阅读说明：本技术 一种适用于煤焦油加氢的低密度保护催化剂的制备方法 (Preparation method of low-density protection catalyst suitable for coal tar hydrogenation ) 是由 孙泓 韩宝亭 于 2021-07-28 设计创作，主要内容包括：本发明公开了一种适用于煤焦油加氢的低密度保护催化剂的制备方法,包括如下步骤：先将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；取去离子水和无机酸进行溶液制备,然后将配制的溶液加入到捏合机中,混捏至产品呈团状物料；将制备好的团状物料转移至挤条机中,选择5.0mm五齿条状模块,挤制成五齿条状催化剂载体；再将挤出的五齿条状催化剂载体转移至切刀中,制成五齿球型载体,静置6小时,然后转移至马弗炉中,以50～100℃条件进行烘干4小时,再以3℃/min速率升温至700～1100℃恒温焙烧4h得到催化剂载体；将制备的浸渍液与上述得到的催化剂载体进行混合浸渍2h,以3℃/min速率升温至300～500℃恒温焙烧4h。该方法能够将成品密度控制在0.50～0.70g/cm～(3)。(The invention discloses a preparation method of a low-density protective catalyst suitable for coal tar hydrogenation, which comprises the following steps: firstly, placing pseudo-boehmite, sesbania powder and hydroxymethyl cellulose in a kneader, and dry-mixing for 10 min; taking deionized water and inorganic acid for solution preparation, then adding the prepared solution into a kneading machine, and kneading until the product is a bulk material; transferring the prepared bulk material into a bar extruder, selecting a 5.0mm five-rack-shaped module, and extruding to obtain a five-rack-shaped catalyst carrier; transferring the extruded five-toothed-rack catalyst carrier into a cutter to prepare a five-toothed spherical carrier, standing for 6 hours, transferring the five-toothed spherical carrier into a muffle furnace, drying for 4 hours at the temperature of 50-100 ℃, heating to 700-1100 ℃ at the speed of 3 ℃/min, and roasting at the constant temperature for 4 hours to obtain the catalyst carrier; mixing and soaking the prepared soaking liquid and the obtained catalyst carrier for 2 hours, heating to 300-500 ℃ at the speed of 3 ℃/min, and baking at constant temperatureAnd (5) burning for 4 hours. The method can control the density of the finished product to be 0.50-0.70 g/cm 3 。)

1. A preparation method of a low-density protective catalyst suitable for coal tar hydrogenation is characterized by comprising the following steps:

the first step is as follows: firstly, placing pseudo-boehmite, sesbania powder and hydroxymethyl cellulose in a kneader, and dry-mixing for 10 min;

the second step is that: taking deionized water and inorganic acid to prepare a solution, adjusting the pH value of the solution to 2-4, adding the prepared solution into a kneader, kneading until the product is a bulk material, and adjusting the addition of water until the humidity of the product is 20% -30%;

the third step: transferring the prepared bulk material into a bar extruder, selecting a 5.0mm five-rack-shaped module, and extruding to obtain a five-rack-shaped catalyst carrier;

the fourth step: transferring the extruded five-toothed-rack catalyst carrier into a cutter to prepare a five-toothed spherical carrier, standing for 6 hours, transferring the five-toothed spherical carrier into a muffle furnace, drying for 4 hours at the temperature of 50-100 ℃, heating to 700-1100 ℃ at the speed of 3 ℃/min, and roasting at the constant temperature for 4 hours to obtain the catalyst carrier;

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

and a sixth step: mixing and soaking the prepared soaking solution and the obtained catalyst carrier for 2 hours, drying for 4 hours at the temperature of 50-100 ℃, and then heating to 300-500 ℃ at the speed of 3 ℃/min and roasting for 4 hours at constant temperature to obtain a catalyst product.

2. The method for preparing the low-density protective catalyst suitable for coal tar hydrogenation according to claim 1, characterized in that: the specific surface of the catalyst product is 70-120 m²The pore volume is 0.3-0.6 ml/g, the aperture of the product is 12-29 nm, and the density of the finished product is controlled to be 0.50-0.70 g/cm³。

3. The method for preparing the low-density protective catalyst suitable for coal tar hydrogenation according to claim 1, characterized in that: the specific surface of the pseudo-boehmite adopted in the first step is 200-320 m²The pore volume is 0.8 to 1.2 ml/g.

4. The method for preparing the low-density protective catalyst suitable for coal tar hydrogenation according to claim 1, characterized in that: the mass ratio of the pseudo-boehmite, the sesbania powder and the hydroxymethyl cellulose in the first step is 100:1: 1.

5. The method for preparing the low-density protective catalyst suitable for coal tar hydrogenation according to claim 1, characterized in that: the mass ratio of the soluble molybdenum salt to the nickel salt to the deionized water in the fifth step is 2:1: 20.

6. The method for preparing the low-density protective catalyst suitable for coal tar hydrogenation according to claim 1, characterized in that: the mass ratio of the impregnation liquid to the catalyst carrier is 11: 10.

Technical Field

The invention relates to the technical field of catalysis, in particular to a preparation method of a low-density protection catalyst suitable for coal tar hydrogenation.

Background

The protective catalyst is a necessary catalyst product for petroleum-based and coal tar-based hydrogenation technologies, the product of the protective catalyst generally needs to have a certain function of removing impurities in raw oil and has high anti-coking capability, the protective catalyst has the fatal defect, and the density of the spherical protective catalyst is 1.10-1.20 g/cm³The high density of the protected catalyst product is lowerThe pore volume and the specific surface area are small, and the service life is from half a year to one year. If the impurity exceeds the holding capacity of the protective agent, the impurity can penetrate through the protective agent to the main catalyst behind the reaction device, so that the main catalyst is polluted and poisoned and loses the hydrogenation activity.

Disclosure of Invention

The invention provides a preparation method of a low-density protective catalyst suitable for hydrogenation of coal tar, which aims to solve the problems in the background technology.

The invention provides a preparation method of a low-density protective catalyst suitable for coal tar hydrogenation, which comprises the following steps:

the first step is as follows: firstly, placing pseudo-boehmite, sesbania powder and hydroxymethyl cellulose in a kneader, and dry-mixing for 10 min;

the second step is that: taking deionized water and inorganic acid to prepare a solution, adjusting the pH value of the solution to 2-4, adding the prepared solution into a kneader, kneading until the product is a bulk material, and adjusting the addition of water until the humidity of the product is 20% -30%;

the third step: transferring the prepared bulk material into a bar extruder, selecting a 5.0mm five-rack-shaped module, and extruding to obtain a five-rack-shaped catalyst carrier;

the fourth step: transferring the extruded five-toothed-rack catalyst carrier into a cutter to prepare a five-toothed spherical carrier, standing for 6 hours, transferring the five-toothed spherical carrier into a muffle furnace, drying for 4 hours at the temperature of 50-100 ℃, heating to 700-1100 ℃ at the speed of 3 ℃/min, and roasting at the constant temperature for 4 hours to obtain the catalyst carrier;

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

and a sixth step: mixing and soaking the prepared soaking solution and the obtained catalyst carrier for 2 hours, drying for 4 hours at the temperature of 50-100 ℃, and then heating to 300-500 ℃ at the speed of 3 ℃/min and roasting for 4 hours at constant temperature to obtain a catalyst product.

Preferably, the specific surface of the catalyst product is 70-120 m²The pore volume is 0.3-0.6 ml/g, the aperture of the product can be several nanometers 12-29 nm, and the finished product is denseThe degree is controlled to be 0.50-0.70 g/cm³。

Preferably, the specific surface of the pseudo-boehmite adopted in the first step is 200-320 m²The pore volume is 0.8 to 1.2 ml/g.

Preferably, the mass ratio of the pseudoboehmite, the sesbania powder and the hydroxymethyl cellulose in the first step is 100:1: 1.

Preferably, the mass ratio of the soluble molybdenum salt to the nickel salt to the deionized water in the fifth step is 2:1: 20.

Preferably, the mass ratio of the impregnation liquid to the catalyst carrier is 11: 10.

The preparation method of the low-density protective catalyst suitable for coal tar hydrogenation provided by the invention has the beneficial effects that: the protective catalyst designed by the invention redesigns raw materials of the product and redesigns a preparation process of the catalyst, wherein the specific surface area of the catalyst product is 70-120 m2/g, the pore volume is 0.3-0.6 ml/g, the aperture of the catalyst product is 12-29 nm, and the density of the finished product is controlled to be 0.50-0.70 g/cm³The service cycle of the product is prolonged by about 1 year, so that the product dosage can be effectively reduced, the use cost is reduced, and the product effect is improved; the catalyst contains 3-10% of molybdenum oxide, 1.3-2.5% of nickel oxide and 1-3% of silicon oxide as active components.

Detailed Description

The invention is further illustrated by the following examples.

Example 1

The invention provides a preparation method of a low-density protective catalyst suitable for coal tar hydrogenation, which comprises the following steps:

the first step is as follows: firstly, pseudo-boehmite, sesbania powder and hydroxymethyl cellulose are placed in a kneader and are dry-mixed for 10min, the mass ratio of the pseudo-boehmite to the sesbania powder to the hydroxymethyl cellulose is 100:1:1, and the specific surface of the adopted pseudo-boehmite is 200-320 m²The pore volume is 0.8-1.2 ml/g;

the second step is that: taking deionized water and inorganic acid to prepare a solution, adjusting the pH value of the solution to 2-4, adding the prepared solution into a kneader, kneading until the product is a bulk material, and adjusting the addition of water until the humidity of the product is 20% -30%;

the third step: transferring the prepared bulk material into a bar extruder, selecting a 5.0mm five-rack-shaped module, and extruding to obtain a five-rack-shaped catalyst carrier;

the fourth step: transferring the extruded five-rack catalyst carrier into a cutter to prepare a five-tooth spherical carrier, standing for 6 hours, transferring the five-tooth spherical carrier into a muffle furnace, drying for 4 hours at 50 ℃, heating to 700 ℃ at the speed of 3 ℃/min, and roasting at the constant temperature for 4 hours to obtain the catalyst carrier;

the fifth step: adding deionized water into soluble molybdenum salt and nickel salt for fully dissolving, wherein the mass ratio of the soluble molybdenum salt to the nickel salt to the deionized water is 2:1:20, and preparing a stable impregnation solution;

and a sixth step: mixing and soaking the prepared soaking solution and the obtained catalyst carrier for 2h, wherein the mass ratio of the soaking solution to the catalyst carrier is 11:10, drying for 4h at 50 ℃, and then heating to 300 ℃ at the speed of 3 ℃/min and roasting at the constant temperature for 4h to obtain a catalyst product.

The specific surface of the catalyst product is 70-120 m²The pore volume is 0.3-0.6 ml/g, the aperture of the product is 12-29 nm, and the density of the finished product is controlled to be 0.50-0.70 g/cm³。

Example 2

The invention provides a preparation method of a low-density protective catalyst suitable for coal tar hydrogenation, which comprises the following steps:

the first step is as follows: firstly, pseudo-boehmite, sesbania powder and hydroxymethyl cellulose are placed in a kneader and are dry-mixed for 10min, the mass ratio of the pseudo-boehmite to the sesbania powder to the hydroxymethyl cellulose is 100:1:1, and the specific surface of the adopted pseudo-boehmite is 200-320 m²The pore volume is 0.8-1.2 ml/g;

the second step is that: taking deionized water and inorganic acid to prepare a solution, adjusting the pH value of the solution to 2-4, adding the prepared solution into a kneader, kneading until the product is a bulk material, and adjusting the addition of water until the humidity of the product is 20% -30%;

the third step: transferring the prepared bulk material into a bar extruder, selecting a 5.0mm five-rack-shaped module, and extruding to obtain a five-rack-shaped catalyst carrier;

the fourth step: transferring the extruded five-rack catalyst carrier into a cutter to prepare a five-tooth spherical carrier, standing for 6 hours, transferring the five-tooth spherical carrier into a muffle furnace, drying for 4 hours at the temperature of 80 ℃, heating to 900 ℃ at the speed of 3 ℃/min, and roasting at the constant temperature for 4 hours to obtain the catalyst carrier;

the fifth step: adding deionized water into soluble molybdenum salt and nickel salt for fully dissolving, wherein the mass ratio of the soluble molybdenum salt to the nickel salt to the deionized water is 2:1:20, and preparing a stable impregnation solution;

and a sixth step: mixing and soaking the prepared soaking solution and the obtained catalyst carrier for 2h, wherein the mass ratio of the soaking solution to the catalyst carrier is 11:10, drying for 4h at 80 ℃, and then heating to 400 ℃ at the speed of 3 ℃/min and roasting at constant temperature for 4h to obtain a catalyst product.

The specific surface of the catalyst product is 70-120 m²The pore volume is 0.3-0.6 ml/g, the aperture of the product is 12-29 nm, and the density of the finished product is controlled to be 0.50-0.70 g/cm³。

Example 3

The invention provides a preparation method of a low-density protective catalyst suitable for coal tar hydrogenation, which comprises the following steps:

the first step is as follows: firstly, pseudo-boehmite, sesbania powder and hydroxymethyl cellulose are placed in a kneader and are dry-mixed for 10min, the mass ratio of the pseudo-boehmite to the sesbania powder to the hydroxymethyl cellulose is 100:1:1, and the specific surface of the adopted pseudo-boehmite is 200-320 m²The pore volume is 0.8-1.2 ml/g;

the second step is that: taking deionized water and inorganic acid to prepare a solution, adjusting the pH value of the solution to 2-4, adding the prepared solution into a kneader, kneading until the product is a bulk material, and adjusting the addition of water until the humidity of the product is 20% -30%;

the third step: transferring the prepared bulk material into a bar extruder, selecting a 5.0mm five-rack-shaped module, and extruding to obtain a five-rack-shaped catalyst carrier;

the fourth step: transferring the extruded five-rack catalyst carrier into a cutter to prepare a five-tooth spherical carrier, standing for 6 hours, transferring the five-tooth spherical carrier into a muffle furnace, drying for 4 hours at the temperature of 100 ℃, heating to 1100 ℃ at the speed of 3 ℃/min, and roasting at the constant temperature for 4 hours to obtain the catalyst carrier;

the fifth step: adding deionized water into soluble molybdenum salt and nickel salt for fully dissolving, wherein the mass ratio of the soluble molybdenum salt to the nickel salt to the deionized water is 2:1:20, and preparing a stable impregnation solution;

and a sixth step: mixing and soaking the prepared soaking solution and the obtained catalyst carrier for 2h, wherein the mass ratio of the soaking solution to the catalyst carrier is 11:10, 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 of the catalyst product is 70-120 m²The pore volume is 0.3-0.6 ml/g, the aperture of the product is 12-29 nm, and the density of the finished product is controlled to be 0.50-0.70 g/cm³。

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.