JPS5820224A - Removal of mercury in gas - Google Patents

Abstract

PURPOSE:To effectively remove mercury in a gas over a long time, by using an adsorbent obtained by treating activated carbon with water soluble amine and carbon disulfide. CONSTITUTION:Water soluble amine such as polyethylene imine is added to activated carbon and, after stirring and filtering, to treated activated carbon, ion exchanged water and carbon disulfide are added to carry out stirring and, after the resulting mixture is heated and aged, washing due to hot water and drying under vacuum are carried out to obtain an adsorbent. Thus obtained adsorbent is packed to form a packing layer and a mercury containing gas from which marcury mist is removed by a glass wool filter is passed through said packing layer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for removing mercury from gas.

Mercury contained in the atmosphere is mercury C due to labor and hygiene reasons.
It is necessary to maintain a tube 1 under the permissible amount of 0.05 Qld kt, and with the recent tightening of all-book regulations, the current situation is that stricter control is gradually becoming required. Against this background, mercury is present in the hydrogen gas obtained by mercury electrolysis in factories that require mercury gas treatment, such as in mercury-method factories and factories that manufacture mercury lamps or mercury thermometers. When hydrogen is used, even in small amounts, in the grafting ring of organic compounds, it becomes a solvent poison, so it is necessary to prepare it in advance. Mercury in incineration gas from a plastic bottle manufacturing plant. The treatment of mercury present in the cast tx of surplus sludge in sewage treatment plants has become a problem.

Conventionally, regarding the mercury ring* in the gas, the mercury is cooled and condensed into fine particles (W), and the deep cooling koji method is known.
The drawback is that it requires huge refrigeration equipment to cool the gas. The mercury-containing gas cleaning method is used to clean the mercury-containing gas with a saline solution containing another C filler or an effective filler, or the water layered with mercury adsorption in the Harukaman yy*Kuratsu-ryu forge building liquid fIIIft! A method of absorbing gaseous mercury into the interior has also been proposed, but there are nine problems with 1%, such as re-contamination by woodcutter, equipment, and economy.

On the other hand, if you decide to use M adsorbent, the holding amount is only ■.

Although it has advantages such as being able to apply a relatively large amount of gas C, it requires an excellent adsorbent with high adsorption capacity. For example, as a lIi adhesive.

Pigeon houses using activated carbon have a short adsorption life (and low adsorption), making them unsuitable for industrial use.

In addition, methods include gas treatment with sulfur dioxide gas, hydrogen sulfide, etc. using an adsorbent that supports more than 10 mineral acids such as hydrochloric acid or sulfuric acid, or an adsorbent that supports inorganic salts such as agglomerated calcium. agent.

A number of methods have been proposed in which organic amine bottles and adsorbents carrying second mercury wood have been proposed, but none have yet been proposed.

The reality is that an adsorbent that satisfies sufficient conditions has not yet been obtained. In particular, although mercury in solutions can be almost completely removed using ion exchange resins and chelate resins, no adsorbent has been established that can remove mercury in gases in a clean and sufficiently effective manner. When trying to adsorb mercury, it was hardly possible to adsorb and remove mercury, and it was only effective for adsorbing mercury in solution.

Previously, the present applicant proposed an adsorbent whose activity was treated with a water-bathable amine and carbon disulfide, in JP-A-55-1598.
No. 55), this adsorbent has high selectivity and adsorption capacity for zero heavy metals, especially mercury.

Moreover, the adsorbent has an excellent service life and is especially used to remove mercury from solutions.

Therefore, as a result of intensive research into a method for removing mercury from gas, the inventors of the present invention discovered that the previously proposed adsorbent, which is obtained by treating the activity with a water-soluble amine and carbon disulfide, is a method for removing mercury from gas. Discovery of scales that remove mercury extremely effectively9
The present invention has been completed.

That is, 1 the present invention is characterized in that when mercury in a gas is removed using an adsorbent, an adsorbent whose activity is treated with a water-soluble amine and carbon disulfide is used as the adsorbent. This is a method for removing mercury.

In order to obtain the adsorbent used in the present invention, JP-A-55-159
It can be obtained from the 855th newsletter. In this case, the activity may be of any value, but in particular
Grain charcoal activated at a relatively low temperature is preferable because it has a high mercury gas adsorption capacity. This is probably YaVKokugangaishiI
This is thought to be due to the lower iron content #1 compared to the e-type and the high adsorption rate of the low-temperature activated leg of the acidic group to the V-thiocarbaturonic acid derivative. Also, the particle size number of l1 adhesive.

It is an important factor governing gas flow rate and pressure loss, and 4
~60 Metsu V Yu, 411C4~B Metsu V work are suitable. In addition, water-soluble amines include a small amount (or 1 molecule) of primary and secondary amino acids in each molecule.

Refers to substances having a solubility in water of at least 511, and a specific example of such a compound is hydrazine.

Ethylene V amine, boopylene V amine, glutinous diamine, Il-phelene V amine, Yasha (theory: p
90:10~10:90) Il, p-kivv
V-amines such as diamines and pipetudine, and devilamines.

Butylamine, aniline, benzylamine and other amines and diethylenetriamine, to! Ethi V ntethumine, tetofeth V ntetamine and its homolog I
9 ethi V imine etc. is raised t'Lle, special Cll1
In addition, the impregnation rate of water-soluble amine and carbon disulfide with respect to the activity *C is 1 to 1 of the active weight.
40 excellent, especially c5 to 2511 are preferable.

To carry out the present invention, for example, an adsorbent with an inner diameter of 25 J111 I
#) Fill Otsugo so that the height of the packed bed is 200-,
Preferably, after removing the mercury mist with a glass wool A/filter, the gas containing mercury may be brought into contact with the gas at 20 to 150C, preferably 20 to 70C. For example, a gas containing /d,
When the gas is passed through the packed bed at a gas velocity of 500 to 40,001/hT, the mercury concentration in the gas can be reduced to 0.05 drop or less.

Invention C can be applied to, for example, hydrogen gas obtained by mercury method alkali salt electrolysis, waste gas generated from mercury-determined γμ power 111 electrolytic stuff, and other air, i1 element, m hydrogen chloride. Removal of mercury in gases - can be applied.

According to the present invention, mercury contained in gas can be efficiently removed, and the adsorbent can be sufficiently absorbed even when used for a long time, so it is practical.

Next E! l! The present invention will be specifically explained by examples.

Reference example 1 Activity 1M (manufactured by Daiichi Carbon Industry Co., Ltd., 4-8 Metsu V, YaF**
, crushed) 5 Q lllFm concentration approximately 50% f) 19
x tyrene imine (Engineering II! Min @ p -1000, E
1 (manufactured by Shokubai Kagaku Kogyo) 250 f was added thereto, and the mixture was stirred at room temperature for 2 hours, and then the activated carbon was filtered off. After that, 250 tons of ion-exchanged water was added, and while stirring, 8.5 tons of carbon disulfide was added.
- was added, stirred as it was at room temperature for 0.5 hour, raised the temperature to 40°C, and aged for 1 hour. moreover.

The temperature was raised to 75°C and aged for 4 hours. After aging, the mixture was cooled to about 5°C and filtered. Add 185f of hot water to this, wash and filter, and repeat this operation for 21 hours! ! l repeated.

Thereafter, it was dried at 80C under reduced pressure for 12 hours to obtain an adsorbent. The resulting adsorbent had an adsorption amount of about 15% by weight of I9ethylimine and carbon disulfide.

Example 1. Comparative Example 1 The adsorbent 300- obtained in Reference Example 1 was filled in a cuff with a cuff diameter of 251 (filled bed 204-), and the cuff was filled with air containing mercury vapor (mercury concentration 9.0/ The mercury concentration after passing was measured by passing through the sample at a gas velocity of 16 j/win for the time shown in Table 1 (the mercury concentration in the gas was measured by cold atomic absorption spectrometry).

The results are shown in Table 1.

For comparison, Table 1 also shows the results of a similar experiment using untreated activated carbon.

Table 1 Example 2 Mercury-containing hydrogen gas (mercury concentration 10.01117W)
Table 2 was prepared in exactly the same manner as in Example 1 except that the
The mercury concentration was measured after the passage of time.

The results are shown in Table 2.

Table 2

Claims (1)

[Claims] (1) When removing mercury from gas using an adsorbent,
**A method for removing mercury in a gas, which is characterized by using an adsorbent made by treating activated carbon with water-soluble aluminum and a disulfide longitudinal cable.