Hydrogenation sulfur supplementing device
By using self-produced sulfur as a vulcanizing agent during the hydrotreatment process and designing a hydrogenated sulfur replenishment device, the problem of reduced catalyst activity is solved, and cost savings, improved catalyst activity and operation safety are achieved.
Patent Information
- Application Number
- CN202421543044.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Utility models(China)
- Current Assignee / Owner
- Filing Date
- 2024-07-02
- Publication Date
- 2025-05-09
- Estimated Expiration
- 2034-07-02
AI Technical Summary
During the hydrotreatment process, the raw oil has a high nitrogen content and a low sulfur content, which leads to a reduction or inactivation of the catalyst activity and increases economic losses. At the same time, the existing vulcanizing agents are costly, toxic and unsafe to operate.
Self-produced sulfur is used as the vulcanizing agent for the hydrogenation process, and by designing a hydrogenation sulfur replenishment device, including a mixing tank, a mixing reflow pipeline and a metering pump, we ensure that the sulfur powder is fully dissolved into the raw oil, and the amount of vulcanizing agent is accurately controlled.
Significantly save production costs, improve the activity and stability of the catalyst, reduce the toxicity and operational risks of the vulcanizing agent, and ensure sufficient hydrogen sulfide content in the hydrogenation reaction system.
Smart Images
Figure CN222846674U_ABST
Abstract
Description
Technical Field
[0001] The utility model belongs to the technical field of hydrogenation treatment, in particular to a hydrogenation sulfur replenishing device. Background Art
[0002] During the hydroprocessing of coal tar, shale oil and other oil products, the nitrogen content of the raw oil is often high, while the sulfur content is low. After the hydrogenation reaction of this type of raw oil, the catalyst may undergo a passivation reaction under this condition, resulting in a decrease in the activity of the catalyst, or even in the deactivation of the catalyst, causing high economic losses. The catalyst in the hydroprocessing process generally exists in an oxidized state and needs to be further reduced or sulfided, which is called catalyst activation. Catalyst activation can further improve the activity and stability of the catalyst. In addition, in the field of hydrogenation of biomass fuels (biodiesel, biojet fuel, etc.), due to the high nitrogen content, the hydrogen sulfide content in the reaction system is very low. Under normal operation, it is also necessary to continuously add sulfur to the reaction system to ensure sufficient hydrogen sulfide content so that the catalyst is always in a sulfided state;
[0003] During the hydrogenation reaction of sulfur-containing oil, the H2S produced will also sulfide the metal catalyst. However, if the sulfur content of the crude oil is low, the sulfidation process is very long. Therefore, in order to shorten the sulfidation process, substances that are easy to produce H2S are generally added artificially to shorten the time required for the sulfidation process. The most widely used sulfiding agent is dimethyl disulfide (DMDS), which has a high market price and will increase production costs. The sulfiding agent CS2, which was commonly used in the early days, is easy to volatilize, leak, and is highly toxic, which can easily cause fire or poisoning accidents. Utility Model Content
[0004] In view of the above technical problems, the utility model provides a hydrogenation sulfur replenishing device, which uses self-produced sulfur as a sulfurizing agent in the hydrogenation process, significantly saving production costs, and through the device design of the raw material adding process, the mixing process and the sulfur-containing raw oil return process, the sulfur powder is fully dissolved in the raw oil and the amount of the sulfurizing agent is accurately controlled.
[0005] In order to achieve the above purpose, the utility model adopts the following technical solutions:
[0006] A hydrogenation and sulfur replenishing device, comprising:
[0007] A mixing tank, wherein the mixing tank has a feed port and a discharge port, wherein the feed port includes a feed port for raw oil and a feed port for sulfur, and the feed port for raw oil is connected to a hot oil pipeline in a hydroprocessing process;
[0008] A mixing return pipeline, one end of which is connected to the discharge port of the mixing tank, and the other end is connected back to the hot oil pipeline, and a flow meter and a metering pump are provided on the mixing return pipeline. The sulfur-containing feedstock oil is injected into the hot oil pipeline again after being controlled by the flow meter through the metering pump.
[0009] In some preferred technical solutions, the sulfur feed port is connected to a sulfur feed pipe, and a hopper is installed at the end of the sulfur feed pipe, and the hopper is used for efficient transportation of sulfur powder.
[0010] In some preferred technical solutions, the particle size of the sulfur powder is less than 10 μm.
[0011] In some preferred technical solutions, the mixing tank is provided with a stirring assembly for fully dissolving sulfur in the crude oil, and the stirring assembly includes a stirring paddle and a driving motor.
[0012] In some preferred technical solutions, the mixing tank is provided with a steam heating structure for keeping the crude oil warm.
[0013] In some preferred technical solutions, the mixing return pipelines are two routes arranged in parallel, and a main metering pump and a backup metering pump are respectively installed on the two routes of mixing return pipelines.
[0014] In some preferred technical solutions, a bypass branch is connected between the front and rear pipe sections of the main metering pump and the backup metering pump.
[0015] In some preferred technical solutions, a circulating pump is also provided on the mixed material return pipeline to provide power for the return of the sulfur-containing crude oil.
[0016] In some preferred technical solutions, the crude oil feed port is connected to a crude oil feed pipe, and a filter is installed at the outlet of the crude oil feed pipe to remove particulate impurities carried in the crude oil.
[0017] In some preferred technical solutions, the mixing tank is further provided with a discharge port, the discharge port is connected to a mixed material discharge pipeline, and the mixed material discharge pipeline is connected to an external storage tank or reaction equipment.
[0018] The utility model adopts the above technical solution to have at least the following beneficial effects:
[0019] 1. The utility model provides a hydrogenation sulfur replenishing device, which uses self-produced sulfur as a sulfurizing agent in the hydrogenation process, significantly saving production costs, and through the device design of the raw material adding process, the mixing process and the sulfur-containing raw oil return process, the sulfur powder is fully dissolved in the raw oil, and the amount of the sulfurizing agent is accurately controlled;
[0020] 2. The utility model provides a hydrogenation sulfur replenishing device, which takes out a portion of hot oil from the pipeline of relatively hot raw oil and mixes it with sulfur in a mixing tank, and at the same time, it is supplemented with steam heating to keep the raw oil warm, so that the sulfur powder is fully dissolved in the raw oil;
[0021] 3. The utility model provides a hydrogenation sulfur replenishing device, in which a hopper is installed at the inlet of the sulfur feeding pipe to prevent the escape of sulfur powder and improve the addition efficiency of sulfur powder;
[0022] 4. The utility model provides a hydrogenation sulfur replenishing device, in which a filter is installed at the outlet of the feed pipe of the crude oil to remove the impurity particles carried in the crude oil and improve the dissolution effect of sulfur;
[0023] 5. The utility model provides a hydrogenation sulfur replenishing device, in which the sulfur-containing raw oil is injected into the hot oil pipeline again after being controlled by a flow meter through the metering pump, so that the return amount of the sulfur-containing raw oil is accurate and reliable; and two metering pumps are arranged, one in operation and one in standby, which can ensure the safety and stability of the operation of the device. BRIEF DESCRIPTION OF THE DRAWINGS
[0024] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following briefly introduces the drawings and their marks required for use in the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.
[0025] Figure 1 It is a schematic structural diagram of the hydrogenation and sulfur replenishing device described in an embodiment of the utility model.
[0026] The meanings of the symbols in the figure are as follows:
[0027] 10—mixing tank, 11—stirring assembly, 12—steam tracing structure, 13—raw oil feed pipe, 14—filter, 15—sulfur feed pipe, 16—hopper;
[0028] 20—mixed material return pipeline, 21—flow meter, 22—main metering pump, 23—standby metering pump, 24—circulation pump;
[0029] 30—Hot oil pipeline. DETAILED DESCRIPTION
[0030] In order to more clearly illustrate the embodiments of the utility model or the technical solutions in the prior art, the specific implementation methods of the utility model will be described below with reference to the accompanying drawings. Obviously, the accompanying drawings described below are only some embodiments of the utility model. For ordinary technicians in this field, other drawings and other implementation methods can be obtained based on these drawings without creative work.
[0031] In order to simplify the drawings, only the parts related to the utility model are schematically shown in each figure, and they do not represent the actual structure of the product. In addition, in order to simplify the drawings and facilitate understanding, in some figures, only one of the parts with the same structure or function is schematically drawn or marked. In this article, "one" not only means "only one", but also means "more than one".
[0032] It should be further understood that the term “and / or” used in the specification and appended claims refers to any combination and all possible combinations of one or more of the associated listed items, and includes these combinations.
[0033] In this article, 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 the internal communication of two components. For ordinary technicians in this field, the specific meanings of the above terms in this utility model can be understood according to specific circumstances.
[0034] In addition, in the description of the present application, the terms "first", "second", etc. are only used to distinguish the description and cannot be understood as indicating or implying relative importance.
[0035] As a specific example, Figure 1 , is a hydrogenation sulfur replenishing device, including a mixing tank 10 and a mixed material return pipeline 20, the mixing tank 10 has a feed port and a discharge port, the feed port includes a feed port for raw oil and a feed port for sulfur, the feed port for raw oil is connected to a hot oil pipeline 30 in a hydrogenation process; one end of the mixed material return pipeline 20 is connected to the discharge port of the mixing tank 10, and the other end is connected back to the hot oil pipeline 30, and a flow meter 21 and a metering pump are arranged on the mixed material return pipeline 20, and the sulfur-containing raw material oil is injected into the hot oil pipeline 30 again after being controlled by the flow meter 21 through the metering pump.
[0036] The present application adopts self-produced sulfur as the vulcanizing agent of hydrogenation process, does not need to be purchased from outside, and local materials are used, and the cost is relatively low. Compared with another widely used dimethyl disulfide (DMDS), the price of sulfur is lower. The market price of dimethyl disulfide (DMDS) is about 16,500 yuan / ton, which is much higher than the market price of about 2,000 yuan / ton of sulfur. Taking a hydrogenation unit with a processing capacity of 400,000 tons / year as an example, it is necessary to add 10 tons of dimethyl disulfide (DMDS) every year. If the sulfur replenishing facility of the present invention is used and self-produced sulfur is used as raw material, the cost can be saved by about 165,000 yuan every year.
[0037] The present application takes out a portion of hot oil from the hotter raw oil pipeline and mixes it evenly in the mixing tank 10, which can make the sulfur more easily and fully dissolved in the raw oil. The sulfur-containing raw oil is injected into the hot oil pipeline 30 again after being controlled by the flow meter 21 through the metering pump, and the hydrogenation reaction process is continued to sulfurize the oxidized catalyst, thereby improving the activity of the catalyst.
[0038] The utility model scheme further enables the sulfur powder to be fully dissolved in the raw oil through the device design of the raw material adding process, the mixing process and the sulfur-containing raw oil return process, thereby additionally supplementing the sulfur replenisher into the hydrogenation reaction system.
[0039] In the above embodiment, the homemade sulfur is ground to a particle size of less than 10 μm; the sulfur feed port is connected to a sulfur feed pipe 15, and a hopper 16 is installed at the end of the sulfur feed pipe 15. The hopper 16 is used for efficient transportation of sulfur powder.
[0040] This embodiment enables the measured sulfur powder to be easily input into the mixing tank 10 to facilitate its dissolution in the crude oil.
[0041] In the above embodiment, the feed oil inlet is connected to the crude oil feed pipe 13, and the outlet of the crude oil feed pipe 13 is equipped with a filter 14 for removing particulate impurities carried in the crude oil and reducing the effect on the dissolution of sulfur powder.
[0042] In the above embodiment, the mixing tank 10 is provided with a stirring assembly 11 for fully dissolving sulfur in the crude oil, and the stirring assembly 11 includes a stirring paddle and a driving motor. The stirring speed can be effectively set according to the needs; the structure of the stirring paddle can also be designed with multiple layers of blades according to the needs, and multiple stirring paddles can be provided, and the configuration of the blades can be selected according to the needs.
[0043] In a preferred embodiment, the mixing tank 10 is provided with a steam tracing structure 12 for keeping the crude oil warm. Specifically, it can be a steam coil, the condensate outlet of the steam coil is connected to an external water tank, the outlet of the water tank is connected to a heater, and the steam outlet of the heater is connected to the inlet of the steam coil; of course, the steam coil can be arranged on the outer wall of the mixing tank 10 or placed in the inner liquid area of the mixing tank 10. In addition, a heat-insulating interlayer can also be arranged on the side wall of the mixing tank 10.
[0044] In the above embodiment, the mixing return pipeline 20 is composed of two parallel paths, and a main metering pump 22 and a backup metering pump 23 are respectively installed on the two mixing return pipelines 20; preferably, a bypass branch is connected between the front and rear pipe sections of the main metering pump 22 and the backup metering pump 23; specifically, a circulating pump 24 is also provided on the mixing return pipeline 20 to provide return power for the sulfur-containing crude oil.
[0045] In the above embodiment, the mixing tank 10 is further provided with a discharge port, the discharge port is connected to a mixed material discharge pipeline, and the mixed material discharge pipeline is connected to an external storage tank or reaction equipment.
[0046] Some crude oils may have a high nitrogen content and a low sulfur content. In this case, the catalyst is easily reduced under the conditions of the hydrogenation reaction, resulting in reduced activity and stability of the catalyst, or even deactivation. The utility model can sulfurize the oxidized catalyst or increase the hydrogen sulfide content in the system to ensure that the catalyst is in a sulfurized state by additionally adding a sulfurizing agent to the reaction system, thereby improving the activity of the catalyst. In addition, the sulfurizing facility of the utility model has a low cost of the sulfurizing agent, low toxicity and high operational safety.
[0047] The utility model uses sulfur as a vulcanizing agent. The sulfur replenishing facility first takes a portion of hot raw oil into the sulfur replenishing facility, adds sulfur powder ground to less than 10 μm, dissolves the sulfur powder with hot oil, and then injects the hot oil containing sulfur back into the system. The sulfur powder will generate H2S in the subsequent hydrogenation reaction, thereby vulcanizing the oxidized catalyst.
[0048] The working principle and working process of the utility model are described in detail below:
[0049] Sulfur needs to be ground in advance to a powder of about less than 10 μm. A portion of the hot oil is taken out from the hotter crude oil pipeline and put into the mixing tank 10, and the sulfur powder is added into the mixing tank 10 through the opening at the top. After stirring, the sulfur powder is fully dissolved in the crude oil. The mixing tank 10 is heated with steam to keep the crude oil warm. The crude oil with dissolved sulfur is passed through a metering pump (two metering pumps are used in a one-on-one standby mode) and controlled by a flow meter 21, and the sulfur-containing crude oil is injected into the crude oil pipeline again. Under the conditions of the hydrogenation reaction, the sulfur powder will generate a certain amount of H2S, thereby vulcanizing the catalyst.
[0050] The above-mentioned embodiments only express several implementation methods of the utility model, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the patent of the utility model. It should be pointed out that, for ordinary technicians in this field, several modifications and improvements can be made without departing from the concept of the utility model, and these all belong to the protection scope of the utility model. Therefore, the protection scope of the utility model shall be based on the attached claims.
Claims
1. A hydrogenation and sulfur replenishing device, characterized in that: include: A mixing tank, wherein the mixing tank has a feed port and a discharge port, wherein the feed port includes a feed port for raw oil and a feed port for sulfur, and the feed port for raw oil is connected to a hot oil pipeline in a hydroprocessing process; A mixing return pipeline, one end of which is connected to the discharge port of the mixing tank, and the other end is connected back to the hot oil pipeline, and a flow meter and a metering pump are provided on the mixing return pipeline. The sulfur-containing feedstock oil is injected into the hot oil pipeline again after being controlled by the flow meter through the metering pump.
2. The hydrogenation and sulfur replenishing device according to claim 1, characterized in that: The sulfur feed port is connected to a sulfur feed pipe, and a hopper is installed at the end of the sulfur feed pipe. The hopper is used for efficiently conveying sulfur powder.
3. The hydrogenation and sulfur replenishing device according to claim 2, characterized in that: The particle size of the sulfur powder is less than 10 μm.
4. The hydrogenation and sulfur replenishing device according to claim 1, characterized in that: The mixing tank is provided with a stirring assembly for fully dissolving sulfur in the crude oil, and the stirring assembly includes a stirring paddle and a driving motor.
5. The hydrogenation and sulfur replenishing device according to claim 1, characterized in that: The mixing tank is provided with a steam tracing structure for keeping the crude oil warm.
6. The hydrogenation and sulfur replenishing device according to claim 1, characterized in that: The mixing material return pipelines are two pipelines arranged in parallel, and a main metering pump and a standby metering pump are respectively installed on the two mixing material return pipelines.
7. The hydrogenation and sulfur replenishing device according to claim 6, characterized in that: A bypass branch is connected between the front and rear pipe sections of the main metering pump and the standby metering pump.
8. The hydrogenation and sulfur replenishing device according to claim 1, characterized in that: The mixed material return pipeline is also provided with a circulation pump for providing return power for the sulfur-containing raw material oil.
9. The hydrogenation and sulfur replenishing device according to claim 1, characterized in that: The crude oil feed port is connected to a crude oil feed pipe, and a filter is installed at the outlet of the crude oil feed pipe to remove particulate impurities carried in the crude oil.
10. The hydrogenation and sulfur replenishing device according to claim 1, characterized in that: The mixing tank is also provided with a discharge port, which is connected to a mixed material discharge pipeline, and the mixed material discharge pipeline is connected to an external storage tank or reaction equipment.