JPS6017373B2 - Method for producing quinone-type crosslinked redox resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention mainly aims at reducing the amount of 2S, R contained as harmful components in waste gas discharged from recovery boilers in paper mills.
This relates to a method for producing a quinone-type crosslinked redox resin suitable for separating and removing SH, SQ, S03, and CO2 gases, etc. by a wet or dry method. By repeating the process (see Examples), it can be easily and permanently restored and reused.

Currently used waste gas treatment agents include alkaline solutions of 1,4 naphthoquinone and thioarsenic acid, which desulfurize the S ratio in waste gas, but these substances are water-portable, so However, since the separation process from sulfur is complicated and it contains harmful components, there are problems such as the use of by-products is limited and it is easily affected by coexisting gases.

The present inventors have obtained a redox polymer (hereinafter referred to as a hydroquinone-type redox polymer) obtained by Tokuka Sho 47-177628 (Japanese Patent Publication No. 50-29954) according to the invention of the present inventors. As a result of applying the quinone type crosslinked redox resin obtained by oxidation to waste gas treatment, it was found that it is suitable for removing harmful components in gas, and the present invention was completed. That is, the gist of the present invention is that the general formula (R,, R2 may be different or the same, H or carbon number 1-3
represents an alkyl group.

1 [A] 1 is a group represented by the general formula -R3N- (R3 represents an alkyl group having 1 to 3 carbon atoms or a pendyl group) or a group represented by the general formula -R4N-R5 -N&1 (R4 and R6 are mutually They may be different or the same and represent an alkyl group having 1 to 3 carbon atoms.R5 represents an alkylene group having 1 to 10 carbon atoms, or a piperazyl group. n
indicates a positive integer. This is a method for producing a quinone-type crosslinked redox resin, which is characterized in that the hydroquinone-type redox polymer shown in ) is crosslinked with a crosslinking agent, and then oxidized in the presence of an alkali. The present invention will be explained in detail below.

Prior to this explanation, the above-mentioned invention of Tokuiso Sho No. 47-77628 (Tokoku Sho 50-129954) will be explained. , H or an alkyl group having 1 to 3 carbon atoms.

) and the general formula Mosquito 3NH2
(R3 represents an alkyl group having 1 to 3 carbon atoms or a pendyl group), or the general formula HR4-R5-NR6 (R4 and R6 are the same even if they are different from each other). or piperazine, or salts thereof, and formalin or paraformaldehyde in the presence of an acid catalyst or in the absence of a catalyst
The following general formula (R,, R2 may be different or the same, H or carbon number 1-3)
represents an alkyl group.

-[A]1 is a group represented by the general formula -R3N- (R3 represents an alkyl group having 1 to 3 carbon atoms or a pendyl group), or a group represented by the general formula -R4N-R5-NR6- (R4, R6
may be different or the same, and represents an alkyl group having 1 to 3 carbon atoms. R5 represents an alkylene group having 1 to 10 carbon atoms. ) or piperazyl group. n indicates a positive integer. ) is a method for producing a hydroquinone-type redox polymer. Therefore, the present invention
The thus obtained hydroquinone type redox polymer is crosslinked with a crosslinking agent and then oxidized in the presence of an alkali to obtain the desired quinone type crosslinked redox resin. Specifically, if the hydroquinone type redox polymer is crosslinked with a dihalide such as Q,Q' monodichloroparaxylene or 1,4-dibromobutene, and then oxidized by blowing air into an alkaline solution, the quinone type crosslinked redox polymer can be easily obtained. Resin is obtained. As described above, the method of the present invention is advantageous in that the loss during oxidation is small and the yield is high compared to the method of oxidizing a hydroquinone type redox polymer to form a quinone type redox polymer and then co-synthesizing this. be.

Next, the removal of harmful components from waste gas by the quinone-type crosslinked redox resin obtained in the present invention, that is, the removal by desulfurization and adsorption/desorption effects will be explained.

This resin can be very easily converted into a quinone type crosslinked resin by crosslinking the hydroquinone type with a crosslinking agent and then performing air oxidation in the presence of an alkali. It is very easy to recycle and use. Usually, a salt of a hydroquinone type redox polymer is dissolved in water, and sodium carbonate or caustic soda is added thereto to prepare a hydroquinone type redox polymer. At this time, unless the matrix is 11.8 or higher, the hydroquinone type redox polymer will precipitate, so the PHIl. A reddish-brown homogeneous solution of hydroquinone type redox polymer is prepared as an alkaline solution on milk. When air is blown into the solution containing the hydroquinone type redox polymer for about 30 minutes, or peroxide is added and stirred for about 2 hours, the solution becomes a quinone type cross-dox resin and the solution becomes blackish brown. However, in the case of hydrogen peroxide, the oxidation efficiency is not good even if a 30% solution of cough hydrogen peroxide is added to 1 g of polymer. This means that when hydrogen sulfide is passed through this solution, the quinone-type crosslinked redox resin is reduced to a hydroquinone-type redox polymer, which precipitates as the pH of the solution decreases. When this precipitate is filtered and the solution is diluted with dilute sulfuric acid, pale yellow powdered sulfur is precipitated and can be easily separated. On the other hand, the previously separated hydroquinone redox polymer is dissolved again as an alkaline solution, oxidized in the air to become a quinone crosslinked redox resin, and hydrogen sulfide gas is passed through it. It is confirmed that it can be used. Quinone-type crosslinked redox resins do not dissolve even in alkaline aqueous solutions, resulting in a heterogeneous reaction.

Therefore, in the case of a crosslinked resin, it can also be packed in a column and carried out by a dry method. Compared to conventionally known redox polymers such as, for example, the quinone-type crosslinked redox resin of the present invention has alkylene amines between the quinone nuclei, so the spacing between the quinone nuclei is long and the molecule is flexible It has the advantage that it is difficult to cut even if it is recycled and used repeatedly because it is abundant.

Further, acidic substances such as C02 and S02 can be removed by being adsorbed onto the amine portion of the redox polymer. The present invention having the configuration as described above has the following features:
It can treat waste gases such as 02, S03, and C02, and in particular it can efficiently treat 2S, so it is useful for solving pollution problems. Since it is easy to use, it is also economically superior.

In addition, these polymers can also be easily obtained using the Mannich reaction.

Moreover, since the hydroquinone type redox polymer after the reaction is automatically precipitated, it is easy to separate it from sulfur. The extracted sulfur has no natural meaning, so it has high utility value.
In addition, it has the ability to adsorb acidic coexisting gases and is not affected by the coexisting gases, so it can be easily reused and has great practical benefits. Next, the present invention will be specifically explained with reference to Examples.

Example 1 Hydroquinone 0.075 mol (8.25 g
) was collected in an autoclave with an internal volume of 200, and DMF3 females were added thereto.

Next, separately from this, 0.075 mol (1
3. A solution was prepared by dissolving 10 mol of 37% formalin aqueous solution (12 ml) of water and adding it to the above DMF solution while cooling slowly. Next, this was cooled and solidified with liquid nitrogen, degassed once, and reacted for 2 hours in an oil bath at 80°C. The reaction mixture was precipitated in a large amount of acetone, dried, and then purified by reprecipitation twice in a methanol-acetone system. Yield 15. A white powder of approximately (yield 70.2%) was obtained. The elemental analysis values for this are: C=49.17%, H=6.24%, N=9.55
%, CI=24.47%.

In addition, the infrared absorption spectrum includes absorption due to the 0-H stretching vibration of the hydroquinone nucleus at 3500 rené-1, absorption due to tertiary amines around 280 rené-1, and stretching of the double bond of the benzene nucleus at 162 rené-1. Absorption by vibration, 1450
Absorption of methylene C-diurnal angular vibration was observed in -1 of 1, and the calculated elemental analysis values of the material C = 49.14%, H = 6.18
%, N=9.55%, CI=24.04%, showing very good agreement.

Next, the white powder 2.0% obtained here was dissolved in 200ml of distilled water. Separately, sodium hydroxide 0. A solution of Sohei in 100 volumes of distilled water was prepared, and this was slowly added to the aforementioned polymer aqueous solution while stirring. The precipitate was filtered through a sieve, washed twice with water, dried in vacuum, and then purified by reprecipitation twice in a DMF-ethyl ether system. Yield 1.0 spots (yield 7
2.8%), a light brown powder was obtained. The elemental analysis values of this substance are C=62.81%, H=? ．． 35%, N=11.94
%, CI = 0%, elemental analysis calculation value of the foundation structure C; 6543%, H = 7.32%, N = 1
2.74%, CI=0%, which showed very good agreement.

Claims (1)

[Claims] 1 General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (R_1, R_2 may be different or the same, H or carbon number 1 to 3
represents an alkyl group. -[A]- is the general formula -R_3N- (R_3 has 1 to 1 carbon atoms
3 represents an alkyl group or a benzyl group. ) or a group represented by the general formula -R_4N-R_5-NR_6-(R
_4 and R_6 may be different or the same and represent an alkyl group having 1 to 3 carbon atoms. R_5 has 1 to 10 carbon atoms
represents an alkylene group. ) or a piperadiyl group. n indicates a positive integer. 1. A method for producing a quinone-type crosslinked redox resin, which comprises crosslinking the hydroquinone-type redox polymer shown in ) with a crosslinking agent, and then oxidizing it in the presence of an alkali.