阅读说明：本技术 一种废润滑油加氢精制催化剂的制备方法 (Preparation method of spent lubricating oil hydrofining catalyst ) 是由 孙泓 韩宝亭 于 2021-07-28 设计创作，主要内容包括：本发明提供了一种废润滑油加氢精制催化剂的制备方法,具体步骤如下：先将大孔拟薄水铝石连同田菁粉、羟甲基纤维素置于捏合机中,干混10min,然后将制备的混合溶液加入到捏合机中,混捏1h至产品呈团状物料；将制备好的团状物料转移至挤条机中,挤制成圆条状催化剂载体；以50-100℃条件进行烘干4小时,再以3℃/min速率升温至500-800℃恒温焙烧4h得到催化剂载体；将可溶性钨盐、钼盐以及镍盐中加入去离子水进行充分溶解,制备成稳定浸渍液；将制备的浸渍液按与上述得到的催化剂载体进行混合浸渍1h,然后以50-100℃条件进行烘干4小时。该催化剂产品可以有效处理废润滑油中有机硫、有机氮等有毒化合物,可以将其转化为易于处理的无机态化学成分。(The invention provides a preparation method of a spent lubricating oil hydrofining catalyst, which comprises the following specific steps: placing macroporous pseudoboehmite, sesbania powder and hydroxymethyl cellulose in a kneader, dry-mixing for 10min, adding the prepared mixed solution into the kneader, and kneading for 1h until the product is a bulk material; transferring the prepared bulk material into a strip extruding machine, and extruding into a round strip-shaped catalyst carrier; drying for 4 hours at the temperature of 50-100 ℃, and then heating to 500-; adding deionized water into soluble tungsten salt, molybdenum salt and nickel salt for fully dissolving to prepare stable impregnation liquid; mixing and soaking the prepared soaking solution with the catalyst carrier obtained above for 1h, and then drying at 50-100 ℃ for 4 h. The catalyst product can effectively treat toxic compounds such as organic sulfur, organic nitrogen and the like in the waste lubricating oil and can convert the toxic compounds into inorganic chemical components which are easy to treat.)

1. A preparation method of a spent lubricating oil hydrofining catalyst is characterized by comprising the following steps:

the method comprises the following steps: placing macroporous pseudoboehmite, sesbania powder and hydroxymethyl cellulose in a kneader, dry-mixing for 10min, adding the prepared mixed solution into the kneader, and kneading for 1h until the product is a bulk material;

step two: transferring the prepared bulk material into a strip extruding machine, selecting a round strip module with the diameter of 2.0mm, extruding the round strip module into a round strip catalyst carrier, and standing for 6 hours;

step three: then transferring the catalyst into a muffle furnace, drying the catalyst for 4 hours at the temperature of 50-100 ℃, and then raising the temperature to 500-800 ℃ at the speed of 3 ℃/min and roasting the catalyst for 4 hours at constant temperature to obtain a catalyst carrier;

step four: adding deionized water into soluble tungsten salt, molybdenum salt and nickel salt for fully dissolving to prepare stable impregnation liquid;

step five: mixing and soaking the prepared soaking solution with the obtained catalyst carrier for 1h, then drying for 4h at the temperature of 50-100 ℃, and then raising the temperature to 300-500 ℃ at the speed of 3 ℃/min and roasting for 4h at constant temperature to obtain the catalyst product.

2. The method for preparing the spent lubricating oil hydrorefining catalyst according to claim 1, wherein the mass ratio of the macroporous pseudoboehmite, the sesbania powder, the hydroxymethyl cellulose and the mixed solution is 100:2:1: 90.

3. The preparation method of the spent lubricating oil hydrorefining catalyst according to claim 1, wherein the mixed solution is composed of deionized water, an auxiliary agent 1 and an auxiliary agent 2, and the mass ratio of the deionized water to the auxiliary agent 1 to the auxiliary agent 2 is 50:1: 1.

4. The method for preparing the spent lubricating oil hydrofining catalyst according to claim 3, wherein the assistant 1 is citric acid, and the assistant 2 is kaolin.

5. The method for preparing the spent lubricating oil hydrorefining catalyst according to claim 1, wherein the specific surface area of the catalyst product is 120-150m²The pore volume is 0.3-0.4ml/g, and the pore diameter can be 13-20 nm.

6. The method for preparing the spent lubricating oil hydrorefining catalyst according to claim 1, wherein the mass ratio of the impregnating solution to the catalyst carrier is 1: 1.

7. The method for preparing the spent lubricating oil hydrofining catalyst according to claim 1, wherein the mass ratio of the soluble tungsten salt, the molybdenum salt, the nickel salt and the deionized water is 4:2:1: 20.

8. The method for preparing the spent lubricating oil hydrorefining catalyst according to claim 1, wherein the specific surface area of the large-pore pseudo-boehmite is 260-320m²The pore volume is 0.9-1.1 ml/g.

Technical Field

The invention relates to the technical field of essential oil preparation, in particular to a catalyst for hydrofining waste lubricating oil and a preparation method thereof.

Background

The lubricating oil consists of base oil and additive, wherein the base oil is the main component of the lubricating oil and generally accounts for 70-100% of the components of the lubricating oil. The multiple functions of the lubricating oil make the lubricating oil widely applied to industries such as metallurgy, electric power, mine, machinery, traffic, military industry, aerospace, communication and the like, and the lubricating oil is called as blood of vehicles, machinery and industrial equipment. The used lubricating oil refers to used lubricating oil that is exchanged from various machines, vehicles, and ships. In the using process of the lubricating oil, because oxides of the lubricating oil generate a large amount of colloids and oxides due to external pollution, the effects of controlling friction, reducing abrasion, cooling, sealing and isolating, reducing vibration and the like of the lubricating oil are reduced or even lost, and the lubricating oil has to be replaced, wherein organic compounds containing chlorine, sulfur, nitrogen, phosphorus and the like have toxicity, and the lubricating oil is listed as dangerous waste in many countries internationally. Waste oil has been classified as one of three major points of major control in the environmental protection field in the 21 st century by the State environmental protection Bureau. The amount of the waste oil is about 80 percent of the consumption amount of the lubricating oil, and about 480 ten thousand tons of the waste lubricating oil are generated in China every year. The waste oil is only waste which is not utilized by less than 10 percent, and more than 90 percent of the waste oil can be reprocessed and reused, and 850-950 kg of lubricating oil base oil can be regenerated by 1 ton of waste oil. The yield of lubricating oil extracted from petroleum is very low, and at least 5 tons of crude oil are needed to prepare 1 ton of lubricating oil. At present, most domestic waste oil is burnt as fuel oil, only a small part of domestic waste oil is regenerated by adopting a process of 'sulfuric acid-white clay method' of 60 foreign years, base oil with poor quality is obtained, and waste gas, waste liquid, waste white clay and acid sludge generated in the production process cause secondary pollution to the environment.

The waste lubricating oil is polluted and a small amount of deteriorated oil after being used, most tissues of the oil are not deteriorated and damaged in the replaced waste oil, only a few percent of hydrocarbons are really deteriorated, and pollutants only account for 1-10 percent of the oil. The waste oil can be regenerated into base oil of satisfactory quality by removing these deteriorated hydrocarbons and various contaminants by an appropriate method. The quality of the regenerated oil can completely reach the standard of the new oil.

Disclosure of Invention

The invention provides a preparation method of a spent lubricating oil hydrofining catalyst, which aims to solve the problems in the background technology.

The invention also provides a preparation method of the spent lubricating oil hydrofining catalyst, which comprises the following steps:

the method comprises the following steps: placing macroporous pseudoboehmite, sesbania powder and hydroxymethyl cellulose in a kneader, dry-mixing for 10min, adding the prepared mixed solution into the kneader, and kneading for 1h until the product is a bulk material;

step two: transferring the prepared bulk material into a strip extruding machine, selecting a round strip module with the diameter of 2.0mm, extruding the round strip module into a round strip catalyst carrier, and standing for 6 hours;

step three: then transferring the catalyst into a muffle furnace, drying the catalyst for 4 hours at the temperature of 50-100 ℃, and then raising the temperature to 500-800 ℃ at the speed of 3 ℃/min and roasting the catalyst for 4 hours at constant temperature to obtain a catalyst carrier;

step four: adding deionized water into soluble tungsten salt, molybdenum salt and nickel salt for fully dissolving to prepare stable impregnation liquid;

step five: mixing and soaking the prepared soaking solution with the obtained catalyst carrier for 1h, then drying for 4h at the temperature of 50-100 ℃, and then raising the temperature to 300-500 ℃ at the speed of 3 ℃/min and roasting for 4h at constant temperature to obtain the catalyst product.

Preferably, the mass ratio of the macroporous pseudo-boehmite, the sesbania powder, the hydroxymethyl cellulose and the mixed solution is 100:2:1: 90.

Preferably, the mixed solution is composed of deionized water, an auxiliary agent 1 and an auxiliary agent 2, and the mass ratio of the deionized water to the auxiliary agent 1 to the auxiliary agent 2 is 50:1: 1.

Preferably, the aid 1 is citric acid, and the aid 2 is kaolin.

Preferably, the specific surface area of the catalyst product is 120-150m2/g, the pore volume is 0.3-0.4ml/g, and the pore diameter can be 13-20 nm.

Preferably, the mass ratio of the impregnation liquid to the catalyst carrier is 1: 1.

Preferably, the mass ratio of the soluble tungsten salt to the molybdenum salt to the nickel salt to the deionized water is 4:2:1: 20.

Preferably, the specific surface area of the large-pore pseudo-boehmite is 260-320m2/g, and the pore volume is 0.9-1.1 ml/g.

Compared with the prior art, the invention has the beneficial effects that: the catalyst product of the invention needs to be vulcanized in a hydrogen atmosphere before use, and a corresponding vulcanized catalyst product is obtained after the vulcanization. The catalyst has good hydrodesulfurization and denitrification functions, high removal efficiency and long service cycle. The catalyst is used in a hydrofining section in the waste lubricating oil treatment process, can effectively treat toxic compounds such as organic sulfur, organic nitrogen and the like in the waste lubricating oil, can convert the toxic compounds into inorganic chemical components easy to treat, is high in processing efficiency and strong in treatment capacity, and contains 16-22% of tungsten oxide, 5-10% of molybdenum oxide, 3-5% of nickel oxide and 1-3% of silicon oxide which are active components.

Detailed Description

The invention is further illustrated by the following examples.

Example 1

The invention also provides a preparation method of the spent lubricating oil hydrofining catalyst, which comprises the following steps:

the method comprises the following steps: placing macroporous pseudoboehmite, sesbania powder and hydroxymethyl cellulose in a kneading machine, dry-mixing for 10min, adding the prepared mixed solution into the kneading machine, kneading for 1h until the product is a bulk material, wherein the mass ratio of the macroporous pseudoboehmite, the sesbania powder, the hydroxymethyl cellulose to the mixed solution is 100:2:1:90, the mixed solution is composed of deionized water, citric acid and kaolin, and the mass ratio of the deionized water, the citric acid and the kaolin is 50:1: 1;

step two: transferring the prepared bulk material into a strip extruding machine, selecting a round strip module with the diameter of 2.0mm, extruding the round strip module into a round strip catalyst carrier, and standing for 6 hours;

step three: then transferring the catalyst to a muffle furnace, drying the catalyst for 4 hours at the temperature of 50 ℃, and then heating the catalyst to 500 ℃ at the speed of 3 ℃/min and roasting the catalyst for 4 hours at constant temperature to obtain a catalyst carrier;

step four: adding deionized water into soluble tungsten salt, molybdenum salt and nickel salt for full dissolution to prepare a stable impregnation solution, wherein the mass ratio of the soluble tungsten salt to the molybdenum salt to the nickel salt to the deionized water is 4:2:1: 20;

step five: mixing and soaking the prepared soaking solution and the obtained catalyst carrier for 1h, wherein the mass ratio of the soaking solution to the catalyst carrier is 1:10, drying for 4h at 50 ℃, and then heating to 300 ℃ at the speed of 3 ℃/min and roasting at constant temperature for 4h to obtain a catalyst product.

The specific surface area of the catalyst product is 120-150m²The pore volume is 0.3-0.4ml/g, and the pore diameter can be 13-20 nm.

The specific surface of the large-pore pseudo-boehmite is 260-320m²The pore volume is 0.9-1.1 ml/g.

Example 2

The invention also provides a preparation method of the spent lubricating oil hydrofining catalyst, which comprises the following steps:

the method comprises the following steps: placing macroporous pseudoboehmite, sesbania powder and hydroxymethyl cellulose in a kneading machine, dry-mixing for 10min, adding the prepared mixed solution into the kneading machine, kneading for 1h until the product is a bulk material, wherein the mass ratio of the macroporous pseudoboehmite, the sesbania powder, the hydroxymethyl cellulose to the mixed solution is 100:2:1:90, the mixed solution is composed of deionized water, citric acid and kaolin, and the mass ratio of the deionized water, the citric acid and the kaolin is 50:1: 1;

step two: transferring the prepared bulk material into a strip extruding machine, selecting a round strip module with the diameter of 2.0mm, extruding the round strip module into a round strip catalyst carrier, and standing for 6 hours;

step three: then transferring the catalyst to a muffle furnace, drying the catalyst for 4 hours at the temperature of 80 ℃, and then heating the catalyst to 650 ℃ at the speed of 3 ℃/min and roasting the catalyst for 4 hours at constant temperature to obtain a catalyst carrier;

step four: adding deionized water into soluble tungsten salt, molybdenum salt and nickel salt for full dissolution to prepare a stable impregnation solution, wherein the mass ratio of the soluble tungsten salt to the molybdenum salt to the nickel salt to the deionized water is 1:1:1: 20;

step five: mixing and soaking the prepared soaking solution and the obtained catalyst carrier for 1h, wherein the mass ratio of the soaking solution to the catalyst carrier is 1:10, drying for 4h at the temperature of 75 ℃, and then heating to 400 ℃ at the speed of 3 ℃/min and roasting for 4h at constant temperature to obtain a catalyst product.

The specific surface area of the catalyst product is 120-150m²The pore volume is 0.3-0.4ml/g, and the pore diameter can be 13-20 nm.

The specific surface of the large-pore pseudo-boehmite is 260-320m²The pore volume is 0.9-1.1 ml/g.

Example 3

The invention also provides a preparation method of the spent lubricating oil hydrofining catalyst, which comprises the following steps:

the method comprises the following steps: placing macroporous pseudoboehmite, sesbania powder and hydroxymethyl cellulose in a kneading machine, dry-mixing for 10min, adding the prepared mixed solution into the kneading machine, kneading for 1h until the product is a bulk material, wherein the mass ratio of the macroporous pseudoboehmite, the sesbania powder, the hydroxymethyl cellulose to the mixed solution is 15:2:1:1, the mixed solution is composed of deionized water, citric acid and kaolin, and the mass ratio of the deionized water, the citric acid and the kaolin is 50:1: 1;

step two: transferring the prepared bulk material into a strip extruding machine, selecting a round strip module with the diameter of 2.0mm, extruding the round strip module into a round strip catalyst carrier, and standing for 6 hours;

step three: then transferring the catalyst to a muffle furnace, drying the catalyst for 4 hours at the temperature of 100 ℃, and then heating the catalyst to 800 ℃ at the speed of 3 ℃/min and roasting the catalyst for 4 hours at constant temperature to obtain a catalyst carrier;

step four: adding deionized water into soluble tungsten salt, molybdenum salt and nickel salt for full dissolution to prepare a stable impregnation solution, wherein the mass ratio of the soluble tungsten salt to the molybdenum salt to the nickel salt to the deionized water is 4:2:1: 20;

step five: mixing and soaking the prepared soaking solution and the obtained catalyst carrier for 1h, wherein the mass ratio of the soaking solution to the catalyst carrier is 1:10, then drying for 4h at the temperature of 100 ℃, and then heating to 500 ℃ at the speed of 3 ℃/min and roasting for 4h at constant temperature to obtain a catalyst product.

The specific surface area of the catalyst product is 120-150m²The pore volume is 0.3-0.4ml/g, and the pore diameter can be 13-20 nm.

The specific surface area of the large-pore pseudo-boehmite is 260-320m2/g, and the pore volume is 0.9-1.1 ml/g.

In conclusion, the catalyst product of the invention needs to be vulcanized in a hydrogen atmosphere before use, and a corresponding vulcanized catalyst product is obtained after the vulcanization. The catalyst has good hydrodesulfurization and denitrification functions, high removal efficiency and long service cycle.

The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.