Preparation method of low-cost slurry bed hydrogenation catalyst

Abstract

The invention discloses a low-cost slurry bed hydrogenation catalyst preparation method, which comprises: carrying out oil removal, crushing and magnetic separation on an inactivated residual oil hydrogenation catalyst to obtain a low magnetic agent, sequentially carrying out acid treatment on the obtained low magnetic agent through oxalic acid and citric acid, and calcining; a regenerated catalyst is obtained; impregnating the regenerated catalyst in the impregnation liquid to obtain a pre-vulcanized powder catalyst, and uniformly mixing the pre-vulcanized powder catalyst with catalytic diesel oil, a dispersant and a stabilizer to obtain the low-cost slurry bed hydrogenation catalyst, the impregnation liquid contains treatment liquid obtained after treatment of sulfide, an inorganic polymerization inhibitor and citric acid. According to the method, through the synergistic effect of the steps of oil removal, magnetic separation, step-by-step acid treatment, roasting, pre-vulcanization, solid dispersion and the like, when the solid powder catalyst obtained through final regeneration is used for slurry bed hydrogenation, compared with the prior art, the hydrodesulfurization activity of the regenerated catalyst can be improved, green coke is reduced, and abrasion of the powder catalyst to equipment is reduced.

Description

Technical Field

[0001] The invention belongs to the technical field of slurry bed hydrogenation catalysts, and in particular relates to a method for preparing a low-cost slurry bed hydrogenation catalyst. Background Art

[0002] Since heavy oils such as residual oil contain a large amount of metal nickel, vanadium, etc. and precursors that are easy to form carbon deposits, the residual oil hydrogenation catalyst is easily deactivated due to metal deposition and carbon deposition, and the catalyst has a short service life of only about one year. The deactivated catalyst caused by this method is not easy to regenerate and is generally only used once. The deactivated catalyst is usually treated by metal recovery. If the deactivated residual oil hydrogenation catalyst can be regenerated and partially or completely replaced by fresh catalyst, it will have important practical significance both in increasing the economic benefits of the refinery and in terms of environmental pollution.

[0003] Over the years, researchers have developed a variety of regeneration methods for deactivated hydrogenation catalysts, such as Chinese patent document CN112337501A, which discloses a method for preparing a sulfurized regenerated hydrogenation catalyst. The method includes: the carbon-deactivated hydrogenation catalyst is first wetted with an oxygen-containing organic solvent, then subjected to a mild sulfur-burning and carbon-burning treatment, and after cooling, a water-soluble sulfur-containing composite solution is used for vacuum impregnation, and a sulfurized regenerated hydrogenation catalyst is obtained after heat treatment. The method can effectively reduce the sulfur-burning and carbon-burning temperature during the regeneration of the carbon-deactivated hydrogenation catalyst, inhibit the agglomeration of active metals, and weaken the strong interaction between the active metals and the carrier; at the same time, the active metals are redispersed and sulfurized in one step to obtain a sulfurized regenerated hydrogenation catalyst with a higher degree of activity recovery. However, this method is only for the regeneration of light oil catalysts (gasoline and diesel hydrogenation catalysts) with a carbon content of less than 5wt% and a harmful metal pollutant (Na+Ca+Fe+V) content of less than 2wt% of the carbon-deactivated hydrogenation catalyst, and cannot treat inferior heavy oil hydrogenation catalysts.

[0004] Chinese patent document CN110201694A discloses a method for regenerating a deactivated catalyst for hydrogenation of residual oil, comprising the following steps: (1) pre-treating the deactivated catalyst with an organic solvent to remove oil and drying; (2) treating the deactivated catalyst obtained in step (1) with an acid solution to effectively remove part of the metal deposited in the deactivated catalyst; (3) decarbonizing the deactivated catalyst obtained in step (2); (4) impregnating the deactivated catalyst obtained in step (3) with a metal solution containing one or two VIB group metal components and one or two VIII group metal components, and then drying. This method can effectively remove deposited metals and carbon deposits, restore the catalyst pore structure, and effectively improve the activity of the regenerated catalyst. The catalyst regenerated by this method is still a fixed bed catalyst. The acid treatment will reduce the mechanical strength of the catalyst particles. If it continues to be used on a fixed bed device, it will cause the bed to collapse and thus affect the operation cycle of the device. Chinese patent document CN101168137A discloses a regeneration and recovery system for FCC equilibrium catalyst, which comprises: the waste equilibrium catalyst to be treated enters a multi-stage magnetic separation device (A) through a material conveying system; the low magnetic agent selected enters an acidification demetallization device (B); the high magnetic agent is unloaded and bagged; the slurry treated by the acidification demetallization device (B) enters an activation device (C), and water and an activator are added to the slurry after the acidification reaction; the slurry after a certain reaction time is treated by a filtering and dehydrating device (D) to form a filter cake; and then enters a drying device (E); the filter cake is roasted in a rotary roasting device (F) to obtain a finished regenerated catalyst, which continuously flows out of the converter and is sieved and packaged; the entire process is controlled and displayed by an automatic control device (G). However, in this method, a large amount of waste liquid will be generated after acid treatment, and some of the waste liquid contains some metal ions, which are not effectively utilized, and improper waste liquid treatment will also cause relatively large harm to the environment.

[0005] At present, there are three forms of slurry bed catalysts: oil-soluble catalysts, water-soluble catalysts and solid powder catalysts. The preparation cost of oil-soluble catalysts and water-soluble catalysts is relatively high, resulting in a generally low addition amount, so it is difficult to have a high hydrogenation activity. In contrast, solid powder catalysts are low-cost and generally added in large amounts, but solid powder catalysts also have disadvantages such as poor dispersibility and easy to become coking centers. In addition, the large particles aggregated by coking also cause wear on the equipment, resulting in increased equipment maintenance costs. Summary of the invention

[0006] In view of the problems existing in the prior art and the directions for improvement, the present invention provides a method for preparing a low-cost slurry bed hydrogenation catalyst. The method uses the synergistic effect of various steps such as oil removal, magnetic separation, step-by-step acid treatment, calcination, presulfurization and solid dispersion to finally regenerate a solid powder catalyst for slurry bed hydrogenation. Compared with the prior art, the solid powder catalyst has excellent catalytic performance, is not easy to coke, and reduces the discharge of waste liquid.

[0007] To achieve the above object, the present invention provides the following technical solutions:

[0008] A method for preparing a low-cost slurry bed hydrogenation catalyst comprises the following steps:

[0009] (1) The deactivated residual oil hydrogenation catalyst is deoiled, crushed, and magnetically separated to obtain a low magnetic agent;

[0010] (2) treating the low magnetic agent with oxalic acid and citric acid in sequence and then calcining the treated agent to obtain a regenerated catalyst;

[0011] (3) impregnating the regenerated catalyst in an impregnation solution to obtain a presulfurized powder catalyst;

[0012] (4) uniformly mixing the presulfurized powder catalyst with catalytic diesel, a dispersant and a stabilizer to obtain the low-cost slurry bed hydrogenation catalyst;

[0013] The impregnation liquid contains sulfide, inorganic inhibitor and the treatment liquid obtained after the citric acid treatment.

[0014] Optionally, in step (1) of the preparation method of the above-mentioned low-cost slurry bed hydrogenation catalyst provided by the present invention, the deoiling step can be carried out by conventional operations in the industry, such as roasting deoiling or organic solvent deoiling. The present invention recommends a method of deoiling with an organic solvent, such as placing the deactivated residual oil hydrogenation catalyst in an organic solvent and treating it at 60 to 150° C. for 1 to 10 hours, so that the oily substances in the deactivated residual oil hydrogenation catalyst will be dissolved in the organic solvent and then separated from the catalyst. The amount and type of the specific organic solvent are not limited, as long as it can dissolve the oil-soluble substances in the catalyst. It can be adjusted according to actual conditions. The mass volume ratio of the deactivated residual oil hydrogenation catalyst to the organic solvent recommended by the present invention is 1g: (1 to 8) ml. The organic solvent can be selected from one or more of petroleum ether, naphtha, kerosene, toluene, etc.

[0015] Optionally, in step (1) of the method for preparing the low-cost slurry bed hydrogenation catalyst provided by the present invention, the particle size of the deactivated residual oil hydrogenation catalyst after crushing and oil removal is 20 to 200 microns, preferably 40 to 100 microns.

[0016] Optionally, in step (1) of the method for preparing the low-cost slurry bed hydrogenation catalyst provided by the present invention, the magnetic separation recommended by the present invention is carried out in a roller magnetic separation device, and the feed amount of the crushed deactivated residual oil hydrogenation catalyst is 50-100 kg / h, preferably 60-80 kg / h; the magnetic roller speed is 100-500 r / min, preferably 200-400 r / min. High magnetic agent and low magnetic agent are obtained through the magnetic separation, wherein the high magnetic agent (deactivated catalyst with high heavy metal content) is discharged into the waste agent tank, and the low magnetic agent (deactivated catalyst with low heavy metal content) is discharged into the recovery agent tank. Taking the total weight of the deactivated residual oil hydrogenation catalyst entering the roller magnetic separation device as 100%, the weight yield of the low magnetic agent is 50%-90%, preferably 70%-90%.

[0017] Optionally, in step (2) of the method for preparing the low-cost slurry bed hydrogenation catalyst provided by the present invention, the high selectivity of oxalic acid for vanadium is first used to remove the vanadium in the low magnetic agent, and then the high selectivity of citric acid for nickel is used to remove the nickel in the low magnetic agent. The present invention recommends using oxalic acid solution and citric acid solution for leaching in sequence, the mass concentration of the oxalic acid solution is 1% to 10%, preferably 5% to 8%; the leaching temperature is 10 to 100°C; the time is 1 to 6h; the mass concentration of the citric acid solution is 10% to 20%, preferably 14% to 18%, the leaching temperature is 10 to 100°C; the time is 1 to 6. More preferably, when leaching with oxalic acid solution, an excess impregnation method is adopted; when leaching with citric acid solution, an equal volume impregnation method is adopted.

[0018] Optionally, in step (2) of the method for preparing the low-cost slurry bed hydrogenation catalyst provided by the present invention, the calcination is carried out in an air atmosphere, first at 200-400°C for 1-4h, and then at 400-600°C for 2-6h.

[0019] Optionally, in step (3) of the method for preparing the low-cost slurry bed hydrogenation catalyst provided by the present invention, the treated liquid obtained after the citric acid treatment contains metallic nickel and citric acid, metallic nickel is a hydrogenation active component, and citric acid is a good complexing agent. The citric acid treated liquid is reused to reduce the cost of waste liquid treatment and the cost of catalyst regeneration.

[0020] Optionally, in the method for preparing the low-cost slurry bed hydrogenation catalyst provided by the present invention, the sulfide is selected from one or more of mercaptans, thiophenols, sulfides, and disulfides;

[0021] The mass ratio of the regenerated catalyst to the sulfide is 20:1-4, preferably 20:1-2.

[0022] Optionally, in step (3) of the method for preparing the low-cost slurry bed hydrogenation catalyst provided by the present invention, the impregnation is an equal volume impregnation.

[0023] Optionally, in the method for preparing the low-cost slurry bed hydrogenation catalyst provided by the present invention, the inorganic inhibitor is selected from one or more of ferric chloride, cuprous chloride, copper sulfate, titanium trichloride, sodium sulfate and ammonium thiocyanate;

[0024] The mass ratio of the regenerated catalyst to the inorganic inhibitor is 100:0.1-1.5.

[0025] Optionally, in step (3) of the method for preparing the low-cost slurry bed hydrogenation catalyst provided by the present invention, after impregnation, it includes a drying step. Preferably, the drying is carried out in a nitrogen atmosphere, the drying temperature is 150 to 300° C., and the drying time is 8 to 24 hours.

[0026] Optionally, in step (4) of the method for preparing the low-cost slurry bed hydrogenation catalyst provided by the present invention, the mass ratio of the presulfurized powder catalyst to the catalytic diesel is 1:2 to 10; preferably 1:2 to 5. Since the catalytic diesel contains a large amount of aromatics, it is easy to combine with the colloidal asphaltene in the heavy oil to promote its phase stability; using it as a continuous phase will make the final slurry bed hydrogenation catalyst more stable and the dispersion degree in the slurry bed reactor will be better, thereby reducing the coking rate. Using other diesels will reduce the dispersion degree of the hydrogenation catalyst in the slurry bed reactor, resulting in a high coking rate.

[0027] Optionally, in step (4) of the method for preparing the low-cost slurry bed hydrogenation catalyst provided by the present invention, the dispersant is selected from one or more of polyoxyethylene ether, polyoxypropylene ether, ethylene oxide and propylene oxide;

[0028] The mass ratio of the presulfurized powder catalyst to the dispersant is 100:0.5-5; preferably 100:1-2.

[0029] Optionally, in step (4) of the method for preparing the low-cost slurry bed hydrogenation catalyst provided by the present invention, the stabilizer is selected from one or more of methyl cellulose, sodium carboxymethyl cellulose and hydroxypropyl cellulose;

[0030] The mass ratio of the presulfurized powder catalyst to the stabilizer is 100:0.1-1.0; preferably 100:0.5-0.8.

[0031] Optionally, in the method for preparing the low-cost slurry bed hydrogenation catalyst provided by the present invention, in step (4), the mixing is stirring mixing, and the mixing temperature is 50 to 100°C.

[0032] Compared with the prior art, the present invention has the following beneficial effects:

[0033] 1. The preparation method of the low-cost slurry bed hydrogenation catalyst provided by the present invention first removes the oily substances in the deactivated catalyst by deoiling, and improves the subsequent use of the physical method of magnetic separation to separate the catalyst (high magnetic agent) with too high metal content and basically lost the meaning of regeneration; while reducing the regeneration cost, it improves the resource utilization rate. Then, the high selectivity of oxalic acid for metal vanadium is used in turn to leach the metal vanadium on the catalyst (which can be recycled and reused), and citric acid is used to leach nickel, effectively removing the metal nickel and vanadium deposited on the catalyst that affect the activity of the catalyst; then by roasting, the pore structure of the catalyst is restored; combined with presulfurization modification and adding inorganic inhibitors, solid dispersion and other means to the presulfurized impregnation liquid to treat the deactivated residual oil hydrogenation catalyst, improve the hydrodesulfurization activity of the regenerated catalyst and reduce coke, and reduce the wear of the powder catalyst on the equipment. In addition, the slurry bed hydrogenation catalyst prepared by this method can also directly avoid the disadvantage of reduced strength of the regenerated catalyst caused by acid treatment. This method makes full use of the deactivated residual oil hydrogenation catalyst, conforms to the development concept of green environmental protection, and greatly reduces the use cost of the slurry bed hydrogenation catalyst.

[0034] 2. In the preparation method of the low-cost slurry bed hydrogenation catalyst provided by the present invention, by further introducing the treatment liquid obtained after the citric acid treatment in step (2) into the impregnation liquid of step (3), combining with sulfide and inorganic inhibitor to mix to obtain the impregnation liquid, combined with other steps, the anti-coking performance and catalytic activity of the catalyst can be further significantly improved, and the emission of hazardous waste can be greatly reduced. Specifically, the impregnation liquid contains citric acid as a complexing agent, which can react and dissolve with the metal oxides formed during the regeneration process to promote the full dispersion of the metal oxides. It further contacts with the sulfide of the impregnation liquid to form a sulfur-containing metal complex. Under nitrogen heating conditions, the sulfur-containing metal complex decomposes in situ to generate active metal sulfides, thereby achieving the dispersion, resurrection and sulfidation of the metal in the regenerated catalyst in one step. At the same time, the nickel ions introduced into the treatment liquid obtained by the citric acid treatment in the impregnation liquid can replenish part of the active metals lost during the operation and regeneration of the catalyst, thereby improving the dispersion and effective utilization rate of the active components. Inorganic inhibitors can reduce the free radical polymerization to form macromolecules during thermal cracking, thereby reducing coking on the catalyst surface, preventing catalyst particles from agglomerating into large coking particles, and preventing macromolecular insolubles in the product oil from clogging the equipment or causing wear to the equipment.

[0035] 3. Catalytic diesel is rich in aromatics and has a high viscosity. It is an ideal oily dispersed phase. Catalyst powder, dispersant and stabilizer are added to it. The catalyst powder can form a relatively stable suspension system with catalytic diesel under the synergistic effect of surfactants. Adding this dispersed catalyst into the reactor can make the catalyst more dispersed, the mixing speed faster, reduce the time required for catalyst dispersion, and increase the reactor space velocity. DETAILED DESCRIPTION

[0036] The present invention is described in detail below by way of examples. It is necessary to point out that the following examples are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Those skilled in the art in this field can make some non-essential improvements and adjustments to the present invention based on the above content of the present invention.

[0037] Example 1

[0038] This embodiment provides a method for preparing a low-cost slurry bed hydrogenation catalyst, comprising the following steps:

[0039] (1) Take 100g of the deactivated residual oil hydrogenation catalyst A after the operation of the industrial device, put it into a Soxhlet extractor, add 500mL of petroleum ether, treat it at 100°C for 6 hours, dry it, and then crush it. Use a standard sieve to control its particle size to be 63-90 microns. The crushed catalyst is separated by a roller magnetic separation device, the feed rate is 60kg / h, the magnetic roller speed is 300r / min, and 75g of low magnetic agent (low metal content catalyst) is obtained (based on the total weight of the deactivated residual oil hydrogenation catalyst A entering the roller magnetic separation device as 100%, the weight yield of the low magnetic agent is 75%);

[0040] (2) The low magnetic agent is first impregnated with an excess of 8% oxalic acid solution at 60°C for 2 hours; and then impregnated with an equal volume of 15% citric acid solution at 80°C for 4 hours. The impregnated catalyst is calcined at 300°C for 2 hours in an air atmosphere, and then calcined at 450°C for 4 hours to obtain a regenerated catalyst;

[0041] (3) The citric acid leaching solution, ethyl mercaptan and ferric chloride obtained in step (2) are mixed to prepare an impregnation solution, and then the regenerated catalyst is added for equal volume impregnation. The mass ratio of the regenerated catalyst, ethyl mercaptan and ferric chloride is 100:10:1, and then dried at 200° C. in a nitrogen atmosphere for 16 hours to obtain a presulfurized powder catalyst;

[0042] (4) The presulfurized powder catalyst and catalytic diesel are stirred and mixed in a mass ratio of 1:5 at a mixing temperature of 50°C, and then polyoxypropylene ether and methyl cellulose are added, wherein the mass ratio of the presulfurized powder catalyst, polyoxypropylene ether and methyl cellulose is 100:2:0.5, and finally a slurry bed hydrogenation catalyst is obtained.

[0043] Example 2

[0044] This embodiment provides a method for preparing a low-cost slurry bed hydrogenation catalyst, comprising the following steps:

[0045] (1) Take 100g of the deactivated residual oil hydrogenation catalyst A after the operation of the industrial device, put it into a Soxhlet extractor, add 100mL of petroleum ether, treat it at 60°C for 10 hours, dry it, and then crush it. Use a standard sieve to control its particle size to 20-58 microns. The crushed catalyst is separated by a roller magnetic separation device, the feed rate is 50kg / h, the magnetic roller speed is 100r / min, and 50g of low magnetic agent (low metal content catalyst) is obtained (the total weight of the deactivated residual oil hydrogenation catalyst A entering the roller magnetic separation device is 100%, and the weight yield of the low magnetic agent is 50%);

[0046] (2) The low magnetic agent is first impregnated with an excess of 10% oxalic acid solution at 100°C for 1 hour; and then impregnated with an equal volume of 20% citric acid solution at 100°C for 1 hour. The impregnated catalyst is calcined at 200°C for 4 hours in an air atmosphere, and then calcined at 400°C for 4 hours to obtain a regenerated catalyst;

[0047] (3) The citric acid leaching solution, ethyl mercaptan and ferric chloride obtained in step (2) are mixed to prepare an impregnation solution, and then the regenerated catalyst is added for equal volume impregnation. The mass ratio of the regenerated catalyst, ethyl mercaptan and ferric chloride is 100:20:1.5, and then dried at 150° C. in a nitrogen atmosphere for 24 hours to obtain a presulfurized powder catalyst;

[0048] (4) The presulfurized powder catalyst and catalytic diesel are stirred and mixed in a mass ratio of 1:2 at a mixing temperature of 80°C, and then polyoxypropylene ether and methyl cellulose are added, wherein the mass ratio of the presulfurized powder catalyst, polyoxypropylene ether and methyl cellulose is 100:5:1, and finally a slurry bed hydrogenation catalyst is obtained.

[0049] Example 3

[0050] This embodiment provides a method for preparing a low-cost slurry bed hydrogenation catalyst, comprising the following steps:

[0051] (1) Take 100g of the deactivated residual oil hydrogenation catalyst A after the operation of the industrial device, put it into a Soxhlet extractor, add 800mL of petroleum ether, treat it at 150°C for 1 hour, dry it, and then crush it. Use a standard sieve to control its particle size to 150-200 microns. The crushed catalyst is separated by a roller magnetic separation device, the feed rate is 100kg / h, the magnetic roller speed is 500r / min, and 90g of low magnetic agent (low metal content catalyst) is obtained (based on the total weight of the deactivated residual oil hydrogenation catalyst A entering the roller magnetic separation device as 100%, the weight yield of the low magnetic agent is 90%);

[0052] (2) The low magnetic agent is first impregnated with an excess of 1% oxalic acid solution at 10°C for 6 hours; and then impregnated with an equal volume of 10% citric acid solution at 10°C for 6 hours. The impregnated catalyst is calcined at 400°C for 1 hour in an air atmosphere, and then calcined at 600°C for 2 hours to obtain a regenerated catalyst;

[0053] (3) The citric acid leaching solution, ethyl mercaptan and ferric chloride obtained in step (2) are mixed to prepare an impregnation solution, and then the regenerated catalyst is added for equal volume impregnation. The mass ratio of the regenerated catalyst, ethyl mercaptan and ferric chloride is 100:5:0.5, and then dried at 300° C. in a nitrogen atmosphere for 8 hours to obtain a presulfurized powder catalyst;

[0054] (4) The presulfurized powder catalyst and catalytic diesel are stirred and mixed in a mass ratio of 1:10 at a mixing temperature of 100° C., and then polyoxypropylene ether and methyl cellulose are added, wherein the mass ratio of the presulfurized powder catalyst, polyoxypropylene ether and methyl cellulose is 100:0.5:0.1, and finally a slurry bed hydrogenation catalyst is obtained.

[0055] Example 4

[0056] This embodiment provides a method for preparing a low-cost slurry bed hydrogenation catalyst, comprising the following steps:

[0057] (1) Take 100g of the deactivated residual oil hydrogenation catalyst A after the operation of the industrial device, put it into a Soxhlet extractor, add 500mL of toluene, treat it at 100°C for 6 hours, dry it, and then crush it. Use a standard sieve to control its particle size to 90-150 microns. The crushed catalyst is separated by a roller magnetic separation device, the feed rate is 70kg / h, the magnetic roller speed is 200r / min, and 80g of low magnetic agent (low metal content catalyst) is obtained (based on the total weight of the deactivated residual oil hydrogenation catalyst A entering the roller magnetic separation device as 100%, the weight yield of the low magnetic agent is 80%);

[0058] (2) The low magnetic agent is first impregnated with an excess of 5% oxalic acid solution at 50°C for 3 hours; then impregnated with an equal volume of 14% citric acid solution at 60°C for 5 hours. The impregnated catalyst is calcined at 300°C for 2 hours in an air atmosphere, and then calcined at 450°C for 4 hours to obtain a regenerated catalyst;

[0059] (3) The citric acid leaching solution obtained in step (2), thiophenol and an inorganic inhibitor (copper sulfate and sodium sulfate mixed in a mass ratio of 1:1) are mixed to prepare an impregnation solution, and then the above-mentioned regenerated catalyst is added for equal volume impregnation. The mass ratio of the regenerated catalyst, thiophenol and inorganic inhibitor is 100:5:0.5, and then dried at 200° C. for 16 hours in a nitrogen atmosphere to obtain a presulfurized powder catalyst;

[0060] (4) The presulfurized powder catalyst and catalytic diesel are stirred and mixed in a mass ratio of 1:3 at a mixing temperature of 50° C., and then polyoxyethylene ether and sodium carboxymethyl cellulose are added, wherein the mass ratio of the presulfurized powder catalyst, polyoxyethylene ether and sodium carboxymethyl cellulose is 100:1:0.7, and finally a slurry bed hydrogenation catalyst is obtained.

[0061] Example 5

[0062] This embodiment provides a method for preparing a low-cost slurry bed hydrogenation catalyst, comprising the following steps:

[0063] (1) Take 100g of the deactivated residual oil hydrogenation catalyst A after the operation of the industrial device, put it into a Soxhlet extractor, add 500mL of petroleum ether, treat it at 100°C for 6 hours, dry it, and then crush it. Use a standard sieve to control its particle size to be 63-90 microns. The crushed catalyst is separated by a roller magnetic separation device, the feed rate is 80kg / h, the magnetic roller speed is 400r / min, and 85g of low magnetic agent (low metal content catalyst) is obtained (based on the total weight of the deactivated residual oil hydrogenation catalyst A entering the roller magnetic separation device as 100%, the weight yield of the low magnetic agent is 85%);

[0064] (2) The low magnetic agent is first impregnated with an excess of 7% oxalic acid solution at 70°C for 2 hours; and then impregnated with an equal volume of 15% citric acid solution at 100°C for 4 hours. The impregnated catalyst is calcined at 300°C for 2 hours in an air atmosphere, and then calcined at 500°C for 5 hours to obtain a regenerated catalyst;

[0065] (3) The citric acid leaching solution obtained in step (2), the sulfiding agent (dimethyl sulfide and dimethyl disulfide mixed in a mass ratio of 1:1) and cuprous chloride are mixed to prepare an impregnation solution, and then the regenerated catalyst is added for equal volume impregnation. The mass ratio of the regenerated catalyst, the sulfiding agent and the cuprous chloride is 100:10:0.1, and then dried at 200° C. in a nitrogen atmosphere for 16 hours to obtain a presulfurized powder catalyst;

[0066] (4) The presulfurized powder catalyst and catalytic diesel are stirred and mixed in a mass ratio of 1:4 at a mixing temperature of 50°C, and then a dispersant (ethylene oxide and propylene oxide are mixed in a mass ratio of 1:1) and a stabilizer (sodium carboxymethyl cellulose and hydroxypropyl cellulose are mixed in a mass ratio of 1:1) are added, wherein the mass ratio of the presulfurized powder catalyst, the dispersant and the stabilizer is 100:1.5:0.8, and finally a slurry bed hydrogenation catalyst is obtained.

[0067] Comparative Example 1

[0068] The preparation method of the slurry bed hydrogenation catalyst provided in this comparative example is similar to that of Example 1, except that the magnetic separation step is omitted in step (1) of this comparative example. The preparation method of the slurry bed hydrogenation catalyst provided in this comparative example is as follows:

[0069] (1) 100 g of deactivated residual oil hydrogenation catalyst A after operation of an industrial device was taken, placed in a Soxhlet extractor, 500 mL of petroleum ether was added, treated at 100° C. for 6 hours, dried, and then crushed. The particle size was controlled to be 63 to 90 μm using a standard sieve to obtain a crushed catalyst;

[0070] (2) The crushed catalyst is first impregnated with an excess of 8% oxalic acid solution at 60°C for 2 hours; then impregnated with an equal volume of 15% citric acid solution at 80°C for 4 hours. The impregnated catalyst is calcined at 300°C for 2 hours in an air atmosphere, and then calcined at 450°C for 4 hours to obtain a regenerated catalyst;

[0071] (3) The citric acid leaching solution, ethyl mercaptan and ferric chloride obtained in step (2) are mixed to prepare an impregnation solution, and then the regenerated catalyst is added for equal volume impregnation. The mass ratio of the regenerated catalyst, ethyl mercaptan and ferric chloride is 100:10:1, and then dried at 200° C. in a nitrogen atmosphere for 16 hours to obtain a presulfurized powder catalyst;

[0072] (4) The presulfurized powder catalyst and catalytic diesel were stirred and mixed in a mass ratio of 1:5 at a mixing temperature of 50°C, and then polyoxypropylene ether and methyl cellulose were added, wherein the mass ratio of the presulfurized powder catalyst, polyoxypropylene ether and methyl cellulose was 100:2:0.5, and finally a slurry bed hydrogenation catalyst B1 was obtained.

[0073] Comparative Example 2

[0074] The preparation method of the slurry bed hydrogenation catalyst provided in this comparative example is similar to that of Example 1, except that in step (2) of this comparative example, oxalic acid and citric acid are mixed and then acid-treated together. The preparation method of the slurry bed hydrogenation catalyst provided in this comparative example is specifically as follows:

[0075] (1) Take 100g of the deactivated residual oil hydrogenation catalyst A after the operation of the industrial device, put it into a Soxhlet extractor, add 500mL of petroleum ether, treat it at 100°C for 6 hours, dry it, and then crush it. Use a standard sieve to control its particle size to be 63-90 microns. The crushed catalyst is separated by a roller magnetic separation device, the feed rate is 60kg / h, the magnetic roller speed is 300r / min, and 75g of low magnetic agent (low metal content catalyst) is obtained (based on the total weight of the deactivated residual oil hydrogenation catalyst A entering the roller magnetic separation device as 100%, the weight yield of the low magnetic agent is 75%);

[0076] (2) placing the low magnetic agent in a mixed acid solution having an oxalic acid mass concentration of 8% and a citric acid mass concentration of 15%, and impregnating the solution at 60° C. for 4 hours; the impregnated catalyst was calcined at 300° C. for 2 hours in an air atmosphere, and then calcined at 450° C. for 4 hours to obtain a regenerated catalyst;

[0077] (3) The leaching solution of step (2), ethyl mercaptan and ferric chloride are mixed to prepare an impregnation solution, and then the regenerated catalyst is added for equal volume impregnation. The mass ratio of the regenerated catalyst, ethyl mercaptan and ferric chloride is 100:10:1, and then dried at 200° C. for 16 hours in a nitrogen atmosphere to obtain a presulfurized powder catalyst;

[0078] (4) The presulfurized powder catalyst and catalytic diesel are stirred and mixed in a mass ratio of 1:5 at a mixing temperature of 50°C, and then polyoxypropylene ether and methyl cellulose are added, wherein the mass ratio of the presulfurized powder catalyst, polyoxypropylene ether and methyl cellulose is 100:2:0.5, and finally a slurry bed hydrogenation catalyst B2 is obtained.

[0079] Comparative Example 3

[0080] The preparation method of the slurry bed hydrogenation catalyst provided in this comparative example is similar to that of Example 1, except that the sulfiding agent ethyl mercaptan is not added to the impregnation solution in step (3) of this comparative example, and finally catalyst B3 is obtained.

[0081] Comparative Example 4

[0082] The preparation method of the slurry bed hydrogenation catalyst provided in this comparative example is similar to that of Example 1, except that the inorganic inhibitor ferric chloride is not added to the impregnation liquid in step (3) of this comparative example, and finally catalyst B4 is obtained.

[0083] Comparative Example 5

[0084] The preparation method of the slurry bed hydrogenation catalyst provided in this comparative example is similar to that of Example 1, except that step (4) is omitted in this comparative example, and catalyst B5 is finally obtained.

[0085] Experimental example

[0086] Using atmospheric residue as raw material, the slurry bed hydrogenation catalyst was evaluated for hydrodesulfurization in an autoclave. The operating conditions were temperature 430°C, pressure 16 MPa, hydrogen-to-oil ratio 1200, feed oil 150g, catalyst powder addition amount 3g, and then the desulfurization rates were calculated respectively.

[0087] Desulfurization rate = (raw material sulfur content - product sulfur content) / raw material sulfur content

[0088] Relative desulfurization rate = reference agent (deactivated or regenerated catalyst) / fresh agent desulfurization rate

[0089] Coke yield = (mass of toluene insoluble matter in the product obtained by hydrodesulfurization - amount of catalyst added) / amount of oil added

[0090] The particle size of the coke particles was obtained by statistically averaging microscopic images (200 times).

[0091] The specific surface area was tested in accordance with GB / T 38691-2020, the pore volume was tested in accordance with GB / T 21650-2018, the Ni content and the V content were measured by ICP spectroscopy. The specific catalyst properties and reaction results are shown in the table below.

[0092] Table 1

[0093]

[0094] Note: The desulfurization rate of fresh agent A is taken as the benchmark, so the relative desulfurization rate of fresh agent A is 100%.

[0095] From the comparison between Example 1 and Comparative Example 1, it can be seen that when magnetic separation is not performed, the catalyst with a higher metal content cannot be separated. Therefore, the Ni and V contents in Example 1 are lower than those in Comparative Example 1, and the desulfurization activity of Example 1 is significantly higher than that of Comparative Example 1. The reason is that the catalyst with a higher metal content still has some Ni and V in the form of metal porphyrin, which blocks part of the catalyst pores and affects the catalytic performance of the catalyst.

[0096] From the comparison between Example 1 and Comparative Example 2, it can be seen that when the step-by-step acid treatment is not performed, the Ni ions in the treated solution obtained by leaching cannot be further used. Therefore, the active metal Ni content in Comparative Example 2 is significantly lower than that in Example 1, and therefore its desulfurization activity is also lower than that in Example 1.

[0097] From the comparison between Example 1 and Comparative Example 3, it can be seen that the properties of the catalysts are basically the same, but the desulfurization activity of Comparative Example 3 is lower than that of Example 1. The reason is that no sulfiding agent is added, and the catalyst form is still in an oxidized state, and the desulfurization activity is low. During the reaction, the catalyst first undergoes a sulfidation reaction in the autoclave to obtain a higher desulfurization activity, resulting in a lower desulfurization activity than the sulfided catalyst in a shorter reaction time.

[0098] From the comparison between Example 1 and Comparative Example 4, it can be seen that the coking rate and coking particle size of Comparative Example 4 are greatly increased. The reason is that there is no inhibitory property, the catalyst becomes the coking center, the coking amount increases, and some catalyst particles aggregate into larger particles.

[0099] From the comparison between Example 1 and Comparative Example 5, it can be seen that the powder catalyst that has not been dispersed requires a longer reaction time to achieve the same desulfurization effect. The reason is that the solid powder catalyst has poor dispersibility and a slow mixing time. The poor dispersion properties also lead to a small increase in the coke rate and coke particles.

[0100] Of course, the present invention may have many other embodiments. Without departing from the spirit and essence of the present invention, technicians familiar with the field may make various corresponding changes and deformations based on the present invention, but these corresponding changes and deformations should all fall within the scope of protection of the claims of the present invention.

Claims

1. A method for preparing a low-cost slurry bed hydrogenation catalyst, characterized in that: The steps include: (1) The deactivated residual oil hydrogenation catalyst is deoiled, crushed, and magnetically separated to obtain a low magnetic agent; (2) treating the low magnetic agent with oxalic acid and citric acid in sequence and then calcining the treated agent to obtain a regenerated catalyst; (3) impregnating the regenerated catalyst in an impregnation solution to obtain a presulfurized powder catalyst; (4) uniformly mixing the presulfurized powder catalyst with catalytic diesel, a dispersant and a stabilizer to obtain the low-cost slurry bed hydrogenation catalyst; The impregnation liquid contains sulfide, inorganic inhibitor and the treatment liquid obtained after the citric acid treatment.

2. The preparation method according to claim 1, characterized in that After crushing, the particle size of the deactivated residue oil hydrogenation catalyst is 20 to 200 microns.

3. The preparation method according to claim 1, characterized in that: The magnetic separation adopts roller magnetic separation, and the rotation speed of the magnetic roller is 100-500r / min.

4. The preparation method according to claim 1, characterized in that: The calcination is carried out in an air atmosphere, first at 200-400° C. for 1-4 hours, and then at 400-600° C. for 2-6 hours.

5. The preparation method according to claim 1, characterized in that: The sulfide is selected from one or more of mercaptans, thiophenols, thioethers, and disulfides; The mass ratio of the regenerated catalyst to the sulfide is 20:1-4.

6. The preparation method according to claim 1, characterized in that: The inorganic inhibitor is selected from one or more of ferric chloride, cuprous chloride, copper sulfate, titanium trichloride, sodium sulfate and ammonium thiocyanate; The mass ratio of the regenerated catalyst to the inorganic inhibitor is 100:0.1-1.

5.

7. The preparation method according to claim 1, characterized in that: The mass ratio of the presulfurized powder catalyst to the catalytic diesel is 1:2-10.

8. The preparation method according to claim 1, characterized in that: The dispersant is selected from one or more of polyoxyethylene ether, polyoxypropylene ether, ethylene oxide and propylene oxide; The mass ratio of the presulfurized powder catalyst to the dispersant is 100:0.5-5.

9. The preparation method according to claim 1, characterized in that: The stabilizer is selected from one or more of methyl cellulose, sodium carboxymethyl cellulose and hydroxypropyl cellulose; The mass ratio of the presulfurized powder catalyst to the stabilizer is 100:0.1-1.

0.

10. The preparation method according to claim 1, characterized in that: In step (4), the mixing temperature is 50-100°C.

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