JPS62106898A - Microbiological treatment of waste liquid containing tetraalkylammonium salt or/and amines having methyl group - Google Patents

Abstract

PURPOSE:To effectively perform the purification of waste water by decomposing amines, by adding Nocardia.SB-S-255 to activated sludge in which nitriding bacteria were propagated to perform the symbiotic propagation of both bacteria. CONSTITUTION:In decomposing tetraalkylammonium salt or trimethylamine, Nocardia.SB-S-255 (FERM P-8471) or a variant thereof is added to activated sludge in which nitriding bacteria were propagated to perform symbiotic propagation. In order to propagate nitriding bacteria present in activated sludge, ammonia or ammonium salt is added to the activated sludge. Further, a liquid medium suitable for the growth of Nocardia.SB-S-255 is put in a culture vessel and sterilized while the sterilized medium is inoculated with seed bacteria to perform aerobic culture. By this method, purification can be performed effectively and inexpensively.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to tetraalkylammonium salts and/or methyl groups? This relates to the treatment of waste liquid containing amines.

[Conventional technology]

In recent years, tetramethylammonium hydroxide natoluamine and the like are often used as developing solutions in the manufacture of integrated circuits (ICs). The developer waste containing these tetraalkylammonium salts, trimethylamine, etc. after urination is poisonous and cannot be discharged as it is due to water pollution problems.

Currently, it is being used as a means to purify the waste liquid by removing these substances from the waste liquid containing such tetraalkylammonium salts and trimethylamine.

Treatment using a reverse osmosis membrane (for example, Japanese Unexamined Patent Application Publication No. 1983-1983) or treatment using an ion exchange resin is generally carried out, but these methods have high processing costs. There is a problem.

[Problem that the invention seeks to solve]

As mentioned above, the treatment methods conventionally used to purify wastewater containing tetraalkylammonium salts, trimethylamine, etc. by removing these substances have the problem of high processing costs. There has been a desire for a solution that can be used at low cost, and the present invention solves this problem.

[Means for solving problems]

The present inventors focused on the use of microorganisms as a means of inexpensively treating the above-mentioned waste liquid, and proceeded with research.

However, tetraalkylammonium salts, trimethylamine, etc. are generally microbiologically extremely difficult to decompose compounds, and cannot be easily removed by conventional so-called microbiological treatment methods.

Therefore, as a result of research to find bacteria that decompose tetraalkylammonium salts and trimethylamine in the natural world, the present inventor finally found tetraalkylammonium salts and amines with 100% methyl groups in activated sludge samples on hand. Nocardia sp.3-a ss (Nocardia sp.
8p, S-2! j) was separated. Furthermore, it was proposed that this bacterium should be added to activated sludge in which mononitrifying bacteria had been grown, and the resulting mixture should be used to treat wastewater containing tetraalkylammonium salts and/or amines having methyl groups. Tetraalkylammonium salt or/and methyl group by SP S-236? ■ Amines are decomposed and removed, and ammonia, which is the decomposed insect residue, is also nitrified by nitrifying bacteria, resulting in Nocardia sp. S-, lj! Is it possible to purify the wastewater effectively and inexpensively by denitrifying it with other bacteria? I found it.

The present invention is based on this detailed observation (one aspect of the present invention is to treat and purify a waste liquid containing nitrate-alkylammonium salts and/or amines having methyl groups). This is a method for treating waste liquid containing amines with methyl groups.

The mycological properties of Nocardia sp. S-, 2J used in the present invention are as follows.

(a) Morphology: Shape and size of M vesicles, bilobal bacilli, 0.7! ×Ha! Pleomorphism of μ cells: Micelle → bacillus motility: - Flagella: - Presence of spores: - Durham staining: + Anti-injection: + (1)) Growth status in each medium Broth agar plate medium: At 28th culture point-like, diameter /~/,
! - Golden edge, cloudy color, no luster, medium growth.

Broth agar slant medium: Symptoms, no luster, medium growth.

Meat juice liquid medium: Sediment, growth is small to medium.

Meat juice gelatin medium: Not liquefied in 16 days at 30°C, not liquefied in / days.

Lidomus milk: 30'G - alkaline on day 17 of shaking culture.

Coagulation, alkaline at 28th Potash, peptone 1 h.

Sucrose/nitrate Agar medium: No growth.

Glycerin/asparagine agar medium: No growth (0) Peptone/yeast iron agar slant medium: Symptoms: pale yellow and cloudy - growth is large.

Sweetened bouillon agar slant medium: spread-like, surface wrinkled, ocher cloudy,
Growth is large.

(c) Physiological properties Nitrate reduction: + MR test: + Indore insect retrieval: − Hydrolysis of starch: + Urease: + Catalase: + Attitude towards oxygen: aerobic Growth pH range: s, 5-to,.

Temperature range for growth: /tag 0 'C Sugar utilization and gas generation: Sugar utilization Gas generation D-fructose 10 -D-glucose + -maltose -
− Mannose − − Rhamnose − − Glycerol − − Mannitol 10 − D-Galactose − − Inositol + − Lactose − − Sucrose − − Adonitol − − L-arabinose − − Ribose 10 − Sorbitol
10 − Trehalose − − Cellbiose − − Xylose − − Dextrin − − (d) Resolution of other basic amines and their amines: Tetramethylammonium hydroxide + Tetramethylammonium chloride + Trimethylamine
+ Dimethylamine + Methylamine + According to the above mycological properties,
ergey's Manual of Determi
native Bacteriology)' ) 1st edition (
/9] The identification of the above-mentioned bacteria from [2] shows that the bacteria belong to the genus Nocardia, but they are particularly unique in their ability to assimilate sugars, and the species (3pcies) are identical. was not found, and it was determined to be a new species.

In addition, this Nocardia sp. S-+26ICNoc
ardia 3p, S-2rs) was submitted to the Institute of Microbiological Technology, Agency of Industrial Science and Technology. 2/issue (F
ERMP-♂4t7/) In the present invention, not only Nocardia sp. .

Here, this Nocardia SP S-2O! The ability to decompose and remove tetraalkylammonium salts and amines containing methyl groups will be explained using experimental examples.

Experimental example Tetramethylammonium hydroxide 100
0m9/E sweetened bouillon (glucose 7%).

Meat extract/%-Peptone 1%%NaC1θ,j%)Km
1) Inoculate Nocardia sp. 3-2t (FERMP-♂Tuffl) into a medium adjusted to H7,
The culture cultured with shaking at 30°C for a day was centrifuged and washed, and the dry weight of bacterial cells/θ0θm9/! Tetramethylammonium hydroxide 1 (TMAHL tetramethylammonium chloride (TMAC), tetra n-propylammonium hydroxide 0 (TPAH), te) n-propylammonium chloride l-' as a carbon source so that (TPAC) - Tetrabutylammonium ha-f-dro, t-ki? I”゛(TBAH)
, tetrabutylammonium chloride (TBAC)-
) dimethylamine CTM, \), dimethylamine (DM
A) and tL θ0 and nb having the composition shown in F containing methylamine (MA), respectively, were inoculated.

Carbon source (m9/1.) 1000 Cohn-Stiegley force (rn9/4) 30
0M//! Phosphate buffer (rn6)
-〇Total capacity (ml) 200
After inoculating the bacteria with a pH adjusted to 7.0°C, the shake culture was carried out at 30°C for 2.2 hours, and after 2 hours, the cells were cultured. H(m9/A)'2 of the above compound as a carbon source in the liquid after 72 hours was measured by high performance liquid chromatography (HPLCi). the result? Shown in Table 1.

Table 1 From the results in Table 1 above, Nocardia Fist SP 5-uj
j is a tetraargylammonium salt or/and which decomposes and removes amines having a methyl group, and is added to the activated sludge in which nitrifying bacteria have been propagated, and allowed to coexist and proliferate.

Nitrifying bacteria have been known since ancient times as agriculturally important soil bacteria that are involved in the oxidation of nitrogen compounds in the soil. (Nitrosomonas) - Obtain energy by oxidizing nitrite to nitric acid. Nitrobacter (N1
trobacter).

Activated sludge can be obtained as usual.

In order to propagate nitrifying bacteria in this activated sludge, ammonia or ammonium salts are usually added to the activated sludge (and in this case, it is preferable to aerate the sludge), and the nitrifying bacteria present in the sludge propagate. Other bacteria have been culled/! Added to activated sludge in which nitrifying bacteria have grown for about 1 day to 1 month.
When culturing, it is best to add cultured bacteria or bacterial cells isolated from this culture. This culture can be carried out in the same way as for general bacteria. In other words, a liquid suitable for the growth of inoculated bacteria should be added. Medium [tetraalkylammonium salt or/and amines having a methyl group as a carbon source, etc.
Add a nitrogen source, inorganic salts if necessary, and other nutrient sources) to a culture vessel (for example, a culture bottle).

Place in a culture tank, etc., sterilize and adjust the temperature to the appropriate temperature for bacterial growth, inoculate with a separately prepared inoculum, and perform aerobic culture such as one-shake rapid culture (1) aerated agitation culture to increase the growth of Kokutai. . At this time, the pH and temperature of the medium are maintained at the optimum growth conditions for j. In this way, a mass culture of inoculation
ff? j%ru. Its product thus obtained or bacterial cells isolated from it.

Add to activated sludge that has grown nitrifying bacteria. The amount of addition can be selected appropriately, but good results will usually be obtained with the amount of culture used for inoculation. After adding the inoculation, add a tetraalkylammonium salt as a carbon source and/or amines that H hydrogen a methyl group, a nitrogen source, an inorganic salt, etc. as necessary.
-io date Waste containing tetraalkylammonium salts and/or amines having methyl groups to be treated with activated sludge in which the inoculated bacteria have been co-propagated (e.g. waste from development in IC manufacturing, etc.) ! Means of processing and purification.

The operation consists of microbial treatment of waste liquid under normal pressure, i.e., BOD removal - nitrification, suitable conditions for denitrification. It can be carried out in the same manner as in the direction of removing organic matter and nitrogen while maintaining the complement of In addition.

When treating the above waste liquid, it is preferable to add an appropriate amount of nitrogen source such as phosphate or corn stew liquor to the waste liquid as necessary.

The tetraalkylammonium salts and/or methyl group-containing amines in the waste liquid, which were difficult to remove by conventional treatments, are decomposed and removed and denitrified by other countries. Waste liquid containing amines having groups can be purified effectively and at low cost.

〔Example〕

Next, examples of the present invention will be shown.

Tetramethylammonium hydroxide CTMA
H) 1000m9/Z'171Q Sugar 7"Iyo7 (!Lucose/%, Meat Extract 1%, Peftone/%. NaC1
θ． ! %). Medium 0 adjusted to pH 7.0, Ko! , Nocardia eS-2! Evening (FERM)
P- and 4t7/) were inoculated. Shaking culture was carried out at 30°C for 3 days. This culture was added to a reaction tank containing activated sludge obtained by adding one hyammonium salt to activated sludge obtained by a conventional method and aerated for several months to propagate nitrifying bacteria. Nocardia sp. 8-2sr was acclimated and grown for about a week using Tetramethylammonium hydroxide (TMAH) in the activated sludge of this reaction tank. The raw water supplemented with corn steep liquor is passed through, under the load conditions shown in Table 2, the treated water is withdrawn and the raw water is added for a 1-hour cycle so that the residence time is 3 hours. We were able to obtain treatment results.Although an example using the intermittent aeration method is shown here, treatment using the normal circulating nitrification and denitrification method is also possible.+ TMA in Table 2
H is measured by high performance liquid chromatography (HPLC method), and factory wastewater test method JIS-Koto Co./9
Measure the TOC (total organic carbon) using the ♂/Part 2 page.
Same (according to page 7! Measured 30D.

Same (page 124, page 130 - page 132, page 73)
Nitrogen compounds were measured according to page J, and the sum was taken as the total nitrogen.

Claims (1)

[Claims] Nocardia sp. S in activated sludge with nitrifying bacteria
-255 (Nocardia sp. S-255) or a mutant strain thereof is added and co-propagated, and is characterized by treating and purifying waste liquid containing amines having tetraalkylammonium salts and/or methyl groups. A method for microbiological treatment of a waste liquid containing amines having a tetraalkylammonium salt and/or a methyl group.