Slurry bed heavy oil hydrogenation efficient catalyst preparation device and use method thereof

Abstract

The invention relates to the technical field of residual oil hydrogenation, and particularly discloses a slurry bed heavy oil hydrogenation efficient catalyst preparation device and a use method thereof.The preparation device comprises a catalyst precursor preparation part, a catalyst preparation part and a plurality of connecting pipelines and further comprises a waste acid collection part. The device is provided with a catalyst precursor preparation part, a catalyst preparation part and a plurality of connecting pipelines, the structure is optimized, the layout is reasonable, the preparation process is smooth and efficient, the performance of the prepared catalyst is optimized and upgraded, preparation technical routes are diversified, raw materials are replaced and optimized, active components are optimized, and the vulcanization mode is changed. The application range is wide, thermal cracking hydrogenation reaction is controlled in a reasonable interval, catalyst efficiency is improved, and catalyst consumption is reduced; the prepared catalyst has good heavy oil conversion activity and rapid hydrogenation performance, is a uniformly dispersed non-loaded nanoscale liquid catalyst, and effectively avoids abrasion of a solid catalyst to pipelines and valves.

Description

Technical Field

[0001] This invention relates to the field of residual oil hydrogenation technology, and in particular to a slurry-bed heavy oil hydrogenation high-efficiency catalyst preparation apparatus and its usage method. Background Technology

[0002] In recent years, hydrogenation processes for residual oil and fuel oil have become new development directions. Fixed bed, fluidized bed, and slurry bed technologies have all been industrialized. Among them, slurry bed hydrogenation technology has made breakthrough progress and has become a new trend in the development of heavy oil hydrogenation. However, the catalyst consumption of existing slurry bed residual oil hydrogenation units is higher than the design value, and the catalyst activity is low and the consumption is large.

[0003] As heavy oil hydrotreating technology has gradually developed, it has become clear that the hydrotreating process is the decisive factor for the efficient and stable conversion of heavy oil. Developing efficient heavy oil hydrotreating catalysts (molybdenum disulfide) is key to the stable operation and cost reduction of slurry bed hydrotreating units. Based on the characteristics of slurry bed hydrotreating processes for heavy oils such as fuel oil and residual oil, and according to the properties of the feedstocks, it is necessary to develop high-efficiency slurry bed hydrotreating catalysts that match these characteristics, producing high-value-added products. Simultaneously, developing equipment for preparing high-efficiency slurry bed hydrotreating catalysts can significantly improve the light oil yield from heavy oil processing, thereby enhancing market competitiveness.

[0004] Currently, the preparation of high-efficiency catalysts for slurry-bed heavy oil conversion, which exhibit excellent heavy oil conversion activity and rapid hydrogenation performance, and are uniformly dispersed non-supported nanoscale liquid catalysts within the slurry-bed reactor, effectively avoiding wear on pipelines and valves caused by solid catalysts, has become a new approach and challenge for the preparation of high-efficiency catalysts for slurry-bed heavy oil hydrogenation. Summary of the Invention

[0005] The purpose of this invention is to solve the problems in the prior art and provide a slurry bed heavy oil hydrogenation high-efficiency catalyst preparation device and its usage method.

[0006] The technical solution of this invention is: A slurry-bed heavy oil hydrogenation high-efficiency catalyst preparation device includes a catalyst precursor preparation section, a catalyst preparation section, and several connecting pipes. The catalyst precursor preparation section and the catalyst preparation section are connected by the connecting pipes. The catalyst precursor preparation section includes a vacuum system, a temperature control system, a catalyst precursor storage tank, a silo, and a reactor. The vacuum system is connected to the silo, and the silo is connected to the reactor. The temperature control system is used to control the reaction temperature of the reactor. The catalyst precursor storage tank is connected to the reactor. The raw material molybdenum salt is added to the silo and enters the reactor through the silo. Organic acid is added to the reactor. The catalyst preparation section includes a feed mixing tank, which is connected to the catalyst precursor storage tank.

[0007] Preferably, it also includes a waste acid collection section, which includes a vacuum system II, a separator, a collection tank and a waste acid storage tank. The vacuum system II is connected to the separator, the separator is connected to the collection tank, and the collection tank is connected to the waste acid storage tank.

[0008] Preferably, the heat source for the temperature control system is heat transfer oil, electric heat tracing, or steam.

[0009] A method for using a slurry-bed heavy oil hydrogenation high-efficiency catalyst preparation apparatus, comprising the following steps: Step 1: Preparation of catalyst precursor molybdate using a slurry bed heavy oil hydrogenation high-efficiency catalyst preparation device: The raw material molybdenum salt and organic acid are mixed in a reactor at a ratio of 0.4:1 to 0.6:1, and the catalyst precursor molybdate is produced at a temperature of 5 to 200°C and a pressure of -0.01 to 0.7 MPa. The raw material molybdenum salt is molybdic acid, ammonium dimolybdate, ammonium tetramolybdate, or ammonium heptamolybdate, and the organic acid is isooctanoic acid, naphthenic acid, dialkyl dithiocarbamate, or fatty acid. Step 2: Sulfurize the catalyst precursor molybdate prepared in Step 1: Inject the catalyst precursor molybdate into the feed mixing tank of the slurry bed, and sulfurize it with sulfur-containing raw materials and hydrogen sulfide gas from the top of the medium-pressure separator at 180℃~350℃ to form the catalyst molybdenum disulfide.

[0010] The preparation of molybdate precursors for catalyst hydrotreating using a slurry-bed heavy oil hydrotreating high-efficiency catalyst preparation device includes the following steps: Step 1: Fill the reaction vessel with raw material molybdenum salt and organic acid in sequence and according to the filling amount, and preheat to 5℃~50℃; Step 2: Continue heating the reactor until the set temperature of 100°C is reached. Maintain the constant temperature for a period of time until the constant temperature is reached. Then, vacuum the reactor and perform a first distillation. Step 3: Continue heating the reactor to 70℃~150℃, maintain constant temperature, vacuum the reactor for secondary distillation, restore atmospheric pressure and raise the temperature to 80℃~180℃; Step 4: The raw material molybdenum salt and organic acid undergo a preliminary reaction to generate the intermediate organic molybdic acid. The system is then evacuated to remove the waste acid, a byproduct of the preliminary reaction. Step 5: Restore atmospheric pressure and increase temperature to complete the final reaction process: the intermediate organic molybdic acid reacts with organic acid to transform into the catalyst precursor molybdate; Step 6: Take samples of the product generated in Step 5 for quality analysis. If the product is qualified, cool the reaction vessel and send the qualified catalyst precursor molybdate to the catalyst precursor storage tank.

[0011] After the raw materials molybdenum salt and organic acid are loaded into the reactor, a trace amount of rare earth additive is added as a catalyst activator component.

[0012] After the second distillation, a trace amount of rare earth additives is added again as a catalyst active agent component, and the temperature is kept constant at 80℃~180℃ during the addition.

[0013] The heat source during the use of the slurry bed heavy oil hydrogenation high-efficiency catalyst preparation unit is provided by heat transfer oil, electric heating or steam.

[0014] The present invention, employing the above-described structure, has the following advantages: 1. This device is equipped with a catalyst precursor preparation section, a catalyst preparation section, and several connecting pipes. The structure is optimized, the layout is reasonable, and the preparation process is smooth and efficient. 2. The prepared catalyst has optimized and upgraded performance, diversified preparation technology routes, optimized raw material substitution, optimized active components, changed sulfidation method, wide adaptability range, and thermal cracking hydrogenation reaction controlled within a reasonable range, thereby improving catalyst efficiency and reducing catalyst consumption; 3. The prepared catalyst has good heavy oil conversion activity and rapid hydrogenation performance. It is a uniformly dispersed unsupported nanoscale liquid catalyst, which effectively avoids the wear of pipelines and valves caused by solid catalysts. Attached Figure Description

[0015] Figure 1 This is a schematic diagram of the preparation device of the present invention.

[0016] In the diagram, 1. Vacuum system one; 2. Silo; 3. Reactor; 4. Temperature control system; 5. Catalyst precursor storage tank; 6. Collection tank; 7. Feed mixing tank; 8. Separator; 9. Vacuum system two. Detailed Implementation

[0017] To make the technical means, technical features, inventive purpose and technical effects of this invention easier to understand, the invention will be further described below with reference to specific illustrations.

[0018] like Figure 1 As shown, a slurry bed heavy oil hydrogenation high-efficiency catalyst preparation device includes a catalyst precursor preparation section, a catalyst preparation section, and several connecting pipes, as well as a waste acid collection section. The catalyst precursor preparation section and the catalyst preparation section are connected by connecting pipes. The catalyst precursor preparation section includes a vacuum system 1, a temperature control system 4, a catalyst precursor storage tank 5, a silo 2, and a reactor 3. The vacuum system 1 and the silo 2 are connected, and the silo 2 and the reactor 3 are connected. The temperature control system 4 is used to control the reaction temperature of the reactor 3. The heat source of the temperature control system 4 is heat transfer oil, electric heating, or steam. The catalyst precursor storage tank 5 is connected to the reactor 3. The raw material molybdenum salt is added to the silo 2 and enters the reactor 3 through the silo 2. Organic acid is added to the reactor 3. The catalyst preparation section includes a feed mixing tank 7, which is connected to the catalyst precursor storage tank 5. The waste acid collection section includes a vacuum system 29, a separator 8, a collection tank 6, and a waste acid storage tank. The vacuum system 29 is connected to the separator 8, the separator 8 is connected to the collection tank 6, and the collection tank 6 is connected to the waste acid storage tank. The reaction produces a byproduct, namely waste acid. When one of the reaction products is removed, the equilibrium will shift to the right. Based on this principle, the byproduct waste acid is removed from the reaction products. A method for using a slurry-bed heavy oil hydrogenation high-efficiency catalyst preparation device includes the following steps: Step 1: Preparation of catalyst precursor molybdate using a slurry bed heavy oil hydrogenation high-efficiency catalyst preparation device: The raw material molybdenum salt and organic acid are mixed in reactor 3 at a ratio of 0.4:1 to 0.6:1, and the catalyst precursor molybdate is produced at a temperature of 5 to 200°C and a pressure of -0.01 to 0.7 MPa. Among them, the molybdenum salts are molybdic acid [H2MoO4] (molybdenum content wt% ≥ 56.00), ammonium dimolybdate [(NH4)2Mo2O7] (molybdenum content wt%, 56.45±0.40), ammonium tetramolybdate [(NH4)2Mo4O13·2H2O] (molybdenum content wt% ≥ 56.00) or ammonium heptamolybdate [(NH4)6Mo7O24·4H2O] (molybdenum content wt%, 54.35±0.40); When selecting molybdenum salts, advanced molybdenum salt preparation processes are adopted to ensure the purity and quality of molybdenum salts. At the same time, impurity metals such as nickel and iron in molybdenum salts are effectively utilized to improve catalyst activity. The source of molybdenum ore is investigated to ensure the purity of molybdenum salts. The organic acids are isooctanoic acid, naphthenic acid, dialkyl (aryl) dithiocarbamate, and fatty acids; After the raw materials molybdenum salt and organic acid are loaded into reactor 3, a trace amount of rare earth additives are added as catalyst active additive components. Rare earth elements stabilize the catalyst system, improve hydrogenation performance, and slow down coking. Step 2: Sulfurize the catalyst precursor molybdate prepared in Step 1: Inject the catalyst precursor molybdate into the feed mixing tank 7 of the slurry bed, and sulfurize it with sulfur-containing raw materials and hydrogen sulfide-containing gas at 180℃~350℃ to form the catalyst molybdenum disulfide.

[0019] The preparation of the catalyst precursor molybdate includes the following steps: Step 1: Fill the reaction vessel 3 with raw material molybdenum salt and organic acid in sequence and according to the filling amount, and preheat to 5℃~50℃; Step 2: Continue heating reactor 3 until the set temperature of 100℃ is reached. Maintain the constant temperature for a period of time until the constant temperature is reached. Then, vacuum the reactor and perform a first distillation. Step 3: Continue heating reactor 3 to 70℃~150℃, maintain constant temperature, vacuum the reactor for secondary distillation, restore atmospheric pressure and raise the temperature to 80℃~180℃; After the second distillation, a trace amount of rare earth additives is added again as a catalyst active agent component, and the temperature is kept constant at 80℃~180℃ during the addition. Step 4: The raw material molybdenum salt and organic acid undergo a preliminary reaction to generate the intermediate organic molybdic acid. The system is then evacuated to remove the waste acid, a byproduct of the preliminary reaction. Step 5: Restore atmospheric pressure and increase temperature to complete the final reaction process: the intermediate organic molybdic acid reacts with organic acid to transform into the catalyst precursor molybdate; Step 6: Take samples of the product generated in Step 5 for quality analysis. After passing the quality analysis, cool the reaction vessel 3 and send the qualified catalyst precursor molybdate to the catalyst precursor storage tank 5. The preparation process of the catalyst precursor molybdate is detailed in the table below: During implementation, the raw material molybdenum salt adopts an advanced metering and weighing system to accurately measure the mass of the added material. The feeding method adopts a combination of manual remote control and intelligent control system to ensure the safety of personnel and the complete conversion of the reaction materials. The entire production process uses an advanced integrated control system to meet the flexible adjustment of production load.

[0020] After implementation of this embodiment, the raw materials are widely adaptable, the catalyst has a high specific surface area, high activity, strong selectivity, and low consumption, and the desulfurization, denitrification, demetallization, and residual carbon removal effects are significant. The sulfur and nitrogen content in the product of the unit is further reduced by about 500 to 2000 ppm. The hydrogenation rate is fast, the reaction process is short, the energy consumption is low, and the economic benefits are extremely high.

[0021] It should be noted that the aforementioned vacuum system is an application of existing technology; the metering and weighing system, the manual remote control and intelligent control system, and the integrated control system are all existing facilities of the slurry bed heavy oil hydrogenation system and are applications of existing technology.

[0022] The above description is merely a preferred embodiment of the present invention and is not intended to limit the scope of the invention. All equivalent changes and modifications made in accordance with the scope of the claims of this invention should fall within the technical scope of this invention.

Claims

1. A slurry-bed heavy oil hydrogenation high-efficiency catalyst preparation device, characterized in that: The catalyst preparation unit includes a catalyst precursor preparation section, a catalyst preparation section, and several connecting pipes. The catalyst precursor preparation section and the catalyst preparation section are connected through the connecting pipes. The catalyst precursor preparation section includes a vacuum system (1), a temperature control system (4), a catalyst precursor storage tank (5), a silo (2), and a reactor (3). The vacuum system (1) and the silo (2) are connected. The silo (2) and the reactor (3) are connected. The temperature control system (4) is used to control the reaction temperature of the reactor (3). The catalyst precursor storage tank (5) and the reactor (3) are connected. The raw material molybdenum salt is added to the silo (2) and enters the reactor (3) through the silo (2). Organic acid is added to the reactor (3). The catalyst preparation section includes a feed mixing tank (7) and the feed mixing tank (7) is connected to the catalyst precursor storage tank (5).

2. The apparatus for preparing a high-efficiency catalyst for slurry-bed heavy oil hydrogenation according to claim 1, characterized in that: It also includes a waste acid collection section, which includes a vacuum system two (9), a separator (8), a collection tank (6) and a waste acid storage tank. The vacuum system two (9) and the separator (8) are connected, the separator (8) and the collection tank (6) are connected, and the collection tank (6) and the waste acid storage tank are connected.

3. The apparatus for preparing a high-efficiency catalyst for slurry-bed heavy oil hydrogenation according to claim 1, characterized in that: The heat source of the temperature control system (4) is heat transfer oil, electric heating or steam.

4. A method for using a slurry-bed heavy oil hydrogenation high-efficiency catalyst preparation device, characterized in that: The preparation of the catalyst using the apparatus for preparing the slurry-bed heavy oil hydrotreating high-efficiency catalyst according to any one of claims 1-3 includes the following steps: Step 1: Prepare catalyst precursor molybdate using a slurry bed heavy oil hydrogenation high-efficiency catalyst preparation device: Mix raw material molybdenum salt and organic acid in a reaction vessel (3) at a ratio of 0.4:1 to 0.6:1, and produce catalyst precursor molybdate at a temperature of 5 to 200°C and a pressure of -0.01 to 0.7 MPa. The raw material molybdenum salt is molybdic acid, ammonium dimolybdate, ammonium tetramolybdate or ammonium heptamolybdate, and the organic acid is isooctanoic acid, naphthenic acid, dialkyl dithiocarbamate, or fatty acid. Step 2: Sulfate the catalyst precursor molybdate prepared in Step 1: Inject the catalyst precursor molybdate into the feed mixing tank (7) of the slurry bed, and sulfate it with sulfur-containing raw materials and hydrogen sulfide gas at the top of the medium-pressure separator (8) at 180℃~350℃ to form the catalyst molybdenum disulfide.

5. The method of using the slurry bed heavy oil hydrogenation high-efficiency catalyst preparation device according to claim 4, characterized in that: The preparation of molybdate precursors for catalyst hydrotreating using a slurry-bed heavy oil hydrotreating high-efficiency catalyst preparation device includes the following steps: Step 1: Fill the reaction vessel (3) with raw material molybdenum salt and organic acid in sequence and in the specified amount, and preheat it to 5℃~50℃; Step 2: Continue heating the reactor (3) until the set temperature of 100°C is reached. Maintain the constant temperature for a period of time until the constant temperature ends. Then, vacuum the reactor and perform a distillation. Step 3: Continue heating the reactor (3) to 70℃~150℃, maintain constant temperature, vacuum for secondary distillation, restore normal pressure and raise the temperature to 80℃~180℃; Step 4: The raw material molybdenum salt and organic acid undergo a preliminary reaction to generate the intermediate organic molybdic acid. The system is then evacuated to remove the waste acid, a byproduct of the preliminary reaction. Step 5: Restore atmospheric pressure and increase temperature to complete the final reaction process: the intermediate organic molybdic acid reacts with organic acid to transform into the catalyst precursor molybdate; Step 6: Take a sample of the product generated in Step 5 for quality analysis. After it passes the test, cool the reactor (3) and send the qualified catalyst precursor molybdate to the catalyst precursor storage tank (5).

6. The method of using the slurry bed heavy oil hydrogenation high-efficiency catalyst preparation device according to claim 5, characterized in that: After the raw materials molybdenum salt and organic acid are loaded into the reactor (3), a trace amount of rare earth additive is added as a catalyst active additive component.

7. The method of using the slurry bed heavy oil hydrogenation high-efficiency catalyst preparation device according to claim 6, characterized in that: After the second distillation, a trace amount of rare earth additive is added again as a catalyst active agent component, and the temperature is kept constant at 80℃~180℃ during the addition.

8. The method of using the slurry bed heavy oil hydrogenation high-efficiency catalyst preparation device according to claim 7, characterized in that: The heat source during the use of the slurry bed heavy oil hydrogenation high-efficiency catalyst preparation unit is provided by heat transfer oil, electric heating or steam.

Images