阅读说明：本技术 过氧化氢的稳定剂组合物和蒽醌法制备双氧水的工艺以及过氧化氢产品 (Stabilizer composition of hydrogen peroxide, process for preparing hydrogen peroxide by anthraquinone method and hydrogen peroxide product ) 是由 贾学五 张帆 钱亚男 刘静如 王振刚 徐伟 于 2020-05-25 设计创作，主要内容包括：本发明涉及过氧化氢制备领域,具体涉及用于过氧化氢的稳定剂组合物和蒽醌法制备双氧水的工艺以及过氧化氢产品。该组合物含有组分A和组分B,所述组分A能够提供氢离子,所述组分B能够提供络合离子,该络合离子能够与铁离子和铜离子发生络合反应。本发明所述稳定剂组合物大幅度降低了双氧水产品中的磷含量,提升双氧水生产工艺的环保水平,同时提升了双氧水生产装置的安全性。(The invention relates to the field of hydrogen peroxide preparation, in particular to a stabilizer composition for hydrogen peroxide, a process for preparing hydrogen peroxide by an anthraquinone method and a hydrogen peroxide product. The composition contains a component A and a component B, wherein the component A can provide hydrogen ions, and the component B can provide complex ions which can perform complex reaction with iron ions and copper ions. The stabilizer composition disclosed by the invention greatly reduces the phosphorus content in hydrogen peroxide products, improves the environmental protection level of a hydrogen peroxide production process, and simultaneously improves the safety of a hydrogen peroxide production device.)

1. A stabilizer composition for hydrogen peroxide, which comprises a component a and a component B, wherein the component a is capable of providing hydrogen ions, and the component B is capable of providing complex ions capable of performing a complex reaction with iron ions and copper ions.

2. The stabilizer composition according to claim 1, wherein in the stabilizer composition, a contains phosphoric acid and sulfuric acid, and the component B contains stannate and tin tetrachloride.

3. The stabilizer composition according to claim 2, wherein the stabilizer composition comprises 1 to 2 parts by weight of phosphoric acid, 0.1 to 1 part by weight of sulfuric acid, 0.1 to 0.6 part by weight of stannate, and 0.1 to 0.6 part by weight of tin tetrachloride.

4. A stabilizer composition according to claim 3, wherein the stabilizer composition comprises 1-2 parts by weight of phosphoric acid, 0.2-0.5 parts by weight of sulfuric acid, 0.2-0.5 parts by weight of stannate, 0.2-0.5 parts by weight of tin tetrachloride.

5. A stabilizer composition according to claim 3, wherein the stabilizer composition comprises 1 to 1.5 parts by weight of phosphoric acid, 0.2 to 0.4 parts by weight of sulfuric acid, 0.2 to 0.4 parts by weight of stannate, 0.2 to 0.4 parts by weight of tin tetrachloride.

6. A stabiliser composition according to any of claims 2 to 5, wherein the stannate is selected from at least one of sodium stannate, potassium stannate and aluminium stannate.

7. A stabilizer composition according to any one of claims 2 to 6, wherein in the stabilizer composition the mass ratio of stannate to tin tetrachloride is from 1 to 4: 1, preferably 1-2: 1.

8. a stabilizer composition according to any one of claims 2 to 7, wherein the mass ratio of phosphoric acid to sulfuric acid in the stabilizer composition is from 1 to 15: 1, preferably 5 to 15: 1.

9. a process for preparing hydrogen peroxide by an anthraquinone method comprises the following steps:

(1) contacting the alkylanthraquinone with hydrogen to react in the presence of a solvent under hydrogenation conditions to generate hydrogenation liquid containing the hydroanthraquinone;

(2) introducing the hydrogenated liquid and the stabilizer composition into an oxidation tower, and in the oxidation tower, contacting the hydrogenated liquid with oxygen to react to obtain an oxidation liquid;

(3) introducing the oxidizing solution and the stabilizer composition into an extraction tower, and extracting with water to obtain aqueous hydrogen peroxide solution;

wherein the stabilizer composition is the stabilizer composition of any one of claims 1 to 8.

10. Process according to claim 9, wherein the sum of the amounts of stabilizer composition used in steps (2) and (3) is 0.1-0.2kg, preferably 0.12-0.18kg, calculated as phosphoric acid, per ton of hydrogen peroxide product, wherein the concentration of the hydrogen peroxide product is 20-70% by weight.

11. The process of claim 9 or 10, wherein the mass ratio of the amount of the stabilizer composition in the oxidation column in the step (2) to the amount of the stabilizer composition in the extraction column in the step (3) is 1-10: 1, preferably 2 to 6: 1.

12. a hydrogen peroxide product comprising the stabilizer composition of any one of claims 1-8;

preferably, each ton of hydrogen peroxide product contains less than 200g of phosphoric acid, preferably 120-180g of phosphoric acid, and the concentration of the hydrogen peroxide product is 20-70 wt%;

preferably, the stability of the hydrogen peroxide product is 90% or more.

Technical Field

The invention relates to the field of hydrogen peroxide preparation, in particular to a stabilizer composition for hydrogen peroxide, a process for preparing hydrogen peroxide by an anthraquinone method and a hydrogen peroxide product.

Background

Hydrogen peroxide is one of the main basic chemical products in the world, and the production process of hydrogen peroxide by an anthraquinone method is the main production method of the hydrogen peroxide. The general anthraquinone process comprises the following steps: in the presence of a catalyst, in a working solution prepared from alkyl anthraquinone and a mixed organic solvent according to a certain proportion, anthraquinone and hydrogen are subjected to hydrogenation reaction to produce corresponding hydroanthraquinone, and at the moment, the working solution becomes hydrogenation solution; the hydrogenated liquid enters an oxidation tower, the hydroanthraquinone reacts with oxygen to produce anthraquinone and hydrogen peroxide, and the hydrogenated liquid becomes oxidation liquid at the moment; the oxidized liquid enters an extraction tower, aqueous hydrogen peroxide solution, namely hydrogen peroxide, is obtained after water extraction, and raffinate becomes working liquid after post-treatment and is circulated back to a hydrogenation unit for continuous hydrogenation reaction.

In the existing production process, the stability of the device is improved by adding phosphoric acid, and the uncontrolled decomposition of hydrogen peroxide is prevented. A part of the phosphoric acid is added before the hydrogenated liquid is fed into the oxidation tower, for neutralizing the potassium carbonate and maintaining the acidity in the oxidation tower, and the other part of the phosphoric acid is added into the pure water fed into the extraction tower. The adding amount of the phosphoric acid of the hydrogen peroxide device is about 1kg/t (27.5 percent hydrogen peroxide).

With the improvement of national environmental protection requirements, the excessive phosphorus content becomes a concern. How to reduce the addition of phosphoric acid becomes an important index of the environment-friendly level of the hydrogen peroxide production process.

However, the technology for preparing hydrogen peroxide by the anthraquinone method is a dangerous technology, and if the content of phosphoric acid is simply reduced, the danger of the device is increased, and even the explosion accident of the device caused by the uncontrolled decomposition of hydrogen peroxide can be caused.

In the existing patents related to hydrogen peroxide stabilizers, the stabilizers are added into the product to increase the stability of hydrogen peroxide. CN109534296A discloses an oxidation residual liquid stabilizer for preparing hydrogen peroxide by an anthraquinone method, wherein the stability of the oxidation residual liquid is improved by adding a stabilizer (0.1-2% of hydroxyethylidene diphosphonic acid, 0.05-1% of organic alcohol amine and 0.05-3% of ethylenediamine-di-o-phenyl sodium acetate). CN106185830A discloses a stabilizer for hydrogen peroxide and a use method thereof, an organic stabilizer for hydrogen peroxide products. However, the organic stabilizer is not suitable for the hydrogen peroxide production process, and because the solubility of the organic stabilizer in the working solution is higher than that of the hydrogen peroxide in the extraction process, the organic stabilizer is extracted into the working solution and loses the stabilizing effect.

Therefore, there is a need for an effective inorganic stabilizer with low phosphorous content.

Disclosure of Invention

The invention aims to solve the problems that a stabilizer has high phosphorus content, an organic stabilizer is not suitable for a hydrogen peroxide production process and the like in the prior art, and provides a stabilizer composition for an anthraquinone hydrogen peroxide preparation process, a anthraquinone hydrogen peroxide preparation process and a hydrogen peroxide product.

In order to achieve the above object, the present invention provides in a first aspect a hydrogen peroxide stabilizer composition comprising a component a and a component B, wherein the component a is capable of providing hydrogen ions and the component B is capable of providing complex ions capable of undergoing a complex reaction with iron ions and copper ions.

The second aspect of the invention provides a process for preparing hydrogen peroxide by an anthraquinone method, which comprises the following steps:

(1) contacting the alkylanthraquinone with hydrogen to react in the presence of a solvent under hydrogenation conditions to generate hydrogenation liquid containing the hydroanthraquinone;

(2) introducing the hydrogenated liquid and the stabilizer composition into an oxidation tower, and in the oxidation tower, contacting the hydrogenated liquid with oxygen to react to obtain an oxidation liquid;

(3) introducing the oxidizing solution and the stabilizer composition into an extraction tower, and extracting with water to obtain aqueous hydrogen peroxide solution;

wherein the stabiliser composition is according to the first aspect of the invention.

In a third aspect, the present invention provides a hydrogen peroxide product comprising a stabiliser composition according to the first aspect of the invention.

Preferably, the hydrogen peroxide product comprises less than 200g of phosphoric acid per ton, preferably 120-180g of phosphoric acid per ton. The concentration of the hydrogen peroxide product is 20-70 wt%.

Preferably, the stability of the hydrogen peroxide product is 90% or more.

The stabilizer composition disclosed by the invention greatly reduces the phosphorus content in hydrogen peroxide products, improves the environmental protection level of a hydrogen peroxide production process, and simultaneously improves the safety of a hydrogen peroxide production device.

Detailed Description

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

The invention provides a stabilizer composition of hydrogen peroxide, comprising a stabilizer composition of hydrogen peroxide, wherein the composition contains a component A and a component B, the component A can provide hydrogen ions, and the component B can provide complex ions.

Preferably, the component a contains phosphoric acid and sulfuric acid, and the component B contains stannate and tin tetrachloride.

More preferably, the composition contains 1 to 2 parts by weight of phosphoric acid, 0.1 to 1 part by weight of sulfuric acid, 0.1 to 0.6 part by weight of stannate, 0.1 to 0.6 part by weight of tin tetrachloride.

Herein, the concentration of the phosphoric acid is 20 to 85 mass%, and the concentration of the sulfuric acid is 20 to 98 mass%.

It has been found that hydrogen peroxide has the highest stability at a pH of 4 to 5, and that either too high or too low a pH is detrimental to stability.

In the invention, the acidity of the working solution is adjusted by sulfuric acid in the stabilizer composition, and stannate and stannic chloride are compounded simultaneously to improve the complexing capability of the stabilizer composition, so that the stabilizing effect is obviously improved.

According to the invention, preferably, the stabilizer composition comprises 1 to 2 parts by weight of phosphoric acid, 0.2 to 0.5 part by weight of sulfuric acid, 0.2 to 0.5 part by weight of stannate, 0.2 to 0.5 part by weight of tin tetrachloride.

More preferably, the stabilizer composition comprises 1 to 1.5 parts by weight of phosphoric acid, 0.2 to 0.4 parts by weight of sulfuric acid, 0.2 to 0.4 parts by weight of stannate, 0.2 to 0.4 parts by weight of tin tetrachloride.

Preferably, the stannate is selected from at least one of sodium stannate, potassium stannate, and aluminum stannate.

In order to further exert the coupling complexation effect of the stabilizer, the mass ratio of the stannate to the stannic chloride in the stabilizer composition is preferably 1-4: 1, preferably 1-2: 1.

in order to further optimize the content of phosphoric acid while providing a suitable acidic environment, it is preferred that the mass ratio of phosphoric acid to sulfuric acid in the stabilizer composition is 1 to 15: 1, preferably 5 to 15: 1.

in the stabilizer composition, sulfuric acid is used for adjusting the acidity of the working solution, and stannate and stannic chloride are compounded simultaneously to improve the complexing capability of the stabilizer composition, particularly complexing iron ions and copper ions, and the stabilizer composition is particularly suitable for the process for preparing hydrogen peroxide by an anthraquinone method.

The stabilizer composition is mainly used for improving the stability of a hydrogen peroxide solution product and/or the safety of a production device by the following two mechanisms: firstly, hydrogen ions provided by the component A are ensured to be in the most stable pH range of hydrogen peroxide; and secondly, the component B can react with iron ions and copper ions in the hydrogen peroxide product, so that free iron ions and copper ions in the hydrogen peroxide solution product are reduced, the metal ions are prevented from catalyzing the decomposition of the hydrogen peroxide, and the stability of the hydrogen peroxide is improved.

In a preferred embodiment, the stabilizer composition comprises 1 to 2 parts by weight of phosphoric acid, 0.2 to 0.5 part by weight of sulfuric acid, 0.2 to 0.5 part by weight of sodium stannate, 0.2 to 0.5 part by weight of tin tetrachloride; in the stabilizer composition, sulfuric acid is used for adjusting the acidity of the working solution, tin element in the stabilizer composition has a stabilizing effect on hydrogen peroxide, and a group formed by tin, sulfate ions and phosphate ions has a strong complexing effect on metal ions (such as iron ions and copper ions) for promoting the decomposition of the hydrogen peroxide, so that impurity ions in the metal ions are removed, and the stability of a hydrogen peroxide product is improved. The effect of the stabilizer prepared by compounding the components in the stabilizer composition is better than that of the stabilizer prepared by singly using the components, and the total dosage is smaller.

The second aspect of the invention provides a process for preparing hydrogen peroxide by an anthraquinone method, which comprises the following steps:

(1) contacting the alkylanthraquinone with hydrogen to react in the presence of a solvent under hydrogenation conditions to generate hydrogenation liquid containing the hydroanthraquinone;

(2) introducing the hydrogenated liquid and the stabilizer composition into an oxidation tower, and in the oxidation tower, contacting the hydrogenated liquid with oxygen to react to obtain an oxidation liquid;

(3) introducing the oxidizing solution and the stabilizer composition into an extraction tower, and extracting with water to obtain aqueous hydrogen peroxide solution;

wherein the stabiliser composition is according to the first aspect of the invention.

In the step (1), the solvent is used for the purpose of dissolving the alkylanthraquinone, and may be a solvent commonly used in the art. Hydrogenation conditions are conditions commonly used in the art, including but not limited to catalysts, temperatures, and pressures commonly used in hydrogenation processes.

Preferably, the sum of the amounts of the stabilizer compositions used in step (2) and step (3) is 0.1 to 0.2kg, preferably 0.12 to 0.18kg, calculated as mass of phosphoric acid, per ton of hydrogen peroxide product, wherein the concentration of the hydrogen peroxide product is 20 to 70% by weight.

In order to further improve the stabilizing effect of the stabilizer composition and simultaneously further reduce the phosphorus content in the hydrogen peroxide product, the mass ratio of the dosage of the stabilizer composition in the oxidation tower in the step (2) to the dosage of the stabilizer composition in the extraction tower in the step (3) is preferably 1-10: 1, preferably 2 to 6: 1.

in the present invention, the conditions in the oxidation column and the extraction column are process conditions commonly used in the art. For example, the pressure of the oxidation tower is 0.2-0.6MPa, and the temperature of the oxidation tower is 45-55 ℃. The extraction tower is operated at normal pressure and the temperature is 40-55 ℃.

In a third aspect, the present invention provides a hydrogen peroxide product comprising a stabiliser composition according to the first aspect of the invention.

Preferably, the hydrogen peroxide product comprises less than 200g of phosphoric acid per ton of hydrogen peroxide product, preferably 120-180g of phosphoric acid, the concentration of the hydrogen peroxide product being 20-70 wt.%.

Preferably, the stability of the hydrogen peroxide product is 90% or more.

Herein, "stability" is measured by the stability test method in GB1616 industrial hydrogen peroxide.

Herein, the phosphorous content in the hydrogen peroxide product is measured by inductively coupled plasma emission spectroscopy.

The present invention will be described in detail below by way of examples.

Example 1

1. Stabilizer composition for formulating hydrogen peroxide

The stabilizer composition B1 contained 1 part by weight of phosphoric acid (40% by mass), 0.2 part by weight of sulfuric acid (20% by mass), 0.1 part by weight of sodium stannate, and 0.1 part by weight of tin tetrachloride.

2. Preparation of hydrogen peroxide product by anthraquinone process

Taking an example of a device which produces 10 million tons of 27.5% hydrogen peroxide per year, assuming that the device operates for 8000 hours per year, the yield of 27.5% hydrogen peroxide per hour is 12.5 tons.

(1) Contacting the alkylanthraquinone with hydrogen to react in the presence of a solvent under hydrogenation conditions to generate hydrogenation liquid containing the hydroanthraquinone;

(2) introducing the hydrogenated liquid and the stabilizer composition into an oxidation tower (the pressure of the oxidation tower is 0.4MPa, the temperature of the oxidation tower is 52 ℃), and in the oxidation tower, contacting the hydrogenated liquid with oxygen to react to obtain an oxidation liquid;

(3) introducing the oxidizing solution and the stabilizer composition into an extraction tower (the extraction tower is operated under normal pressure, the temperature of the extraction tower is 50 ℃), and extracting with water to obtain aqueous hydrogen peroxide.

Wherein, for each ton of hydrogen peroxide product with the mass fraction of 27.5 percent, the total dosage of the stabilizer composition in the step (2) and the step (3) is 0.1kg (calculated by phosphoric acid), and the ratio of the dosage of the stabilizer composition in the oxidation tower in the step (2) to the dosage of the stabilizer composition in the extraction tower in the step (3) is 1: 1.

finally, the stability of the obtained hydrogen peroxide product was 92%, as shown in table 1.

Examples 2 to 12

A stabilizer composition for hydrogen peroxide was prepared according to the method described in example 1 and used for the anthraquinone process for producing hydrogen peroxide products under the different conditions shown in Table 1, and the other conditions were the same as in example 1. The test results of the obtained hydrogen peroxide product are shown in table 1.

Comparative examples 1 to 4

A stabilizer composition for hydrogen peroxide was prepared according to the method described in example 1 and used for the anthraquinone process for producing hydrogen peroxide products under the different conditions shown in Table 1, and the other conditions were the same as in example 1. The test results of the obtained hydrogen peroxide product are shown in table 1.

TABLE 1

The sum of the amounts of the stabilizer compositions in step (2) and step (3) for 27.5 wt% hydrogen peroxide per ton of hydrogen peroxide product is indicated in "﹡" in table 1.

As shown in Table 1, the stabilizer composition of the present invention not only can effectively improve the stability of hydrogen peroxide with a small amount of the stabilizer composition, but also can greatly reduce the consumption of phosphoric acid and the content of phosphorus in a hydrogen peroxide product.

The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.