CN117085693A

CN117085693A - Preparation method and application of regenerated slurry bed hydrogenation catalyst

Info

Publication number: CN117085693A
Application number: CN202310841283.1A
Authority: CN
Inventors: 曹澎锐; 楼巧琳; 奚俊; 许杰
Original assignee: Ningbo Zhongjin Petrochemical Co ltd
Current assignee: Ningbo Zhongjin Petrochemical Co ltd
Priority date: 2023-07-10
Filing date: 2023-07-10
Publication date: 2023-11-21

Abstract

The application relates to the petrochemical field, and discloses a preparation method and application of a regenerated slurry bed hydrogenation catalyst, wherein the preparation method comprises the following steps: 1) The waste fixed bed hydrogenation catalyst is burnt, pulverized and sieved to obtain particles; 2) Adding iron powder into the particles and uniformly mixing; 3) And 3) impregnating the product obtained in the step 2) with a thiol polyoxyethylene ether type surfactant solution, and drying and cooling to obtain the regenerated slurry bed hydrogenation catalyst. The application uses the waste fixed bed hydrogenation catalyst as a main component and iron powder as an auxiliary component, and the obtained catalyst not only has excellent hydrogenation activity, but also has the advantages of simple process, low cost, low carbon and environmental protection. The regenerated slurry bed hydrogenation catalyst and the slurry bed hydrogenation process are adopted to treat the inferior heavy oil, so that the inferior heavy oil with low added value can be converted into combustible gas, the feeding of a fixed bed hydrogenation device and the like, and finally converted into a clean fuel product, and the economical efficiency can be remarkably improved.

Description

Preparation method and application of regenerated slurry bed hydrogenation catalyst

Technical Field

The application relates to the petrochemical field, in particular to a preparation method and application of a regenerated slurry bed hydrogenation catalyst.

Background

Slurry bed hydrogenation technology began at the earliest in germany in the third and forty of the last century. China was combined with autonomous research and development to form a slurry bed hydrogenation technology in China on the basis of the introduction of foreign technology by Shenhua group company. After that, companies such as an extended petroleum group, beijing trimerization new environment-friendly material, neymond Qinghua and the like have slurry bed hydrogenation projects successively.

The hydrotreating technology of inferior heavy oil is three main technologies of fixed bed hydrogenation, ebullated bed hydrogenation and slurry bed hydrogenation in turn according to the advancement of the process technology, namely the inferior degree of the raw materials. Wherein: the fixed bed hydrogenation technology can only treat the raw oil with the metal (Ni+V) content less than 200 mug/g and the asphaltene content less than 1%; slurry bed hydrogenation is a technique that can currently handle more inferior raw oil; the inferior degree of the raw oil of the ebullated bed hydrogenation technology is between the two. The low-quality heavy oil such as vacuum residuum, ethylene tar, catalytic slurry oil and the like has the asphaltene content of more than 5 percent, and is a raw material which cannot be treated by the conventional fixed bed and ebullated bed hydrogenation technology. Industrially, the number of fixed bed hydrogenation devices in China is the largest, and the number of ebullated bed and slurry bed devices is smaller. The slurry bed hydrogenation technology is a main means for processing inferior heavy oil in the future because of the characteristics of being capable of processing inferior raw materials, high conversion rate, high clean fuel yield, long operation period, good product quality and the like.

Among the existing slurry bed hydrogenation catalysts, the slurry bed hydrogenation catalyst disclosed in China patent CN104826662A adopts iron-based FeOOH as a main catalyst, molybdenum as an auxiliary agent and dry coal powder and activated carbon powder as carriers; the slurry bed hydrogenation catalyst disclosed in Chinese patent CN106622268B has the carrier of silicon oxide-aluminum oxide and aluminum oxide, and the content of iron, calcium and molybdenum is 10-40m% in terms of oxide; the slurry bed hydrogenation catalyst disclosed in Chinese patent CN104907078B adopts red mud or hematite powder containing molybdenum as main body, and activated carbon as carrier; chinese patent CN113145106 discloses slurry bed hydrogenation catalyst, which is a transition metal tungsten catalyst supported on carbonaceous particles. However, the catalyst can play a role in catalysis only by additionally loading a certain amount of active metal, and the processing cost of the catalyst is high.

With regard to waste hydrogenation catalysts, about 75 ten thousand tons of waste hydrogenation catalyst are currently produced worldwide each year, and the number of incomplete statistics in China is about 3 ten thousand tons. If the waste hydrogenation catalysts belong to HW50 dangerous wastes and are piled in open air for a long time, a large amount of land resources are occupied, toxic and harmful components in the waste hydrogenation catalysts can enter water and soil along with rainwater, harm is caused to the environment, vegetation and living things, and the health of a human body can be endangered through a food chain.

At present, the recycling methods of the waste hydrogenation catalysts mainly comprise: and (3) a step of: regenerated and reprocessed to be used as a fixed bed hydrogenation catalyst again; and II: recovering metal components; thirdly,: and (5) landfill treatment. The metal component recovery method has the problems of long processing flow, low utilization rate of the waste hydrogenation catalyst and poor comprehensive economy; landfill disposal is becoming increasingly impractical due to the increasing expense and environmental concerns. Therefore, how to provide a simple, low-cost, environment-friendly and efficient waste hydrogenation catalyst regeneration method has important significance.

Disclosure of Invention

In order to solve the technical problems, the application provides a preparation method and application of a regenerated slurry bed hydrogenation catalyst. The application uses the waste fixed bed hydrogenation catalyst which is harmful to the environment as a main component and uses the low-cost iron powder as an auxiliary component, and the low-cost iron powder is used as a slurry bed hydrogenation catalyst to be applied to the hydroprocessing of inferior heavy oil, thereby not only having excellent hydrogenation activity, but also having the advantages of simple process, low cost, low carbon and environmental protection. The regenerated slurry bed hydrogenation catalyst and the slurry bed hydrogenation process are adopted to treat the inferior heavy oil, so that the inferior heavy oil with low added value can be converted into combustible gas, the feeding of a fixed bed hydrogenation device and the like, and finally converted into a clean fuel product, and the economical efficiency can be remarkably improved.

The specific technical scheme of the application is as follows:

in a first aspect, the present application provides a method for preparing a regenerated slurry bed hydrogenation catalyst, comprising the steps of:

1) The waste fixed bed hydrogenation catalyst is burnt, pulverized and sieved to obtain particles with the particle diameter of 50-90 mu m.

2) Adding iron powder with the granularity of 50-75 mu m and the particle size dispersion of less than 10% into the particles in the step 1) according to the mass ratio of 1-4:100, and uniformly mixing.

3) Impregnating the product obtained in the step 2) with 4-10wt% of thiol polyoxyethylene ether type surfactant solution according to the volume ratio of 1-3:1, drying and cooling to obtain the regenerated slurry bed hydrogenation catalyst with the particle size of 60-100 mu m.

The regenerated slurry bed hydrogenation catalyst takes the waste fixed bed hydrogenation catalyst which is harmful to the environment as a main component, takes low-cost iron powder as an auxiliary component, can effectively utilize the hydrogenation activity of the original metal components (W, mo, ni and the like) of the waste fixed bed hydrogenation catalyst, and cooperates with iron, so that the regenerated slurry bed hydrogenation catalyst is used as the slurry bed hydrogenation catalyst for the hydroprocessing of inferior heavy oil, has excellent hydrogenation activity, and has the advantages of changing waste into valuables, fully utilizing resources, and being low in carbon and environment-friendly. It is emphasized that the regenerated slurry bed hydrogenation catalyst of the application has the following points in the preparation process:

first, in terms of particle size: the method of the application burns off carbon deposition, impurities, dirty oil and the like on the inner and outer surfaces of the waste fixed bed hydrogenation catalyst at high temperature, thereby obtaining particles with proper particle size, having more active sites than the original shape, optimizing the particle size of iron powder, leading the prepared regenerated slurry bed hydrogenation catalyst to have better activity and richer inner and outer surface areas and pore channels, and leading the macromolecule asphalt and colloid which influence the service life of a downstream fixed bed hydrogenation device in inferior heavy oil to be removed by deposition and/or hydrogenation conversion method, thereby having higher liquid phase product yield and lower gas phase product yield (higher added value of liquid phase product) than the existing slurry bed catalyst, optimizing the product distribution. If the particle size is too large, the combination of the catalyst and the oil phase reactant is not facilitated, the active sites of the catalyst are few, and the reaction is not completed; meanwhile, the abrasion to equipment is serious, and the running cost of the device is increased; if the particle size is too small, the surface energy becomes high, the interaction force among particles becomes strong, agglomeration is easy to occur, and the hydrogenation reaction is not easy to carry out.

Secondly, in terms of the ratio of spent fixed bed hydrogenation catalyst particles to iron powder: the application strictly controls the proportion of the waste fixed bed hydrogenation catalyst particles to the iron powder to be 1-4:100. If the proportion of the iron powder is too high, the active metal points of the waste fixed bed hydrogenation catalyst are reduced to influence the hydrogenation effect; if the iron powder fraction is too low, the deposition or conversion of the larger molecular asphaltenes or colloids (materials that cannot be handled by fixed bed hydrogenation) in the slurry bed feed will be affected, resulting in a reduced conversion.

Finally, in the case of thiol polyoxyethylene ethers: as is known in the industry, the smaller the particle size of the slurry bed hydrogenation catalyst, the higher the surface energy, the stronger the interaction force among particles, the easier the agglomeration, and the adverse effect on the hydrogenation reaction. Therefore, the application discovers that after the catalyst is impregnated by adopting the specific thiol polyoxyethylene ether type surfactant, the interaction force among catalyst particles can be obviously reduced, the binding force of the catalyst and the oil phase reaction feeding material is enhanced, and the macromolecular compound in the feeding material is better adsorbed on the active site, so that the hydrogenation reaction is better promoted, and the macromolecular compound is converted into the micromolecular compound; even if the catalyst cannot be hydrogenated, the catalyst particles are discharged out of the reactor together with reaction products, so that the coke yield is reduced, and the effect of optimizing the product distribution is also achieved. In addition, more importantly, after the catalyst is subjected to surface modification by a thiol polyoxyethylene ether type surfactant, the thiol group on the compound is converted into H through hydrogenation reaction ₂ S, can improve H in the reaction system ₂ S concentration can effectively ensure the activity stability of the regenerated slurry bed hydrogenation catalyst, and is beneficial to the hydrogenation reaction. Further, to make it betterThe thiol polyoxyethylene ether functions, and the concentration of the solution and the ratio of the thiol polyoxyethylene ether to the catalyst in the impregnation process need to be optimized.

Preferably, in step 1), the carrier of the waste fixed bed hydrogenation catalyst is selected from alumina and silica alumina, and the active ingredient is selected from one or more of W, mo and Ni.

Preferably, in step 1), the firing temperature is 1300-1750 ℃ and the firing time is 1-8h.

Preferably, in step 2), the iron powder is added to the granules of step 1) in a rounded manner at 20-35 ℃ at a rate of 0.1-0.4g/s.

Preferably, in the step 3), the thiol polyoxyethylene ether type surfactant is tertiary hexyl thiol polyoxyethylene (11-12) ether and/or tertiary nonyl thiol polyoxyethylene (17) ether.

Preferably, in the step 3), the temperature of the impregnation is 20-35 ℃ and the time is 1-10h; the drying temperature is 100-130 ℃ and the drying time is 1-10h.

In a second aspect, the application provides an application of the regenerated slurry bed hydrogenation catalyst in the poor heavy oil slurry bed hydrogenation.

Preferably, the application comprises the steps of:

a) Mixing inferior heavy oil, sulfur powder and regenerated slurry bed hydrogenation catalyst to form a slurry hydrogenation bed.

B) The slurry hydrogenation bed is subjected to a hydrogenation reaction under an atmosphere comprising hydrogen.

C) And separating the obtained hydrogenation product to obtain a gas, liquid and solid three-phase product.

The regenerated slurry bed hydrogenation catalyst is mixed with inferior heavy oil and sulfur powder, and then enters a slurry bed hydrogenation reactor for reaction, and hydrogenation products are separated to obtain relatively more liquid-phase products, relatively less gas-phase products and solid-phase products, so that the product distribution is optimized. Wherein, the gas phase product (comprising C1-C4 alkanes, wherein C1-C2 is refinery dry gas and C3-C4 is liquefied gas main component) can be used as fuel gas; liquid phase products (including gasoline, diesel oil, wax oil fraction mixtures and the like) with dry points less than 520 ℃ have highest economic value, and can be used as fixed bed hydrogenation device feed (a fixed bed hydrogenation device generally refers to a hydrocracking device of a refinery) for producing clean gasoline and diesel oil products; the minor amount of solid phase product is predominantly coke. Therefore, the regenerated slurry bed hydrogenation catalyst and the slurry bed hydrogenation process are adopted to treat the inferior heavy oil, so that the inferior heavy oil with low added value can be converted into combustible gas, the feeding of a fixed bed hydrogenation device and the like, and finally converted into a clean fuel product, and the economical efficiency can be remarkably improved.

Preferably, the inferior heavy oil is selected from vacuum residuum, ethylene tar, catalytic slurry oil or coal tar; vacuum residuum refers to the heavier fraction obtained from the petrochemical industry during vacuum distillation.

Preferably, in the step A), the regenerated slurry bed hydrogenation catalyst accounts for 0.1-0.5wt% of the inferior heavy oil and accounts for 80-100wt% of the sulfur powder.

Preferably, in the step B), the temperature of the hydrogenation reaction is 400-450 ℃, the pressure is 12-24MPa, the stirring speed is 350-450r/min, the heating speed in the range of 200-250 ℃ is 40-50 ℃/h when the hydrogenation reaction is heated, the heating speed in the range of 250-450 ℃ is 180-220 ℃/h, and the reaction is carried out for 30-60min after the reaction temperature is reached.

In the hydrogenation process of inferior heavy oil, the sulfur powder is added, and a slower heating rate is adopted in the range of 200-250 ℃, so that the active metal component in an oxidation state is completely reduced to a vulcanization state, and the hydrogenation activity can be obviously improved.

Compared with the prior art, the application has the following technical effects:

(1) The regenerated slurry bed hydrogenation catalyst is prepared by taking the waste fixed bed hydrogenation catalyst which is harmful to the environment as a main component and taking the low-cost iron powder as an auxiliary component, and has the advantages of simple process, low cost, low carbon and environmental protection.

(2) The catalyst has excellent hydrogenation activity in the poor heavy oil hydrogenation reaction by optimizing the particle size and the component proportion of the catalyst, and has higher liquid phase product yield and lower gas phase product yield than the existing slurry bed catalyst, thereby optimizing the product distribution and having higher economic value.

(3) According to the application, the thiol polyoxyethylene ether is adopted to impregnate the catalyst, so that the interaction force among catalyst particles can be obviously reduced, the binding force of the catalyst and the oil phase reaction feed is enhanced, and the macromolecular compound in the feed is better adsorbed on an active site, thereby better promoting the hydrogenation reaction and converting the macromolecular compound into a micromolecular compound; even if it cannot be hydrogenated, it is discharged from the reactor together with the catalyst and the reaction product, thereby reducing the coke yield. In addition, after the catalyst is subjected to surface modification of thiol polyoxyethylene ether, thiol groups are converted into H through hydrogenation reaction ₂ S, can improve H in the reaction system ₂ S concentration, thereby effectively guaranteeing the activity stability of the regenerated slurry bed hydrogenation catalyst.

(4) The regenerated slurry bed hydrogenation catalyst and the slurry bed hydrogenation process are adopted to treat the inferior heavy oil, so that the inferior heavy oil with low added value can be converted into combustible gas, the feeding of a fixed bed hydrogenation device and the like, and finally converted into a clean fuel product, and the economical efficiency can be remarkably improved.

(5) In the hydrogenation process of inferior heavy oil, the sulfur powder is added, and a slower heating rate is adopted in the range of 200-250 ℃, so that the active metal component in an oxidation state is completely reduced to a vulcanization state, and the hydrogenation activity can be obviously improved.

Detailed Description

The application is further described below with reference to examples.

General examples

A method for preparing a regenerated slurry bed hydrogenation catalyst, comprising the following steps:

1) The waste fixed bed hydrogenation catalyst (carrier is selected from alumina and silica alumina, active component is selected from W, mo and Ni) is burned for 1-8h at 1300-1750 ℃, pulverized and sieved to obtain particles with the particle diameter of 50-90 μm.

2) Adding iron powder with the granularity of 50-75 mu m and the particle size dispersion of less than 10% into the particles in the step 1) according to the mass ratio of 1-4:100 in a circle drawing mode at the temperature of 20-35 ℃ for uniform mixing, wherein the adding rate is 0.1-0.4g/s.

3) Immersing the product obtained in the step 2) for 1-10h at 20-35 ℃ by using 4-10wt% of thiol polyoxyethylene ether type surfactant (preferably tert-hexyl thiol polyoxyethylene (11-12) ether and/or tert-nonyl thiol polyoxyethylene (17) ether) solution according to the volume ratio of 1-3:1, drying for 1-10h at 100-130 ℃, and cooling to room temperature to obtain the regenerated slurry bed hydrogenation catalyst with the particle size of 60-100 mu m.

The application of the regenerated slurry bed hydrogenation catalyst in the poor heavy oil slurry bed hydrogenation comprises the following steps:

a) Mixing inferior heavy oil, sulfur powder and regenerated slurry bed hydrogenation catalyst to form a slurry hydrogenation bed. Wherein, the inferior heavy oil is selected from vacuum residuum, ethylene tar, catalytic slurry oil or coal tar; vacuum residuum refers to the heavier fraction obtained in the petrochemical industry by vacuum distillation; the regenerated slurry bed hydrogenation catalyst accounts for 0.1-0.5wt% of the inferior heavy oil and 80-100deg.wt% of the sulfur powder.

B) The slurry hydrogenation bed is subjected to hydrogenation reaction under the atmosphere containing hydrogen at 400-450 ℃, 12-24MPa and 350-450 r/min. Wherein, when the hydrogenation reaction is heated, the heating rate in the range of 200-250 ℃ is 40-50 ℃/h, the heating rate in the range of 250-450 ℃ is 180-220 ℃/h, and the reaction is carried out for 30-60min after the reaction temperature is reached.

C) Separating the obtained hydrogenation product to obtain a gas-liquid-solid three-phase product, wherein the gas-phase product is used as fuel gas; liquid phase products with dry points less than 520 ℃ are fed as a fixed bed hydrogenation device, and the fixed bed hydrogenation device generally refers to a hydrocracking device of a refinery and is used for producing clean gasoline and diesel products; the solid phase product is coke.

DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION

The physical and chemical properties of the waste fixed bed hydrogenation catalyst of each of the hydrogenation protectant, the hydrogenation refiner, the hydrocracking agent and the like are shown in table 1.

Table 1: physical and chemical properties of waste fixed bed hydrogenation catalyst

The iron powder used in the examples and comparative examples below was a polishing gold plate iron powder produced by Shijia polishing gold mineral products Co., ltd. And had a particle size of 200 mesh (75 μm), 250 mesh (58 μm) and 300 mesh (50 μm), that is, particle sizes of 75 μm, 58 μm and 50 μm, respectively, and an iron content of 97% or more.

The waste fixed bed hydrogenation catalyst burns by using a ZCGWL high temperature box type electric furnace with a model of silicon molybdenum rod as a medium-Chen heating element produced by Shandong Zhongchen electric furnace Co.

In addition, the raw materials, solvents and reagents used in the following examples and comparative examples of the present application were all obtained by conventional commercial use unless otherwise specified.

Example 1

1. 100g of waste fixed bed hydrogenation catalyst A is taken, burned for 3 hours at 1750 ℃ in a high temperature box type electric furnace to obtain powdery substances, and then sieved by a 300-mesh sieve to obtain particles with the particle size of about 50 mu m for standby.

2.4 g of iron powder with a particle size of 200 meshes and a particle size dispersion of 7% were added to the 1 product at a rate of 0.2g/s by rounding at 25 ℃.

3. After impregnating with 200ml of a 6wt% solution of a tertiary hexyl mercaptan polyoxyethylene (11-12) ether surfactant at 25℃for 10 hours, a solid phase product was obtained, which was dried at 100℃for 10 hours and naturally cooled to 25℃to obtain a regenerated slurry bed hydrogenation catalyst C1 having a particle size of about 65. Mu.m.

Example 2

1. 100g of waste fixed bed hydrogenation catalyst B is taken, burned for 8 hours in a high-temperature box type electric furnace at 1600 ℃ to obtain powdery substances, and then screened by a 180-mesh screen to obtain particles with the diameter of about 88 mu m for standby.

2. 3g of iron powder with a particle size of 250 meshes and a particle size dispersion of 8% were added to the 1 product at a rate of 0.4g/s by rounding at 20 ℃.

3. After 1h of impregnation with 100ml of a solution of a polyoxyethylene (11-12) tertiary hexyl mercaptan ether surfactant at a concentration of 8wt% at 20℃a solid phase product was obtained, which was dried at 140℃for 7h and naturally cooled to 20℃to obtain a regenerated slurry bed hydrogenation catalyst C2 having a particle size of about 70. Mu.m.

Example 3

1. 100g of waste fixed bed hydrogenation catalyst B is taken, burned for 1h in a high temperature box type electric furnace at 1450 ℃ to obtain powdery substances, and then screened by a 260-mesh screen to obtain particles with the particle size of about 57 mu m for standby.

2. 2g of iron powder with a particle size of 300 meshes and a particle size dispersion of 6% are added to the 1 product at a rate of 0.3g/s by means of rounding at 30 ℃.

3. After 7h of impregnation with 300ml of a solution of a polyoxyethylene (17) tertiary nonylthiol ether surfactant at a concentration of 4wt% at 30℃a solid phase product was obtained, which was dried at 120℃for 4h and naturally cooled to 30℃to obtain a regenerated slurry bed hydrogenation catalyst C3 having a particle size of about 55. Mu.m.

Example 4

1. 100g of waste fixed bed hydrogenation catalyst C is taken, burned for 6 hours in a high-temperature box type electric furnace at 1300 ℃ to obtain powdery substances, and then screened by a 200-mesh screen to obtain particles with the particle size of about 75 mu m for standby.

2. 1g of iron powder having a particle size of 250 mesh and a particle size dispersion of 5% was added to the 1 product by rounding at a rate of 0.1g/s at 35 ℃.

3. After impregnating with 200ml of a 10wt% tertiary nonylthiol polyoxyethylene (17) ether surfactant solution at 35℃for 4 hours, a solid phase product was obtained, which was dried at 160℃for 1 hour, and naturally cooled to 35℃to obtain a regenerated slurry bed hydrogenation catalyst C4 having a particle size of about 75. Mu.m.

Examples 1-4 above illustrate the preparation of regenerated slurry bed hydrogenation catalysts, and examples below illustrate the use of each of the catalysts described above in performing slurry bed hydrogenation of vacuum residuum.

The raw materials used for evaluating the activity of the regenerated slurry bed hydrogenation catalyst returning to home C1-C4 obtained in the examples 1-4 of the present application adopt vacuum residuum provided by a certain refinery in the south, and the specific properties are shown in Table 2.

Table 2: : properties of vacuum residuum for slurry bed hydrogenation

Raw oil name	Vacuum residuum
		Density (20 ℃ C.) kg/m ³	1034.5
Residual carbon/%	23.4
		Four components, m%	/
Saturation fraction	23.8
		Aromatic components	35.9
Colloid	22.6
		Asphaltenes	17.7
Distillation range, DEG C	376-648(70v％)
		Solids content, g/L	0.3
Metal content, μg.g ^-1	362

The regenerated slurry bed hydrogenation catalyst obtained in the embodiment 1-4 of the application returns to home C1-C4 activity evaluation equipment adopts a BS series stirring type high-pressure reaction kettle (volume 0.25L, design pressure 35MPa, design temperature 500 ℃ C., stirring rotation speed 0-1500 rpm) of Shanghai Lai North scientific instrument limited, and hydrogenation products are separated by adopting an SH/T0165 type reduced pressure distillation instrument produced by Sichuan Living experiment equipment limited.

Examples 5 to 8

The regenerated slurry bed hydrogenation catalyst C1-C4 obtained in the embodiment 1-4 is subjected to slurry bed hydrogenation reaction, hydrogen is firstly introduced into a reaction kettle to enable the pressure in the kettle to reach 24MPa for leak detection operation, meanwhile, air in the kettle is discharged, hydrogen is then introduced into the kettle to enable the reaction pressure to reach the reaction temperature, the temperature is raised to the reaction temperature, heating and stirring are stopped after the reaction is carried out for a certain time at a certain stirring rate, the temperature in the kettle is cooled to the room temperature, and the reaction is terminated. Slurry bed hydrogenation reaction conditions correspond to examples 5-8, respectively, and are specifically set forth in Table 3. The temperature rise rate at the reaction of these 4 examples was 50℃per hour at 200-250℃for examples 5 and 6, 40℃per hour at 200-250℃for examples 7 and 8, and 200℃per hour at 250-450℃for these 4 examples.

The sulfur powder used in the experiment is a reagent pure product. The amount of regenerated slurry bed hydrogenation catalyst added to the feed and to the sulfur fines is also shown in Table 3.

After the reaction is finished, collecting products in the reaction kettle, weighing, then carrying out reduced pressure distillation, washing residues in the distillation flask with toluene after the distillation is finished, and obtaining the coke in a liquid phase after centrifugation and drying.

The experimental evaluation indexes include raw material conversion rate (namely total yield), distillate yield, metal removal rate and coking rate:

feedstock conversion= (distillate + gas)/feedstock x 100%.

Distillate yield = less than 520 ℃ distillate/feed oil x 100%.

Metal removal = (metal content in 1-liquid phase product/metal content in raw oil) ×100%.

Coke formation = toluene insoluble material/feed oil x 100%.

Table 3: EXAMPLES 5-8 regenerated slurry bed hydrogenation catalyst Performance evaluation results

As can be seen from Table 3, the regenerated slurry bed hydrogenation catalyst prepared by adopting the waste fixed bed hydrogenation catalyst and the iron powder which affect the environment has better catalytic activity, high raw material conversion rate and high distillate yield, and higher metal removal rate, especially the distillate yield less than 520 ℃, when the inferior heavy oil-vacuum residuum is treated, the activity stability of the catalyst can be better protected, and finally the clean gasoline and diesel products with high added value can be obtained. The economy of the vacuum residuum with low added value is improved; on the other hand, the coking rate is less than 1%, which shows that the catalyst has very wide industrial application prospect, and can lead the device to stably operate when being applied to industrial devices. In conclusion, the catalyst, the preparation method and the application thereof provided by the embodiment of the application can generate good economic benefit and social benefit after industrialization.

Comparative example 1

The spent fixed bed hydrogenation catalyst powder in step 1 of example 1 was replaced with alumina powder, the others being unchanged, to give catalyst DC1. The catalyst was subjected to catalytic hydrogenation reaction under the conditions of example 5, and the obtained feedstock had a conversion of 68.2%, a metal removal rate of 85.0% and a coking rate of 4.8%. The catalyst is obviously different from the embodiment 1 of the application, and the application has better catalytic hydrogenation effect by adopting the waste fixed bed hydrogenation catalyst as the slurry bed hydrogenation catalyst.

Comparative example 2

The powder particle size of the spent fixed bed hydrogenation catalyst in step 1 of example 1 was replaced with 350 mesh particle size, the others being unchanged, to give catalyst DC2. The catalyst was subjected to catalytic hydrogenation under the conditions of example 5, and the obtained feedstock was 86.5% in conversion, 84.4% in metal removal and 4.6% in coking. Significantly worse than example 1.

Comparative example 3

The powder particle size of the spent fixed bed hydrogenation catalyst in step 1 of example 1 was replaced with 160 mesh particle size, the others being unchanged, to give catalyst DC3. The catalyst was subjected to catalytic hydrogenation reaction under the conditions of example 5, and the obtained feedstock was converted to 87.0%, metal removal to 85.2% and coke formation to 3.6%. Significantly worse than example 1.

Comparative example 4

The iron powder in step 2 of example 1 was replaced with a powder of the same particle size but with a particle size dispersion of 20%, the others being unchanged, to give catalyst DC4. The catalyst was subjected to catalytic hydrogenation under the conditions of example 5, and the obtained feedstock had a conversion of 78.4%, a metal removal rate of 75.8% and a coking rate of 4.6%. Significantly worse than inventive example 1.

Comparative example 5

The iron powder in step 2 of example 1 was replaced with a powder having the same particle size dispersion but a mesh number of 160 mesh, the others being unchanged, to obtain catalyst DC5. The catalyst was subjected to catalytic hydrogenation under the conditions of example 5, and the obtained feedstock had a conversion of 79.0%, a metal removal rate of 76.1% and a coking rate of 3.9%. Significantly worse than inventive example 1.

Comparative example 6

The iron powder in step 2 of example 1 was replaced with a powder having the same particle size dispersion but a mesh number of 350 mesh, the others being unchanged, to obtain catalyst DC6. The catalyst was subjected to catalytic hydrogenation under the conditions of example 5, and the obtained feedstock was converted to 83.90%, the metal removal rate was 80.7% and the coke formation rate was 4.1%. Significantly worse than inventive example 1.

Comparative example 7

The iron powder in step 2 of example 1 was replaced with alumina powder, the others being unchanged, to give catalyst DC7. The catalyst was subjected to catalytic hydrogenation reaction under the conditions of example 5, and the obtained feedstock had a conversion of 64.1%, a metal removal rate of 81.9% and a coking rate of 4.8%. Significantly worse than example 1. The iron powder preferred by the application has obvious catalytic hydrogenation effect as an additive component of the slurry bed hydrogenation catalyst.

Comparative example 8

Selecting a C1 catalyst to perform slurry bed hydrogenation reaction, wherein the temperature rising rate of the reaction kettle is 100 ℃/h in the range of 200-250 ℃; still 200 ℃/h in the temperature range of 250-450 ℃ and the other conditions are the same as in example 5. The conversion rate of the obtained raw material is 91.0%, the metal removal rate is 88.9%, and the coking rate is 4.1%. Significantly less effective than example 5.

Comparative example 9

The tertiary hexyl mercaptan polyoxyethylene (11-12) ether of example 1, step 3, was replaced with sodium alkylbenzenesulfonate anionic surfactant, the others being unchanged, to give catalyst DC8. The catalyst was subjected to catalytic hydrogenation under the conditions of example 5, and the obtained feedstock had a conversion of 82.4%, a metal removal rate of 80.6% and a coking rate of 6.1%. Significantly worse than example 1.

Comparative example 10

The tertiary hexyl mercaptan polyoxyethylene (11-12) ether of example 1, step 3, was replaced with other nonionic surfactant alkylphenol polyoxyethylene, the others being unchanged, to give catalyst DC9. The catalyst was subjected to catalytic hydrogenation under the conditions of example 5, and the obtained feedstock was 86.1% in conversion, 85.0% in metal removal and 5.3% in coking. Significantly worse than example 1.

Comparative example 11

200ml of the t-hexylthiol polyoxyethylene (11-12) ether solution in step 3 of example 1 was replaced with 1000ml, and the other was unchanged, to obtain a catalyst DC10. The catalyst was subjected to catalytic hydrogenation under the conditions of example 5, and the obtained feedstock had a conversion of 79.3%, a metal removal of 74.1% and a coking rate of 5.8%. Significantly worse than example 1.

Comparative example 12

100g of the spent fixed bed hydrogenation catalyst A from step 3 of example 1 was replaced with 1000g, the others being unchanged, to give catalyst DC11. The catalyst was subjected to catalytic hydrogenation under the conditions of example 5, and the obtained feedstock had a conversion of 82.8%, a metal removal rate of 78.2% and a coking rate of 5.3%. Significantly worse than example 1.

The raw materials and equipment used in the application are common raw materials and equipment in the field unless specified otherwise; the methods used in the present application are conventional in the art unless otherwise specified.

The foregoing description is only a preferred embodiment of the present application, and is not intended to limit the present application, and any simple modification, variation and equivalent transformation of the above embodiment according to the technical substance of the present application still fall within the scope of the technical solution of the present application.

Claims

1. The preparation method of the regenerated slurry bed hydrogenation catalyst is characterized by comprising the following steps:

1) The waste fixed bed hydrogenation catalyst is burnt, pulverized and sieved to obtain particles with the particle diameter of 50-90 mu m;

2) Adding iron powder with the granularity of 50-75 mu m and the particle size dispersion of less than 10% into the particles in the step 1) according to the mass ratio of 1-4:100, and uniformly mixing;

2. The method of manufacturing according to claim 1, wherein: in the step 1), the carrier of the waste fixed bed hydrogenation catalyst is selected from aluminum oxide and silicon aluminum oxide, and the active ingredient is one or more of W, mo and Ni.

3. The preparation method according to claim 1 or 2, characterized in that: in the step 1), the firing temperature is 1300-1750 ℃ and the firing time is 1-8h.

4. The method of manufacturing according to claim 1, wherein: in the step 2), the iron powder is added into the particles in the step 1) in a round-drawing manner at the temperature of 20-35 ℃ with the addition rate of 0.1-0.4g/s.

5. The method of manufacturing according to claim 1, wherein: in the step 3), the thiol polyoxyethylene ether type surfactant is tert-hexyl thiol polyoxyethylene (11-12) ether and/or tert-nonyl thiol polyoxyethylene (17) ether.

6. The method of claim 1 or 5, wherein: in the step 3) of the method,

the temperature of the soaking is 20-35 ℃ and the time is 1-10h;

the drying temperature is 100-130 ℃ and the drying time is 1-10h.

7. Use of the regenerated slurry bed hydrogenation catalyst obtained by the preparation method according to any one of claims 1 to 6 in the slurry bed hydrogenation of inferior heavy oil.

8. The use according to claim 7, characterized by the steps of:

a) Mixing inferior heavy oil, sulfur powder and regenerated slurry bed hydrogenation catalyst to form a slurry hydrogenation bed;

b) Subjecting the slurry hydrogenation bed to a hydrogenation reaction under an atmosphere comprising hydrogen;

c) Separating the obtained hydrogenation product to obtain a gas-liquid-solid three-phase product, wherein the gas-phase product is used as fuel gas; the liquid phase product with the dry point less than 520 ℃ is used as a fixed bed hydrogenation device for feeding and is used for producing clean gasoline and diesel products; the solid phase product is coke.

9. Use according to claim 7 or 8, characterized in that: the inferior heavy oil is selected from vacuum residuum, ethylene tar, catalytic slurry oil or coal tar.

10. Use according to claim 7 or 8, characterized in that:

in the step A), the regenerated slurry bed hydrogenation catalyst accounts for 0.1-0.5wt% of the inferior heavy oil and accounts for 80-100wt% of the sulfur powder;

in the step B), the temperature of the hydrogenation reaction is 400-450 ℃, the pressure is 12-24MPa, the stirring speed is 350-450r/min, the heating speed in the range of 200-250 ℃ is 40-50 ℃/h when the hydrogenation reaction is heated, the heating speed in the range of 250-450 ℃ is 180-220 ℃/h, and the reaction is carried out for 30-60min after the reaction temperature is reached.