Hydrogenation process in hydrogen peroxide production
By dividing the anthraquinone working liquid and hydrogen into two parts, the residence time of anthraquinone macromolecules in the catalyst channel is reduced, combined with dissolved gas equipment and temperature control, the side reaction and degradation problems in the hydrogenation process are solved, and more efficient is achieved hydrogenation reaction control and product quality.
Patent Information
- Application Number
- CN202411439036.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-15
- Publication Date
- 2025-01-14
AI Technical Summary
In the hydrogenation process in hydrogen peroxide production, the anthraquinone macromolecular organic matter stays in the catalyst channel for too long, resulting in aggravation of side reactions and serious degradation, making it difficult to effectively control the degree of hydrogenation.
The anthraquinone working liquid and hydrogen are divided into two parts. One is directly in contact with the working liquid, and the other is blown to the catalyst bed as supplementary hydrogen to reduce the residence time of macromolecules, and ensure hydrogen and anthraquinone through dissolved gas equipment and temperature control. Mix and react thoroughly.
It effectively reduces the residence time of anthraquinone macromolecules in the catalyst pores, avoids excessive hydrogenation and side reactions, strengthens the control and efficiency of the hydrogenation reaction, and improves the hydrogenation degree and utilization rate of the product.
Smart Images
Figure CN119306180A_ABST
Abstract
Description
Technical Field
[0001] The present application relates to the field of hydrogen peroxide production technology, and in particular to a hydrogenation process in hydrogen peroxide production. Background Art
[0002] Hydrogen peroxide is an important inorganic chemical product. It is often used as an oxidant, bleaching agent, disinfectant, deoxidizer, polymer, initiator and cross-linking agent in chemical, textile, papermaking, military, electronics, medicine, environmental protection and other industries.
[0003] The main industrial production method of hydrogen peroxide is the anthraquinone method. The anthraquinone method mostly uses a fixed bed reactor. A target catalyst bed is arranged in the fixed bed reactor. After the anthraquinone working solution and hydrogen are introduced into the reactor, a hydrogenation reaction occurs on the palladium catalyst bed. The working solution after the hydrogenation reaction is sent to an oxidation tower. The oxygen in the oxidation tower oxidizes the working solution after the hydrogenation reaction to obtain a hydrogen peroxide product.
[0004] From the perspective of the hydrogenation reaction process in the production of hydrogen peroxide by the anthraquinone method, the amount of anthraquinone hydrogenation is measured by the degree of hydrogenation (the degree of hydrogenation is the ratio of the mole of hydrogen anthraquinone generated by hydrogenation of the total anthraquinone in the working solution to the total effective anthraquinone). The control of the degree of hydrogenation varies with the selectivity of the catalyst. Regardless of the catalyst used, excessive hydrogenation is likely to cause the side reactions to intensify, and anthraquinone will be significantly or even severely degraded. In the hydrogenation process, the factors causing degradation are related to factors such as the catalyst type, reaction temperature, reaction pressure, hydrogen flow rate, and residence time of the working solution. However, under specific catalysts and reaction conditions, since anthraquinone is a macromolecular organic substance, its degradation reaction is mainly determined by the residence time of anthraquinone in the catalyst pores. Therefore, in the hydrogenation process for hydrogen peroxide production, it is necessary to reduce the residence time of anthraquinone macromolecular organic substances in the catalyst pores, that is, to reduce the time to achieve complete hydrogenation reaction, and diffuse the anthraquinone macromolecular organic substances in the catalyst pores in a timely manner. Summary of the invention
[0005] In order to reduce the residence time of anthraquinone macromolecular organic matter in the catalyst pores in the hydrogenation process of hydrogen peroxide production, that is, to reduce the time to reach a complete hydrogenation reaction, the anthraquinone macromolecular organic matter in the catalyst pores is diffused out in time, the present application provides a hydrogenation process in hydrogen peroxide production.
[0006] The hydrogenation process in the production of hydrogen peroxide provided in this application adopts the following technical solution: A hydrogenation process in the production of hydrogen peroxide comprises the following steps: S1: introducing anthraquinone working solution and hydrogen into a reaction tank, wherein a target catalyst bed is arranged in the reaction tank; S2: Adding supplementary hydrogen into the reaction tank, and blowing the supplementary hydrogen toward the target catalyst bed along the flow direction of the anthraquinone working solution; S3: Extract the product at the bottom of the reaction tank.
[0007] By adopting the above technical scheme, after the anthraquinone working solution and hydrogen are passed into the reactor, under the action of the catalyst in the target catalyst bed, a hydrogenation reaction occurs to obtain a working solution product after the hydrogenation reaction, and the working solution product after the hydrogenation reaction will fall to the bottom of the reactor and can be used after being extracted. The present application divides the hydrogen acting on the anthraquinone working solution into two parts, one part is directly contacted and mixed with the anthraquinone working solution, and the other part is supplemented into the reactor as supplementary hydrogen. When the anthraquinone working solution flows to the target catalyst bed, the supplementary hydrogen blown to the target catalyst bed can produce a disturbing effect, thereby avoiding the anthraquinone macromolecular byproduct from clogging the target catalyst bed pores, reducing the residence time of macromolecular anthraquinone and its derivatives in the target catalyst bed pores, and diffusing the anthraquinone macromolecular organic matter in the target catalyst bed pores in time.
[0008] In addition to the above effects, the method of adding hydrogen to the anthraquinone working solution in two parts can also prevent all the hydrogen required for the hydrogenation reaction from entering the reaction tank together with the anthraquinone working solution, resulting in excess hydrogen in a short period of time, which in turn leads to the occurrence of excessive hydrogenation reaction, aggravated side reactions, and serious degradation of anthraquinone.
[0009] Optionally, in step S1, before the anthraquinone working solution and hydrogen are introduced into the reaction tank, a gas dissolving device is used to dissolve the hydrogen in the anthraquinone working solution.
[0010] By adopting the above technical solution, the gas dissolving equipment dissolves hydrogen in the anthraquinone working liquid, especially allows the hydrogen to be fully mixed with the anthraquinone working liquid to obtain a mixed working liquid, the hydrogen in the mixed working liquid is evenly distributed, and after subsequently passing into the reaction tank, it can cooperate with the catalyst to undergo a continuous and uniform hydrogenation reaction, thereby allowing the product to achieve an ideal degree of hydrogenation; in addition, the efficiency of the hydrogenation reaction can be improved by pre-intervention treatment of the hydrogen neutralized in the anthraquinone working liquid, rather than just allowing the hydrogen to diffuse freely in the reaction tank and react with the anthraquinone working liquid.
[0011] Optionally, a temperature sensor and a cooling element are provided in the reaction tank. In step S1, after the anthraquinone working solution and hydrogen are introduced into the reaction tank, the temperature in the reaction tank is monitored in real time by the temperature sensor. When the temperature in the reaction tank reaches a set value, the cooling element operates to reduce the temperature in the reaction tank.
[0012] By adopting the above technical solution, the anthraquinone hydrogenation reaction is an exothermic reaction. During the hydrogenation reaction, the temperature in the reaction tank will increase. As the temperature increases, the positive and side reactions of hydrogenation will be accelerated. The side reaction is a degradation reaction, which will lead to a decrease in the effective anthraquinone content in the working fluid and cause changes in the physical properties of the working fluid. Therefore, the temperature in the reaction tank is monitored in real time by a temperature sensor. When the temperature in the reaction tank reaches the set value, the cooling component operates to reduce the temperature in the reaction tank, thereby controlling the temperature in the reaction tank to avoid the influence of temperature factors on the hydrogenation reaction.
[0013] Optionally, the cooling component includes a condenser disposed in the reaction tank. In step S1, when the temperature in the reaction tank reaches a warning value, a condensing medium is circulated into the condenser.
[0014] By adopting the above technical solution, when the temperature in the reaction tank reaches the set value, the condensing medium is circulated into the condenser tube, and the condensing medium performs heat exchange in the reaction tank to reduce the temperature in the reaction tank. The operation is simple and convenient.
[0015] Optionally, the condenser is arranged in a spiral shape, and a feed pipe and a discharge pipe are arranged on the reaction tank. The height corresponding to the position of the feed pipe on the reaction tank is higher than that of the discharge pipe, and both the feed pipe and the discharge pipe are connected to the condenser; in step S1, when the temperature in the reaction tank reaches the warning value, the condensing medium is introduced into the condenser through the feed pipe, and the condensing medium is extracted through the discharge pipe.
[0016] By adopting the above technical scheme, when the temperature in the reaction tank reaches the set value, the condensing medium is circulated into the condenser, the condensing medium is sent into the condenser through the feed pipe, and the condensing medium is extracted through the discharge pipe, thereby completing the circulation of the condensing medium. Since the height corresponding to the position of the feed pipe on the reaction tank is higher than that of the discharge pipe, the condensing medium entering the feed pipe will automatically flow toward the discharge pipe under the action of gravity, thereby facilitating the extraction of the condensing medium in the condenser; in addition, since the condenser is spirally arranged in the reaction tank, the condenser has a wider contact range for heat exchange, and the temperature control effect is better and the efficiency is higher.
[0017] Optionally, the reaction tank includes an outer tank body and an inner tank body, the target catalyst bed is arranged in the inner tank body, a receiving cavity is formed between the inner tank body and the outer tank body, and the condenser is arranged in the receiving cavity.
[0018] By adopting the above technical solution, the condenser is arranged in the containing cavity between the outer tank body and the inner tank body, thereby preventing the anthraquinone working liquid and the product in the hydrogenation reaction process from contacting the condenser and then being retained on the condenser, resulting in residue of the anthraquinone working liquid and the product, and reducing the utilization rate of the anthraquinone working liquid and the product; in addition, by avoiding direct contact between the anthraquinone working liquid and the product and the condenser, the condenser can also be prevented from corrosion, thereby increasing the service life of the condenser.
[0019] Optionally, in step S3, before extracting the product at the bottom of the reaction tank, additional hydrogen is introduced into the bottom of the reaction tank.
[0020] By adopting the above technical solution, the product after the hydrogenation reaction falls to the bottom of the reaction tank. Before the product is extracted from the bottom of the reaction tank for utilization, additional hydrogen is introduced into the bottom of the reaction tank again. The additional hydrogen can react again with the anthraquinone working solution that has not completely reacted in the product, thereby further ensuring the integrity of the hydrogenation reaction and avoiding the mixing of the anthraquinone working solution that has not completely reacted in the product, which on the one hand affects the subsequent utilization of the product, and on the other hand causes the anthraquinone working solution to be not fully utilized, resulting in waste of the anthraquinone working solution.
[0021] Optionally, a gas disperser is provided at the bottom of the reaction tank, and in step S3, supplementary hydrogen is introduced into the reaction tank through the gas disperser.
[0022] By adopting the above technical solution, the supplementary hydrogen introduced into the bottom of the reaction tank enters the reaction tank through the gas disperser, and the gas disperser can disperse the supplementary hydrogen and introduce it into the product, so that the supplementary hydrogen has a wider range of action, can more effectively and thoroughly contact the product and react again with the anthraquinone working solution therein.
[0023] Optionally, a hydrogen pipeline network is provided in the reaction tank, and a plurality of nozzles are provided on the hydrogen pipeline network, and the jet directions of the plurality of nozzles are all toward the target catalyst bed and consistent with the flow direction of the anthraquinone working solution; in step S2, supplementary hydrogen is introduced into the hydrogen pipeline network.
[0024] By adopting the above technical solution, when supplementary hydrogen is introduced into the reaction tank, the supplementary hydrogen is introduced through the hydrogen pipeline network, and multiple nozzles work together to spray the hydrogen in the hydrogen pipeline network to the target catalyst bed. On the one hand, the hydrogen is sprayed to the target catalyst bed in a wider range, so that the hydrogen can quickly and effectively contact the anthraquinone working solution to react. On the other hand, the setting of the nozzle makes the impact force of the sprayed hydrogen greater, so that the hydrogen can more forcefully blow out the large molecular anthraquinone and its derivatives in the pores of the target catalyst bed.
[0025] In summary, the present application includes at least one of the following beneficial technical effects: 1. The present application divides the hydrogen that reacts with the anthraquinone working solution into two parts, one part is directly contacted and mixed with the anthraquinone working solution, and the other part is added to the reaction tank as supplementary hydrogen. When the anthraquinone working solution flows to the target catalyst bed, the supplementary hydrogen blown to the target catalyst bed can produce a disturbance effect, thereby preventing the anthraquinone macromolecular byproduct from clogging the target catalyst bed pores, reducing the residence time of macromolecular anthraquinone and its derivatives in the target catalyst bed pores, and diffusing the anthraquinone macromolecular organic matter in the target catalyst bed pores in a timely manner; 2. The method of adding hydrogen to the anthraquinone working solution in two parts can also prevent all the hydrogen required for the hydrogenation reaction from entering the reaction tank together with the anthraquinone working solution, resulting in excess hydrogen in a short period of time, which in turn leads to the occurrence of excessive hydrogenation reaction, aggravated side reactions, and serious degradation of anthraquinone; 3. The gas dissolving equipment dissolves hydrogen in the anthraquinone working liquid, especially allows the hydrogen to be fully mixed with the anthraquinone working liquid to obtain a mixed working liquid. The hydrogen in the mixed working liquid is evenly distributed. After being subsequently introduced into the reaction tank, it can cooperate with the catalyst to undergo a continuous and uniform hydrogenation reaction, thereby allowing the product to achieve an ideal degree of hydrogenation. In addition, the efficiency of the hydrogenation reaction can be improved by pre-intervention treatment of the anthraquinone working liquid with hydrogen, rather than just allowing the hydrogen to diffuse freely in the reaction tank and react with the anthraquinone working liquid. BRIEF DESCRIPTION OF THE DRAWINGS
[0026] Figure 1 It is a schematic cross-sectional view of a reaction tank in a hydrogenation process in hydrogen peroxide production according to an embodiment of the present application.
[0027] Explanation of the accompanying drawings: 1. reaction tank; 101. inner tank body; 102. outer tank body; 2. target catalyst bed; 3. temperature sensor; 4. condenser; 5. containing chamber; 6. gas disperser; 7. hydrogen pipe network; 8. nozzle. DETAILED DESCRIPTION
[0028] The following is combined with Figure 1 This application is described in further detail.
[0029] The present application embodiment discloses a hydrogenation process in the production of hydrogen peroxide. Figure 1 , the hydrogenation process in hydrogen peroxide production includes the following steps: S1: passing anthraquinone working solution and hydrogen into a gas dissolving device, and the gas dissolving device dissolves hydrogen in the anthraquinone working solution; The anthraquinone working solution and hydrogen are introduced into the reaction tank 1, a plurality of target catalyst beds 2 parallel to each other are arranged in the anthraquinone hydrogenation reaction tank 1, a plurality of hydrogen pipelines 7 are arranged in the anthraquinone hydrogenation reaction tank 1, each hydrogen pipeline 7 corresponds to a target catalyst bed 2 and is located above the corresponding target catalyst bed 2, a plurality of nozzles 8 are arranged on the anthraquinone hydrogenation reaction hydrogen pipeline 7, and the jetting direction of the plurality of nozzles 8 is vertically downward; S2: Adding supplementary hydrogen to the hydrogen pipe network 7, and multiple nozzles 8 work together to spray the hydrogen in the hydrogen pipe network 7 to the target catalyst bed 2; S3: Adding supplementary hydrogen to the bottom of the reaction tank 1, and the supplementary hydrogen is introduced into the reaction tank 1 through the gas disperser 6; The product at the bottom of reaction tank 1 is extracted.
[0030] In the embodiment of the present application, a temperature sensor 3 is provided in the anthraquinone hydrogenation reaction tank 1, and the anthraquinone hydrogenation reaction tank 1 includes an outer tank body 102 and an inner tank body 101. The anthraquinone hydrogenation reaction target catalyst bed 2 is arranged in the inner tank body 101 of the anthraquinone hydrogenation reaction. A accommodating chamber 5 is formed between the inner tank body 101 of the anthraquinone hydrogenation reaction and the outer tank body 102 of the anthraquinone hydrogenation reaction. A condenser 4 spirally arranged outside the inner tank body 101 is provided in the accommodating chamber 5. A feed pipe and a discharge pipe are provided on the outer tank body 102. The height corresponding to the position of the anthraquinone hydrogenation reaction feed pipe on the outer tank body 102 is higher than that of the anthraquinone hydrogenation reaction discharge pipe. The anthraquinone hydrogenation reaction feed pipe and the anthraquinone hydrogenation reaction discharge pipe are both connected to the anthraquinone hydrogenation reaction condenser 4.
[0031] Anthraquinone hydrogenation reaction is an exothermic reaction. During the hydrogenation reaction, the temperature in the reaction tank 1 will increase. As the temperature increases, both the positive and side reactions of hydrogenation will be accelerated. The side reaction is a degradation reaction, which will lead to a decrease in the effective anthraquinone content in the working fluid and cause changes in the physical properties of the working fluid. Therefore, the temperature in the reaction tank 1 is monitored in real time by the temperature sensor 3. When the temperature sensor 3 detects that the temperature in the reaction tank 1 reaches the set value, the condensing medium is circulated into the condenser 4, and the condensing medium is fed into the condenser 4 through the feed pipe, and the condensing medium is extracted through the discharge pipe, thereby completing the circulation of the condensing medium. The condensing medium undergoes heat exchange in the accommodating chamber 5 to reduce the temperature in the reaction tank 1.
[0032] The implementation principle of the hydrogenation process in the production of hydrogen peroxide in an embodiment of the present application is as follows: the gas dissolving equipment dissolves hydrogen in the anthraquinone working liquid, especially allows the hydrogen to be fully mixed with the anthraquinone working liquid to obtain a mixed working liquid, the hydrogen in the mixed working liquid is evenly distributed, and after it is introduced into the reaction tank 1, it can cooperate with the catalyst to undergo a continuous and uniform hydrogenation reaction to obtain a working liquid product after the hydrogenation reaction, and the working liquid product after the hydrogenation reaction will fall to the bottom of the reaction tank 1. Before the product is extracted from the bottom of the reaction tank 1 for use, additional hydrogen is introduced into the bottom of the reaction tank 1 again, and the additional hydrogen can react again with the anthraquinone working liquid that has not reacted completely in the product, thereby further ensuring the integrity of the hydrogenation reaction.
[0033] In the present application, the hydrogen that reacts with the anthraquinone working solution is divided into two parts, one part is directly contacted and mixed with the anthraquinone working solution, and the other part is added to the reaction tank 1 as supplementary hydrogen. When the anthraquinone working solution flows to the target catalyst bed 2, the supplementary hydrogen blown to the target catalyst bed 2 can produce a disturbing effect, thereby avoiding the anthraquinone macromolecular by-products from clogging the pores of the target catalyst bed 2, reducing the residence time of the macromolecular anthraquinone and its derivatives in the pores of the target catalyst bed 2, and diffusing the anthraquinone macromolecular organic matter in the pores of the target catalyst bed 2 in a timely manner.
[0034] In addition to the above effects, the method of adding hydrogen to the anthraquinone working solution in two parts can also prevent all the hydrogen required for the hydrogenation reaction from entering the reaction tank 1 together with the anthraquinone working solution, resulting in excess hydrogen in a short period of time, which in turn leads to the occurrence of excessive hydrogenation reaction, aggravated side reactions, and serious degradation of anthraquinone.
[0035] The above are all preferred embodiments of the present application, and the protection scope of the present application is not limited thereto. Therefore, any equivalent changes made according to the structure, shape, and principle of the present application should be included in the protection scope of the present application.
[0036] In the description of the present application, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inside", "outside" and the like indicate positions or positional relationships based on the positions or positional relationships shown in the accompanying drawings, which are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as a limitation of the present invention. In addition, the terms "first", "second", and "third" are only used for descriptive purposes and cannot be understood as indicating or implying relative importance. In the description of the present application, it should be noted that, unless otherwise clearly specified and limited, the terms "installed", "connected", and "connected" should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection, or it can be indirectly connected through an intermediate medium, or it can be a connection between the two elements. For those of ordinary skill in the art, the specific meanings of the above terms in the present application can be understood according to specific circumstances.
Claims
1. A hydrogenation process in the production of hydrogen peroxide, characterized in that: The following steps are involved: S1: introducing anthraquinone working solution and hydrogen into a reaction tank (1), wherein a target catalyst bed (2) is arranged in the reaction tank (1); S2: introducing supplementary hydrogen into the reaction tank (1), and blowing the supplementary hydrogen toward the target catalyst bed (2) along the flow direction of the anthraquinone working solution; S3: Extract the product at the bottom of the reaction tank (1).
2. The hydrogenation process in the production of hydrogen peroxide according to claim 1, characterized in that: In step S1, before the anthraquinone working solution and hydrogen are introduced into the reaction tank (1), a gas dissolving device is used to dissolve hydrogen in the anthraquinone working solution.
3. The hydrogenation process in the production of hydrogen peroxide according to claim 1, characterized in that: The reaction tank (1) is provided with a temperature sensor (3) and a cooling element. In step S1, after anthraquinone working solution and hydrogen are introduced into the reaction tank (1), the temperature in the reaction tank (1) is monitored in real time by the temperature sensor (3). When the temperature in the reaction tank (1) reaches a set value, the cooling element is operated to reduce the temperature in the reaction tank (1).
4. The hydrogenation process in the production of hydrogen peroxide according to claim 3, characterized in that: The cooling element comprises a condenser (4) arranged in the reaction tank (1). In step S1, when the temperature in the reaction tank (1) reaches a warning value, a condensing medium is circulated into the condenser (4).
5. The hydrogenation process in the production of hydrogen peroxide according to claim 4, characterized in that: The condenser (4) is arranged in a spiral shape, and a feed pipe and a discharge pipe are arranged on the reaction tank (1). The height corresponding to the position of the feed pipe on the reaction tank (1) is higher than that of the discharge pipe, and the feed pipe and the discharge pipe are both connected to the condenser (4). In step S1, when the temperature in the reaction tank (1) reaches the warning value, the condensing medium is introduced into the condenser (4) through the feed pipe, and the condensing medium is extracted through the discharge pipe.
6. The hydrogenation process in the production of hydrogen peroxide according to claim 4, characterized in that: The reaction tank (1) comprises an outer tank body (102) and an inner tank body (101), the target catalyst bed (2) is arranged in the inner tank body (101), a receiving cavity (5) is formed between the inner tank body (101) and the outer tank body (102), and the condenser (4) is arranged in the receiving cavity (5).
7. The hydrogenation process in the production of hydrogen peroxide according to claim 1, characterized in that: In step S3, before the product at the bottom of the reaction tank (1) is extracted, additional hydrogen is introduced into the bottom of the reaction tank (1).
8. The hydrogenation process in the production of hydrogen peroxide according to claim 7, characterized in that: A gas disperser (6) is provided at the bottom of the reaction tank (1). In step S3, supplementary hydrogen is introduced into the reaction tank (1) through the gas disperser (6).
9. The hydrogenation process in the production of hydrogen peroxide according to claim 1, characterized in that: A hydrogen pipe network (7) is arranged in the reaction tank (1), and a plurality of nozzles (8) are arranged on the hydrogen pipe network (7), and the jetting directions of the plurality of nozzles (8) are all toward the target catalyst bed (2) and consistent with the flow direction of the anthraquinone working solution; In step S2, supplementary hydrogen is introduced into the hydrogen pipeline network (7).