CN1351955A

CN1351955A - Integrated equipment and process for hydrogen antiraquinone oxidation and H2O2 extraction in producing H2O2

Info

Publication number: CN1351955A
Application number: CN01134355A
Authority: CN
Inventors: 马忠龙; 颜廷则; 王莅; 王亚权; 米镇涛
Original assignee: Tianjin University
Current assignee: Tianjin University
Priority date: 2001-11-01
Filing date: 2001-11-01
Publication date: 2002-06-05
Anticipated expiration: 2021-11-01
Also published as: CN1136146C

Abstract

The present invention discloses an integrated one-tower hydrogen antithraquinone oxidation and H2O2 extraction equipment and process in producing H2O2. The tower is one filled tower of two sections in different diameters, i.e., greater diameter in the upper section and smaller diameter in the lower section. The tower has tower-stritching mixed material inlet pipe for dispersing phase, and reaction, and disturbing gas and extracted product outlet in the bottom, extracting phase outlet over the packed section inside the tower, and gas outlet after-extraction phase outlet in the top. The technological conditions includes the inlet temperature of the dispersing phase 30-35 deg.C, after-extraction phase outlet temperature 40-50 deg.c and normal pressure operation of the whole tower. Combining oxidation and extraction can save investment in equipment and has the features of high oxidation and extraction efficiency and low power consumption.

Description

Production of H2O2Oxidation of medium hydroanthraquinone with H2O2Extraction integrated apparatus and process

Technical Field

The invention relates to a method for producing H₂O₂Oxidation of medium hydroanthraquinone with H₂O₂Extraction integrated apparatus and process. Is H₂O₂A production technology.

Background

Hydrogen peroxide is a very widely used green strong oxidant. At present, the production method of the product mostly adopts the anthraquinone method at home and abroad. The reaction principle of the method comprises two steps: 1. ；2、 . The industrial production process mainly comprises hydrogenation of anthraquinone, oxidation of hydroanthraquinone and H₂O₂And (3) extraction separation and other independent unit operations. At present, manufacturers still continue to make the production flow, wherein the diameter of an adopted oxidation tower is larger than that of a common tower reactor, the operating pressure is 0.15-0.30 MPa, the diameter of an extraction tower is 2-3 m generally, and the height of the extraction tower is 10-20 m. Therefore, the process flow is long, the equipment investment is large, the operation energy consumption is high, and the production cost is high. To overcome the above disadvantages, JIkka Turunen in US5725837 proposes a method of anthraquinone oxidation and H₂O₂The extraction process is carried out in the same reactor, and the device adopts three sections of same tubular reactors with a plurality of static mixing elements and three corresponding phase separators, so the equipment is complex. The reactor was horizontally placed and operated at 0.4Mpa pressure and 50 c, which still showed high energy consumption.

Disclosure of Invention

The invention aims to provide a method for producing H₂O₂Oxidation of medium hydroanthraquinone with H₂O₂Extraction integrated apparatus and process. The equipment and the process are simple, the oxidation and the extraction are integrated, the efficiency is high, and the energy consumption is low.

In order to achieve the above object, the present invention is realized by the following technical solutions. Production of H by anthraquinone process with one tower equipment₂O₂Oxidation of medium hydroanthraquinone with H₂O₂The extraction integration process is characterized in that: tower equipment

Is a two-section reducing packed tower with large diameter at the upper section and small diameter at the lower section. The operating conditions of the tower process are as follows:the bottom of the tower is provided with a dispersed phase (hydrogenation working solution) and a mixed feeding pipe of reaction and disturbance gas (oxygen or air) which extend into the tower and an extraction product phase (H)₂O₂Aqueous solution), an extract phase (pure water) outlet is arranged on the upper tower wall of a packing section in the tower, a gas outlet and a raffinatephase (organic phase after oxidation and extraction) outlet are arranged on the tower top, the inlet temperature of a disperse phase at the tower bottom is 30-35 ℃, the outlet temperature of the raffinate phase at the tower top is 40-50 ℃, and the whole tower is operated under normal pressure.

The tower filler is a Raschig ring, a step ring, a rectangular saddle ring and a theta ring filler of particle filler; or plate ripple and wire mesh ripple packing adopting regular packing.

The present invention is described in detail below. The tower equipment operation process comprises the following steps: oxygen or air which is used as reaction and disturbance enters a mixing feeding pipe 10 from an inlet 1, is mixed and oxidized with hydrogenation working solution entering from an inlet 2, and is sprayed out from a spray head 9 to enter a packed tower to ascend for continuous reaction; the extraction phase (pure water) enters from an inlet 4 and is sprayed on the filler layer through a distributor 7, flows downwards and fully contacts with the rising gas-liquid to realize the generation of H after the reaction₂O₂Extracting, wherein qualified extraction product phase flows out from a tower bottom outlet 3; the ascending raffinate phase exits through outlet 6 and the ascending gas is vented or sent to the compressor through outlet 5. In the continuous countercurrent operation process, the dispersed phase at the bottom of the tower is controlled to be 0-35 ℃, the water outlet at the bottom of the tower and the raffinate phase outlet at the top of the tower are controlled to be 40-50 ℃, and the whole tower is operated under normal pressure. The longitudinal tower can be divided into three areas from top to bottom, namely an organic phase clarification section, an oxidation extraction section and a water phase clarification section.

The organic phase clarification section is positioned above theextraction phase distributor and is basically positioned in the large-diameter tower section, and the turbidity reduction and clarification of the liquid phase are facilitated because the ascending gas velocity is reduced and the gas disturbance is weakened due to the increase of the tower diameter. The oxidation and extraction section is located in the whole filling section in the tower. The filler has large specific surface area, which is favorable forIntensification of the contact reaction of the gas with the dispersed phase and H₂O₂Has the function of hindering the coalescence of gas and dispersed phases, thus greatly improving the efficiency of reaction and extraction. The water phase clarifying section is positioned from the outlet of the reaction mixture feeding pipe to the bottom of the tower. Because this section is designed to have sufficient height, acceptable H production can be guaranteed₂O₂And (4) preparing an aqueous solution product.

The invention has the advantages of integrating oxidation and extraction into a whole, saving equipment investment, and having the characteristics of high oxidation and extraction efficiency and low energy consumption. The power consumption can be reduced by about 1/2.

Drawings

FIG. 1 is a schematic diagram of the structure and process of an oxidation extraction tower of the present invention.

In fig. 1: 1 is an inlet for reaction and disturbance gas, 2 is an inlet for dispersed phase (hydrogenation working solution), and 3 is an extraction product phase (H)₂O₂Aqueous solution) outlet, 4 is extraction phase (pure water) inlet, 5 is gas outlet, 6Is a raffinate phase outlet, 7 is a distributor, 8 is a packing section, 9 is a nozzle, and 10 is a mixing pipe.

Detailed Description

Example 1 the reactive extraction column had a diameter of 20mm, a diameter of 35mm at the top of the column, a height of 2m at the top of the column, a height of 1m at the packing section, a height of 0.4m at the top of the column, and a height of 0.4m at the bottom of the column. The filler section is filled with passivated stainless steel theta ring filler with the size of phi 2 mm. The flow rate of the aqueous phase was 9ml/min, the flow rate of the organic phase was 5ml/min, and the degree of hydrogenation of the organic phase was 4gH₂O₂The oxygen flow rate was 141.6 ml/min. The tower is operated at normal pressure and constant temperature, and the extraction temperature is 48 ℃. The results of the oxidative extraction are shown in the following table.

TABLE 1 results of the oxidative extraction in a packed column

Oxidation by oxygen Flow rate ml/min	In the raw oil Concentration of hydrogen anthralin Degree g/l	Tower water out Phase H₂O₂Concentration of g/l	Oil phase coming out of tower H₂O₂Concentration g/l	Extraction yield (oxidation extraction) H of (A) to (B)₂O₂Amount/raw material H₂O₂Measuring)
Oxidation by oxygen Flow rate ml/min		Tower water out Phase H₂O₂Concentration of g/l	Oil phase coming out of tower H₂O₂Concentration g/l		141.6	4.00	2.2	9.90×10^-6	99.0％
141.6	4.00	2.1	9.07×10^-6	94.5％	141.6	4.00	2.2	9.90×10^-6	99.0％
141.6	4.00	2.1	9.07×10^-6	94.5％	141.6	4.00	2.2	9.90×10^-6	99.0％

Example 2 comparative example. The column equipment is as above, without packing. The degree of hydrogenation of the working liquid was 4gH₂O₂The flow rate into the column was 2.5ml/min, the flow rate of the aqueous phase was 9ml/min, and the flow rate of the oxygen was 72.7 ml/min. The tower was operated at atmospheric pressure and constant temperature, and the extraction temperature was 42 ℃. The results of the oxidative extraction are shown in the following table.

TABLE 2 empty column oxidative extraction results

Oxidation by oxygen Flow rate ml/min	In the raw oil Concentration of hydroanthraquinone Degree g/l	Tower water out Phase H₂O₂Concentration of g/l	Oil phase coming out of tower H₂O₂Concentration g/l	Extraction yield (oxidation extraction) H of (A) to (B)₂O₂Amount/raw material H₂O₂Measuring)
Oxidation by oxygen Flow rate ml/min		Tower water out Phase H₂O₂Concentration of g/l	Oil phase coming out of tower H₂O₂Concentration g/l		72.7	4.00	0.88	0.82	79.2％
72.7	4.00	0.88	0.83	79.2％	72.7	4.00	0.88	0.82	79.2％
72.7	4.00	0.88	0.83	79.2％	72.7	4.00	0.87	0.83	78.3％

Claims

1. Production of H₂O₂Oxidation of medium hydroanthraquinone with H₂O₂Extraction integrated equipment and process, it uses a tower equipment to implement anthraquinone process to produce H₂O₂Oxidation of medium hydroanthraquinone with H₂O₂The extraction integration process is characterized in that: the tower equipment is a two-section reducing packed tower with large upper section diameter and small lower section diameter, the technological operation conditions of the tower are that the tower bottom is provided with a dispersed phase extending into the tower, a reaction and disturbance gas mixed feeding pipe and an outlet of an extraction product phase, the upper tower wall of the packing section in the tower is provided with an extraction phase outlet, the tower top is provided with a gas outlet and a raffinate phase outlet, the inlet temperature of the dispersed phase at the tower bottom is 30-35 ℃, the temperature of the raffinate phase outlet at the tower top is 40-50 ℃, and the whole tower is operated under normal pressure.

2. Production of H as claimed in claim 1₂O₂Oxidation of medium hydroanthraquinone with H₂O₂Extraction integrated equipment and process, its characterized in that: the tower filler is granular fillerA Raschig ring, a step ring, a rectangular saddle ring and a theta ring filler; or plate ripple and wire mesh ripple packing adopting regular packing.