JPS58187775A - Manufacture of argon - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention is a method for separating and manufacturing T
Regarding how to

In general, argon production involves extracting oxygen with a large amount of argon mold from the upper rectification column of an air cryogenic separation device, transferring it to a crude argon column, converting it into a crude argon column, and converting it into crude argon. This is done by deoxidizing the oxygen inside and then using a high purity argon column to obtain tlnl,m pure argon. However, in this method, air-cooled fraction 1
If the nitrogen concentration in the raw material gas extracted from the upper phase distillation column of the argon reactor reaches 3 or more, the rectification in the crude argon column becomes 4, so it is necessary to always keep the nitrogen concentration within the specified S table. This severely restricts the operating conditions of the upper S rectification column.
The membership fee is il &degree's iron storm technique.

Furthermore, membership fees are required for many facilities, which is disadvantageous in terms of equipment cost, and furthermore, heating and cooling are repeated, which is uneconomical in terms of energy.

In addition, an argon separation force method based on a low-temperature ablation method, which does not rely on the n-trade method, as described by OS Kechika, has been widely used. (Refer to Publication No. 55-16088) This method uses a mixed gas of argon and oxygen with a vM cumulative concentration k of α1% or less.
Oxygen is removed by passing through a mu-type zeolite at a low temperature of 86 to -135'C and a pressure of L5 to 30'JQ,
After separating the argon, the pressure is reduced to atmospheric pressure (
Furthermore, by reducing the pressure at O, at ~ IgLigt, the i! B for 12 ropes? ,7fif,
This is a product that produces zeolite of the zeolite type. However, in this low-temperature adsorption method, during the absorption process, the temperature rises from 5 to 10°/3 to
The disadvantages of using f1ia roots are that temperature control is troublesome, and that desorption of oxygen is performed under vacuum fILIjt, which requires a vacuum device, which increases equipment and power costs. There is a fee to remove O, 1% or less, and there are disadvantages such as am of raw material gas is required.

The purpose of this invention was to provide a method for producing argon using a low-temperature adsorption method that requires less manufacturing and equipment, is easy to operate, and has a high recovery rate of argon. Hereinafter, the present invention will be explained in detail with reference to the drawings.

FIG. 1 shows an example of a production line used in the argon shaking method of the present invention.

The upper part of the distillation tower 1 in the cooling section 2
The gas extracted from the interlayer film, for example, 5 to 1 stroke of argon, 1 to 1 concentration of W, the remainder of oxygen, and an expansion temperature of -180°C is introduced from the pipe 3 into the heat exchanger 4. It is humidified by return gas, which will be described later, and introduced from the lightning 5 to the pressure gas 6.

Here, the raw material gas is in the state of 3 to 5 degrees Celsius and O to -100 degrees Celsius, and is made up of square 7A, which consists of Il intake cylinder M-1 and second intake cylinder M-2. Mu series adsorber kO 1st suction cylinder &-
sent to 1. First adsorption cylinder Mu 1 and second absorption cylinder A
-2 is filled with mu-type zeolite as an adsorbent, and is maintained at a temperature of -1 degrees Celsius and 0 to -1 degrees Celsius relative to the raw material gas temperature. The raw material gas introduced into the first adsorption cylinder M1 is where the vjI wood is removed by suction, and then it passes through the pipe 8m and enters the second suction cylinder A-2, where it is further mixed with the #M element. Ti & layer removed, valve 9^, pipe 10, ajl adjustment piece 1
1 and the product argon is pumped out from the government school.

Immediately before the absorbent in the 12th adsorption tank 2 is saturated with oxygen, the raw material gas is supplied from the 1st &*t&JA-1 to the B series adsorber B, which is associated with the A series adsorbent and fMJ stock. Switch to the first & bulky cylinder B-1. At this time, 1st Wj1. Shield part &-1
The capacity of each suction movement A-4 and A-2 is set in accordance with the composition of the feed gas so that the capacity of each suction movement A-4 and A-2 is on the verge of being saturated with suction. However, due to the good composition of the raw material gas, even if a small amount of feeder flows into the second fuel tube A-2, it will not become a good friend.

Next, I smoked 11 A-itoyu! It enters the depressurized single pole in the second vessel, and enters the above-mentioned layer in the D-series adsorber B.

That is, the valve 9A is closed, the square 13A is turned off by 1J, and the inside of the second absorption layer @ A-2 is brought to normal pressure, so that the oxygen adsorbed in the eyelid is made into a film layer. q) Argon is sent to the exchanger 4 via the argon gas 14 that was pumped into the adsorption tank Mu 2, where it is cooled and sent to the intermediate station of the upper shaft W tower 2. be returned. In addition, the valve 16m is closed and the valve 15m is opened to make the inside of the laminate holder 1 at normal pressure, and the electric charge that was being held on the adsorbent is desorbed. This desorbed nitrogen and the first nitrogen layer in the cylinder A-1*
The oxygen and argon contained in the tube 17 are discharged to the outside.

Then, the cleaning process continues. That is, a pipe 18, a pressure reducing valve 19, a pipe 20, and a valve 21 are installed in the second absorbent tank 2, and the product argon is introduced at normal pressure, and the residual stratified on the adsorbent is removed. expel oxygen. The waste gas after washing is sent from the second @tube mounting room 2 to the heat exchanger 64 via the valve 13A and L#t14, where it is cooled and returned to the upper top pipe #12.

In addition, low-temperature oxygen generated in the air cryogenic separation iron a1 is introduced into the first tank 1 at almost normal pressure through valves 22 and 23, and becomes an adsorbent. & Get rid of the remaining nitrogen layer. Washing his waste gas is the first step from step 1 to valve 15,
It is discharged to the outside through a pipe 17. In this way, the thickness of the yarn layer is improved and used in the next V&layer process. ^ While the suction 7III unit is in the depressurization and cleaning process, the B system suction *
ItlB is located in the above-mentioned suction equipment and manufactures the product argon. And, the B series suction! Product argon can be produced continuously by switching IB alternately.

Next, the raw salt used in the method for producing argon according to the present invention will be explained with reference to Figure 2. The graph in Figure 2 shows the absorption percentage of argon, nitrogen, and oxygen in the temperature range of 00 to -200°C for M type zeolite using data when the pressure cuff is 00 Hg. It shows the number of adsorbed molecules in one cavity of the zeolite type, and the horizontal is the temperature. As is clear from this graph, in the range 4 of 1-temperature storms from 0 to -100℃,
The 9 & layer i of argon is much lower than that of nitrogen. %K and around -50°C, the difference in I & shield amount is maximum. Therefore, O~-100℃,
Preferably -50°CliI followed by argon.

# Filled with mu type zeolite mixed gas of nitrogen and oxygen
By sequentially flowing nitrogen into the first suction cylinder M-1 and the second suction cylinder M-2, nitrogen flows into the first suction cylinder M-1 and then into the second +&
The mixture is adsorbed to A-2, and almost no argon is adsorbed and returned to the mountain from the ttsz suction cylinder M-2. Argon can be separated from gas.

According to this method of producing argon, t&
The layer temperature table does not have to be measured very strictly, making it easier to operate the clamping operation. In addition, since oxygen and nitrogen are not desorbed by vacuum reduction, a vacuum device such as a vacuum pump is not required, and equipment costs and power costs are low. Furthermore, suction 5v
We selected a temperature range of O to -100°C, where the mu-type zeolite absorbs both W1 element and mature wood at the same time.
It is not necessary to remove nitrogen in advance as in the conventional low-temperature suction method, and gas with a large nitrogen content can be used as the raw material gas. Since there are no restrictions on the nitrogen-containing side, the degree of confinement in the operation of the air cryogenic separator O for the production of argon by the conventional a method is reduced to the acid phase. Also,
Separate the A yarn adsorption device A into the first stratification layer 1 and the second absorption layer 2, and add nitrogen to the first (& dipping layer 1) and oxygen to the second absorption tube (-2). Make sure to remove it and add it to the stratified paper A.
Since the cleaning fIkK of -i was designed to use low-temperature oxygen from air slow cooling distribution box 1, there is no need to use expensive argon, the loss of argon is reduced, and the special cooling of the oxygen causes stratification. This compensates for the cooling loss in the chamber, making it easier to maintain the low temperatures necessary for adsorption. Furthermore, when cleaning and regenerating the second vacuum cleaner Mu2, argon and 1! Since the waste gas from the & element is returned to the upper jnlIIIl column 2 after 1 m of air cooling, the loss of argon and iI2 elements can be prevented. In addition, the oxygen returned to the upper ellipse ws2 is
Since there is no fuel returning from the upper rectification column 2 to the adsorption device, there is no need to increase the capacity of the pressure male 6 and th2 adsorption device 2.

In addition, in the above implementation, an explanation has been given of an operation in which two lines, ie, a MU-series animal-mounted system and a B-series adsorption device B, are alternately cut, but the operation is not limited to this. The above can also be used.

As explained above, according to the method for producing argon of the present invention, compared to the conventional low-temperature adsorption method, it is not necessary to pack vI & layer straightness so densely, and operation 1 becomes easier. Further, since the adsorbent is regenerated by washing and regenerating with #kX or argon, a vacuum device such as a vacuum pump is not required, and the installation cost and power cost are reduced. Furthermore, the argon used for washing and regeneration (1) is returned to the upper rectification column (2), which is the raw material system, so there is less loss of argon and the yield of argon is increased. In addition, since it can be operated separately from the Il rectification column, the operational difficulties associated with extracting argon from the air-deep-cooled fraction 111MK are alleviated. Furthermore, the conventional coffin retention method (also known as O) has advantages such as no need to worry about repeated cooling and heating, less energy loss, and high economic efficiency.

[Brief explanation of drawings]

FIG. 1 is a block diagram showing an example of production and KO used in the method for producing argon of the present invention, and FIG. 2 is a graph showing the adsorption characteristics of mu-type zeolite. l...Il Kozue Soto, 2.・・・・・・Upper rectification tower,
4...Nezushi Kakene Sushi, 6...Pressure machine, Mu-1.
....Lth suction tube, A-2...VSZTJ & Yotsutsu, 13.21.23 ....Valve, 14.18.
20.22...Pipe, 19...Reducing valve. 320- Figure 2 hate □j grave degree ('C)

Claims (1)

[Claims] The raw material gas is a mixed gas of argon, carbon dioxide, and nitrogen discharged from the NW tower of the air cryogenic analyzer. A step of sequentially flowing argon from the filled 81@11 tank to the 21st barrel filled with Mu-type zeolite to obtain several argon products; Then, the pressure is reduced to normal pressure in the second absorption tube to desorb nitrogen and #I element, and the desorption residue from the 1st and 11th cylinders is discharged, and the desorption gas from the 2nd cylinder is returned to the Fime column, and then the product A part of the argon was flowed through 2 g of fume and bed glass to wash the inside of the cylinder and returned to the upper 1nI distillation column, and then O2 from the air-cooled separated iron 1 was flowed through the 1st FJ and bed glass to clean the inside of the cylinder. A method for producing argon, comprising producing argon by a step of regenerating an adsorption cylinder by using it as an upper plate, J