阅读说明：本技术 一种耐水型催化剂载体 (Water-resistant catalyst carrier ) 是由 姚光纯 徐斌 于 2020-12-21 设计创作，主要内容包括：本发明公开一种耐水型催化剂载体,包括以下质量百分比含量的制备原料：氢氧化铝1-80%,拟薄水铝石1-70%,田菁粉0.5-5%,二氧化钛1-10%,酸性溶剂1-8%,辅助材料0.5-3%；上述各原料的质量百分比之和为100%；所述耐水型催化剂载体的外形为高径比为0.45-0.9的带通孔的圆柱体,外径为5-45mm,所述通孔目数为80-900目；本发明具有丰富的通孔,孔隙率高、比表面积大、机械强度高的优点。(The invention discloses a water-resistant catalyst carrier, which comprises the following preparation raw materials in percentage by mass: 1-80% of aluminum hydroxide, 1-70% of pseudo-boehmite, 0.5-5% of sesbania powder, 1-10% of titanium dioxide, 1-8% of an acid solvent and 0.5-3% of an auxiliary material; the sum of the mass percentages of the raw materials is 100 percent; the shape of the water-resistant catalyst carrier is a cylinder with through holes with the height-diameter ratio of 0.45-0.9, the outer diameter is 5-45mm, and the number of the through holes is 80-900 meshes; the invention has the advantages of abundant through holes, high porosity, large specific surface area and high mechanical strength.)

1. The water-resistant catalyst carrier is characterized by comprising the following preparation raw materials in percentage by mass: 1-80% of aluminum hydroxide, 1-70% of pseudo-boehmite, 0.5-5% of sesbania powder, 1-10% of titanium dioxide, 1-8% of an acid solvent and 0.5-3% of an auxiliary material; the sum of the mass percentages of the raw materials is 100 percent; the shape of the water-resistant catalyst carrier is a cylinder with through holes with the height-diameter ratio of 0.45-0.9, the outer diameter is 5-45mm, and the number of the through holes is 80-900 meshes.

2. The water-tolerant catalyst carrier according to claim 1, wherein the cross-sectional shape of the through-hole is one of a regular hexagon, a triangle, a square, or a circle.

3. The water-tolerant catalyst carrier according to claim 1, wherein the acidic solvent is one or a combination of nitric acid, citric acid and phosphoric acid.

4. The water-resistant catalyst support according to claim 1, wherein the auxiliary material is methylcellulose or carboxymethylcellulose.

5. A method for preparing a water-resistant catalyst support according to any of claims 1 to 4, comprising the steps of:

(1) powder mixing: weighing the preparation raw materials according to a formula ratio, and putting aluminum hydroxide, pseudo-boehmite, sesbania powder, titanium dioxide and auxiliary materials into a kneader or a mixer;

(2) fully mixing the powder in the step (1), adding an acidic solvent and a certain proportion of water and oil to knead the pug to obtain uniformly mixed pug;

(3) filtering the pug obtained in the step (2) by a screen, refining the pug in vacuum, testing the temperature of the pug by a thermometer, and putting the pug into a heat preservation room for aging;

(4) carrying out extrusion molding on the pug obtained in the step (3) through a die to obtain a blank body;

(5) and (4) cutting the blank in the step (4) into a cylinder according with the height-diameter ratio, drying, and roasting at high temperature to obtain the water-resistant catalyst carrier.

6. The method for preparing a water-resistant catalyst carrier according to claim 5, wherein the water is added in the step (2) in a proportion of 20-50% by weight of the raw material in the step (1), and the oil is added in a proportion of 1-5% by weight of the raw material in the step (1); the oil can be rape oil or waste oil.

7. The method for preparing a water-resistant catalyst carrier according to claim 5, wherein the drying condition in step (5) is drying in the shade at room temperature for 2-3 days, and then drying at 40-70 ℃ for 2-3 days.

8. The method for preparing a water-resistant catalyst carrier as recited in claim 5, wherein the calcination temperature in step (5) is 650-850 ℃ and the calcination time is 12-20 hours.

Technical Field

The invention relates to the technical field of catalyst carrier preparation, in particular to a water-resistant catalyst carrier.

Background

The development goal of petroleum refining industry is to improve the yield of light oil and the quality of products, the yield and quality of products in general petroleum processing processes are often contradictory, and the catalytic hydrogenation process can almost simultaneously meet the two requirements. The purpose of the hydrogenation treatment is to remove impurities such as sulfur, nitrogen, oxygen, metal and the like in the oil product, and simultaneously, selectively hydrogenate and saturate olefins, dienes, aromatic hydrocarbons and polycyclic aromatic hydrocarbons, thereby improving the quality of raw materials and the service performance of products. The hydrotreatment has the advantages of wide raw oil range, high product flexibility, high liquid product yield, high product quality, environmental friendliness, low labor intensity and the like, and is widely applied to raw material pretreatment and product refining.

Most of the prior hydrogenation catalyst carriers are strip-shaped, clover-shaped or ball-shaped. The structure is simple, the requirement on the production process is low, the large-scale industrialization is realized, the market is good, but the bottleneck which is difficult to break through is formed in the using process, such as: low porosity, small specific surface area, large bulk specific gravity and the like, and the mechanical strength of the catalyst is continuously reduced in the using process, so that the catalyst has low catalytic efficiency and short service life.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a water-resistant catalyst carrier which is provided with abundant through holes, high porosity, large specific surface area and high mechanical strength.

In order to solve the technical problems, the invention adopts the technical scheme that: a water-resistant catalyst carrier comprises the following preparation raw materials in percentage by mass: 1-80% of aluminum hydroxide, 1-70% of pseudo-boehmite, 0.5-5% of sesbania powder, 1-10% of titanium dioxide, 1-8% of an acid solvent and 0.5-3% of an auxiliary material; the sum of the mass percentages of the raw materials is 100 percent; the shape of the water-resistant catalyst carrier is a cylinder with through holes with the height-diameter ratio of 0.45-0.9, the outer diameter is 5-45mm, and the number of the through holes is 80-900 meshes. The cross section of the through hole is in one of a regular hexagon shape, a triangular shape, a square shape or a circular shape.

The acidic solvent is one or a combination of several of nitric acid, citric acid and phosphoric acid.

The auxiliary material is methyl cellulose or carboxymethyl cellulose.

The preparation method of the water-resistant catalyst carrier comprises the following steps:

(1) powder mixing: weighing the preparation raw materials according to a formula ratio, and putting aluminum hydroxide, pseudo-boehmite, sesbania powder, titanium dioxide and auxiliary materials into a kneader or a mixer;

(2) fully mixing the powder in the step (1), adding an acidic solvent and a certain proportion of water and oil to knead the pug to obtain uniformly mixed pug;

(3) filtering the pug obtained in the step (2) by a screen, refining the pug in vacuum, testing the temperature of the pug by a thermometer, and putting the pug into a heat preservation room for aging;

(4) carrying out extrusion molding on the pug obtained in the step (3) through a die to obtain a blank body;

(5) and (4) cutting the blank in the step (4) into a cylinder according with the height-diameter ratio, drying, and roasting at high temperature to obtain the water-resistant catalyst carrier.

The proportion of the water added in the step (2) is 20-50% of the weight of the raw material in the step (1), and the proportion of the oil added is 1-5% of the weight of the raw material in the step (1); the oil can be rape oil or waste oil.

The drying condition in the step (5) is drying for 2-3 days at room temperature in shade and then drying for 2-3 days at 40-70 ℃.

The roasting temperature in the step (5) is 650-850 ℃, and the roasting time is 12-20 hours.

The invention has the beneficial effects that: in the preparation process, pseudo-boehmite, aluminum hydroxide and corresponding auxiliary materials are used, a proper amount of acid solvent is added, and after molding and roasting, the prepared catalyst carrier has higher mechanical strength, larger specific surface area and pore volume, and proper acidity, the hydrothermal strength of the catalyst carrier is improved, and the catalyst carrier has longer service life and higher catalytic activity in the catalytic hydrogenation process after being impregnated with the catalyst. The method of the invention adopts a mechanical mixing method to prepare the catalyst carrier, the mud material is aged in the preparation process to ensure that the moisture in the mud material is more uniformly distributed, the plasticity and the forming performance of the mud material are improved, and the formed product has good mechanical strength and good consistency. Meanwhile, more through holes are arranged in the unit section of the product, so that the external specific surface area of the product is greatly increased, and the reaction raw material and the catalyst carrier have larger contact and reaction areas.

Detailed Description

The present invention will be described in further detail below by way of examples, but the present invention is not limited to only the following examples. The raw materials and mechanical equipment used in the following examples of the present invention are not specifically described, and are all conventional products or commercially available products in the industry.

Example 1

The formula of the catalyst carrier is as follows: 55% of pseudo-boehmite, 35% of aluminum hydroxide, 0.5% of sesbania powder, 3% of titanium dioxide, 5% of an acid solvent and 1.5% of an auxiliary material.

The acidic solvent is a mixture of nitric acid and citric acid; the auxiliary material is methyl cellulose.

The preparation steps of the catalyst carrier are as follows:

(1) weighing the raw materials except the acid solvent according to the formula proportion.

(2) And (2) mixing the raw materials in the step (1), putting the raw materials into a kneader, uniformly mixing, adding water (40% of the weight of the added powder), an acid solvent and rape oil (3% of the weight of the powder) to knead the mixture to obtain uniformly kneaded mixture.

(3) And (3) filtering the pug obtained in the step (2) by using a screen, putting the filtered pug into a pug mill, and pressing the pug into a cylindrical pug section after vacuum pugging. Putting into a heat preservation room for constant temperature aging.

(4) And extruding and molding the aged pug into a blank with through holes with regular hexagonal sections by using a 600-mesh honeycomb mold.

(5) Cutting the blank into cylinders with certain length by using a cutting wire, drying in the shade at room temperature for 2-3 days, and drying at 40-70 ℃ for 2-3 days. Roasting at 850 deg.c for 20 hr. The catalyst carrier A was obtained.

Example 2

The formula of the catalyst carrier is as follows: 50% of pseudo-boehmite, 40% of aluminum hydroxide, 5% of titanium dioxide, 2.5% of an acid solvent, 0.5% of sesbania powder and 2.0% of an auxiliary material. The preparation method is the same as example 1, and the catalyst carrier B is obtained.

Example 3

The formula of the catalyst carrier is as follows: 40% of pseudo-boehmite, 45% of aluminum hydroxide, 5% of an acid solvent, 7% of titanium dioxide, 2% of sesbania powder and 1% of an auxiliary material. The preparation method was the same as example 1. catalyst support C was obtained.

Table 1 properties and specifications of samples of various examples of the invention.

Note: the strength in table 1 above is the carrier lateral crush strength, i.e., the strength that can be withstood by applying pressure to the lateral 2-end.

The embodiment shows that the water-resistant catalyst carrier has more and denser through holes in unit area, greatly increases the porosity and the external specific surface area of the carrier, and provides larger contact and reaction area for the catalyst and reaction raw materials. The product of the invention has higher mechanical strength and hydrothermal strength, and ensures the integrity of the carrier and longer service life.

The properties of the catalyst support are as follows: the total pore volume is 0.6-1.1mL/g, the specific surface area is 150-²(iv) a lateral pressure mechanical strength of 60 to 300N/cm, particularly a hydrothermal mechanical strength of 50 to 250N/cm.

The hydrothermal test method comprises the steps of placing a carrier in a self-pressure sealing kettle, adding deionized water for sealing, and carrying out hydrothermal treatment at a constant temperature of 90 ℃. The treatment time was 24 hours. After the hydrothermal treatment, the carrier was recovered by filtration and dried at 120 ℃.

The above-described embodiments are illustrative of the present invention and are not to be construed as limiting the invention, and any modifications and variations of the present invention are within the spirit of the invention and the scope of the appended claims.