阅读说明：本技术 一种高活性加氢脱金属催化剂的制备方法 (Preparation method of high-activity hydrodemetallization catalyst ) 是由 季洪海 凌凤香 王少军 张会成 沈智奇 于 2019-04-18 设计创作，主要内容包括：本发明公开了一种高活性加氢脱金属催化剂的制备方法,包括：(1)将处理后的废加氢处理催化剂浸入碳酸氢铵水溶液中热处理,物料经干燥,然后用聚乙二醇溶液浸泡,干燥,得到预处理物料A；(2)将氧化铝粉浸入碳酸氢铵水溶液中密封热处理,热处理后物料经干燥,用含加氢活性组分I的浸渍液浸渍上述物料,得到预处理物料B；(3)将拟薄水铝石、预处理物料A和预处理物料B混捏成型,成型物经干燥、焙烧得到载体；(4)用含加氢活性组分II的浸渍液浸渍载体,载体经干燥、焙烧制得加氢脱金属催化剂。该方法利用废催化剂制备加氢脱金属催化剂,降低生产成本的同时减少污染,具有较高的加氢脱金属活性及较强的沥青质转化能力。(The invention discloses a preparation method of a high-activity hydrodemetallization catalyst, which comprises the following steps: (1) immersing the treated waste hydrotreating catalyst into an ammonium bicarbonate water solution for heat treatment, drying the material, then immersing the material in a polyethylene glycol solution, and drying to obtain a pretreated material A; (2) immersing alumina powder into an ammonium bicarbonate aqueous solution for sealing heat treatment, drying the heat-treated material, and immersing the material in an immersion liquid containing a hydrogenation active component I to obtain a pretreated material B; (3) kneading and molding pseudo-boehmite, the pretreatment material A and the pretreatment material B, and drying and roasting the molded product to obtain a carrier; (4) impregnating the carrier with an impregnation liquid containing a hydrogenation active component II, and drying and roasting the carrier to obtain the hydrogenation demetallization catalyst. The method utilizes the waste catalyst to prepare the hydrodemetallization catalyst, reduces the production cost and pollution, and has higher hydrodemetallization activity and stronger asphaltene conversion capacity.)

1. A preparation method of a high-activity hydrodemetallization catalyst is characterized by comprising the following steps: (1) crushing the waste hydrotreating catalyst, roasting, soaking the treated material in ammonium bicarbonate water solution, sealing, heat treating, filtering, drying, soaking in polyethylene glycol solution, filtering, and drying to obtain pretreated material A; (2) immersing alumina powder into an ammonium bicarbonate aqueous solution for sealing heat treatment, drying the heat-treated material, and immersing the material in an immersion liquid containing a hydrogenation active component I to obtain a pretreated material B; (3) kneading and molding pseudo-boehmite, the pretreatment material A and the pretreatment material B, and drying and roasting molded objects to obtain carriers; (4) impregnating the carrier with impregnation liquid containing a hydrogenation active component II, and then drying and roasting to prepare the high-activity hydrogenation demetallization catalyst; wherein the hydrogenation active component I is W, Co, and the hydrogenation active component II is Mo and Ni.

2. The method of claim 1, wherein: the waste hydrotreating catalyst in the step (1) comprises active metal sulfide and an alumina carrier; the active metal content on the spent hydroprocessing catalyst is 1wt% to 40wt% of the weight of the catalyst.

3. The method of claim 1, wherein: the roasting temperature in the step (1) is 700-950 ℃, and the roasting time is 6-12 hours.

4. The method of claim 1, wherein: the dosage of the ammonium bicarbonate aqueous solution in the step (1) is at least to immerse the waste hydrotreating catalyst after roasting treatment, and the mass percentage concentration of the ammonium bicarbonate aqueous solution is 15-25%.

5. The method of claim 1, wherein: the sealing heat treatment temperature in the step (1) is 120-180 ℃, and the treatment time is 4-8 hours.

6. The method of claim 1, wherein: the drying conditions in step (1) are as follows: the drying temperature is 100-160 ℃, and the drying time is 6-10 hours.

7. The method of claim 1, wherein: the pretreatment material A in the step (1) is of a mutually staggered columnar structure, the length of the columnar structure is 0.5-2 mu m, and the diameter of the columnar structure is 50-200 nm.

8. The method of claim 1, wherein: the amount of the ammonium bicarbonate aqueous solution in the step (2) is that at least alumina powder is immersed, and the mass concentration of the ammonium bicarbonate aqueous solution is 15-25%.

9. The method of claim 1, wherein: the sealing heat treatment temperature in the step (2) is 120-160 ℃, and the treatment time is 4-8 hours.

10. The method of claim 1, wherein: the pretreatment material B in the step (2) is a cluster structure formed by disordered and staggered rod-shaped alumina, the outer diameter of the rod-shaped alumina cluster is 5-20 mu m, rod-shaped alumina accounts for more than 85% of the rod-shaped alumina cluster, preferably more than 90%, the rest is spherical or ellipsoidal alumina, the length of a single rod-shaped alumina is 1-5 mu m, and the diameter is 100-300 nm.

11. The method of claim 1, wherein: the mass ratio of the pretreatment material A, the pretreatment material B and the pseudo-boehmite in the step (3) is 1:10:30-1:2: 15.

12. The method of claim 1, wherein: the content of Co in the dipping solution containing the hydrogenation active component I in the step (2) is 2.0-4.5g/100mL calculated by oxide, the content of W is 0.5-1.0g/100mL calculated by metal oxide, and the using amount of the solution is the saturated water absorption amount of the material after hydrothermal treatment; the content of Mo in the dipping solution containing the hydrogenation active component II in the step (4) is 8-15g/100mL calculated by oxide, and the content of Ni is 2.5-4.0g/100mL calculated by metal oxide.

Technical Field

The invention relates to the field of catalyst preparation, in particular to a preparation method of a high-activity hydrodemetallization catalyst.

Background

With the deterioration and heaviness of crude oil, the efficient conversion of heavy oil and the improvement of the yield of light oil products become an important trend in the development of oil refining technology. The residue fixed bed hydrogenation technology is an effective means for realizing the high-efficiency conversion of heavy oil. By adopting the technical route, the impurities such as metal, sulfur, nitrogen, carbon residue and the like in the residual oil can be effectively removed, high-quality feed is provided for catalytic cracking, and the strict environmental protection regulation requirements are met while the yield of light oil products is increased. During the processing of heavy oil, the metal compounds in the heavy oil are decomposed, and metal impurities are deposited on the inner surface and the outer surface of the catalyst to block the pore channels, so that the catalyst is even poisoned and deactivated.

In the using process of the catalyst, the catalyst becomes waste due to the loss of the original activity, and the waste catalyst rich in metal is not used, so that resources are wasted and the environment is polluted. Recently, environmental regulations have become more stringent for the disposal of spent catalysts. The waste catalyst is treated by several methods, such as landfill treatment, metal recovery, regeneration or recycling, and is used as a raw material to generate other useful products to solve the problem of the waste catalyst.

Disclosure of Invention

Aiming at the defects in the prior art, the invention provides a preparation method of a high-activity hydrodemetallization catalyst. The method utilizes the waste catalyst to prepare the hydrodemetallization catalyst, reduces the production cost and environmental pollution, and the hydrodemetallization catalyst has higher hydrodemetallization activity and stronger asphaltene conversion capability.

The preparation method of the high-activity hydrodemetallization catalyst comprises the following steps:

(1) the waste hydrotreating catalyst is crushed and then roasted. Immersing the treated material into an ammonium bicarbonate aqueous solution for sealing heat treatment, drying the treated material, then soaking the treated material in a polyethylene glycol solution, filtering and drying to obtain a pretreated material A;

(2) immersing alumina powder into an ammonium bicarbonate aqueous solution for sealing heat treatment, drying the heat-treated material, and immersing the material in an immersion liquid containing a hydrogenation active component I to obtain a pretreated material B;

(3) kneading and molding pseudo-boehmite, the pretreatment material A and the pretreatment material B, and drying and roasting molded objects to obtain carriers;

(4) and (3) impregnating the carrier with an impregnating solution containing a hydrogenation active component II, and then drying and roasting to obtain the hydrogenation demetallization catalyst.

In the method of the present invention, the spent hydrotreating catalyst in step (1) refers to a hydrotreating catalyst such as hydrodesulfurization, denitrification, etc. of distillate oil and residual oil which has not achieved the reaction requirement or has not been completely deactivated due to gradation. The hydrotreating catalyst contains hydrogenation active metal, the active metal is one or more of VIB and VIII group metals, and the waste hydrotreating catalyst contains sulfide and alumina of the active metal, and also contains other oxides such as titanium oxide, silicon oxide, boron oxide, molecular sieves and the like, and impurities such as carbon deposition, heavy metals and the like. The active metal content on the spent hydroprocessing catalyst is typically from 1wt% to 40wt% of the catalyst weight and the metal impurities are typically from 0.1wt% to 30 wt%. The shape is generally cylindrical, spherical or multi-lobed. The waste hydrotreating catalyst is crushed to be more than 200 meshes, and preferably 400-800 meshes. The roasting temperature is 700-950 ℃, and the roasting time is 6-12 hours.

In the method, the dosage of the ammonium bicarbonate aqueous solution in the step (1) is at least used for immersing and roasting the waste hydrotreating catalyst, and the mass percentage concentration of the ammonium bicarbonate aqueous solution is 15-25%.

In the method, the sealing heat treatment temperature in the step (1) is 120-180 ℃, preferably 120-160 ℃, and the treatment time is 4-8 hours.

In the method of the present invention, the drying conditions in step (1) are as follows: the drying temperature is 100-160 ℃, and the drying time is 6-10 hours.

According to the method, the pretreated material A in the step (1) is of a mutually staggered columnar structure, the length of the columnar structure is 0.5-2 mu m, and the diameter of the columnar structure is 50-200 nm.

In the method of the invention, the alumina powder in the step (2) is gamma-alumina powder which is prepared according to the prior art or is commercially available. The preparation method is generally a pseudo-boehmite roasting method, wherein the roasting temperature is 450-600 ℃, and the roasting time is 4-8 hours. The dosage of the ammonium bicarbonate aqueous solution is that at least alumina powder is immersed, and the mass concentration of the ammonium bicarbonate aqueous solution is 15-25%. The sealing heat treatment temperature is 120-160 ℃, and the treatment time is 4-8 hours. The drying conditions were as follows: the drying temperature is 100-160 ℃, and the drying time is 6-10 hours.

In the method, the pretreatment material B in the step (2) is a cluster structure formed by disordered and staggered rod-shaped alumina, the outer diameter of the rod-shaped alumina cluster is 5-20 mu m, wherein the rod-shaped alumina accounts for more than 85% of the rod-shaped alumina cluster, preferably more than 90%, the rest is spherical or ellipsoidal alumina, the length of a single rod-shaped alumina is 1-5 mu m, and the diameter is 100-300 nm.

In the method, the mass ratio of the pretreatment material A, the pretreatment material B and the pseudo-boehmite in the step (3) is 1:10:30-1:2: 15.

In the method of the invention, the kneading molding in the step (3) is carried out by adopting a conventional method in the field, and in the molding process, conventional molding aids, such as one or more of peptizing agents, extrusion aids and the like, can be added according to the needs. The peptizing agent is one or more of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid and the like; the extrusion aid is sesbania powder. The drying temperature is 100-160 ℃, and the drying time is 6-10 hours; the roasting temperature is 600-750 ℃, and the roasting time is 4-6 hours; the calcination is carried out in an oxygen-containing atmosphere, preferably an air atmosphere.

In the method, the content of Co in the dipping solution containing the hydrogenation active component I is 2.0-4.5g/100mL calculated by oxide, the content of W is 0.5-1.0g/100mL calculated by metal oxide, and the using amount of the solution is the saturated water absorption capacity of the material after hydrothermal treatment; the content of Mo in the dipping solution containing the hydrogenation active component II is 8-15g/100mL calculated by oxide, and the content of Ni is 2.5-4.0g/100mL calculated by metal oxide.

In the method, the drying temperature in the step (4) is 100-160 ℃, and the drying time is 6-10 hours; the roasting temperature is 400-550 ℃, and the roasting time is 4-6 hours; the calcination is carried out in an oxygen-containing atmosphere, preferably an air atmosphere.

Compared with the prior art, the invention has the following advantages:

(1) the invention takes the waste hydrogenation catalyst as the raw material, obtains the mutually staggered columnar structure through the simple pretreatment process, forms larger through pore channels by forming with pseudo-boehmite and dispersing in a carrier, and the pore channels are mutually communicated, thereby being beneficial to the mass transfer and the diffusion of macromolecular reactants, having higher metal-containing capability, further concentrating active metal in the waste catalyst by the columnar structure, simultaneously exposing more surfaces by the columnar structure, increasing more active sites by further loading active components, ensuring that the catalyst has higher activity, simultaneously ensuring that the catalyst has good stability, and prolonging the operation period of the device.

(2) In the invention, part of alumina powder with a rod-like cluster structure is added and doped into an alumina carrier, and the rod-like cluster structure is integrally dispersed in the carrier to form a larger through pore channel, thus being beneficial to the mass transfer and diffusion of macromolecular reactants; in addition, active metal W, Co is introduced into the rod-shaped alumina cluster structure in advance, and active metals Mo and Ni are introduced during later impregnation, so that a multi-component composite component structure of W, Co, Mo and Ni is formed at the rod-shaped alumina cluster structure, and the composite component is organically combined with the pore channel of the carrier, so that the hydrodemetallization activity and the asphaltene conversion capability of the catalyst are improved.

(3) The method is simple, and the alumina raw material is replaced by partial waste catalyst, so that the waste is changed into valuable, the production cost is reduced, and the environmental pollution is reduced.

Drawings

FIG. 1 SEM images of pretreated materials A-I.

FIG. 2 SEM images of pretreated materials B-I.

Detailed Description

The technical solutions and effects of the present invention are further described below with reference to the following examples, but the present invention is not limited to the following examples. Wherein, in the present invention, wt% represents a mass fraction.

The BET method: application N₂Physical adsorption-desorption characterization of the pore structures of the carriers of the examples and the comparative examples, the specific operations are as follows: adopting ASAP-2420 type N₂And the physical adsorption-desorption instrument is used for characterizing the pore structure of the sample. A small amount of samples are taken to be treated for 3 to 4 hours in vacuum at the temperature of 300 ℃, and finally, the product is placed under the condition of liquid nitrogen low temperature (-200 ℃) to be subjected to nitrogen absorption-desorption test. Wherein the specific surface area is obtained according to a BET equation, and the distribution rate of the pore volume and the pore diameter below 30nm is obtained according to a BJH model.

Mercury pressing method: the pore diameter distribution of the samples of the examples and the comparative examples is characterized by applying a mercury porosimeter, and the specific operation is as follows: and characterizing the distribution of sample holes by using an American microphone AutoPore9500 full-automatic mercury porosimeter. The samples were dried, weighed into an dilatometer, degassed for 30 minutes while maintaining the vacuum conditions given by the instrument, and filled with mercury. The dilatometer was then placed in the autoclave and vented. And then carrying out a voltage boosting and reducing test. The mercury contact angle is 130 degrees, and the mercury interfacial tension is 0.485N.cm^-1The distribution ratio of the pore diameter of 100nm or more is measured by mercury intrusion method.

The scanning electron microscope is used for representing the microstructure of a sample, and the specific operation is as follows: and a JSM-7500F scanning electron microscope is adopted to represent the microstructure of the sample, the accelerating voltage is 5kV, the accelerating current is 20 muA, and the working distance is 8 mm.

The method adopts NB/SH/T0704-.

The sulfur content in the oil product is determined by adopting an SH/T0689-.

The content of carbon residue in the oil product is determined by adopting an SH/T0266-92 standard method.

And the contents of Ni and V in the oil product are determined by adopting a GB/T34099-2017 standard method.