CN108114666B

CN108114666B - Catalyst grading method for anthraquinone hydrogenation

Info

Publication number: CN108114666B
Application number: CN201611065926.4A
Authority: CN
Inventors: 贾立明; 徐会青; 刘全杰; 李爱婷; 王伟
Original assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Current assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Priority date: 2016-11-28
Filing date: 2016-11-28
Publication date: 2021-02-05
Anticipated expiration: 2036-11-28
Also published as: CN108114666A

Abstract

The catalyst grading method for anthraquinone hydrogenation includes two sections of upper and lower anthraquinone hydrogenation towers, the upper tower being filled with catalyst with low relative activity and small relative grain size and the lower tower being filled with catalyst with high relative activity and large relative grain size. Can be applied to the anthraquinone hydrogenation process for producing hydrogen peroxide by the anthraquinone method. The invention provides a simple and easy catalyst grading method according to the process characteristics of the anthraquinone hydrogenation process, effectively solves the problems of lower tower pressure drop and liquid loading, and in the grading, the upper tower can adopt a regenerated catalyst, and the regenerated catalyst which does not meet the independent use standard after regeneration is arranged, thereby ensuring the full exertion of the activity of the catalyst, further improving the performance and the service life of the catalyst by the integral grading design, and reducing the industrial production cost.

Description

Catalyst grading method for anthraquinone hydrogenation

Technical Field

The invention relates to a catalyst grading method for anthraquinone hydrogenation, in particular to an anthraquinone hydrogenation process in the process of producing hydrogen peroxide by an anthraquinone method.

Background

The hydrogen peroxide is an important chemical product and is widely applied in the fields of papermaking, chemical industry, food, environmental protection and the like. Starting from hydrogen peroxide, many valuable chemical products can be prepared, such as inorganic peroxy acids and salts thereof, epoxides, organic peroxides and interesting chemical reaction intermediates. Hydrogen peroxide is used as a weaker oxidant and has much higher selectivity in organic synthesis than other oxidants. Hydrogen peroxide is used as a bleaching agent in the textile and paper industries, as an oxidant in chemical synthesis, as a disinfectant and bactericide in the food and pharmaceutical industries, and for treating toxic wastewater in the environmental aspect, with sulfide, cyanide and phenolic compounds being the most and most effective to treat. Hydrogen peroxide can also be used to treat toxic waste gases, such as SO₂NO and H₂S and the like. And also used for oxidative degradation of organic pollutants in water bodies. The final reaction product of the hydrogen peroxide is water, so that the hydrogen peroxide does not produce secondary pollution and is an excellent green industrial raw material and disinfectant. In recent years, the demand of hydrogen peroxide is increasing with the development of new applications of hydrogen peroxide in environmental protection and other aspects.

The preparation method of the hydrogen peroxide mainly comprises the following steps: electrolytic processes, air cathode processes, anthraquinone processes, direct synthesis of hydrogen and oxygen, methyl benzyl alcohol oxidation, isopropanol oxidation, fuel cell processes, and processes for producing hydrogen peroxide from carbon monoxide in aqueous solutions. The anthraquinone process has advanced technological process, large production scale, high automation degree, low cost, low power consumption, easy treatment of three wastes and other advantages.

The anthraquinone process comprises hydrogenation, oxidation, extraction, post-treatment and other parts, wherein the hydrogenation part is a key part. At present, the hydrogenation part generally adopts a form of two towers, an upper tower and a lower tower which are connected in series, and a gas-liquid separator is arranged below the lower tower. In the industrial application process, more problems are encountered at present that more anthraquinone hydrogenation reaction occurs in an upper tower, hydrogen entering a reactor is consumed in the upper tower, the reaction occurring in a lower tower is less, the pressure drop of the lower tower is smaller, liquid is easily accumulated above a catalyst in the lower tower, and the service performance and the service life of the catalyst are influenced.

Disclosure of Invention

In order to solve the problems that in the prior art, the performance and the service life of the integral catalyst are affected due to small lower tower pressure drop and easy liquid accumulation caused by small lower tower reaction between two sections of towers which are connected in series up and down in the anthraquinone hydrogenation process, the invention provides a grading method of an anthraquinone hydrogenation catalyst, which effectively solves the problems of lower tower pressure drop and liquid accumulation.

The technical purpose of the invention is realized by the following technical scheme:

the catalyst grading method for anthraquinone hydrogenation includes two sections of upper and lower anthraquinone hydrogenation towers, the upper tower being filled with catalyst with low relative activity and small relative grain size and the lower tower being filled with catalyst with high relative activity and large relative grain size.

In the above-mentioned catalyst grading method for anthraquinone hydrogenation, the relative activity and relative particle size refer to the relative nature of the catalyst between the upper and lower columns, and the ranges of the absolute activity and absolute particle size of the catalyst are understood by those skilled in the art, and the catalyst satisfying the relative activity and relative particle size requirements of the upper and lower columns is selected within the range.

In the catalyst grading method for anthraquinone hydrogenation, as a preferable technical scheme, the particle size of the catalyst in the upper tower is 1.8-2.4 mm, the particle size of the catalyst in the lower tower is 2.2-2.8 mm, and the particle size of the catalyst in the lower tower is always larger than that of the catalyst in the upper tower.

In the catalyst grading method for anthraquinone hydrogenation, as a preferable technical scheme, the activity of the catalyst in the upper tower is 70-95% of that of the catalyst in the lower tower. As a further preference, the upper column can be filled with regenerated catalyst and the lower column with fresh catalyst.

In the anthraquinone hydrogenation catalyst grading method, as a preferable technical scheme, the volume ratio of the catalyst filling of the upper tower to the catalyst filling of the lower tower is 1-3: 3-1.

The catalyst grading method for anthraquinone hydrogenation is particularly suitable for the anthraquinone hydrogenation process for producing hydrogen peroxide by the anthraquinone method, the selection and hydrogenation operating conditions of the catalyst are well known to those skilled in the art, and if the reaction pressure is 0.1-0.6 MPa generally, the reaction temperature is 40-70 ℃.

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

according to the process characteristics of the anthraquinone hydrogenation process, the invention provides a simple and feasible catalyst grading method aiming at the problems of small lower tower pressure drop and easy liquid accumulation, thereby affecting the performance and service life of the whole catalyst, and the invention adopts an upper tower to fill the catalyst with low relative activity and small relative particle size, and slows down the reaction amount and reaction rate of the upper tower, thereby leading more hydrogen to enter the lower tower, solving the problem of lower tower pressure drop, leading the pressure drop to be normal, and aiming at the problem of liquid accumulation of the lower tower, adopting the lower tower to fill the catalyst with high relative activity and large relative particle size, and effectively solving the phenomena of lower tower reaction rate and liquid accumulation; in the grading process, the upper tower can adopt a regenerated catalyst, and the regenerated catalyst which does not meet the independent use standard after regeneration is adopted is arranged, so that the full exertion of the activity of the catalyst is ensured, the performance and the service life of the catalyst are further improved by the integral grading design, and the industrial production cost is reduced.

Additional features and advantages of the invention will be set forth in the detailed description which follows.

Detailed Description

The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.

The following examples are given by way of illustration of Pd-containing hydrogenation catalysts

The catalyst takes active alumina as a carrier and Pd as active metal, and is spherical. The catalyst properties generally applied in the field of anthraquinone hydrogenation are as follows: the particle diameter of the regenerated catalyst A alumina ball is 1.8-2.4 mm, and the specific surface area is 150 m²/g～200m²G, pore volume 0.50 cm³/g～0.80cm³The compressive strength is more than or equal to 15N per grain; wherein the Pd content is 0.2 wt% to 0.5 wt%, preferably 0.3wt% to 0.35 wt%. The alumina ball of the new catalyst B has the grain diameter of 2.2-2.8 mm and the specific surface area of 150 m²/g～180m²G, pore volume 0.50 cm³/g～0.80cm³The compressive strength is more than or equal to 12N per grain; wherein the Pd content is 0.2 wt% to 0.5 wt%, preferably 0.3wt% to 0.35 wt%.

Example 1

Preparation of the catalyst

The hydrogenation catalyst with the same composition after industrial application in different operation periods is taken, the particle size is 2.0mm, and the hydrogenation catalyst is regenerated by adopting a conventional noble metal catalyst regeneration method, and the catalyst is numbered as A-1, A-2 and A-3.

Taking an appropriate amount of alumina sphere type carrier with the particle size of 2.2-2.8 mm, and using PdCl₂The solution was saturated and impregnated, then dried at 110 ℃ for 6 hours, and calcined at 500 ℃ for 4 hours in an air atmosphere to obtain a catalyst B containing 0.3wt% Pd.

Through evaluation, the activity of the regenerated catalysts A-1, A-2 and A-3 is respectively 78%, 85% and 92% of that of the new catalyst B, which does not meet the requirement of completely independent use and generally needs metal recovery treatment.

Examples 2 to 4 experiments with catalyst grading loading and anthraquinone hydrogenation

Example 2

Filling a catalyst A-1 and a catalyst B in an upper tower and a lower tower for anthraquinone hydrogenation respectively, wherein the catalyst A-1: catalyst B ═ 1: 2 (volume ratio), the working solution with anthraquinone solubility of 140g/L was used as the raw material, and the evaluation conditions and results are shown in Table 1.

Example 3

Filling a catalyst A-2 and a catalyst B in an upper tower and a lower tower for anthraquinone hydrogenation respectively, wherein the catalyst A-2: catalyst B ═ 1: 1 (volume ratio), the working solution with anthraquinone solubility of 140g/L was used as the raw material, and the evaluation conditions and results are shown in Table 1.

Example 4

Filling a catalyst A-3 and a catalyst B in an upper tower and a lower tower for anthraquinone hydrogenation respectively, wherein the catalyst A-3: catalyst B ═ 2: 1 (volume ratio), the working solution with anthraquinone solubility of 140g/L was used as the raw material, and the evaluation conditions and results are shown in Table 1.

Comparative example 1

Catalyst B was filled in both the upper and lower columns for hydrogenation of anthraquinone, a working solution having an anthraquinone solubility of 140g/L was used as the raw material, and the evaluation conditions and results are shown in Table 1.

Comparative example 2

Catalyst A-3 was filled in both the upper and lower columns for the hydrogenation of anthraquinone, the starting material was a working solution with solubility of anthraquinone of 140g/L, and the evaluation conditions and results are shown in Table 1.

TABLE 1 conditions and results for anthraquinone hydrogenation evaluation

Claims

1. The catalyst grading method for anthraquinone hydrogenation is characterized by comprising the following steps: in the upper tower and the lower tower for anthraquinone hydrogenation, the upper tower is filled with a catalyst with low relative activity and small relative particle size, and the lower tower is filled with a catalyst with high relative activity and large relative particle size;

specifically, the particle size of the catalyst in the upper tower is 1.8-2.4 mm, the particle size of the catalyst in the lower tower is 2.2-2.8 mm, and the particle size of the catalyst in the lower tower is always larger than that of the catalyst in the upper tower; the activity of the catalyst in the upper tower is 70-95% of that of the catalyst in the lower tower.

2. The catalyst grading process according to claim 1, characterized in that: the catalyst in the upper tower is regenerated catalyst.

3. The catalyst grading process according to claim 1, characterized in that: the catalyst filling volume ratio of the upper tower to the lower tower is 1-3: 3-1.

4. The use of the grading method of any one of claims 1 to 3 in the hydrogenation process of anthraquinone to produce hydrogen peroxide by the anthraquinone process.