CN110624364A - Organic absorbent for removing sulfur dioxide in mixed gas and preparation method - Google Patents

Organic absorbent for removing sulfur dioxide in mixed gas and preparation method Download PDF

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Publication number
CN110624364A
CN110624364A CN201910865470.7A CN201910865470A CN110624364A CN 110624364 A CN110624364 A CN 110624364A CN 201910865470 A CN201910865470 A CN 201910865470A CN 110624364 A CN110624364 A CN 110624364A
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China
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gas
sulfur dioxide
organic absorbent
mixed gas
acid
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Chinese (zh)
Inventor
毛松柏
杨继
汪东
郭本帅
丁雅萍
叶宁
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China Petroleum and Chemical Corp
China Petrochemical Corp
Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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China Petrochemical Corp
Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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Priority to CN201910865470.7A priority Critical patent/CN110624364A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1456—Removing acid components
    • B01D53/1481—Removing sulfur dioxide or sulfur trioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1493—Selection of liquid materials for use as absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/204—Amines
    • B01D2252/2041—Diamines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/205—Other organic compounds not covered by B01D2252/00 - B01D2252/20494
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/302—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/025—Other waste gases from metallurgy plants

Abstract

The invention relates to the field of gas purification, and mainly aims at the characteristics of tail gas emission of steel plants, smelting plants, sulfuric acid plants, power plants and the like to design and develop an organic absorbent for removing sulfur dioxide in mixed gas. The organic absorbent developed by the invention introduces succinic acid and hydroxyl diamine as main components, and simultaneously takes hydrochloric acid and phosphoric acid as pH regulators to form the organic absorbent which can be used for SO2An absorbed and regenerated organic buffer. The ratio of different solution components is determined. The invention also provides a preparation method of the organic absorbent for removing sulfur dioxide in the mixed gas, and the organic absorbent can treat SO in the feed gas under the condition that the gas-liquid ratio is 10002The concentration is 0-15000 mg/m3Purifying the gas SO2The content is less than 15mg/m3Relieving the SO2The concentration of by-products is more than 99%.

Description

Organic absorbent for removing sulfur dioxide in mixed gas and preparation method
Technical Field
The invention belongs to the field of gas purification, and mainly aims at the characteristics of tail gas emission of steel plants, smelting plants, sulfuric acid plants, power plants and the like to design and develop an organic absorbent for removing sulfur dioxide in mixed gas and a preparation method thereof.
Background
Fossil fuels contain a large amount of sulfides, and the burning of fossil fuels discharges SO2 to the atmosphere. Statistically, the amount of SO2 emitted by burning coal is two thirds of the total amount of SO2 emitted worldwide, and therefore, it is a particular concern to the energy industry if a suitable method for controlling SO2 could be found during the burning of coal.
With environmental regulations becoming more stringent and world crude oil quality becoming worse, the demands on industrial desulfurization technology will only become higher and higher. Flue Gas Desulfurization (FGD) is currently the most widely used and most effective sulfur emission control technology in the world, and it is also the most common mode of post-combustion desulfurization. In the process of removing SO2, the renewable adsorbent is used, SO that sulfur can be recovered and can be prepared into sulfur or hydrochloric acid and other chemicals, and the possibility of removing nitrogen oxides while high desulfurization is achieved is provided. Among them, the wet desulfurization technique has advantages of large throughput, low investment and operation costs, continuous operation, etc., and thus the most commonly used method for removing SO2 is the wet desulfurization method in industry. The method generally adopts a liquid desulfurizing agent to carry out physical or chemical absorption on SO2 to form an SO 2-rich solution, and then the SO 2-rich solution regenerates the desulfurizing agent by means of desorption to release SO 2.
Among these methods, the use of an organic amine desulfurization agent for SO2 removal is one of the most successful methods currently used industrially. The technology for removing SO2 by using an organic amine method generally comprises the steps of taking an amine liquid containing organic amine as an SO2 absorbent, then carrying out selective absorption on SO2 by the organic amine liquid, and then reacting amine in the organic amine with SO2 to generate unstable amine imido salt SO as to realize the effect of desulfurization. The flue gas absorbed by the organic amine liquid can be directly discharged after reaching the discharge standard, and the organic amine rich liquid absorbing SO2 is sent to a desorption tower to be heated, vaporized and desorbed for recovery, SO that the organic amine barren liquid is regenerated.
The flue gas desulfurization technology has the advantages of high desulfurization efficiency, good absorption selectivity to SO2, strong adjustability, capability of recycling the absorbent, no secondary pollution and the like. However, this desulfurizing agent also has the following disadvantages. In the organic amine flue gas desulfurization, the performance of the absorbent is an essential factor determining the efficiency of the SO2 absorption operation, and therefore the performance of the absorbent is the core technology of the technology. In the process of chemically absorbing SO2 in flue gas, certain requirements on a desulfurization device and operation are required in order to strengthen the mass transfer process, improve the desulfurization efficiency, reduce the investment and the operation cost of equipment.
Disclosure of Invention
1. The technical problem to be solved is as follows:
the prior technology for removing SO2 by an organic amine method has the following disadvantages: the performance of the absorbent is the fundamental factor determining the efficiency of the SO2 absorption operation, and therefore the performance of the absorbent is the core technology of this technology. Chemical absorption of SO for flue gas2The process of (2) has to meet certain requirements on a desulfurization device and operation in order to strengthen the mass transfer process, improve the desulfurization efficiency and reduce the investment and the operating cost of equipment.
2. The technical scheme is as follows:
the invention provides an organic absorbent for removing sulfur dioxide in mixed gas, aiming at the characteristics of tail gas emission of steel plants, smelting plants, sulfuric acid plants, power plants and the like, and the organic absorbent is a solvent formed by mixing 0-10% of succinate, 0-10% of hydrochloric acid, 0-10% of phosphoric acid, 10-50% of hydroxyl diamine and the balance of water, wherein the percentages are mass percentages.
The hydroxyl diamine is a compound with 2 amino groups and more than 1 hydroxyl group in one molecule.
The compound having 2 amino groups and 1 or more hydroxyl groups is one or a mixture of 2-hydroxypropylenediamine, 1- (2-hydroxyethyl) piperazine, 1- (3-hydroxypropyl) piperazine, 1, 4-bis (2-hydroxyethyl) piperazine, 2-hydroxyethylethylenediamine (. beta. -aminoethylethanolamine), 2-hydroxyethylpropylenediamine (. beta. -aminopropylethanolamine), N ' -bis-2-hydroxyethylethylenediamine, N ' -bis-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine (. beta. -aminoethylpropanolamine), N ' -bis-2-hydroxypropylethylenediamine.
The succinate is one or more of sodium succinate, potassium succinate and succinic acid.
The pH value of the solvent is between 6 and 9.
The solvent is used for absorbing sulfur dioxide in steel mill tail gas, smelting plant tail gas, sulfuric acid plant tail gas, power plant tail gas and Claus tail gas.
Under the condition of gas-liquid ratio of 650-1000, the concentration of SO2 in the absorbent-treated feed gas is 0-15000 mg/m3, the content of purified gas SO2 is 15-200 mg/m3, and the concentration of desorbed SO2 byproduct is more than 99%.
The invention also provides a preparation method of the organic absorbent for removing sulfur dioxide in the mixed gas.
3. Has the advantages that:
the organic absorbent for removing the sulfur dioxide in the mixed gas provided by the invention is an organic amine composite absorbent, is compatible with the excellent performance of a single absorbent, and can provide higher mass transfer driving force, higher absorption rate and regeneration rate and higher absorption capacity in the absorption process. Has the advantages of strong stability, high absorption capacity, low solvent viscosity, simple components, abundant sources and low price.
Detailed Description
The present invention will be described in detail with reference to examples.
The invention provides an organic absorbent for removing sulfur dioxide in mixed gas, which is a solvent formed by mixing 0-10% of succinate, 0-10% of hydrochloric acid, 0-10% of phosphoric acid, 10-50% of hydroxyl diamine and the balance of water, wherein the mass percentage of the solvent is as follows.
Sodium succinate is also called disodium succinate, is white crystalline powder, can be dissolved in water, and two carboxyl groups on succinic acid can play a role of a buffering agent; the sodium succinate has better thermal stability and can keep excellent performance in the repeated thermal regeneration process; meanwhile, sodium succinate is a nonvolatile acid, so that the loss of the solvent is avoided. ,
the organic absorbent organic amine composite absorbent for removing the sulfur dioxide in the mixed gas is compatible with the excellent performance of a single absorbent, and the organic amine composite absorbent can provide higher mass transfer driving force, higher absorption rate and regeneration rate and higher absorption capacity in the absorption process.
The hydroxyl diamine is a compound with 2 amino groups and more than 1 hydroxyl group in one molecule.
The compound having 2 amino groups and 1 or more hydroxyl groups is one or a mixture of 2-hydroxypropylenediamine, 1- (2-hydroxyethyl) piperazine, 1- (3-hydroxypropyl) piperazine, 1, 4-bis (2-hydroxyethyl) piperazine, 2-hydroxyethylethylenediamine (. beta. -aminoethylethanolamine), 2-hydroxyethylpropylenediamine (. beta. -aminopropylethanolamine), N ' -bis-2-hydroxyethylethylenediamine, N ' -bis-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine (. beta. -aminoethylpropanolamine), N ' -bis-2-hydroxypropylethylenediamine.
Hydroxyl in the hydroxyl diamine is hydrophilic group and can form hydrogen bond with water molecules, the solubility of the organic amine liquid in water is improved, the problems of crystallization, precipitation and the like of a salt solution are solved, the absorption rate and the absorption capacity of the amine solution can be further improved by introducing the diamine, and the performance of the composite absorbent is improved.
The invention also provides a preparation method of the organic absorbent for removing sulfur dioxide in the mixed gas, which comprises the following steps: the first step is as follows: preparing raw materials comprising succinate, hydrochloric acid or phosphoric acid or a mixture of the two, hydroxyl diamine and water; the second step is that: using water as a solvent, dissolving hydrochloric acid or phosphoric acid or a mixture of the hydrochloric acid and the phosphoric acid in the water, then adding succinic acid, adding hydroxyl diamine under ice bath, and uniformly stirring; the third step: removing the ice bath, and cooling to room temperature; the fourth step: and then, adjusting the pH value of the solution obtained in the third step to 6-9 by adding hydrochloric acid or phosphoric acid or a mixture of the hydrochloric acid and the phosphoric acid to obtain the organic absorbent for removing the sulfur dioxide in the mixed gas, wherein the mass ratio of succinate to hydrochloric acid is 0-10%, the mass ratio of phosphoric acid is 0-10% and the mass ratio of hydroxy diamine is 10-50% in the obtained organic absorbent for removing the sulfur dioxide in the mixed gas.
The introduction of carboxyl on succinic acid, hydroxyl on hydroxydiamine, phosphoric acid and hydrochloric acid provides a pH buffering range for the organic amine solution, SO that the pH adaptability of the solution can be improved, the solution maintains a relatively stable pH before and after SO2 absorption, and the absorption and regeneration stability of the solution is improved.
Example 1
The method of the embodiment has the following steps:
(1) preparation of organic absorbent: using water as a solvent, firstly dissolving 18 g of concentrated hydrochloric acid in water, then adding 43 g of succinic acid, adding 161 g of 2-hydroxypropanediamine under ice bath, uniformly stirring, removing the ice bath, and cooling to room temperature. Then adding a proper amount of hydrochloric acid to adjust the pH value of the solution to about 8, and finally adding 1.1% by mass of hydrochloric acid, 6.7% by mass of succinic acid and 24.8% by mass of 2-hydroxy propane diamine in the organic amine solution.
(2) The whole absorption-regeneration process flow of this example is: preparing SO in gas preparation tank2 5%，CO2 10%，N285% (volume ratio) of simulated flue gas enters from the bottom of the absorption tower and moves upwards along the tower at the temperature of 40 ℃, the organic amine solution adopted by the invention sprays from the top of the tower, the gas and the liquid are in countercurrent contact on the filler, and the acid gas is absorbed to become purified gas and is discharged from the top of the tower. Absorption of SO2The rich liquid is pumped from the bottom of the absorption tower to the top of the regenerating tower, and after heating and regeneration, the regenerated acid gas is exhausted from the top of the tower. And cooling the regenerated lean solution, and pumping the cooled lean solution from the bottom of the regeneration tower to the top of the absorption tower for continuous recycling.
(3) In this example, the simulated flue gas was treated with the organic amine solution used in the present invention at a gas-to-liquid ratio of 800 to purify SO in the flue gas2The content is less than 45 mg/m3More than 58% of sulfur dioxide in the rich solution can be regenerated, and the SO sucked out can be desorbed2The concentration of by-products is more than 99%. This example shows that the organic amine solution can be used as a desulfurization solvent for sulfur-containing compounds having a high SO concentration2The flue gas is purified and removed.
Example 2
The method of the embodiment has the following steps:
(1) preparation of organic absorbent: using water as a solvent, firstly dissolving 90 g of concentrated phosphoric acid in water, then adding 62 g of succinic acid, adding 162 g of 2-hydroxypropanediamine under ice bath, uniformly stirring, removing the ice bath, and cooling to room temperature. Then adding a proper amount of hydrochloric acid to adjust the pH value of the solution to about 8, and finally, the mass fraction of phosphoric acid, succinic acid and 2-hydroxy propane diamine in the organic amine solution is 6.7%, 5.7% and 14.9%, respectively.
(2) The whole absorption-regeneration process flow of this example is: preparing SO in gas preparation tank2 5%，CO2 10%，N285% (volume ratio) of simulated flue gas enters from the bottom of the absorption tower and moves upwards along the tower at the temperature of 40 ℃, the organic amine solution adopted by the invention sprays from the top of the tower, the gas and the liquid are in countercurrent contact on the filler, and the acid gas is absorbed to become purified gas and is discharged from the top of the tower. Absorption of SO2The rich liquid is pumped from the bottom of the absorption tower to the top of the regenerating tower, and after heating and regeneration, the regenerated acid gas is exhausted from the top of the tower. And cooling the regenerated lean solution, and pumping the cooled lean solution from the bottom of the regeneration tower to the top of the absorption tower for continuous recycling.
(3) In this example, the simulated flue gas was treated with the organic amine solution used in the present invention at a gas-to-liquid ratio of 1000 to purify SO in the flue gas2The content is less than 40 mg/m3More than 57% of sulfur dioxide in the pregnant solution can be regenerated, and the SO absorbed can be desorbed2The concentration of by-products is more than 99%. This example shows that the organic amine solution can be used as a desulfurization solvent for sulfur-containing compounds having a high SO concentration2The flue gas is purified and removed.
Example 3
The method of the embodiment has the following steps:
(1) preparation of organic absorbent: using water as a solvent, firstly dissolving 50 g of hydrochloric acid and phosphoric acid in total mass in water, then adding 63 g of succinic acid, adding 171 g of 2-hydroxypropanediamine under ice bath, uniformly stirring, removing the ice bath, and cooling to room temperature. Then adding a proper amount of hydrochloric acid to adjust the pH value of the solution to about 8, and finally, the total mass fraction of the hydrochloric acid and the phosphoric acid in the organic amine solution is 5.5%, the mass fraction of the succinic acid is 6.9%, and the mass fraction of the 2-hydroxy propane diamine is 18.6%.
(2) The whole absorption-regeneration process flow of this example is: preparing SO in gas preparation tank2 5%，CO2 10%，N285% (volume ratio) of simulated flue gas enters from the bottom of the absorption tower and moves upwards along the tower at the temperature of 40 ℃, the organic amine solution adopted by the invention sprays from the top of the tower, the gas and the liquid are in countercurrent contact on the filler, and the acid gas is absorbed to become purified gas and is discharged from the top of the tower. Absorption of SO2The rich liquid is pumped from the bottom of the absorption tower to the top of the regenerating tower, and after heating and regeneration, the regenerated acid gas is exhausted from the top of the tower. And cooling the regenerated lean solution, and pumping the cooled lean solution from the bottom of the regeneration tower to the top of the absorption tower for continuous recycling.
(3) In this example, the simulated flue gas was treated with the organic amine solution used in the present invention at a gas-to-liquid ratio of 1000 to purify SO in the flue gas2The content is less than 15mg/m3More than 58% of sulfur dioxide in the rich solution can be regenerated, and the SO sucked out can be desorbed2The concentration of by-products is more than 99%. This example shows that the organic amine solution can be used as a desulfurization solvent for sulfur-containing compounds having a high SO concentration2The flue gas is purified and removed.
Example 4
The method of the embodiment has the following steps:
(1) preparation of organic absorbent: using water as a solvent, firstly dissolving 50 g of hydrochloric acid and phosphoric acid in total mass in water, then adding 63 g of succinic acid, adding 169 g of 2-hydroxypropanediamine under ice bath, uniformly stirring, removing the ice bath, and cooling to room temperature. Then adding a proper amount of hydrochloric acid to adjust the pH value of the solution to be about 7.5, and finally, the total mass fraction of the hydrochloric acid and the phosphoric acid in the organic amine solution is 5.5%, the mass fraction of the succinic acid is 6.9%, and the mass fraction of the 2-hydroxy propane diamine is 18.6%.
(2) The whole absorption-regeneration process flow of this example is: preparing SO in gas preparation tank2 5%，CO2 10%，N285% (all)Volume ratio) of the acid gas, at the temperature of 40 ℃, the acid gas enters from the bottom of the absorption tower and moves upwards along the tower, the organic amine solution adopted by the invention is sprayed from the top of the tower, the gas and the liquid are in countercurrent contact on the filler, and the acid gas is absorbed to become purified gas and is discharged from the top of the tower. Absorption of SO2The rich liquid is pumped from the bottom of the absorption tower to the top of the regenerating tower, and after heating and regeneration, the regenerated acid gas is exhausted from the top of the tower. And cooling the regenerated lean solution, and pumping the cooled lean solution from the bottom of the regeneration tower to the top of the absorption tower for continuous recycling.
(3) In this example, the simulated flue gas was treated with the organic amine solution used in the present invention at a gas-to-liquid ratio of 1000 to purify SO in the flue gas2The content is less than 30 mg/m3More than 65% of sulfur dioxide in the pregnant solution can be regenerated, and the SO absorbed can be desorbed2The concentration of by-products is more than 99%. This example shows that the organic amine solution can be used as a desulfurization solvent for sulfur-containing compounds having a high SO concentration2The flue gas is purified and removed.
Example 5
The method of the embodiment has the following steps:
(1) preparation of organic absorbent: using water as a solvent, firstly dissolving 50 g of hydrochloric acid and phosphoric acid in total mass in water, then adding 63 g of succinic acid, adding 169 g of 2-hydroxypropanediamine under ice bath, uniformly stirring, removing the ice bath, and cooling to room temperature. Then adding a proper amount of hydrochloric acid to adjust the pH value of the solution to about 7, and finally, the total mass fraction of the hydrochloric acid and the phosphoric acid in the organic amine solution is 5.5%, the mass fraction of the succinic acid is 6.9%, and the mass fraction of the 2-hydroxy propane diamine is 18.6%.
(2) The whole absorption-regeneration process flow of this example is: preparing SO in gas preparation tank2 5%，CO2 10%，N285% (volume ratio) of simulated flue gas enters from the bottom of the absorption tower and moves upwards along the tower at the temperature of 40 ℃, the organic amine solution adopted by the invention sprays from the top of the tower, the gas and the liquid are in countercurrent contact on the filler, and the acid gas is absorbed to become purified gas and is discharged from the top of the tower. Absorption of SO2The rich liquid is pumped from the bottom of the absorption tower to the top of the regeneration tower, and after heating and regeneration, the regenerated acid gas is regenerated in the towerThe top was evacuated. And cooling the regenerated lean solution, and pumping the cooled lean solution from the bottom of the regeneration tower to the top of the absorption tower for continuous recycling.
(3) In this example, the simulated flue gas was treated with the organic amine solution used in the present invention at a gas-to-liquid ratio of 1000 to purify SO in the flue gas2The content is less than 50 mg/m3More than 72% of sulfur dioxide in the rich solution can be regenerated, and the SO sucked out can be desorbed2The concentration of by-products is more than 99%. This example shows that the organic amine solution can be used as a desulfurization solvent for sulfur-containing compounds having a high SO concentration2The flue gas is purified and removed.
Example 6
The method of the embodiment has the following steps:
(1) preparation of organic absorbent: using water as a solvent, firstly dissolving 50 g of hydrochloric acid and phosphoric acid in total mass in water, then adding 63 g of succinic acid, adding 169 g of 2-hydroxypropanediamine under ice bath, uniformly stirring, removing the ice bath, and cooling to room temperature. Then adding a proper amount of hydrochloric acid to adjust the pH value of the solution to about 6.5, and finally, the total mass fraction of the hydrochloric acid and the phosphoric acid in the organic amine solution is 5.5%, the mass fraction of the succinic acid is 6.9%, and the mass fraction of the 2-hydroxy propane diamine is 18.6%.
(2) The whole absorption-regeneration process flow of this example is: preparing SO in gas preparation tank2 5%，CO2 10%，N285% (volume ratio) of simulated flue gas enters from the bottom of the absorption tower and moves upwards along the tower at the temperature of 40 ℃, the organic amine solution adopted by the invention sprays from the top of the tower, the gas and the liquid are in countercurrent contact on the filler, and the acid gas is absorbed to become purified gas and is discharged from the top of the tower. Absorption of SO2The rich liquid is pumped from the bottom of the absorption tower to the top of the regenerating tower, and after heating and regeneration, the regenerated acid gas is exhausted from the top of the tower. And cooling the regenerated lean solution, and pumping the cooled lean solution from the bottom of the regeneration tower to the top of the absorption tower for continuous recycling.
(3) In this example, the simulated flue gas was treated with the organic amine solution used in the present invention at a gas-to-liquid ratio of 650 to purify SO in the flue gas2The content is less than 50 mg/m3More than 77% of sulfur dioxide in the pregnant solution can be regeneratedAnd desorb the SO drawn2The concentration of by-products is more than 99%. This example shows that the organic amine solution can be used as a desulfurization solvent for sulfur-containing compounds having a high SO concentration2The flue gas is purified and removed.
Example 7
The method of the embodiment has the following steps:
(1) preparation of organic absorbent: using water as a solvent, firstly dissolving 50 g of hydrochloric acid and phosphoric acid in total mass in water, then adding 63 g of succinic acid, adding 169 g of 2-hydroxypropanediamine under ice bath, uniformly stirring, removing the ice bath, and cooling to room temperature. Then adding a proper amount of hydrochloric acid to adjust the pH value of the solution to about 6, and finally, the total mass fraction of the hydrochloric acid and the phosphoric acid in the organic amine solution is 5.5%, the mass fraction of the succinic acid is 6.9%, and the mass fraction of the 2-hydroxy propane diamine is 18.6%.
(2) The whole absorption-regeneration process flow of this example is: preparing SO in gas preparation tank2 5%，CO2 10%，N285% (volume ratio) of simulated flue gas enters from the bottom of the absorption tower and moves upwards along the tower at the temperature of 40 ℃, the organic amine solution adopted by the invention sprays from the top of the tower, the gas and the liquid are in countercurrent contact on the filler, and the acid gas is absorbed to become purified gas and is discharged from the top of the tower. Absorption of SO2The rich liquid is pumped from the bottom of the absorption tower to the top of the regenerating tower, and after heating and regeneration, the regenerated acid gas is exhausted from the top of the tower. And cooling the regenerated lean solution, and pumping the cooled lean solution from the bottom of the regeneration tower to the top of the absorption tower for continuous recycling.
(3) In this example, the simulated flue gas was treated with the organic amine solution used in the present invention at a gas-to-liquid ratio of 1000 to purify SO in the flue gas2The content is more than 200 mg/m3More than 80% of sulfur dioxide in the pregnant solution can be regenerated, and the SO absorbed can be desorbed2The concentration of by-products is more than 99%. This example shows that the organic amine solutions described above do not remove SO well when the pH of the solution is less than 62。
As can be seen from the above 7 examples, the organic absorbent is apt to have a pH of more than 6 and less than 9 and a purified gas SO2 content of less than 50 mg/m at a gas-liquid ratio of 10003Desorption ofThe concentration of SO2 byproduct is greater than 99%, with best results in example 3, and SO in the purified gas2The content is less than 15mg/m3。
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (8)

1. An organic absorbent for removing sulfur dioxide in mixed gas is characterized in that: the solvent is formed by mixing 0-10% of succinate, 0-10% of hydrochloric acid, 0-10% of phosphoric acid, 10-50% of hydroxyl diamine and the balance of water, wherein the mass percentage is as follows.
2. The organic absorbent for removing sulfur dioxide from a mixed gas according to claim 1, wherein: the hydroxyl diamine is a compound with 2 amino groups and more than 1 hydroxyl group in one molecule.
3. The organic absorbent for removing sulfur dioxide from a mixed gas according to claim 2, wherein: the compound having 2 amino groups and 1 or more hydroxyl groups is one or a mixture of 2-hydroxypropylenediamine, 1- (2-hydroxyethyl) piperazine, 1- (3-hydroxypropyl) piperazine, 1, 4-bis (2-hydroxyethyl) piperazine, 2-hydroxyethylethylenediamine (. beta. -aminoethylethanolamine), 2-hydroxyethylpropylenediamine (. beta. -aminopropylethanolamine), N ' -bis-2-hydroxyethylethylenediamine, N ' -bis-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine (. beta. -aminoethylpropanolamine), N ' -bis-2-hydroxypropylethylenediamine.
4. The organic absorbent for removing sulfur dioxide from a mixed gas according to any one of claims 1 to 3, wherein: the succinate is one or more of sodium succinate, potassium succinate and succinic acid.
5. The organic absorbent for removing sulfur dioxide from a mixed gas according to any one of claims 1 to 3, wherein: the pH value of the solvent is between 5 and 9.
6. The organic absorbent for removing sulfur dioxide from a mixed gas according to any one of claims 1 to 3, wherein: the solvent is used for absorbing sulfur dioxide in steel mill tail gas, smelting plant tail gas, sulfuric acid plant tail gas, power plant tail gas and Claus tail gas.
7. The organic absorbent for removing sulfur dioxide from a mixed gas according to any one of claims 1 to 3, wherein: under the condition of gas-liquid ratio of 650-1000, the concentration of SO2 in the absorbent-treated feed gas is 0-15000 mg/m3, the content of purified gas SO2 is less than 15mg/m3, and the concentration of desorbed SO2 byproduct is more than 99%.
8. A method for preparing the organic absorbent for removing sulfur dioxide in the mixed gas as defined in any one of claims 1 to 7, comprising the steps of: the first step is as follows: preparing raw materials comprising succinate, hydrochloric acid or phosphoric acid or a mixture of the two, hydroxyl diamine and water; the second step is that: using water as a solvent, dissolving hydrochloric acid or phosphoric acid or a mixture of the hydrochloric acid and the phosphoric acid in the water, then adding succinic acid, adding hydroxyl diamine under ice bath, and uniformly stirring; the third step: removing the ice bath, and cooling to room temperature; the fourth step: and then, adjusting the pH value of the solution obtained in the third step to 5-9 by adding hydrochloric acid or phosphoric acid or a mixture of the hydrochloric acid and the phosphoric acid to obtain the organic absorbent for removing the sulfur dioxide in the mixed gas, wherein the mass ratio of succinate to hydrochloric acid is 0-10%, the mass ratio of phosphoric acid is 0-10% and the mass ratio of hydroxy diamine is 10-50% in the obtained organic absorbent for removing the sulfur dioxide in the mixed gas.
CN201910865470.7A 2019-09-12 2019-09-12 Organic absorbent for removing sulfur dioxide in mixed gas and preparation method Pending CN110624364A (en)

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