Washing recovery system for propylene carbonylation catalyst
By designing a water washing and recovery system for propylene carbonylation catalysts and employing methods such as oxygen deprivation control and pH adjustment, the problem of reduced catalyst activity was solved, achieving efficient catalyst recovery and activity restoration, and ensuring the stability and safety of subsequent reactions.
Patent Information
- Application Number
- CN202423073330.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Utility models(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-12
- Publication Date
- 2026-02-17
- Estimated Expiration
- 2034-12-12
AI Technical Summary
In the prior art, the activity of propylene carbonylation catalysts decreases after a strongly exothermic reaction due to the generation of acidic substances, which affects their recycling. In addition, there is a problem of catalyst activity reduction caused by oxygen.
A water washing and recovery system for propylene carbonylation catalyst was designed, comprising a water washing tower, a detergent preparation tank, and a storage tank. By controlling oxygen deprivation and pH adjustment, acidic substances in the catalyst are neutralized using detergents such as disodium hydrogen phosphate, and oxygen is removed by a vacuum pump and nitrogen gas, thereby achieving continuous and stable washing of the catalyst.
This enables continuous and efficient washing and recovery of the catalyst, restoring its catalytic activity and ensuring the safety and efficiency of subsequent reactions.
Smart Images
Figure CN223915427U_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The utility model relates to the technical field of chemical synthesis, specifically relates to a kind of propylene carbonylation catalyst's water washing recovery system. BACKGROUND
[0002] Butyl octanol product is important basic organic synthesis raw material, mainly used for producing plasticizer, solvent, dehydrating agent, defoaming agent, dispersing agent, flotation agent, petroleum additive and synthetic perfume etc.Butyl octanol's extensive use promotes the dosage and yield of butyl octanol increase year by year.
[0003] Propylene low-pressure carbonyl synthesis method is most widely used in butyl octanol production, which uses n-butyraldehyde as solvent, propylene and synthesis gas to produce n-butyraldehyde and isobutyraldehyde under the action of catalyst, n / isobutyraldehyde can be hydrogenated to produce n-butanol and isobutanol, and n-butanol and isobutanol products are obtained by rectification separation; n / isobutyraldehyde can also be separated into n-butyraldehyde and isobutyraldehyde by isomerization column, isobutyraldehyde as byproduct, n-butyraldehyde is condensed and dehydrated to produce octylene aldehyde under the catalysis of sodium hydroxide, and crude octylene alcohol is produced by hydrogenation, and product octylene alcohol is obtained by rectification.
[0004] The catalyst used in propylene carbonylation reaction is generally rhodium phosphine catalyst, such as acetylacetone triphenyl phosphine rhodium carbonyl, which contains rhodium, a rare noble metal. After the completion of the carbonylation reaction, the catalyst needs to be recovered in the product-catalyst separation process, and the recovered catalyst is recycled after supplementing new catalyst. However, due to the strong exothermic carbonylation process, some side reactions occur, producing acidic substances, which reduces the activity of the catalyst. In order to maintain the catalytic activity of the catalyst, a part of the recovered catalyst can be washed with a weakly alkaline chemical agent to neutralize the acidic substances in the catalyst and restore its catalytic activity. Providing a continuous and stable catalyst washing recovery system that is conducive to maintaining the activity of the catalyst is an urgent technical problem to be solved. UTILITY MODEL CONTENT
[0005] In view of the deficiencies in the prior art, the utility model discloses a kind of propylene carbonylation catalyst's water washing recovery system, system can realize absolute oxygen control, pH value regulation, continuously, stably washes the catalyst after propylene carbonylation reaction.
[0006] In order to achieve the above technical purposes, the utility model provides a kind of propylene carbonylation catalyst's water washing recovery system, comprising: water washing tower, the sidewall of water washing tower is sequentially arranged by from lower to upper to be washed catalyst inlet, detergent inlet and water inlet, the top of water washing tower is arranged after washing catalyst sampling outlet, column kettle is arranged washing water sampling outlet;Washing water tank, the first feed inlet of washing water tank is connected washing water input pipe;The first discharge port of washing water tank is connected with the water inlet of water washing tower, second discharge port connects vacuum pump;Detergent preparation tank, the first feed inlet of detergent preparation tank is connected washing water input pipe, second feed inlet is used to input detergent;Detergent storage tank, the first discharge port of detergent preparation tank is connected the first feed inlet of detergent storage tank, the second feed inlet of detergent storage tank is connected washing water input pipe;The first discharge port of detergent storage tank is connected with the detergent inlet of water washing tower, second discharge port connects vacuum pump.
[0007] In the above technical solution, the catalyst to be washed output from the upstream product-catalyst separation process is continuously input from the catalyst-to-be-washed inlet at the lower part of the water washing tower, and is washed by contacting with deoxygenated water and chemical detergent solution input from the upper part of the water washing tower from lower to upper to remove impurities and residues attached to the surface of the catalyst and neutralize acidic substances in the catalyst. It should be noted that an important purpose of the water washing recovery system of the utility model is that the rhodium phosphine catalyst used in propylene carbonylation reaction needs to function best in a neutral environment with a pH value of 6.8-7.0, but acidic substances are also generated in the ligand process, which can affect the service life of the catalyst. Therefore, in order to achieve the best effect of catalyst recycling, the utility model sets a detergent inlet on the water washing tower to input a detergent for neutralizing acidic substances in the catalyst, such as disodium hydrogen phosphate, so that the catalyst after water washing is neutralized, thereby playing a better catalytic activity in the subsequent carbonylation reaction.
[0008] The above technical solution sets technical features for promoting deoxygenation control in the water washing process. Specifically, ① the second discharge port of the washing water tank is connected to the vacuum pump, so that the washing water tank is in a state of negative pressure or micro-negative pressure, which is conducive to the precipitation of dissolved oxygen in the washing water; ② the second discharge port of the detergent storage tank is connected to the vacuum pump, so that the detergent storage tank is in a state of negative pressure or micro-negative pressure, which promotes the precipitation of dissolved oxygen therein. Thus, by controlling the deoxygenation of the washing water and the detergent input into the water washing tower, the catalytic activity of the catalyst is prevented from being reduced or the safety of the subsequent carbonylation reaction is prevented from being affected due to the presence of oxygen in the water washing process.
[0009] In addition, the above technical solution sets a detergent supply section including a detergent preparation tank and a detergent storage tank, which can reduce the frequency of detergent preparation under limited production area and equipment conditions, and continuously input an appropriate amount of detergent into the water washing tower.
[0010] Compared with the prior art, the utility model discloses a washing tower sets the detergent entrance, through introducing the detergent in the catalyst washing process to adjust the acidity and alkalinity of catalyst, be favorable to the activity of catalyst to give play to, through washing water jar and detergent storage tank respectively connect vacuum pump to realize the anaerobic control and pH value control, promote the precipitation of dissolved oxygen in washing water and detergent, can avoid the existence of oxygen in the washing tower and reduce the activity of catalyst and influence the safety of subsequent carbonylation reaction. BRIEF DESCRIPTION OF DRAWINGS
[0011] The drawings accompanying the specification of this application provide further understanding of the utility model, the illustrative embodiment of the utility model and the explanation thereof are used to explain the utility model, and do not constitute improper limitation to the utility model. In the drawings:
[0012] Figure 1 Show the structure diagram of the utility model propylene carbonylation catalyst washing recovery system.
[0013] Among them, the above drawing includes the following figure marks:
[0014] 1-washing tower, 11-waiting to be washed catalyst entrance, 12-detergent entrance, 13-water inlet, 14-washed catalyst outlet, 15-washing water outlet, 2-washing water jar, 3-detergent preparation jar, 4-detergent storage jar, 51-washing water input pipe, 52-first nitrogen input pipe, 53-second nitrogen input pipe, 54-third nitrogen input pipe, 6-vacuum pump, 71-bubbling device, 72-liquid distributor, 81-first flowmeter, 82-interface meter, 83-second flowmeter, 84-pH detection meter, 85-third flowmeter, 91-first switch valve, 92-second switch valve, 93-third switch valve. DETAILED DESCRIPTION
[0015] In order to facilitate understanding of the utility model, the utility model will be described more comprehensively below, and the preferred embodiment of the utility model is given. But it should be understood that these embodiments are only used for more detailed description, and should not be understood as limiting the utility model in any form, that is, not intended to limit the protection scope of the utility model.
[0016] Except for the definition, the technical terms used in the following embodiments have the same meaning as generally understood by the person skilled in the art to which the utility model belongs. The test reagents used in the following embodiments are conventional biochemical reagents, unless otherwise specified. The experimental methods described, unless otherwise specified, are conventional methods.
[0017] In this invention, unless otherwise explicitly specified and limited, "above" or "below" the second feature can include direct contact between the first and second features, or contact between the first and second features through another feature between them. Furthermore, "above," "over," and "on top" of the second feature includes the first feature being above or diagonally above the second feature, or simply indicates that the first feature is at a higher level than the second feature. "Below," "below," and "under" the second feature includes the first feature being below or diagonally below the second feature, or simply indicates that the first feature is at a lower level than the second feature.
[0018] Furthermore, the terms "first," "second," "third," "fourth," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Thus, a feature defined with "first," "second," etc., may explicitly or implicitly include one or more of that feature. In the description of this invention, unless otherwise stated, "a plurality of" means two or more.
[0019] Example 1
[0020] A water washing and recovery system for propylene carbonylation catalyst, such as Figure 1 As shown, it includes:
[0021] The water washing tower 1 has a catalyst inlet 11, a detergent inlet 12 and a water inlet 13 arranged sequentially from bottom to top on its side wall. The top of the water washing tower 1 is provided with a catalyst outlet 14 after washing and the bottom of the tower is provided with a wash water outlet 15. The wash water tank 2 has a first feed port connected to a wash water input pipe 51.
[0022] The first outlet of the washing tank 2 is connected to the inlet 13 of the washing tower 1, and the second outlet is connected to the vacuum pump 6.
[0023] Detergent preparation tank 3, the first inlet of detergent preparation tank 3 is connected to wash water input pipe 51, and the second inlet is used to input detergent;
[0024] The detergent storage tank 4 has a first discharge port connected to the first inlet of the detergent preparation tank 3, and a second inlet of the detergent storage tank 4 connected to the wash water input pipe 51; the first discharge port of the detergent storage tank 4 is connected to the detergent inlet 12 of the water washing tower 1, and the second discharge port is connected to the vacuum pump 6.
[0025] This embodiment enables continuous catalyst washing. By introducing detergent into the catalyst washing process through a detergent inlet 12 in the water washing tower 1, the pH of the catalyst can be neutralized and controlled, which is beneficial to the catalyst activity. This embodiment incorporates a vacuum oxygen-free technical feature in the washing water tank 2 and the detergent storage tank 4, which can promote the release of dissolved oxygen in the washing water and detergent, thus preventing the catalyst activity from being reduced due to the presence of oxygen in the water washing tower 1.
[0026] It should be noted that, in order to improve process efficiency, those skilled in the art may, based on this utility model, install devices or equipment such as circulating pumps or compressors on pipelines used for circulating liquid or gaseous materials to improve material flow efficiency, without limiting the scope of protection of this utility model.
[0027] Optionally, a stirring paddle is provided in the detergent preparation tank 3 and / or detergent storage tank 4 to promote thorough mixing and homogenization of the detergent and demineralized water.
[0028] Example 2
[0029] Based on the water washing and recovery system of the propylene carbonylation catalyst shown in Example 1, in this example, the second inlet of the washing water tank 2 is connected to the first nitrogen input pipe 52 and the first nitrogen input pipe 52 extends into the washing water tank 2. Thus, by introducing nitrogen into the washing water tank 2 below the liquid surface, the effect of dissolved oxygen release in the washing water is optimized in combination with the vacuum pump 6 to draw a vacuum.
[0030] Example 3
[0031] Based on the water washing and recovery system of the propylene carbonylation catalyst shown in Example 1, in this example, the third inlet of the detergent storage tank 4 is connected to the second nitrogen input pipe 53 and the second nitrogen input pipe 53 extends into the detergent storage tank 4. By introducing nitrogen into the liquid surface of the detergent storage tank 4, the detergent solution is disturbed, and the deoxygenation effect of the detergent is further enhanced on the basis of vacuuming.
[0032] Example 4
[0033] Based on the water washing and recovery system of the propylene carbonylation catalyst shown in Example 1, the structure of the detergent preparation tank 3 has been optimized in this example.
[0034] Optionally, the second outlet of the detergent preparation tank 3 is connected to a vacuum pump 6. The vacuum pump 6 creates a vacuum, resulting in a negative or slightly negative pressure inside the detergent preparation tank 3, which promotes the release of dissolved oxygen from the prepared detergent solution.
[0035] Alternatively, the third inlet of the detergent preparation tank is connected to the third nitrogen input pipe 54, and the third nitrogen input pipe 54 extends into the detergent preparation tank 3. By introducing nitrogen into the detergent preparation tank 3 below the liquid level, the oxygen evolution effect in the detergent solution is optimized in conjunction with the vacuum pump 6.
[0036] Example 5
[0037] Based on the water washing and recovery system of the propylene carbonylation catalyst shown in any one of Examples 2-4, in this example, the first nitrogen input pipe 52, the second nitrogen input pipe 53, or the third nitrogen input pipe 54 are respectively connected to the bubbling device 71. Nitrogen gas is bubbled out below the liquid surface of the washing water tank 2, the detergent outlet storage tank 4, and the detergent preparation tank 3 through the bubbling device 71 to enhance the disturbance effect of nitrogen gas and promote the release of dissolved oxygen.
[0038] Optionally, the bubbling device 71 includes an annular tube with an outlet hole connected to the nitrogen inlet pipe. Those skilled in the art can select a suitable bubbling device 71 as needed to promote the uniform distribution of nitrogen below the liquid surface.
[0039] Optionally, a pressure gauge is installed on the pipeline connected to the vacuum pump; a switching valve and / or a flow meter connected to the pressure gauge signal are respectively installed on the first nitrogen input pipe 52 and / or the second nitrogen input pipe 53 and / or the third nitrogen input pipe 54, so as to realize the regulation of the pressure in the washing water tank 2, the detergent preparation tank 3 and the detergent storage tank 4, and optimize the dissolved oxygen release effect.
[0040] Example 6
[0041] Based on the water washing and recovery system of the propylene carbonylation catalyst shown in Example 1, in this example, a first flow meter 81 is installed on the pipeline connected to the inlet 11 of the catalyst to be washed, and a first switching valve 91 connected to the outlet 14 of the washed catalyst is installed on the pipeline.
[0042] In the water washing tower 1, the oil phase catalyst to be washed enters from the bottom and comes into countercurrent contact with the washing water entering from the top, forming an oil-water interface inside the tower. In order to promote sufficient contact between the catalyst to be washed and the washing water, in this embodiment, the output of the catalyst after washing can be interlocked and controlled according to the first flow meter 81 on the pipeline connected to the inlet 11 of the catalyst to be washed, thereby regulating the height of the oil-water interface and further improving the oil-water separation effect.
[0043] Example 7
[0044] Based on the water washing and recovery system for the propylene carbonylation catalyst shown in Example 1, an interface meter 82 is installed at the top of the water washing tower 1 in this example. A second flow meter 83 and a second switching valve 92 connected to the interface meter 82 are installed on the pipeline connected to the wash water outlet 15. The interface meter 82 can monitor the changes in the oil-water interface. At the same time, the flow rate of the washed water can be controlled by interlocking the second switching valve 92 and the second flow meter 83 on the wash water outlet pipeline according to the operating conditions, thereby realizing the regulation of the oil-water interface height and improving the catalyst washing effect.
[0045] Optionally, the number of interface gauges 82 can be multiple, such as three, to monitor the liquid level at different positions in the upper and top parts of the water washing tower 1. Further optionally, two interface gauges 82 are installed at the top of the water washing tower 1 to monitor the total liquid level changes, serving as a dual-interface safety measure. Even more optionally, at least one interface gauge 82 is installed in the upper part of the water washing tower 1 to serve as an oil phase safety measure, monitoring the liquid level changes in the upper half of the water washing tower 1.
[0046] Example 8
[0047] Based on the water washing and recovery system of the propylene carbonylation catalyst shown in Example 1, in this example, a pH meter 84 is respectively installed on the pipeline connecting the detergent inlet 12 and the wash water outlet 15. A third switching valve 93 and / or a third flow meter 85 connected to the pH meter 84 are installed on the pipeline connecting the detergent inlet 12. The pH meter 84 is connected to the second flow meter 83 and the second switching valve 92.
[0048] This embodiment detects the pH value of the detergent input to the washing tower 1 and the pH value of the collected wash water, and controls the flow rate of the detergent output pipeline and the closing of the third switch valve 93 through interlocking, as well as the flow rate of the wash water outlet 15 output pipeline and the closing of the second switch valve 92 through interlocking, thereby achieving the regulation of the acidity and alkalinity of the catalyst after washing, so as to facilitate the catalytic activity of the catalyst in the subsequent carbonylation reaction.
[0049] Optionally, a pH meter 84 is installed on the pipeline connecting the detergent preparation tank 3 and the detergent storage tank 4 to facilitate the monitoring of the pH value of the detergent solution input to the detergent storage tank 4, thereby improving the operability of process pH monitoring and control.
[0050] Example 9
[0051] Based on the water washing and recovery system for the propylene carbonylation catalyst shown in Example 1, the water washing tower 1 in this example is a packed tower. By filling the water washing tower 1 with packing material, mass transfer contact between the wash water and the catalyst to be washed can be promoted. Optionally, at least three sections of packing material are provided in the water washing tower 1. Each section of packing material can be optionally located below the catalyst inlet 11, the detergent inlet 12, and the water inlet 13, respectively, thereby promoting sufficient mass transfer between the oil and water phases and improving the catalyst washing effect.
[0052] Example 10
[0053] Based on the water washing and recovery system for the propylene carbonylation catalyst shown in Example 1, in this example, the catalyst inlet 11 to be washed and / or the detergent inlet 12 are connected to a liquid distributor 72. Through the dispersing effect of the liquid distribution, the catalyst to be washed or the detergent comes into more uniform contact with the material in the water washing tower 1, thereby improving the accuracy of the catalyst pH control.
[0054] It should be noted that the specific type of liquid distributor 72 in this utility model is not limited. For example, it can be selected as a ring tube structure including a liquid outlet. Those skilled in the art can select a device or equipment that can promote the uniformity of liquid distribution as needed, and this does not limit the scope of protection of this utility model.
[0055] It should be noted that the above description is a further detailed explanation of the present invention in conjunction with specific embodiments, and should not be construed as limiting the specific implementation of the present invention to these descriptions; the dimensional data in this embodiment do not limit the technical solution, but merely illustrate one specific working condition. For those skilled in the art to which this invention pertains, several simple improvements and modifications can be made without departing from the concept of the present invention, and all such improvements and modifications should be considered to fall within the scope of protection of the present invention.
Claims
1. A water washing and recovery system for a propylene carbonylation catalyst, characterized in that, include: A water washing tower (1) is provided with a catalyst inlet (11), a detergent inlet (12) and a water inlet (13) arranged sequentially from bottom to top on the side wall of the water washing tower (1). A catalyst outlet (14) is provided at the top of the water washing tower (1) and a wash water outlet (15) is provided at the bottom of the tower. Washing tank (2), the first inlet of the washing tank (2) is connected to the washing water input pipe (51); the first outlet of the washing tank (2) is connected to the water inlet (13) of the washing tower (1), and the second outlet is connected to the vacuum pump (6). The detergent preparation tank (3) has a first inlet connected to a wash water input pipe (51) and a second inlet for inputting detergent. The detergent storage tank (4) has its first outlet connected to the first inlet of the detergent preparation tank (3), and its second inlet connected to the wash water input pipe (51). The first outlet of the detergent storage tank (4) is connected to the detergent inlet (12) of the water washing tower (1), and its second outlet is connected to the vacuum pump (6).
2. The water washing and recovery system for the propylene carbonylation catalyst according to claim 1, characterized in that, The second inlet of the washing tank (2) is connected to the first nitrogen input pipe (52), and the first nitrogen input pipe (52) extends into the washing tank (2).
3. The water washing and recovery system for the propylene carbonylation catalyst according to claim 1, characterized in that, The third inlet of the detergent storage tank (4) is connected to the second nitrogen input pipe (53), and the second nitrogen input pipe (53) extends into the detergent storage tank (4).
4. The water washing and recovery system for the propylene carbonylation catalyst according to claim 1, characterized in that, The second outlet of the detergent preparation tank (3) is connected to a vacuum pump (6).
5. The water washing and recovery system for the propylene carbonylation catalyst according to claim 4, characterized in that, The third inlet of the detergent preparation tank (3) is connected to the third nitrogen input pipe (54), and the third nitrogen input pipe (54) extends into the detergent preparation tank (3).
6. The water washing and recovery system for the propylene carbonylation catalyst according to claim 1, characterized in that, A first flow meter (81) is installed on the pipeline connected to the inlet (11) of the catalyst to be washed, and a first switching valve (91) connected to the outlet (14) of the washed catalyst is installed on the pipeline. The first flow meter (81) is connected to the first switching valve (91) for signal communication.
7. The water washing and recovery system for the propylene carbonylation catalyst according to claim 1, characterized in that, An interface meter (82) is installed on the upper part of the water washing tower (1), and a second flow meter (83) and a second switching valve (92) connected to the interface meter (82) are installed on the pipeline connected to the washing water outlet (15).
8. The water washing and recovery system for the propylene carbonylation catalyst according to claim 1, characterized in that, A pH meter (84) is installed on the pipeline connecting the detergent inlet (12) and the wash water outlet (15). A third switch valve (93) and / or a third flow meter (85) connected to the pH meter (84) are installed on the pipeline connecting the detergent inlet (12). The pH meter (84) is connected to the second flow meter (83) and the second switch valve (92).
9. The water washing and recovery system for the propylene carbonylation catalyst according to claim 1, characterized in that, The water washing tower (1) is a packed tower.
10. The water washing and recovery system for the propylene carbonylation catalyst according to claim 1, characterized in that, The catalyst inlet (11) to be washed and / or the detergent inlet (12) are connected to the liquid distributor (72).