85.9 68 18 Comparative Example 7 79.9 58 22

[0109] According to the experimental data of the experimental examples 1-3, in the prior art, the conversion rate of propylene is about 80% when preparing butyl aldehyde-butyl alcohol, and the proportion of butyl alcohol is about 60%, and the proportion of butyl aldehyde is about 20%. According to Tables 1-3 above, compared with the prior art, the propylene conversion rate of the examples of the present application is significantly improved, and the proportion of butyl alcohol and the proportion of butyl aldehyde in the product are also significantly higher than those of the prior art, and the propylene conversion rate of example 1 reaches 99.9%.

[0110] And, from Table 1-3, it can be seen that the embodiment 1 of the present application is the optimal embodiment, regardless of the change of the use ratio of the catalyst, the embodiment 1 of the present application is the optimal embodiment. This is because the reaction system of the embodiment 1 uses the bubble breaking machine set in cooperation with the high-pressure reactor, and makes a differentiated design according to the focus of different reactions in the first reaction zone and the second reaction zone, and the proportion of butanol in the obtained product is obviously higher than that of the prior art and other embodiments and comparative examples, because the unique system design of the embodiment 1 of the present application improves the conversion rate of butanol. It can be seen that the preparation system of the embodiment 1 has high raw material conversion rate and good preparation effect.

[0111] Among them, the propylene conversion rate of comparative example 1 is lower than that of embodiment 1, because comparative example 1 does not set the first bubble breaking machine set, which cannot fully break and disperse the reaction raw materials in the first reaction zone, resulting in low conversion rate of propylene, and further resulting in low proportion of butanol and butyraldehyde in the whole product.

[0112] And the propylene conversion rate and the proportion of butanol in the product of comparative example 2 are also obviously lower than those of embodiment 1, because comparative example 2 does not set the second bubble breaking machine set, which cannot fully break and disperse the raw materials and hydrogen in the second reaction zone, resulting in low conversion rate of butyraldehyde, and further low proportion of butanol in the reaction product.

[0113] It can be seen from the experimental data of experimental examples 1-3 that among the catalysts, the reaction effect is the best when triphenylphosphine-ruthenium, triphenylphosphine-rhodium and toluene are selected as the catalysts, and the mass ratio of triphenylphosphine-rhodium to triphenylphosphine-ruthenium is 10:100.

[0114] Experimental example 4

[0115] The reaction system of embodiment 1 is used to prepare butyraldehyde-butanol mixture. The specific experimental conditions select different types of catalysts for catalytic reaction, and the experimental results of the corresponding catalysts in the reaction system of embodiment 1 are shown in Table 4.

[0116]

[0117]

[0118] From the experimental data of Table 4 and the experimental data of Table 1-3 of embodiment 1, it can be seen that only when the catalysts are selected as triphenylphosphine-ruthenium, triphenylphosphine-rhodium and toluene, and the mass ratio of triphenylphosphine-rhodium to triphenylphosphine-ruthenium is 10:100, the reaction effect is the best, and the single metal catalyst based on rhodium can only be used to prepare butyraldehyde, but cannot further reduce butyraldehyde to generate butanol.

[0119] The application also provides a preparation method of butyraldehyde-butanol mixture, comprising the following steps: hydrogen replacement for a catalyst system, after the replacement is completed, adding propylene, carbon monoxide and hydrogen in sequence for catalytic reaction, and directly obtaining butyraldehyde-butanol mixture.

[0120] Preferably, the catalyst system is an organic phosphine-rhodium or organic phosphine-ruthenium catalyst system.

[0121] Preferably, the organic phosphine ligand comprises one or more of triphenylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,8-bis(diphenylphosphino)naphthalene, 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene monophosphine or bisphosphine ligand.

[0122] Preferably, the mass ratio of the organic phosphine-rhodium and organic phosphine-ruthenium is (0-200):100.

[0123] Preferably, the added catalyst is 0.005-2.0% of the solvent in mass percentage.

[0124] Preferably, the total pressure of the propylene, carbon monoxide and hydrogen is 0.5-3.0 MPa.

[0125] Preferably, the partial pressure ratio of the propylene and hydrogen is 10:1-1:10.

[0126] Preferably, the reaction temperature of the catalytic reaction is 80-160℃.

[0127] Compared with the prior art, the preparation method of the application significantly simplifies the reaction process and effectively improves the reaction efficiency.

[0128] Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the application, and not to limit them; although the application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that they can still modify the technical solutions recorded in the foregoing embodiments, or make equivalent replacement for part or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the application.

Claims

1. A system for the production of a butyraldehyde-butanol mixture, characterized in that The application relates to a butyraldehyde-butanol mixture preparation system. The high-pressure reactor is provided with a partition plate; a first reaction zone is arranged above the partition plate, and a second reaction zone is arranged below the partition plate; a catalyst inlet is arranged on the side wall of the first reaction zone and the second reaction zone; A propylene inlet and a carbon monoxide inlet are arranged on the side wall of the first reaction zone; a first bubble breaker set is arranged in the first reaction zone; A mixed gas inlet is arranged on the side wall of the second reaction zone; a second bubble breaker set is arranged in the second reaction zone; The first bubble breaker set comprises a first bubble breaker arranged at the bottom of the first reaction zone and a plurality of diffusion discs arranged above the first bubble breaker; an air layer exists between adjacent diffusion discs; A plurality of crossbeams for supporting the diffusion discs are connected between adjacent diffusion discs, and the air layer is divided into a plurality of independent areas by the crossbeams; The second bubble breaker set comprises a second bubble breaker and a third bubble breaker; the second bubble breaker is arranged above the third bubble breaker and is arranged in a same straight line with the third bubble breaker; a communication pipeline is arranged between the second bubble breaker and the third bubble breaker; an output hole for outputting internal materials is arranged at the middle part of the communication pipeline; A plurality of throttle discs are arranged in the communication pipeline; the distance between adjacent throttle discs is equal; A stirring assembly is arranged below the second bubble breaker set; the stirring assembly comprises a stirring shaft and stirring blades arranged at the end of the stirring shaft; An overflow pipe is arranged in the first reaction zone; the overflow pipe penetrates through the partition plate and communicates the first reaction zone and the second reaction zone; the product generated in the first reaction zone enters the second reaction zone through the overflow pipe; A gas collecting chamber is arranged at the top of the first reaction zone; the gas collecting chamber is higher than the liquid surface in the first reaction zone; a gas outlet of the gas collecting chamber is connected with the first bubble breaker set for recycling unreacted gas in the first reaction zone; A defoaming disc is arranged below the gas collecting chamber; the defoaming disc is arranged above the first bubble breaker set and below the liquid surface of the first reaction zone.

2. The system for the production of butyraldehyde-butanol mixture according to claim 1, characterized in that, The butyraldehyde-butanol mixture preparation system further comprises: A propylene storage tank, a carbon monoxide storage tank and a hydrogen storage tank; the propylene storage tank and the carbon monoxide storage tank are connected with the propylene inlet and the carbon monoxide inlet on the side wall of the first reaction zone respectively; the hydrogen storage tank is mixed with the carbon monoxide storage tank through a mixed gas storage tank and is connected with the mixed gas inlet on the side wall of the second reaction zone; A gas-liquid separator is connected with the outlet at the bottom end of the high-pressure reactor; A condenser is connected with the bottom end of the gas-liquid separator.

3. A method for producing a butyral-butanolic mixture, characterized by using the butyral-butanolic mixture production system according to any one of claims 1 to 2, wherein The application further relates to a butyraldehyde-butanol mixture preparation method. The catalyst system is an organic phosphine-rhodium catalyst system and an organic phosphine-ruthenium catalyst system in a proper proportion; propylene, carbon monoxide and hydrogen are sequentially added after hydrogen replacement of the catalyst system for catalytic reaction, and a butyraldehyde-butanol mixture is directly obtained.

4. The process for the preparation of butyraldehyde-butanol mixtures according to claim 3, characterized in that, ​ The organic phosphine ligand includes one or more of triphenylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,8-bis(diphenylphosphino)naphthalene, 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene monophosphine or bisphosphine ligand.

5. The process for the preparation of butyraldehyde-butanol mixtures according to claim 4, characterized in that, The mass ratio of the organic phosphine-rhodium and the organic phosphine-ruthenium is (0-200):

100.

6. The process for the preparation of butyraldehyde-butanol mixture as claimed in claim 3, wherein, The total pressure of the propylene, carbon monoxide and hydrogen is 0.5-3.0 MPa. The partial pressure ratio of the propylene to hydrogen is 10:1-1:

10. The reaction temperature of the catalytic reaction is 80-160℃.

Images