Hydrotreatment method

Abstract

A hydrotreating method belongs to the technical field of energy and chemical industry. The hydrotreating method comprises the following steps: hydrotreating a raw material by adopting a hydrogenation device, wherein the raw material is a heavy or inferior oil product; the heavy or inferior oil product is a fossil oil product or biomass waste grease, and when the conversion rate of the fossil oil product in the reaction system is reduced to 70%-90% of the original design value or the deoxidation rate of the biomass waste grease is reduced to 70%-90% of the original design value, adding a liquid catalyst into the reaction system; the liquid catalyst comprises an oil-soluble metal organic salt. When the activity of the original hydro-conversion catalyst in the system is reduced to a certain degree, the liquid catalyst is added into the system, so that the reaction activity of the system is improved, and the stable operation of the reaction system at a relatively high conversion rate is maintained at a relatively low temperature; the replacement frequency of an original hydro-conversion catalyst is reduced, the operation period of a hydrogenation device is prolonged, and the productivity and the utilization efficiency of the hydrogenation device are ensured.

Description

Technical Field

[0001] The invention belongs to the technical field of energy chemical industry, and specifically relates to a hydrogenation treatment method. Background Art

[0002] In chemical production processes, heavy or low-quality oil products are generally treated by hydroprocessing processes. Common heavy or low-quality oil products include fossil oil products, biomass waste oils, etc., and are usually treated by fixed beds, suspended beds, and fluidized beds. In actual industrial production, no matter what kind of oil products are used or what kind of equipment is used, because this type of heavy or low-quality oil raw materials have high metal impurity content, many heavy components, and many coking precursors, it is easy to cause the system's hydroconversion catalyst to deactivate during the operation of the reaction system, making it difficult to meet the requirements of raw material conversion rate or target product yield in production, and thus the hydroconversion catalyst needs to be frequently replaced.

[0003] There are two common solutions to this problem:

[0004] Method 1: By increasing the hydrogenation reaction temperature, the reaction activity of the hydroconversion catalyst in the system is further activated to maintain the normal operation of the system. However, high-temperature operation will affect the life of the hydroconversion catalyst, resulting in a shorter life of the hydroconversion catalyst, and it still needs to be replaced frequently.

[0005] Method 2: Without considering the activation of the reaction activity of the hydroconversion catalyst, the raw material conversion rate or the target product yield is increased by reducing the fresh feed amount or reducing the space velocity, but this will affect the overall production capacity and utilization efficiency of the device operation cycle. Summary of the invention

[0006] In order to solve the above problems, the present invention provides a hydroprocessing method, which adds a liquid catalyst into the system when the activity of the original hydroconversion catalyst in the system decreases to a certain level, thereby improving the reaction activity of the system, maintaining the stable operation of the reaction system at a high conversion rate at a lower temperature, reducing the replacement frequency of the original hydroconversion catalyst, increasing the operation cycle of the hydrogenation unit, and ensuring the production capacity and utilization efficiency of the hydrogenation unit.

[0007] To this end, the present invention provides the following technical solutions.

[0008] The present invention provides a hydroprocessing method, comprising: using a hydrogenation device to perform hydroprocessing on a raw material, wherein the raw material is a heavy or low-quality oil product;

[0009] The heavy or inferior oil product is a fossil oil product or a biomass waste oil. When the conversion rate of the fossil oil product in the reaction system is reduced to 70% to 90% of the original design value or the deoxygenation rate of the biomass waste oil is reduced to 70% to 90% of the original design value, a liquid catalyst is added to the reaction system;

[0010] The liquid catalyst includes an oil-soluble metal organic salt.

[0011] The liquid catalyst is a liquid product whose main component is an oil-soluble metal organic salt, which can be obtained by mixing the oil-soluble metal organic salt with a solvent or directly purchased.

[0012] In an optional embodiment, the active metal element in the oil-soluble metal organic salt is selected from at least one of molybdenum, nickel, iron, cobalt and tungsten.

[0013] In an optional embodiment, the step of adding a liquid catalyst to the reaction system comprises:

[0014] The liquid catalyst is added to the raw material so that the content of active metal elements in the raw material is 50-1500 ppm, and then the raw material with the liquid catalyst added is sent to the hydrogenation device.

[0015] In an optional embodiment, the step of adding a liquid catalyst to the reaction system comprises:

[0016] Mixing part of the raw materials with the liquid catalyst, stirring at 50°C to 80°C for 30 to 60 minutes to prepare a mixed solution, and mixing the mixed solution with the remaining raw materials so that the content of active metal elements in the raw materials is 50 to 1500 ppm;

[0017] Optionally, the mass concentration of the liquid catalyst in the mixed liquid is 10% to 50%.

[0018] In an optional embodiment, when the conversion rate of fossil oil products is reduced to 80% to 90% of the original design value or the deoxidation rate of biomass waste oil is reduced to 80% to 90% of the original design value, the content of active metal elements in the raw material is 50 to 300 ppm;

[0019] Optionally, the active metal element is molybdenum and / or nickel, and the content of the active metal element in the raw material is 50 to 100 ppm;

[0020] Optionally, the active metal element is iron, and the content of the active metal element in the raw material is 100 to 300 ppm.

[0021] In an optional embodiment, when the conversion rate of fossil oil products is reduced to 70% to 80% of the original design value or the deoxidation rate of biomass waste oil is reduced to 70% to 80% of the original design value, the content of active metal elements in the raw material is 100 to 1500 ppm;

[0022] Optionally, the active metal element is molybdenum and / or nickel, and the content of the active metal element in the raw material is 100 to 500 ppm;

[0023] Optionally, the active metal element is iron, and the content of the active metal element in the raw material is 300 to 1500 ppm.

[0024] In an optional embodiment, the active metal is a combination of molybdenum and nickel, and the mass ratio of molybdenum to nickel is (1-8): (1-2).

[0025] In an optional embodiment, the liquid catalyst includes one or more of molybdenum isooctanoate, nickel isooctanoate, iron isooctanoate, molybdenum cyclopentaneate, nickel cyclopentaneate, iron cyclopentaneate, long-chain fatty acid molybdenum, dialkyl dithiophosphate oxymolybdenum and dialkyl dithiocarbamate molybdenum.

[0026] In an optional embodiment, the hydrogenation unit is a fixed bed, a suspended bed or an ebullating bed.

[0027] In an optional embodiment, the fossil oil product includes at least one of medium-low temperature coal tar, full fraction or fraction oil of high temperature coal tar, atmospheric residue oil, vacuum residue oil, heavy oil, catalytic cracking slurry, ethylene cracking tar, waste engine oil, waste tire oil, waste plastic oil and waste clay oil; and / or The biomass waste oil includes at least one of crude oil, acidified oil, kitchen waste oil, sewage oil, vegetable asphalt, animal oil, wood tar and straw tar. The following are definitions of some terms: "Heavy or inferior oil products" refer to heavy crude oil with an API gravity of less than 22.3. Heavy crude oil contains a large amount of other impurities in addition to hydrocarbons, such as sulfur, nitrogen, phosphorus, silicon, oxygen, chlorine and other metal elements.

[0031] Low-temperature coal tar is a liquid product produced by dry distillation or pyrolysis of coal at a relatively low temperature (usually below 650°C). This type of coal tar is rich in aromatics and other organic compounds.

[0032] High-temperature coal tar is a by-product obtained from high-temperature dry distillation of coal. It is a black oily liquid with a special odor, and its main components are aromatic hydrocarbons and organic compounds containing oxygen, nitrogen or sulfur.

[0033] Atmospheric residue is a heavy oil obtained during the atmospheric distillation of crude oil. It is usually collected at the bottom of an atmospheric distillation tower and usually contains high levels of sulfur, nitrogen, heavy metals, asphaltene and other components.

[0034] Vacuum residue is the heavy oil obtained by vacuum distillation of crude oil. It is usually collected at the bottom of the vacuum distillation tower and is a heavier hydrocarbon compound with a higher boiling point in crude oil.

[0035] Heavy oil, also known as heavy crude oil, is a type of crude oil with high viscosity and density.

[0036] Catalytic cracking slurry is a by-product of the catalytic cracking process. It has a high density, a low hydrogen-to-carbon atomic ratio, a high aromatic content, a low resin and asphaltene content, and a low carbon residue value.

[0037] Ethylene cracking tar, also known as ethylene tar, is the product of high-temperature condensation of raw materials and products during the steam cracking process of ethylene cracking raw materials. It is a by-product obtained by cracking hydrocarbons to produce ethylene. It exists in liquid form at room temperature and has the characteristics of high viscosity and high volatility.

[0038] Waste oil refers to recycled motor oil or lubricant that can no longer be used.

[0039] Waste tire oil is an oil byproduct extracted from waste tires through pyrolysis or other processes.

[0040] Waste plastic oil refers to the oil by-product extracted from waste plastics through pyrolysis or other processes.

[0041] Spent clay oil is an oil byproduct extracted from recycled clay through pyrolysis or other processes.

[0042] Biomass waste oils and fats, one is the by-products obtained during the preparation, processing and utilization of bio-oils, which are mainly organic liquid substances composed of carbon, hydrogen and oxygen, such as waste cooking oil, sewage oil, vegetable asphalt, animal fats and other lipid substances and fatty acids such as acidified oils; the other refers to the organic liquid by-products obtained during the processing and utilization of biomass raw materials such as agricultural and forestry wastes, such as straw tar, wood tar, etc.

[0043] Conversion rate of fossil oil products = 100% - mass of fraction with temperature greater than 500° C. in the product / mass of fraction with temperature greater than 500° C. in the raw material * 100%.

[0044] The deoxygenation rate of biomass waste oil = 100% - the mass of oxygen in the oil product after the reaction / the mass of oxygen in the raw material * 100%.

[0045] The technical solution of the present invention has the following advantages:

[0046] 1. The hydroprocessing method of the present invention comprises: using a hydrogenation device to perform hydroprocessing on a raw material, wherein the raw material is a heavy or low-quality oil product; the heavy or low-quality oil product is a fossil oil product or a biomass waste oil; when the conversion rate of the fossil oil product is reduced to 70% to 90% of the original design value or the deoxygenation rate of the biomass waste oil is reduced to 70% to 90% of the original design value, a liquid catalyst is added into the system; the liquid catalyst comprises an oil-soluble metal organic salt.

[0047] With the operation of the hydrogenation system, the activity of the original hydroconversion catalyst will continue to decrease. When it is reduced to a level that cannot meet production needs, it is necessary to shut down and replace the catalyst. When the activity of the original hydroconversion catalyst in the system of this application is reduced to a certain extent (that is, when the conversion rate of fossil oil products is reduced to 70% to 90% of the original design value or the deoxygenation rate of biomass waste oil is reduced to 70% to 90% of the original design value), adding a liquid catalyst to the system can increase the reaction activity of the system, and the conversion rate or deoxygenation rate can be increased without reducing production capacity and / or replacing the original hydroconversion catalyst; without increasing the temperature, the reaction system can still maintain stable operation at a higher conversion rate at a lower temperature, thereby extending the operation cycle of the hydrogenation unit; at the same time, the additional addition of a liquid catalyst can also reduce the decay rate of the original hydroconversion catalyst, thereby extending the life of the original hydroconversion catalyst, so that the original hydroconversion catalyst is brought into play to the extreme, and the operation cycle of the device is further extended.

[0048] The present invention adopts a liquid catalyst as a supplementary catalyst. On the one hand, the liquid catalyst supplementary catalyst is applicable to fixed beds, suspended beds, and fluidized beds, thereby solving the defect that the original hydroconversion catalyst of fixed beds, fluidized beds, and the like cannot be replaced or adjusted. On the other hand, the liquid catalyst is oil-soluble, and the adding process is simple, and it will not affect the reaction, separation, and other systems, thereby avoiding the damage to the existing system caused by the addition of a solid catalyst. On the third hand, the liquid catalyst is used as a supplementary catalyst and is added when the activity of the original hydroconversion catalyst decreases to a certain level, thereby significantly reducing the cost compared to using the liquid catalyst from the beginning.

[0049] 2. The step of adding a liquid catalyst to the reaction system comprises: mixing part of the raw materials with the liquid catalyst, stirring at 50° C. to 80° C. for 30 to 60 minutes to prepare a mixed liquid, and mixing the mixed liquid with the remaining raw materials so that the content of active metal elements in the raw materials is 50 to 1500 ppm.

[0050] Stirring at 50°C to 80°C allows the liquid catalyst to be highly dispersed in part of the raw materials, and then mixing it with the remaining raw materials. This can make the liquid catalyst more evenly dispersed in the raw materials, which is beneficial to the hydrogenation reaction and avoids uneven dispersion (such as enrichment) that causes local excessive temperature to produce coking. BRIEF DESCRIPTION OF THE DRAWINGS

[0051] In order to more clearly illustrate the specific implementation methods of the present invention or the technical solutions in the prior art, the drawings required for use in the specific implementation methods or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0052] Figure 1 The figure is a flow chart of the hydrogenation method of the present invention. DETAILED DESCRIPTION

[0053] The following examples are provided for a better understanding of the present invention, but are not intended to limit the best mode of implementation, nor to limit the content and protection scope of the present invention. Any product identical or similar to the present invention obtained by anyone under the inspiration of the present invention or by combining the features of the present invention with other prior arts shall fall within the protection scope of the present invention.

[0054] If no specific experimental steps or conditions are specified in the examples, the conventional experimental steps or conditions described in the literature in the field can be used. If no manufacturer is specified for the reagents or instruments used, they are all conventional reagent products that can be obtained commercially.

[0055] Example 1

[0056] This embodiment provides a hydroprocessing method, such as Figure 1 As shown, including:

[0057] Medium and low temperature coal tar is used as raw material, and a fixed bed is used as a hydrogenation device to hydrogenate the coal tar. The active components of the original hydrogenation conversion catalyst in the fixed bed are nickel and molybdenum, and the hydrogenation treatment conditions are 400°C and 15MPa.

[0058] When the raw material conversion rate is reduced to 75% of the original design value, a liquid catalyst (active component is molybdenum cyclohexane acid) is added to the raw material that has not yet been fed into the fixed bed, so that the molybdenum content in the raw material is 100ppm. The method of adding the liquid catalyst includes: firstly mixing part of the raw material with the liquid catalyst, stirring at 80°C for 30 minutes to prepare a mixed liquid, and mixing the mixed liquid with the remaining raw material, so that the molybdenum content in the raw material is 100ppm.

[0059] After adding the liquid catalyst in this embodiment, the raw material conversion rate is increased to 83% of the original design value, and the reaction system can continue to operate stably at a higher conversion rate at the original reaction temperature, thereby extending the operation cycle of the device.

[0060] Example 2

[0061] This embodiment provides a hydroprocessing method, which is basically the same as that of Embodiment 1, except that in this embodiment, after adding a liquid catalyst, the molybdenum content in the raw material is 200 ppm.

[0062] After adding the liquid catalyst in this embodiment, the raw material conversion rate is increased to 91%.

[0063] Example 3 This embodiment provides a hydroprocessing method, comprising: Using waste cooking oil as raw material, a suspended bed is used as a hydrogenation device to hydrogenate the raw material. The original hydrogenation conversion catalyst in the suspended bed is a micron-sized solid deoxygenation catalyst, and the active ingredients are iron and molybdenum. The hydrogenation treatment conditions are 15MPa and 380℃. The waste cooking oil is hydrogenated to obtain water and oil products.

[0064] When the deoxidation rate is reduced to 83% of the original design value, a liquid catalyst (active ingredient is molybdenum isooctanoate) is added to the waste cooking oil that has not yet been sent to the suspension bed, so that the molybdenum content in the raw material is 50ppm. The method of adding the liquid catalyst includes: firstly mixing part of the raw material with the liquid catalyst, stirring at 50°C for 30 minutes to prepare a mixed liquid, and mixing the mixed liquid with the remaining raw material, so that the molybdenum content in the raw material is 50ppm.

[0067] After adding the liquid catalyst in this embodiment, the deoxidation rate is increased to 90%.

[0068] Example 4

[0069] This embodiment provides a hydroprocessing method, which is basically the same as that of Embodiment 3, except that in this embodiment, after adding a liquid catalyst, the molybdenum content in the raw material is 100 ppm.

[0070] After adding the liquid catalyst in this embodiment, the deoxidation rate is increased to 97%.

[0071] Example 5

[0072] This embodiment provides a hydroprocessing method, comprising:

[0073] Using vacuum residue as raw material, an ebullated bed is used as a hydrogenation unit to carry out hydrogenation treatment on the raw material. The original hydrogenation conversion catalyst in the ebullated bed is a nickel-molybdenum catalyst, and the hydrogenation treatment conditions are 350°C and 15MPa.

[0074] When the raw material conversion rate is reduced to 80% of the original design value, a liquid catalyst (active components are molybdenum isooctanoate and nickel isooctanoate) is added to the residual oil that has not yet been sent to the fixed bed, so that the molybdenum content in the residual oil is 50ppm and the nickel content is 50ppm. The method of adding the liquid catalyst comprises: firstly mixing part of the raw material with the liquid catalyst, stirring at 80°C for 60min to prepare a mixed liquid, and mixing the mixed liquid with the remaining raw material, so that the molybdenum content in the raw material is 50ppm and the nickel content is 50ppm.

[0075] After adding the liquid catalyst in this embodiment, the conversion rate is increased to 85% of the original design value.

[0076] Example 6

[0077] This embodiment provides a hydroprocessing method, which is basically the same as that of Embodiment 5, except that, in this embodiment, after adding the liquid catalyst, the molybdenum content in the raw material is 100 ppm and the nickel content is 100 ppm.

[0078] After adding the liquid catalyst in this embodiment, the conversion rate is increased to 93%.

[0079] Example 7

[0080] This embodiment provides a hydroprocessing method, which is basically the same as that of Embodiment 1, except that in this embodiment, after adding a liquid catalyst, the molybdenum content in the raw material is 50 ppm, and the raw material conversion rate is increased to 78%.

[0081] Example 8

[0082] This embodiment provides a hydroprocessing method, which is basically the same as that of embodiment 1, except that:

[0083] The active components of the liquid catalyst added in this embodiment are nickel isooctanoate and molybdenum isooctanoate. After adding the liquid catalyst, the molybdenum content in the raw material is 100 ppm, the nickel content is 100 ppm, and the conversion rate is increased to 89%.

[0084] Example 9

[0085] This embodiment provides a hydroprocessing method, which is basically the same as that of Embodiment 1, except that the active ingredient of the liquid catalyst in this embodiment is nickel isooctanoate.

[0086] In this embodiment, after adding the liquid catalyst, the nickel content in the raw material is 100 ppm, and the conversion rate is increased to 80%.

[0087] Example 10

[0088] This embodiment provides a hydroprocessing method, which is basically the same as that of Embodiment 1, except that the active ingredient of the liquid catalyst in this embodiment is iron isooctanoate.

[0089] In this embodiment, after adding the liquid catalyst, the iron content in the raw material is 100 ppm, and the conversion rate is increased to 79%.

[0090] Embodiment 11

[0091] This embodiment provides a hydroprocessing method, which is basically the same as that of embodiment 1, except that:

[0092] In this embodiment, after adding the liquid catalyst, the molybdenum content in the raw material is 750 ppm, and the conversion rate is increased to 94%.

[0093] Example 12

[0094] This embodiment provides a hydrogenation treatment method, which is basically the same as that of Embodiment 1, except that, in this embodiment, after adding a liquid catalyst, the molybdenum content in the raw material is 1500 ppm, and the conversion rate is increased to 97%.

[0095] Obviously, the above embodiments are merely examples for the purpose of clear explanation, and are not intended to limit the implementation methods. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived from these are still within the scope of protection of the invention.

Claims

1. A hydroprocessing method, characterized in that: include: The raw material is subjected to hydrogenation treatment by using a hydrogenation unit, and the raw material is a heavy or low-quality oil product; The heavy or inferior oil product is a fossil oil product or a biomass waste oil. When the conversion rate of the fossil oil product in the reaction system is reduced to 70% to 90% of the original design value or the deoxygenation rate of the biomass waste oil is reduced to 70% to 90% of the original design value, a liquid catalyst is added to the reaction system; The liquid catalyst includes an oil-soluble metal organic salt.

2. The hydroprocessing method according to claim 1, characterized in that: The active metal element in the oil-soluble metal organic salt is selected from at least one of molybdenum, nickel, iron, cobalt and tungsten.

3. The hydroprocessing method according to claim 2, characterized in that: The step of adding a liquid catalyst into the reaction system comprises: The liquid catalyst is added to the raw material so that the content of active metal elements in the raw material is 50-1500 ppm, and then the raw material with the liquid catalyst added is sent to the hydrogenation device.

4. The hydroprocessing method according to claim 3, characterized in that: The step of adding a liquid catalyst into the reaction system comprises: Mixing part of the raw materials with the liquid catalyst, stirring at 50°C to 80°C for 30 to 60 minutes to prepare a mixed solution, and mixing the mixed solution with the remaining raw materials so that the content of active metal elements in the raw materials is 50 to 1500 ppm; Optionally, the mass concentration of the liquid catalyst in the mixed liquid is 10% to 50%.

5. The hydroprocessing method according to claim 3, characterized in that: When the conversion rate of fossil oil products is reduced to 80% to 90% of the original design value or the deoxidation rate of biomass waste oil is reduced to 80% to 90% of the original design value, the content of active metal elements in the raw materials is 50 to 300 ppm; Optionally, the active metal element is molybdenum and / or nickel, and the content of the active metal element in the raw material is 50 to 100 ppm; Optionally, the active metal element is iron, and the content of the active metal element in the raw material is 100 to 300 ppm.

6. The hydroprocessing method according to claim 3, characterized in that: When the conversion rate of fossil oil products is reduced to 70% to 80% of the original design value or the deoxidation rate of biomass waste oil is reduced to 70% to 80% of the original design value, the content of active metal elements in the raw materials is 100 to 1500 ppm; Optionally, the active metal element is molybdenum and / or nickel, and the content of the active metal element in the raw material is 100 to 500 ppm; Optionally, the active metal element is iron, and the content of the active metal element in the raw material is 300 to 1500 ppm.

7. The hydroprocessing method according to any one of claims 2 to 6, characterized in that: The active metal is a combination of molybdenum and nickel, and the mass ratio of the molybdenum to nickel is (1-8): (1-2).

8. The hydroprocessing method according to any one of claims 1 to 6, characterized in that: The liquid catalyst includes one or more of molybdenum isooctanoate, nickel isooctanoate, iron isooctanoate, molybdenum naphthenate, nickel naphthenate, iron naphthenate, long-chain fatty acid molybdenum, dialkyl dithiophosphoryl molybdenum and dialkyl dithiocarbamate molybdenum.

9. The hydroprocessing method according to any one of claims 1 to 6, characterized in that: The hydrogenation device is a fixed bed, a suspended bed or a fluidized bed.

10. The hydroprocessing method according to any one of claims 1 to 6, characterized in that: The fossil oil product includes at least one of medium-low temperature coal tar, full fraction or fraction oil of high temperature coal tar, atmospheric residue oil, vacuum residue oil, heavy oil, catalytic cracking slurry, ethylene cracking tar, waste engine oil, waste tire oil, waste plastic oil and waste clay oil; and / or The biomass waste oil includes at least one of crude oil, acidified oil, kitchen waste oil, sewage oil, vegetable asphalt, animal oil, wood tar and straw tar.

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