JPH04197435A - Aldehyde adsorbent - Google Patents

Abstract

PURPOSE:To obtain an adsorbent capable of efficiently removing aldehydes and usable repeatedly by bonding an amino compound having a primary or secondary amino group to an ion exchange resin having an acidic group by an ionic bond. CONSTITUTION:An aldehyde adsorbent is prepared by bonding an amino compound having a primary or secondary amino group to an ion exchange resin having an acidic group an ionic bond. As the ion exchange resin, an ion exchange resin having a sulfonic acid group is pref. Further, an ion exchange resin having porous type resin physical properties is pref. used because the aldehyde adsorbing speed is faster than that of a gel type ion exchange resin. As the amino compound, a compound having two or more amino groups in its molecule is pref. This aldehyde adsorbent is brought into contact with aldehydes to adsorb aldehydes. This aldehyde adsorbent can efficiently adsorb and remove not only aldehydes in a solvent but also gaseous aldehydes.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to an aldehyde adsorbent and a method for removing aldehydes using the same. More specifically, the present invention relates to an aldehyde adsorbent using an ion exchange resin and its use.

<Prior Art> In recent years, various problems related to odor have arisen, and the removal of aldehydes has become an important issue from the viewpoint of odor threshold.

Activated carbon,
Inorganic adsorbents such as activated clay, silica gel, and alumina are known. In addition, basic ion exchange resins having primary or secondary amino groups as functional groups are also known to have aldehyde adsorption ability ("Practical Ion Exchange" by Miyahara, Ohmagari, and Sakai, Kagaku Kogyosha, Published in 1972, pages 152 onwards).

<Problems to be Solved by the Invention> These adsorbents have a low equilibrium adsorption amount for aldehydes at low concentrations, and therefore cannot necessarily provide a satisfactory deodorizing effect. Furthermore, these have the disadvantage that they are difficult to regenerate after aldehyde adsorption and cannot be used repeatedly.

In view of these circumstances, the present inventors conducted intensive research to find an adsorbent that can efficiently remove aldehydes and can be used repeatedly, and as a result, they completed the present invention.

<Means for solving the problem> That is, the present invention provides an ion exchange resin having an acidic group,
Provided is an aldehyde adsorbent formed by ionically bonding an amino compound having a primary or secondary amino group. The present invention also provides a method for removing aldehydes contained in a liquid or gas by using such an aldehyde adsorbent and bringing it into contact with a liquid or gas containing the aldehydes.

The ion exchange resin having an acidic group, which is a constituent component of the aldehyde adsorbent according to the present invention, may be one that forms a salt with an amino compound, and there are no special restrictions on the resin base, shape, resin manufacturing method, etc. do not have.

Generally, commercially available ion exchange resins having acidic groups can be used as they are, and examples include the following.

Ion exchange resins having sulfonic acid groups, such as Duolite@C-20, Duolite@C-26, Amberlite@[R-1208 (manufactured by Rohm and Haas), Diaion@5K-18 (manufactured by Mitsubishi Kasei Co., Ltd.) made)
, Revachit S-100 (manufactured by Bayer), DOWEX@HCR-S, DOWEX HGR-W2 (manufactured by Dow Chemical), etc.; Ion exchange resins having carboxyl groups, such as Duolite I C-464, Duolite @ C-433,
Duolite @ C-436, Duolite @ C-4
76, Du:t Raih @C-476CI, Amber Light @ [RC-75, Amber Light @ IRC-
50 (manufactured by Rohm and Haas), Diaion @
WK-20, Diaion 0W to -10 (manufactured by Mitsubishi Kasei), Revachit @ CNP-80 (manufactured by Bayer), DOWEX 0CCR-2 (manufactured by Dow Chemical), etc. Chelating properties with aminocarboxylic acid groups Ion exchange resins, such as Sumikilate@MC-75, Sumikilate
) @ MC-75S, Sumikylate @ MC-76
, Sumikylate @ MC-30 (manufactured by Sumitomo Chemical), Duolite @ C-466 (manufactured by Rohm and Haas), Revachit @ TP-207 (manufactured by Bayer)
, DOWEX@A-1 (manufactured by Dow Chemical Company), UNICEREC @ 0R-10 (manufactured by Yu-Chika Ki), Evolus @M
X-8 (manufactured by Miyoshi Oil ■), etc. Chelating ion exchange resins having aminomethylphosphonic acid groups, such as Sumikylate @ MC-95 (manufactured by Sumitomo Chemical ■), Duolite @ C-467 (manufactured by Rohm and Haas) , Rehatchi) @0C-10601D (
Bayer), UNICEREC @ IJR-3300 (
(manufactured by Unitika) etc.

Among these, ion exchange resins having sulfonic acid groups are preferred. Further, an ion exchange resin having porous resin physical properties is preferably used because it has a faster aldehyde adsorption rate than a gel type ion exchange resin.

In the present invention, an aldehyde adsorbent is obtained by ionically bonding an amino compound having a primary or secondary amino group to an ion exchange resin having an acidic group as described above. The amino compound used here is preferably a compound having two or more amino groups in the molecule, such as the following.

■ Aliphatic aminated products such as ethylene diamino, trimethylene diamino, tetramethylene diamino, hexamethylene diamino, diethylene triamino, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, hexaethylene hebutamine, hydrazine, and guanidine; ■ Tolui Aromatic aminos such as diamino and phenylene diamino; ■ diaminocyclobutane, diaminocyclopentane,
Cycloaliphatic aminos such as diaminocyclohexane, diaminocyclohebutane, diaminocyclooctane; ■ Aminos containing heteroatoms (oxygen, nitrogen or sulfur) such as diaminofuran, diaminothiophene, diaminobilane, diaminothiobilane, diaminopyridine kind.

Among these, (poly)alkylene polyaminos such as ethylene diamino, diethylene triamino, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, and hexamethylene diamino are particularly preferred because they can increase the adsorption capacity of the resulting resin. used.

The aldehyde adsorbent of the present invention can be produced by contacting an ion exchange resin having an acidic group as described above with an amino compound. The contact treatment time, contact treatment temperature, and contact method here are not particularly limited, and a conventional neutralization treatment method of acid or base using an ion exchange resin can be employed as is. Specific processing conditions can be set through simple preliminary experiments.

Also, there are no particular restrictions on the contact ratio between the ion exchange resin having acidic groups and the amino compound used in the contact treatment, or if the amount of amino compound used relative to the acidic group is small, the aldehyde adsorption capacity will be reduced. On the other hand, if an amino compound is used in excess of the required amount, it becomes necessary to recover the excess amino compound, which is uneconomical, and therefore, generally, the exchange capacity of the ion exchange resin having an acidic group is reduced to 0.
The amino compound is used in an amount of 5 to 1.2 moles, preferably 0.8 to 1.0 moles.

The resin in which an amino compound is ionically bonded to an ion exchange resin having an acidic group by the above method can be used as the aldehyde adsorbent of the present invention as it is or after being filtered and washed with water if necessary. .

When removing aldehydes using the aldehyde adsorbent of the present invention, the aldehyde adsorbent is brought into contact with the aldehydes, and the aldehydes are adsorbed onto the adsorbent. This aldehyde adsorbent can absorb aldehydes in solution.
Even gaseous aldehydes can be efficiently adsorbed and removed. Therefore, it is effective for, for example, wastewater treatment in chemical factories, deodorization in wet oxidation treatment factories for human waste, and removal of irritating components such as cigarette smoke.

The aldehydes to be treated in the present invention are not particularly limited as long as they are aldehyde compounds that can be adsorbed by contact with the aldehyde adsorbent of the present invention. for example,
Formaldehyde, acetaldehyde, butyraldehyde, valeraldehyde, hexaldehyde, enantaldehyde, acrolein, crotonaldehyde, α-methylacrolein, α-ethyl acrolein, α-methylcrotonaldehyde, β-methylcrotonaldehyde, hexenal, propinal, 2-butinal The aldehyde adsorbent of the present invention Applies to nurturing effects.

The method of bringing the aldehyde adsorbent of the present invention into contact with aldehydes is not particularly limited, and examples thereof include a continuous method in which a liquid or gas containing hair aldehydes is passed through a column packed with an aldehyde adsorbent, and a method in which aldehydes are brought into contact with aldehydes is Examples include a method in which an aldehyde adsorbent is added to a container containing a liquid or gas, and the mixture is stirred or left standing. Aldehydes can be effectively removed by any of these methods.

The temperature at which the liquid or gas containing aldehydes is brought into contact with the aldehyde adsorbent is not particularly limited, and is usually carried out at 100°C or less. Further, the contact time is not particularly limited, and can be set by conducting preliminary experiments as appropriate.

After adsorbing aldehydes as described above, the aldehyde adsorbent can be brought into contact with an eluent consisting of a mineral acid such as hydrochloric acid, sulfuric acid, nitric acid, or phosphoric acid to elute the aldehydes. The mineral acid used for elution may have a concentration of about 0.1N or more, but it is generally preferable to use one with a concentration of 0.5 to 4N. If the acid concentration is as low as, for example, less than 0.1 normal, it is not preferable because it becomes necessary to use a large amount of eluent. The amount of eluent used may be at least the exchange capacity of the ion exchange resin having acidic groups, or is generally about 1.2 to 3 times the theoretical amount.

The resin from which the adsorbed aldehyde has been eluted in this manner can be used as an aldehyde adsorbent as it is, or by washing it with water if necessary and bringing it into contact with the above-mentioned amino compound again.

<Example> The present invention will be explained in more detail with reference to Examples below.
The present invention is not limited to these examples. Note that the percentages in the examples are based on weight.

Example 1 Macroporous ion exchange resin Duolite 0C-2 having a sulfonic acid group with an exchange capacity of -1.8 eq/f
6 (manufactured by Rohm and Haas) 147, 103g/i
diethylenetriamino aqueous solution with a concentration of 1.8 j7, 2
After contacting at 5°C for 3 hours, filtration and washing with water yielded an ion exchange resin having a group consisting of diethylenetriamine sulfonate (hereinafter, this resin will be referred to as aldehyde adsorbent A). .

10■/I of acetaldehyde! 25℃ aqueous solution containing 2
50-, the above aldehyde adsorbent A is 1rd! In addition, after stirring for 3 hours and performing a single contact treatment, the acetaldehyde concentration of the treated solution was analyzed and found to be 0.3 .mu./l, and the amount of acetaldehyde adsorbed on the adsorbent was 24 .mu./-.

Examples 2 to 6 The same procedure as in Example 1 was used, except that ion exchange resin 11 having acidic groups and exchange capacity as shown in Table 1 and diethylenetriamino aqueous solution with a concentration of 103 g/f were used in the amounts shown in the table. ion exchange resin (aldehyde adsorbent B) having a group consisting of a salt of diethylenetriamino
-F) was obtained.

When an aldehyde adsorption test was conducted in the same manner as in Example 1 using each aldehyde adsorbent, the results shown in Table 1 were obtained.

Examples 7 to 10 The same treatment as in Example 1 was performed except that the type and concentration of the amino compound were changed. That is, an aqueous solution containing the amino compounds shown in Table 2 at the concentrations listed in the table was brought into contact with the same ion exchange resin used in Example 1, and ions containing the sulfonate group of each amino compound were extracted. An exchange resin (aldehyde adsorbent G-J) was obtained.

When an aldehyde adsorption test was conducted using each aldehyde adsorbent in the same manner as in Example 1, the results shown in Table 2 were obtained.

Table 2 Example 11 The aldehyde adsorbent A20- obtained in the first half of Example 1 was packed into a column with an inner diameter of 12 mm, and 3VIOh-
The liquid was passed at a speed of '. When the acetaldehyde concentration of the effluent was analyzed, the results shown in Table 3 were obtained.

Table 3 Examples 12 to 16 An aldehyde adsorption test was conducted in the same manner as in Example 1 except that the type of aldehyde was changed. The results are shown in Table 4.

Table 4 Example 17 1 g of aldehyde adsorbent A obtained in the first half of Example 1 was added to air 11 containing both 10 ppm acetaldehyde and 10 ppm formaldehyde, and after standing at 25°C for 24 hours, air Analysis of aldehyde in the phase revealed that both acetaldehyde and formaldehyde were below 0.01 ppm. Note that ppm in this example is based on capacity.

<Effects of the Invention> The aldehyde adsorbent of the present invention has a larger adsorption capacity and adsorption speed for aldehydes than conventional adsorbents, so it can remove aldehydes to a low concentration and has a low aldehyde concentration. can also be treated effectively. Moreover, this aldehyde adsorbent can be recycled and reused. Therefore, the industrial value of the present invention is extremely large.

Claims (4)

[Claims] (1) Add primary or secondary ion exchange resin to the ion exchange resin having acidic groups.
An aldehyde adsorbent made by ionic bonding of an amino compound having a class amino group. (2) Claim 1 wherein the amino compound is a (poly)alkylene polyamino compound having a primary or secondary amino group.
The aldehyde adsorbent described. (3) The aldehyde adsorbent according to claim 1 or 2, wherein the acidic group of the ion exchange resin is a sulfonic acid group. (4) A resin in which an amino compound having a primary or secondary amino group is ionically bonded to an ion exchange resin having an acidic group is used, and a liquid or gas containing an aldehyde is brought into contact with the resin. How to remove aldehydes.