CN117696066A

CN117696066A - Slurry bed hydrogenation catalyst, preparation method and application thereof

Info

Publication number: CN117696066A
Application number: CN202211037647.2A
Authority: CN
Inventors: 尹宏峰; 许杰
Original assignee: Ningbo Institute of Material Technology and Engineering of CAS
Current assignee: Ningbo Institute of Material Technology and Engineering of CAS
Priority date: 2022-08-24
Filing date: 2022-08-24
Publication date: 2024-03-15

Abstract

The invention discloses a slurry bed hydrogenation catalyst, a preparation method and application thereof. The slurry bed hydrogenation catalyst comprises a carrier and an active metal catalytic component arranged on the surface of the carrier, wherein the carrier is iron-based metallurgical powder; wherein the mass fraction of the active metal catalytic component calculated by active metal oxide is 1-3%; the granularity of the iron-based metallurgical powder is 200-250 meshes, and the particle size dispersion is below 10%. According to the slurry bed hydrogenation catalyst and the preparation method thereof, the iron-based metallurgical powder is used as a carrier, so that the effect of better catalytic performance can be achieved under the conditions of smaller active metal loading and using amount; the catalyst has the advantages of low metal loading, low price of the used iron-based metallurgical powder, simple and convenient catalyst preparation process, low processing cost and low cost, and can convert the catalytic slurry oil with low added value into the raw material of the fixed bed hydrogenation device with low cost and high efficiency, thereby being beneficial to improving the economical efficiency of the industrial device.

Description

Slurry bed hydrogenation catalyst, preparation method and application thereof

Technical Field

The invention relates to the technical field of catalytic hydrogenation, in particular to the technical field of a hydrogenation method of inferior heavy oil in the petrochemical industry, and especially relates to a slurry bed hydrogenation catalyst, a preparation method and application thereof.

Background

Catalytic slurry oils are resids from refinery catalytic cracker units, typically containing greater than about 30% saturated hydrocarbons, greater than about 50% aromatic hydrocarbons, and greater than about 10% gums and asphaltenes, and a small amount of catalytic cracking catalyst dust. As a product of the catalytic cracking process, it was previously treated as waste, and is also called catalytic external slurry oil.

The yield of the catalytic slurry oil is generally about 6-8% of the processing amount of catalytic cracking, and the catalytic slurry oil has the characteristics of high density, low hydrogen-carbon atomic ratio, high aromatic hydrocarbon content, high carbon residue value and the like. At present, the heavy fuel oil is generally delivered from the factory, the added value is low, and the waste of resources is caused. Other uses are: blending as a delayed coker feed; the catalytic slurry oil with the dust content of the catalyst less than or equal to 100 mug/g and low sulfur content can be used for preparing needle coke; used for preparing carbon fiber, used as strengthening distillation agent, used as asphalt blending component and rubber additive, etc. (the comprehensive utilization technique of catalytic slurry oil is Duan Qingchun, liu Zhichuan, etc. the fine petrochemical industry progress 2020, 21 (2) P54-57). These uses generally have problems such as low raw material utilization, environmental pollution, and low comprehensive economy.

Along with the improvement of petroleum refining technology and the enhancement of environmental awareness, catalytic slurry oil is utilized at present, and the processing process of inferior heavy oil such as catalytic slurry oil and residual oil comprises two processes of decarburization and hydrogenation. The former mainly comprises coking, solvent deasphalting process and the like; the latter is mainly of the three process types, fixed bed, ebullated bed and suspended bed. Coking and hydrogenation are widely used heavy oil processing techniques. The coking process can process high sulfur, high metal, high carbon residue and partial catalytic slurry oil, but has the problems of low liquid product yield, poor comprehensive economy and the like due to the generation of a large amount of gas and inferior coke, and is difficult to realize the efficient utilization of the catalytic slurry oil.

The slurry bed hydrogenation process belongs to a green chemical route and can be used for processing inferior heavy oil such as catalytic slurry oil and the like. Early stages of the technology, such as German VCC technology, adopt substances, such as lignite, blast furnace ash and the like, as additives for slurry bed hydrogenation, and the homology technology HDH/HDHPLUS technology adopts coal and refractory minerals as additives for slurry bed hydrogenation. In the 90 th century of the 20 th century, the SOC process developed by companies such as Asahi, nippon Mining and Chiyoda, japan, used a molybdenum compound and carbon black as a catalyst. Canadian CANMET process uses subbituminous coal, lignite-supported iron sulfate or other metals as catalysts. HC and EST technologies use oil-soluble catalysts. Water-soluble catalysts (progress of slurry bed residuum hydrogenation catalyst research, wang Mingjin et al, industrial catalysis, 2015, 23 (9) P659-665) were adopted by the university of chinese petroleum (china east), dow chemical company.

For a specific slurry bed hydrogenation catalyst, the slurry bed hydrogenation catalyst disclosed in Chinese patent No. 106622268A is prepared from silica-alumina and alumina as carriers, iron, calcium and molybdenum as active metals, wherein the content of the active metals is 10-40 wt% in terms of oxide, and the conversion rate of raw materials is 91.2% at most; the Chinese patent CN105771992A prepares a slurry bed hydrogenation catalyst by using titanium white waste ferrous sulfate and alkali liquor, and the conversion rate of heavy oil is more than 50%; the transition metal tungsten catalyst supported on carbonaceous particles in Chinese patent No. 113145106A has the advantages of simple synthesis process and good raw material adaptability; chinese patent No. 107670699A adopts semi-coke pore-enlarging material, molecular sieve and catalytic cracking waste catalyst as composite carrier to obtain slurry bed hydrogenation catalyst.

However, in the prior art disclosed at present, when the slurry bed hydrogenation catalyst catalyzes slurry bed hydrogenation, a larger active metal load is required to play a role in catalysis, the cost is higher, and even so, the catalytic hydrogenation conversion rate of the raw material in the prior art is still lower.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide a slurry bed hydrogenation catalyst, a preparation method and application thereof.

In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:

in a first aspect, the invention provides a slurry bed hydrogenation catalyst comprising a carrier and an active metal catalytic component arranged on the surface of the carrier, wherein the carrier is an iron-based metallurgical powder;

the mass fraction of the active metal catalytic component in the slurry bed hydrogenation catalyst is 1-3% based on active metal oxide;

the granularity of the iron-based metallurgical powder is 200-250 meshes, and the particle size dispersion is below 10%.

In a second aspect, the present invention also provides a method for preparing a slurry bed hydrogenation catalyst, comprising:

1) Providing a carrier, wherein the carrier is an iron-based metallurgical powder, the granularity of the iron-based metallurgical powder is 200-250 meshes, and the particle size dispersion is below 10%;

2) Adding the carrier into an aqueous solution containing active metal to form a reaction system;

3) Adding ammonia water into the reaction system to obtain metal crystal precipitate;

4) Roasting the metal crystal precipitate to obtain the slurry bed hydrogenation catalyst.

In a third aspect, the invention also provides the use of the slurry bed hydrogenation catalyst described above in catalytic slurry oil processing.

In a fourth aspect, the present invention also provides a slurry bed hydrogenation process for catalytic slurry oils comprising:

mixing catalytic slurry oil, sulfur and the slurry bed hydrogenation catalyst to form a slurry hydrogenation bed;

the slurry hydrogenation bed is subjected to a hydrogenation reaction under an atmosphere comprising hydrogen.

Based on the technical scheme, compared with the prior art, the invention has the beneficial effects that:

according to the slurry bed hydrogenation catalyst and the preparation method thereof, the iron-based metallurgical powder is used as a carrier, and the particle size of the iron-based metallurgical powder is consistent and the particle size is small, so that the total surface area in the same volume space is large, more active metal loading areas are provided, and the catalyst has uniform catalytic efficiency on inferior heavy oil in a reactor due to consistent specification and consistent amount of active metal loaded in unit volume; in addition, the iron, molybdenum and tungsten d electron layers are all metal elements with unfilled electron numbers, so the iron, molybdenum and tungsten d electron layers are suitable to be used as active components of hydrogenation catalysts, and because 6 electrons in the iron d electron layers are different from molybdenum (5) and tungsten (4), and are different from covalent bonds formed by the two latter metals and reactant molecules, the adsorption heat of adsorption molecules on the surface of the catalyst is reduced by the synergistic effect of the two metals, so that better catalytic activity is obtained compared with the single molybdenum or tungsten serving as the active components of the metals. The two aspects have the common effect, so that the load of active metal and the usage amount of the catalyst in catalytic hydrogenation can be effectively reduced, but the catalytic effect is not affected; on the other hand, the iron powder with small granularity and consistent specification provides a uniform and large amount of positions for unreacted asphaltenes in the raw materials. The two aspects of the combined action enable the slurry bed hydrogenation catalyst provided by the invention to achieve the effect of better catalytic performance under the conditions of smaller active metal loading and using amount.

The slurry bed hydrogenation catalyst provided by the invention has the advantages of small active metal load, low price of the used iron-based metallurgical powder, and simple and convenient catalyst preparation procedure, namely the prepared catalyst has low processing cost and low cost, and is beneficial to improving the economical efficiency of the used industrial device.

The slurry bed hydrogenation catalyst and the slurry bed hydrogenation process provided by the invention are used for treating the catalytic slurry oil, so that the petrochemical byproducts with low added value can be converted into raw materials of a fixed bed hydrogenation device with low cost and high efficiency, and finally can be converted into clean fuel oil products, and the economical efficiency of the catalyst is obviously improved.

The foregoing description is only an overview of the present invention and is intended to enable those skilled in the art to make more clear the scope of the present invention and to be practiced in accordance with the present invention as described below with reference to the preferred embodiments thereof.

Detailed Description

In view of the shortcomings in the prior art, the inventor of the present invention has long studied and practiced in a large number of ways to propose the technical scheme of the present invention. The technical scheme, the implementation process, the principle and the like are further explained as follows.

The invention mainly aims at providing a preparation method and application of a slurry bed hydrogenation catalyst, which comprises the steps of firstly impregnating ferrous metallurgical powder with an active metal solution, then dripping ammonia water into an impregnated product until the mixture is uniform, and drying, crushing and sieving the impregnated product. The catalyst provided by the invention enables the catalytic slurry oil to undergo slurry bed hydrogenation reaction to obtain combustible gas, liquid-phase products and a small amount of coke, wherein the liquid-phase products with a dry point less than 520 ℃ are used as the feed of a fixed bed hydrogenation device and are used for producing clean gasoline and diesel products.

In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced otherwise than as described herein, and therefore the scope of the present invention is not limited to the specific embodiments disclosed below.

The embodiment of the invention provides a slurry bed hydrogenation catalyst, which comprises a carrier and an active metal catalytic component arranged on the surface of the carrier, wherein the carrier is iron-based metallurgical powder; the mass fraction of the active metal catalytic component in the slurry bed hydrogenation catalyst is 1-3% based on active metal oxide; the granularity of the iron-based metallurgical powder is 200-250 meshes, and the particle size dispersion is below 10%.

In some embodiments, the active metal catalytic component may include any one or a combination of two of oxides of molybdenum, tungsten; more preferably molybdenum trioxide.

In some embodiments, the slurry bed hydrogenation catalyst may have a particle size of from 60 to 80 μm.

The embodiment of the invention also provides a preparation method of the slurry bed hydrogenation catalyst, which comprises the following steps:

1) Providing a carrier, wherein the carrier is an iron-based metallurgical powder, the granularity of the iron-based metallurgical powder can be 200-250 meshes, and the particle size dispersion is below 10%.

2) The carrier is added into an aqueous solution containing active metal to form a reaction system.

3) And adding ammonia water into the reaction system to obtain metal crystal precipitate.

As some typical application examples of the above exemplary technical solutions, the above preparation method may be implemented by the following steps:

s1, dissolving a certain amount of ammonium molybdate tetrahydrate in deionized water to obtain an ammonium molybdate aqueous solution, wherein in some more specific embodiments, the dissolution temperature is 20-40 ℃.

S2, taking a certain mesh of ferrometallurgy powder, and soaking the ferrometallurgy powder in the aqueous solution obtained in the step S1.

And S3, dropwise adding ammonia water into the product obtained in the step S2, and uniformly stirring by adopting magnetic stirring to obtain a metal crystal precipitation mixture.

S4, washing the product of the step S3 with water and ethanol in sequence, and drying, roasting, crushing and sieving to obtain the prize-bed hydrogenation catalyst.

In some embodiments, step 2) may specifically comprise:

the support is immersed in the aqueous solution at ambient temperature (preferably 20-30 ℃) for 30-150min.

In some embodiments, the volume ratio of carrier to aqueous solution may be from 1:1 to 1:2.

In some embodiments, ammonium molybdate and/or ammonium metatungstate may be included in the aqueous solution.

In some embodiments, the aqueous solution may have a concentration of 5-50g/100mL.

In some embodiments, the concentration of the aqueous ammonia may be 10-15% and the dropping rate may be 1-5mL/s.

In some embodiments, the ratio of the added volume of the aqueous ammonia to the volume of the reaction system may be from 1:1 to 2:1. In this step, the dropping temperature is preferably room temperature, which may be 15 to 30 ℃, the stirrer is rotated at 600r/m, and the amount of aqueous ammonia added is the same as the volume of the active metal-containing aqueous solution in step 1.

In some embodiments, the firing treatment may be at a temperature of 220 ℃ to 300 ℃ for a time of 5 to 7 hours.

In some embodiments, the calcination treatment is performed under negative pressure, and the vacuum may be 50kPa to 60kPa.

As a specific application example of the above technical solution, in step S4, the water and ethanol are used in an amount 2 times that of the ferrous metallurgical powder, and the washing temperature is room temperature; the drying and roasting are carried out in a negative pressure mode, the vacuum degree is 50KPa, the drying is carried out for 5-7h at 80 ℃, and then the roasting is carried out for 5-7h at 220 ℃; the crushing is carried out by adopting a crusher to crush to the granularity of 180-240 meshes.

In some embodiments, step 4) specifically comprises: washing and drying the metal crystals, roasting, crushing and sieving.

In some embodiments, the metal crystals are crushed to 180-240 mesh after firing.

The embodiment of the invention also provides an application of the slurry bed hydrogenation catalyst provided by any embodiment in catalytic slurry oil processing. The catalytic slurry oil refers to byproducts generated in the heavy oil catalytic cracking process in the petrochemical industry, and is also called catalytic external throwing slurry oil

Specifically, the embodiment of the invention also provides a slurry bed hydrogenation method of catalytic slurry oil, which comprises the following steps:

the slurry hydrogenation catalyst provided by any one of the embodiments is mixed with the catalytic slurry oil, sulfur and the slurry bed hydrogenation catalyst to form a slurry hydrogenation bed.

In some embodiments, the slurry bed hydrogenation catalyst in the slurry hydrogenation bed comprises 0.1-0.5% by mass of the catalytic slurry oil and 70-100% by mass of the sulfur.

In some embodiments, the hydrogenation reaction is carried out at a temperature of 400 to 450 ℃, a pressure of 12 to 24MPa, and a reaction time of 30 to 60 minutes.

In some embodiments, the temperature increase rate in the temperature range of 200 to 250 ℃ is below 50 ℃/h, preferably 40 to 50 ℃ when the hydrogenation reaction is warmed.

In some embodiments, further comprising: and carrying out surface oxidation ablation treatment on the slurry bed hydrogenation catalyst after the hydrogenation reaction and separation, so that the slurry bed hydrogenation catalyst is reused.

As a typical example of the technical scheme, the slurry bed hydrogenation catalyst performs slurry bed hydrogenation reaction on the catalytic slurry oil, and sulfur powder is added while the catalytic slurry oil is added.

Further, the slurry bed hydrogenation process conditions are that the reaction temperature is 400-450 ℃, the reaction pressure is 12.0-24.0MPa, the stirring speed is 400r/min, and the heating speed is 50 ℃/h in the range of 200-250 ℃; and reacting for 30-60min after the reaction temperature is reached at the temperature of 250-450 ℃ at 200 ℃/h.

Further, after the slurry bed hydrogenation product is separated, a gas, liquid and solid three-phase product is obtained, wherein the gas product can be used as fuel gas, a small amount of unconverted components containing the slurry bed hydrogenation catalyst can be used as the slurry bed hydrogenation catalyst component for recycling after carbon deposit on the surface of the unconverted components is burnt by introducing air; the obtained 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.

Further, the fixed bed hydrogenation device is generally referred to as a hydrocracking device of a refinery.

Based on the technical scheme, the slurry bed hydrogenation catalyst prepared by the embodiment of the invention adopts the ferrometallurgy powder with small granularity and consistent specification as the carrier, so that the active metal loading amount of the catalyst in unit volume is basically consistent, i.e. the active components are distributed more uniformly, and the catalyst has the effects of small metal loading amount and good catalytic activity; meanwhile, the small and consistent carrier particles not only can provide larger surface area for raw material molecules to react, but also can provide more deposition positions for larger molecular compounds which are not easy to react in the raw materials, such as asphaltene, so that the catalyst can leave the reaction system along with the catalyst, the reaction is further promoted, and the conversion rate of the raw materials is improved; finally, the ferrous metallurgical powder discharged out of the reactor along with unconverted components can be recycled by burning off the carbon deposited on the surface of the ferrous metallurgical powder, and the ferrous metallurgical powder can be continuously used as a slurry bed hydrogenation catalyst carrier, which is beneficial to reducing carbon emission. The embodiment of the invention adopts a slurry bed hydrogenation process to convert the catalytic slurry oil which is a byproduct of refining into a clean gasoline and diesel oil product with high added value, which is beneficial to improving the comprehensive economy of refining enterprises.

According to the preparation method and the application method of the slurry bed hydrogenation catalyst provided by the embodiment of the invention, after the ferrous metallurgy powder is soaked by the active metal solution, ammonia water is added dropwise into the ferrous metallurgy powder and stirred uniformly to obtain a metal mixture, and the slurry bed hydrogenation catalyst is finally obtained by adopting negative pressure drying and roasting. The catalyst is mixed with catalytic slurry oil and sulfur powder, and then enters a slurry bed hydrogenation reactor for reaction, and hydrogenation products are separated to obtain combustible gas, liquid phase products and a small amount of coke. The liquid phase product with the dry point less than 520 ℃ is fed as a fixed bed hydrogenation unit. The addition of sulfur powder and the temperature rising rate below 50 ℃/h in the range of 200-250 ℃ are adopted, so that the active metal component in the oxidation state is completely reduced to the vulcanization state, and the hydrogenation activity of the latter is higher. According to the invention, the catalyst can be vulcanized better in different temperature ranges by adopting different heating rates, so that the catalyst can be vulcanized more completely, and the activity of the catalyst can be exerted best.

The technical scheme of the invention is further described in detail through a plurality of embodiments. However, the examples are chosen to illustrate the invention only and are not intended to limit the scope of the invention.

The iron metallurgical powder used in the examples below was gold-grade iron powder produced by Zhengzhou gold-grade metal materials Co., ltd. And had particle sizes of 200 mesh (75 μm), 230 mesh (62 μm), 240 mesh (61 μm) and 250 mesh (58 μm), namely particle sizes of 75 μm, 62 μm, 61 μm, 58 μm and densities of 5.8 to 7.2g/cm, respectively ³ 。

The pulverizer used in the examples below was a WFS-250 pulverizer manufactured by Santa Classification powder devices Co., ltd. In the city of tin-free Jiangyin, and fine particles having a particle size of 60 to 80. Mu.m.

In addition, the starting materials, solvents and reagents employed in the examples of the present invention described below were all obtained by conventional commercial methods, unless otherwise specified.

Example 1

The preparation flow of the slurry bed hydrogenation catalyst is illustrated in the embodiment, and specifically is as follows:

1. 3.5g of ammonium molybdate tetrahydrate was dissolved in 20ml of deionized water at 25℃to obtain an aqueous ammonium molybdate solution.

2. 100g of a ferrous metallurgical powder having a particle size of 230 mesh and a particle size dispersion of 9% was impregnated with the aqueous solution obtained in step 1 at 25℃for 90min.

3. To the product obtained in the step 2, 20mL of 10% ammonia water was added dropwise at a rate of 1mL/s at 25℃while stirring was performed by starting a magnetic stirrer at 600r/min, to obtain a metal crystal precipitate mixture.

4. Washing the product obtained in the step 3 with 40ml of deionized water and 40ml of ethanol respectively at 25 ℃, drying at the vacuum degree of 50KPa and 80 ℃ for 5 hours, roasting at 220 ℃ for 7 hours, crushing by a crusher, and finally screening by a 200-mesh screen to obtain the slurry bed hydrogenation catalyst C1. The active metal (molybdenum) content was tested to be 2.8wt% as oxide and the particle size was 75 μm.

Example 2

1. A certain amount of 6.0g of ammonium metatungstate hydrate is taken and dissolved in 60ml of deionized water at 20 ℃ to obtain an ammonium molybdate aqueous solution.

2. 180g of ferrometallurgical powder with a particle size of 200 meshes and a particle size dispersion of 8% were immersed in the aqueous solution obtained in 1 for 150min at 20 ℃.

3. 60ml of 12% ammonia water is added dropwise to the product 2 at a rate of 3ml/s at 20 ℃, and a magnetic stirrer with 600r/min revolution is started for stirring, so that a metal crystal precipitation mixture is obtained.

4. Washing the 3 product with 60ml deionized water and 60ml ethanol at 20 deg.c, stoving at 80 deg.c and 60KPa vacuum degree for 6 hr, roasting at 260 deg.c for 6 hr, crushing in a crusher, and sieving with 180 mesh sieve to obtain slurry bed hydrogenation catalyst C2. The active metal content was 2.0wt% as oxide and the particle size was 80. Mu.m.

Example 3

1. An amount of 2.0g of ammonium molybdate tetrahydrate was taken and dissolved in 40ml of deionized water at 15℃to obtain an aqueous ammonium molybdate solution.

2. 240g of ferrometallurgical powder with a particle size of 250 mesh and a particle size dispersion of 7% were impregnated with the aqueous solution obtained in 1 for 30min at 30 ℃.

3. 40ml of 13% ammonia water was added dropwise to the product 2 at a rate of 4ml/s at 15℃while stirring was carried out by starting a magnetic stirrer at 600r/min, to obtain a metal crystal precipitate mixture.

4. Washing the 3 product with 80ml deionized water and 80ml ethanol at 15 deg.c, stoving at 80 deg.c and 50KPa vacuum degree for 7 hr, roasting at 300 deg.c for 5 hr, crushing in a crusher, and sieving with 240 mesh sieve to obtain slurry bed hydrogenation catalyst C3. The active metal content was 1.6wt% as oxide and the particle size was 61. Mu.m.

Example 4

1. A certain amount of 3.6g of ammonium metatungstate hydrate is taken and dissolved in 50ml of deionized water at 30 ℃ to obtain an ammonium molybdate aqueous solution.

2. 300g of ferrometallurgical powder with a particle size of 240 mesh and a particle size dispersion of 6% were impregnated with the aqueous solution obtained in 1 for 90min at 30 ℃.

3. 100ml of 13% ammonia water was added dropwise to the product 2 at a rate of 4ml/s at 30℃while stirring was carried out by starting a magnetic stirrer at 600r/min, to obtain a metal crystal precipitate mixture.

4. Washing the 3 product with 100ml deionized water and 100ml ethanol at 30 deg.c, stoving at 80 deg.c and 60KPa vacuum degree for 6 hr, roasting at 260 deg.c for 6 hr, crushing in a crusher, and final sieving with 230 mesh sieve to obtain slurry bed hydrogenating catalyst C4. The active metal content was 1.2wt% as oxide and the particle size was 62. Mu.m.

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

The raw materials used for evaluating the activity of the C1-C4 catalysts obtained in experimental examples 1-4 of the present invention are catalytic slurries provided by a certain refinery in the north, and the specific properties are shown in Table 1.

Table 1 properties of catalytic slurry for slurry bed hydrogenation

Raw oil name	Catalytic slurry oil
		Density (20 ℃ C.) kg/m3	1002.0
Residual carbon/%	12.4
		Four components, wt%	/
Saturation fraction	29.9
		Aromatic components	54.2
Colloid	14.1
		Asphaltenes	1.8
Distillation range, DEG C	202-552(95v％)
		Solids content, g/L	0.3
Metal content, mug.g-1	2460

The equipment for evaluating the activity of the C1-C4 catalyst obtained in the examples 1-4 of the invention 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 Co., ltd.) and adopts an SH/T0165 type reduced pressure distillation instrument produced by Sichuan Living experiment instrument Co., ltd.) for separating hydrogenation products.

Examples 5 to 8

The C1-C4 slurry bed hydrogenation catalyst obtained in the examples 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 2. The temperature rise rate in the reaction of these four examples was 50℃per hour in the range of 200-250℃for examples 5 and 6, 40℃per hour in the range of 200-250℃for examples 7 and 8, and 200℃per hour in the range of 250-450 ℃.

The sulfur powder used in the experiment is a reagent pure product. The amount of slurry bed hydrogenation catalyst added to the feed and to the sulfur fines is also shown in Table 2.

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 2 evaluation results of the Performance of slurry bed hydrogenation catalysts of examples 5 to 8

As can be seen from Table 2, the slurry bed hydrogenation catalyst adopting the low-cost iron-based metal powder in the metallurgical industry as a carrier has better catalytic activity, high raw material conversion rate and distillate oil yield, and higher metal removal rate and yield of each component yield when low-quality heavy oil-catalytic slurry is treated, and the latter means that the activity stability of the catalyst can be better protected when the catalyst is subjected to the next fixed bed hydrogenation reaction, and finally clean gasoline and diesel products with high added values are obtained. The economical efficiency of the catalytic slurry oil 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 invention can generate good economic benefit and social benefit after industrialization.

Comparative example 1

The iron-treated gold powder in step 2 of example 1 was replaced with alumina powder, and the others were unchanged, to obtain a catalyst DC1. The catalyst was subjected to catalytic hydrogenation under the conditions of example 5, and the obtained feedstock had a conversion of 65.1%, a metal removal rate of 84.2% and a coking rate of 5.6%. Significantly worse than the catalyst provided in example 1 of the present invention, it is demonstrated that the preferred iron-based metallurgical powder of the present invention as a carrier is capable of significantly reducing the content of active metal components and the amount of catalyst used.

Comparative example 2

The iron-treated gold powder in step 2 of example 1 was replaced with 100g of a ferrous metallurgical powder having a 230 mesh particle size dispersion of 20%, the others being unchanged, to give catalyst DC2. The catalyst was subjected to catalytic hydrogenation reaction under the conditions of example 5, and the obtained feedstock was 88.3% in conversion, 89.0% in metal removal and 3.0% in coking. Significantly worse than the catalyst of the invention provided in example 1.

Comparative example 3

The iron-treated gold powder in step 2 of example 1 was replaced with 100g of iron-metallurgical powder having a particle size of 80 mesh and a particle size dispersion of 9%, and the other was unchanged, to obtain catalyst DC3. The catalyst was subjected to catalytic hydrogenation reaction under the conditions of example 5, and the obtained feedstock had a conversion of 90.1%, a metal removal rate of 88.6% and a coking rate of 3.8%. Significantly worse than the catalyst provided in example 1 of the present invention.

Comparative example 4

The iron-treated gold powder in step 2 of example 1 was replaced with 100g of a 300 mesh iron metallurgical powder having a particle size dispersion of 9%, and the other was unchanged, to obtain catalyst DC4. The catalyst was subjected to catalytic hydrogenation under the conditions of example 5, and the obtained feedstock had a conversion of 91.1%, a metal removal of 90.0% and a coking rate of 4.3%. Significantly worse than the catalyst provided in example 1 of the present invention.

Comparative example 5

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 92.4%, the metal removal rate is 91.5%, and the coking rate is 3.7%. Significantly worse than the catalyst provided in example 1 of the present invention.

Comparative example 6

The iron-treated gold powder in step 2 of example 1 was replaced with silicon carbide ceramic powder, and the others were unchanged, to obtain catalyst DC6. The catalyst was subjected to catalytic hydrogenation under the conditions of example 5, and the obtained feedstock had a conversion of 66.8%, a metal removal rate of 85.6% and a coking rate of 5.2%. Significantly worse than the catalyst of the present invention. Illustrating that the preferred iron-based metallurgical powder of the present invention as a carrier is capable of significantly reducing the content of active metal components and the amount of catalyst used.

Comparative example 7

The iron-treated gold powder in step 2 of example 1 was replaced with aluminum powder, and the others were unchanged, to obtain catalyst DC7. The catalyst was subjected to catalytic hydrogenation under the conditions of example 5, and the obtained feedstock had a conversion of 65.6%, a metal removal rate of 84.8% and a coking rate of 5.0%. Significantly worse than the catalysts of the present invention, the preferred iron-based metallurgical powders of the present invention are illustrated as carriers to significantly reduce the content of active metal components and the amount of catalyst used.

Based on the above examples and comparative examples, it can be seen that the slurry bed hydrogenation catalyst and the preparation method thereof provided by the embodiment of the invention adopt the iron-based metallurgical powder as the carrier, so that the slurry bed hydrogenation catalyst provided by the invention can achieve the effect of better catalytic performance under the conditions of smaller active metal loading and using amount.

The slurry bed hydrogenation catalyst provided by the embodiment of the invention has the advantages of small active metal load, low price of the used iron-based metallurgical powder, and simple and convenient catalyst preparation procedure, namely the prepared catalyst has low processing cost and low cost, and is beneficial to improving the economical efficiency of the used industrial device.

By adopting the slurry bed hydrogenation catalyst and the slurry bed hydrogenation process provided by the embodiment of the invention to treat the catalytic slurry oil, the petrochemical byproducts with low added value can be converted into the raw materials of the fixed bed hydrogenation device with low cost and high efficiency, and finally can be converted into clean fuel oil products, thereby remarkably improving the economical efficiency.

In addition, the inventors have conducted experiments with other materials, process operations, and process conditions as described in this specification with reference to the foregoing examples, and have all obtained desirable results.

The various aspects, embodiments, features and examples of the invention are to be considered in all respects as illustrative and not intended to limit the invention, the scope of which is defined solely by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.

The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the present invention.

Throughout this disclosure, where a composition is described as having, comprising, or including a particular component, or where a process is described as having, comprising, or including a particular process step, it is contemplated that the composition of the teachings of the present invention also consist essentially of, or consist of, the recited component, and that the process of the teachings of the present invention also consist essentially of, or consist of, the recited process step.

It should be understood that the order of steps or order in which a particular action is performed is not critical, as long as the present teachings remain operable. Furthermore, two or more steps or actions may be performed simultaneously.

It should be understood that the above embodiments are merely for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and implement the same according to the present invention without limiting the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.

Claims

1. The slurry bed hydrogenation catalyst comprises a carrier and an active metal catalytic component arranged on the surface of the carrier, and is characterized in that the carrier is iron-based metallurgical powder;

2. The slurry bed hydrogenation catalyst of claim 1, wherein said active metal catalytic component comprises any one or a combination of molybdenum oxide and tungsten oxide;

preferably, the active metal catalytic component comprises molybdenum trioxide;

and/or the slurry bed hydrogenation catalyst has a particle size of 60-80 μm.

3. A method for preparing a slurry bed hydrogenation catalyst, comprising:

4. A method according to claim 3, wherein step 2) comprises:

immersing the carrier in the aqueous solution at 20-30 ℃ for 30-150min;

preferably, the volume ratio of the carrier to the aqueous solution is 1:1-1:2;

and/or, the aqueous solution comprises ammonium molybdate and/or ammonium metatungstate;

and/or the concentration of the aqueous solution is 5-50g/100mL.

5. The method according to claim 3, wherein the concentration of the aqueous ammonia is 10-15%, and the dropping rate is 1-5mL/s;

preferably, the volume ratio of the ammonia water to the reaction system is 1:1-2:1.

6. The method according to claim 3, wherein the baking treatment is carried out at a temperature of 220 ℃ to 300 ℃ for a time of 5 to 7 hours;

preferably, the roasting treatment is carried out under negative pressure, and the vacuum degree is 50kPa-60kPa;

and/or, the step 4) specifically comprises: washing and drying the metal crystals, roasting, crushing and sieving;

preferably, the metal crystals are crushed to 180-240 mesh after firing.

7. Use of a slurry bed hydrogenation catalyst according to any one of claims 1-2 in catalytic slurry processing.

8. A slurry bed hydrogenation process for catalytic slurry oils comprising:

mixing catalytic slurry oil, sulfur and the slurry bed hydrogenation catalyst according to any one of claims 1-2 to form a slurry hydrogenation bed;

9. The slurry bed hydrogenation method according to claim 8, wherein the slurry bed hydrogenation catalyst in the slurry hydrogenation bed accounts for 0.1-0.5% of the mass fraction of the catalytic slurry oil and accounts for 70-100% of the mass fraction of the sulfur;

and/or the temperature of the hydrogenation reaction is 400-450 ℃, the pressure is 12-24MPa, and the reaction time is 30-60min;

preferably, when the hydrogenation reaction is heated, the heating rate in the temperature range of 200-250 ℃ is 40-50 ℃/h.

10. The slurry bed hydrogenation process according to claim 8, further comprising:

and carrying out surface oxidation ablation treatment on the slurry bed hydrogenation catalyst after the hydrogenation reaction is completed and separated.