JPS5978915A - Manufacture of activated carbon supporting sulfur - Google Patents

Abstract

PURPOSE:To obtain activated carbon supporting sulfur and having superior adsorbing power for mercury vapor, etc. by mixing activated carbon with fine sulfur granules, and heating the mixture at a specified temp. CONSTITUTION:Activated carbon having about 200-2,000m<2>/g specific surface area is mixed with fine sulfur granules having <= about 8 mesh grain size in water of a solvent. The mixture is heated to 110-400 deg.C, preferably 120-350 deg.C to deposit uniformly sulfur in the pores in the activated carbon. The amount of sulfur to be deposited on the activated carbon is usually about 5-500mg/g. By this method activated carbon supporting sulfur and having superior power of adsorbing mercury vapor, cadmium, etc. is obtd. by simpl operation.

Description

[Detailed description of the invention] The present invention relates to a method for producing sulfur-supported activated carbon.

Sulfur-supported activated carbon is known to efficiently adsorb and remove mercury vapor, and its manufacturing method includes (15) dissolving sulfur in carbon disulfide, impregnating the activated carbon, and desorbing carbon disulfide. ,■ Vaporizes sulfur at a temperature of 450°C or higher,
A method of adsorption by contacting with activated carbon is known. ■
In this method, the carbon disulfide used therein has a flash point (-80
It is a flammable solvent with a low ignition point (100"C), low boiling point (46°C), and is highly toxic and difficult to handle.
Carbon disulfide generated during impregnation and desorption operations must be recovered using activated carbon, which is impractical. It is necessary to circulate through the layer and be adsorbed.
The equipment is complicated and the amount of sulfur supported on the activated carbon tends to be uneven.

In view of the above circumstances, the present inventors conducted various studies and succeeded in uniformly supporting sulfur on the inner surface of activated carbon using fine sulfur powder and a simple operation.

That is, the present invention is a method for producing sulfur-supported activated carbon, which is characterized by mixing activated carbon and sulfur fine particles and heating the mixture to 400° C. for 110 minutes.

The activated carbon used in the present invention may be of any type as long as it is made of wood flour, charcoal, coal, coconut shell, resin, etc. as a raw material and activated in an appropriate manner, and its shape may be crushed or pelleted. , powder, fiber, etc., with a specific surface area of 200 to 2000 Jf.

The sulfur fine particles used in the present invention have a particle size of 8 mesh.
The following may be sufficient, but preferably 10 mes
h or less. The amount of sulfur supported on activated carbon is usually 5 to 500 mf per gram of activated carbon.

In the method of the present invention, first, 1t7i of activated carbon and sulfur is
fi, )L by uniformly mixing them.

This mixing may be done by mixing activated carbon and sulfur fine particles as they are;
Kotoe 6. It is preferable to use a mixed solvent of water and alcohol, etc. When using water or a solvent, first suspend the sulfur imitation particles in water or a solvent, and then impregnate the activated carbon with the particles. , a method of impregnating or spraying activated carbon with water or a solvent and coating it with fine sulfur powder. When carrying out the method of the present invention, in addition to sulfur, other chemicals (e.g. acids such as sulfuric acid, nitric acid, phosphoric acid, iodic acid, oxalic acid, citric acid, etc., e.g. A1.V, Fe, Co
.

Ni, (: u, Zn, N1 (4 sulfates, nitrates,
Iodates, such as Nci, bromide or iodide of NlI4, such as Ni12. Na, ni, My
, Ca, Sr thiocyanate, thiosulfate, sulfamate or sulfide, iodine oxides such as 1,05, etc.); in this case, activated carbon supports one or more of the following: It is preferred that the components to be treated be dissolved or suspended in the water or solvent in advance. The amount of these components supported on activated carbon is usually 5-5-5 per gram of activated carbon.
O0, preferably 10 to 400 mg.

As the mixing means, any means used for mixing solids may be used, such as a mixer, sugar coating machine, and stirrer.

The mixture of activated carbon, sulfur particles, and other components as required is then heated to 110" () - 400°C, preferably 12
Heated to 0°C to 350°C. Heating can be carried out, for example, in the presence of nitrogen gas, carbon dioxide gas, water vapor, combustion gas, air, oxygen-containing gas, or a mixed gas thereof. Although any heating means may be used, for example, a method of heating the above gas and bringing it into contact with the 64 compound of activated carbon and sulfur is preferably used. In this case, contact methods include a fixed bed method, a moving bed method, a fluidized bed method, a slurry one method, and a rotary kiln method. The heating time varies depending on the type of atmospheric gas, temperature, etc., but is usually 80 minutes or more, preferably 1 hour to 240 hours.

In addition, the above addition λ! , iJ, below 110"C, sulfur does not reach the inner surface of the activated carbon, making it impossible to obtain sulfur-supported activated carbon charcoal with superior rejuvenation effect1; conversely, when the heating temperature is 400"C If the temperature is higher than this, sulfur vapor will be generated, which is undesirable.The sulfur-supported activated carbon obtained by the method described in 1.-- carries sulfur uniformly on the pore surface of the activated carbon,
! Adsorption of steam, cadmium, etc.: exerts its own power.

Below are 12 actual M12 examples! The present invention will be explained more specifically in Section 21.

Example 1 NET Exposure] 10 nnI/! i'16-2
Regarding activated carbon A of 4 me sb, sulfur-supported activated carbon of 10 Or+y/f was prepared in the following manner.

■Sulfur supported activated carbon ISo-B3 50mcsh or more F fine powder sulfur 10. Of90+nl
? of water, and pour this liquid onto activated carbon at 100f.
It was evenly distributed.

A part of this material was sampled and heated to 90°C in the air.
120"Q, 150'(, L) Heated at each temperature of 200°C for 1 hour.

■Sulfur-supported activated carbon C3, ~C3 50+nes I+ fine powder sulfur 10. (1 g was uniformly suspended in 90 me water, and this liquid was added to 1 g of activated carbon A.
001 was uniformly dispersed.

A portion of this was sampled and
Heating was performed at a nominal temperature of 0.2501-3.400°C for V2 hours.

■ Sulfur-supported activated carbon After uniformly spraying water at 90 m/F per 1 g of activated carbon A, add fine powder sulfur HI O, Oy of less than 5° Ine s b to the wet activated carbon while stirring with JW2. The activated carbon particle surface m1 was coated with sulfur by uniformly spreading.

A portion of this was sampled and heated at 150° C. for 1 hour in heavy oil combustion exhaust gas.

■Sulfur-supported activated carbon En 50me s h or less finely powdered sulfur 10.077 is dissolved in carbon disulfide 120m/'fl'Ji! L/, this liquid was evenly sprinkled on 100 g of activated carbon A3. A part of this was sumpped and heated for 80 minutes in nitrogen gas.
It was heated at a temperature of C.

■) Sulfur-supported activated carbon 11'.

A quartz glass T4 of 2.0 (m, $) was filled with 15f of activated carbon, heated to 140°C, and II,
1.5 g of sulfur was supported on the entire activated carbon by flowing air at a linear flow rate of 15 CmAec (at 25') for 15 hours.

In the activated carbon packed bed, the supported amount of sulfur decreases in the order of waste inlet side, middle;
and 6 flI O+19 AC:. Let this intermediate layer be Fo.

Activated carbon samples A and Bo-B3゜(
-+;~'-3. I-), J(:++ and!?.

6m7 each? was packed in a 1.6 cm1 glass column, and air at 25 °C containing 2.0 my/m of mercury vapor was passed through at a linear flow rate of 2 (X, 'TJ/sec) to conduct a breakthrough adsorption test of mercury vapor. The results are shown in Table 1.

(The following is a blank space) Example 2 For activated carbon G of 10 to 24 mesh having an I3ET surface area of 950 myg, a mixed supported activated carbon with sulfur and other components was prepared.

■s-t<i-supported activated carbon H 100y of activated carbon G (y2. While stirring, 45ml of an aqueous solution of K1-1.0 dissolved in this activated carbon is uniformly sprinkled to impregnate K I. 5 g of sulfur of 20 mesh or less was added and stirring was continued for about 10 minutes to coat the surface of the activated carbon with sulfur. The material thus obtained was heated in air at 180° C. for 2 hours.

■S-K l-FcSO4 supported activated carbon I activated carbon G 10
While stirring 047, I < I −1,
After uniformly spreading 45ml of an aqueous solution containing Ofl and FeSO4-2,01 to impregnate KI and Fe5(')4, 3f of sulfur of 20mesh or less was added and stirring was continued for about 10 minutes to remove sulfur. was coated on the surface of activated carbon. The material thus obtained was heated in air at 150° C. for 2 hours.

■5-KBr-Fe(NO3)a supported activated carbon J activated carbon G
While stirring the 1007, KBr-1, KBr-1,
0g, I”e(N('),)3-2.Of w 10
11101l + 48 containing less than or equal to sulfur -8,0//
ml of an aqueous ethanol solution (ethanol 5me, everything else is water, except for sulfur in suspension) was uniformly spread on a cloth, and then heated at 115°C for 1 hour in a nitrogen gas atmosphere. Note that H, I, and J In all activated carbon samples, sulfur was deposited almost uniformly within the pores of the activated carbon.

Activated carbon sample 11.1 thus obtained. and J
25m7 each? Fill a glass tube of 4 (x g6) with
A breakthrough adsorption test for mercury vapor was conducted by flowing nitrogen gas at 25°C containing 5.01 ng/'7)L of mercury vapor at a linear flow rate of 60 cm and 'sc c.The results are shown in Table 2. It is.

Table 2 Proceedings Amendment (Spontaneous) July 7, 1937 Mr. Commissioner of the Japan Patent Office 1. Indication of the case Patent Application No. 7 of 1939? i 72/No. 2, Title of the invention: Process for producing sulfur-loaded activated carbon 3, Relationship with the case of the person making the amendment Patent applicant address: 2-27 Doshomachi, Higashi-ku, Osaka Name (
293) Takeda Pharmaceutical Co., Ltd. Representative Hayashi Kura
Iku Part 4, t (embedded Tokyo contact information (Patent Laws and Regulations Division) Part II 278-22195,
Column 6 for detailed explanation of the invention in the specification subject to amendment Contents of amendment (1) Mei 1111 +1. F page 6 lines 6-8 [50
The mesh size (■) was uniformly spread on Shigeru powder 11. ] to "Activated carbon A (z) 100gK: line 7, 9
After applying 0tne (IJ) water evenly to the K fit cloth, this A
! 711 activated carbon 1'X) - 50 mesh with stirring
l;1 below L...'! fO゛2) End flU5〒1 (1
, (I spread IQ uniformly on Il' and coated the surface of the active layer with yellow.).

　　　　　d sound

Claims (1)

[Claims] Activated carbon and sulfur fine particles are mixed and heated to 110°C to 400°C.
'(Method for producing sulfur-supported activated carbon characterized by heating to J