CN102164850A - Process for producing high-purity chlorine - Google Patents
Process for producing high-purity chlorine Download PDFInfo
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- CN102164850A CN102164850A CN2009801376565A CN200980137656A CN102164850A CN 102164850 A CN102164850 A CN 102164850A CN 2009801376565 A CN2009801376565 A CN 2009801376565A CN 200980137656 A CN200980137656 A CN 200980137656A CN 102164850 A CN102164850 A CN 102164850A
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- zeolite
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/07—Purification ; Separation
- C01B7/075—Purification ; Separation of liquid chlorine
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
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- Chemical Kinetics & Catalysis (AREA)
- Filling Or Discharging Of Gas Storage Vessels (AREA)
- Separation Of Gases By Adsorption (AREA)
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Abstract
Disclosed is a process for producing high-purity chlorine, which is characterized in that liquefied chlorine is contacted with zeolite to produce purified liquefied chlorine, the purified liquefied chlorine is filled in a cylinder, and the generation of oxygen gas in the cylinder is prevented. In this manner, the generation of oxygen gas in the cylinder can be prevented. The purification by contacting with zeolite enables the prevention of the generation of impurities such as oxygen gas even when high-purity chlorine is filled in the cylinder, and also enables the production of liquefied chlorine that can keep its purity for a long period.
Description
Technical field
The present invention relates to the manufacture method of high-purity chloro.More specifically, the present invention relates to after cylinder is filled liquid chlorine, can suppress the oxygen manufacture method that produce, high-purity chloro of impurity.Use in dry-etching that the high-purity chloro of making by this manufacture method can carry out when making VLSI (very-large-scale integrated circuit, super large-scale integration) etc.s semiconductor element, optical fiber, display panels etc. and the cleaning etc.
Background technology
Generally it can be filled to the high pressure gas cylinder in transportation during liquid chlorine, and after being filled to cylinder, impurity such as can produce oxygen in the liquid chlorine sometimes, the problem of the liquid chlorine purity drop that existence causes thus.
As the method for non-condensable gasess such as the oxygen of removing the impurity in the liquid chlorine, nitrogen, the method for removing based on rectifying of disclosing is (for example with reference to patent documentation 1.)。In addition, also known have a purification process that makes zeolite adsorption impurity.For example, known have in liquid helium, contact activated carbon, synthetic zeolite is removed the moisture of the trace impurity in the liquid helium, the method for carbonic anhydride, particularly disclose by low temperature down removing of bringing of the absorption content that effect can increase (for example with reference to patent documentation 2.)。And then, as the method for from chlorine, removing impurity such as oxygen, disclose by making zeolite, charcoal absorption chlorine, making it discharge adsorbed chlorine to improve the method for purity of chlorine gas feeding to be different from pressure when importing then (for example with reference to patent documentation 3 and 4.)。
Yet,, unexposed about keeping the content of the purity that is filled to the liquid chlorine in the cylinder though useful these methods are removed the record of oxygen of impurity etc.In addition, though in the patent documentation 1 relevant for the record of removing the oxygen in the liquid chlorine, the oxygen after removing is not produced not provide and inquires into and enlightenment.
And then, though in the patent documentation 2 relevant for the record of removing impurity such as moisture by zeolite, not about the record of oxygen, in addition, also the impurity that preservation after is not thus caused produces once again to provide and inquires into and enlightenment.Moreover, though in the patent documentation 2 relevant for the record of the impurity of removing liquid nitrogen and liquid helium, not about the record of liquid chlorine.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2002-316804 communique
Patent documentation 2: Japanese kokai publication hei 03-59385 communique
Patent documentation 3: Japanese kokai publication hei 04-367504 communique
Patent documentation 4: Japanese kokai publication hei 05-155603 communique
Summary of the invention
The problem that invention will solve
The present invention is used to solve above-mentioned existing issue, and its purpose is to be provided at the oxygen that can suppress impurity in the cylinder behind filling liquid chlorine manufacture method that produce, high-purity chloro.
The scheme that is used to deal with problems
The present invention is as follows.
1. the manufacture method of a high-purity chloro is characterized in that, liquid chlorine is contacted with zeolite, will be filled to cylinder by the purifying liquid chlorine that this contact obtains, thereby the oxygen that suppresses in this cylinder produces.
2. according to the manufacture method of above-mentioned 1 described high-purity chloro, wherein, to liquefy above-mentioned liquid chlorine before obtaining contacting of the chlorine that the salt solution electrolysis is obtained with above-mentioned zeolite; (1) after this carry out rectifying and separate non-condensable gases, then rectifying separates high boiling point composition impurity, after this contacts with zeolite, then is filled to above-mentioned cylinder; Perhaps, (2) after this contact with zeolite and obtain above-mentioned purifying liquid chlorine, then this purifying liquid chlorine rectifying are separated non-condensable gases, after this carry out rectifying and separate high boiling point composition impurity, then are filled to above-mentioned cylinder.
3. according to above-mentioned 1 or the manufacture method of 2 described high-purity chloros, wherein, contacting the above-mentioned concentration of oxygen that comprises in the above-mentioned purifying liquid chlorine after back 25 days with above-mentioned zeolite is 0.01～1.5vol.ppm.
4. according to the manufacture method of each the described high-purity chloro in above-mentioned 1～3, wherein, the effective diameter of the pore of above-mentioned zeolite is more than the 0.3nm.
5. according to the manufacture method of each the described high-purity chloro in above-mentioned 1～4, wherein, be 0.01～1.0vol.ppm with the above-mentioned concentration of oxygen that comprises in the above-mentioned above-mentioned purifying liquid chlorine that contacts with zeolite after back 25 days.
6. according to the manufacture method of each the described high-purity chloro in above-mentioned 1～5, wherein, the effective diameter of the pore of above-mentioned zeolite is more than the 0.4nm.
7. according to the manufacture method of each the described high-purity chloro in above-mentioned 3～6, wherein, it is filled to the ratio (X of above-mentioned cylinder oxygen concentration after with 1 day, that comprise in this liquid chlorine after 25 days from above-mentioned liquid chlorine is contacted with above-mentioned zeolite
1) be 2.3～6.0; From the ratio (X that above-mentioned purifying liquid chlorine is filled to above-mentioned cylinder oxygen concentration after with 1 day, that comprise in this liquid chlorine after 25 days
2) be 1.0～2.1; Above-mentioned X
2/ above-mentioned X
1Be 0.2～0.4.
The effect of invention
According to the manufacture method of high-purity chloro of the present invention, by liquid chlorine being contacted with zeolite, also will being filled to cylinder by the purifying liquid chlorine that this contact obtains, the oxygen that can suppress in the cylinder produces.By carry out such based on the purifying that contacts of zeolite, also can suppress impurity such as oxygen and produce even in existing cylinder, fill high-purity chloro, and can make the liquid chlorine that can keep purity for a long time.In addition, because it, does not therefore need the periodical operation as the purifying that carries out based on absorption and desorption for based on purifying of carrying out of contact, can carry out the successive manufacturing.
And then, to liquefy liquid chlorine before obtaining contacting of the chlorine that the salt solution electrolysis is obtained with zeolite; (1) after this rectifying of gained liquid chlorine is separated non-condensable gases, then carry out rectifying and separate high boiling point composition impurity, after this contact, then will be filled to cylinder by the purifying liquid chlorine that contact obtains with zeolite; Perhaps, (2) after this make it contact with zeolite and obtain the purifying liquid chlorine, then the rectifying of purifying liquid chlorine are separated except that non-condensable gases, after this carry out rectifying and separate high boiling point composition impurity, then are filled to cylinder; In this case, can obtain to suppress the effect that the oxygen in the cylinder produces.In addition, under the situation of (1), by with zeolite contact operation before carry out rectifying, can prevent that the powder of the zeolite that contacted from sneaking into cylinder by rectification process.In addition, under the situation of (2),, can easily change used zeolite by carrying out rectifying with contacting between operation and the cylinder filling work procedure of zeolite.
In addition, under the situation that the scope of the oxygen concentration that comprises limits, can in the time of the common maintaining period of so enough conducts in 25 days, keep the purity of high-purity chloro for a long time in to the liquid chlorine after the process specified time.
And then, under the situation of effective diameter in specialized range of the pore that makes zeolite, can further improve the effect of the oxygen generation that suppresses in the cylinder, can keep the purity of high-purity chloro for a long time.
In addition, the ratio X of the oxygen concentration that in making liquid chlorine and purifying liquid chlorine, comprises
1, X
2And X
2/ X
1Under the situation in specialized range, pass through X
1And X
2The effect that can obtain to follow inhibition oxygen effluxion, that bring by the contact zeolite to produce, and pass through X
2/ X
1Can obtain and whether contact the effect that the relevant inhibition oxygen of zeolite produces, therefore can in the time of the common maintaining period of so enough conducts in 25 days, obtain to suppress the effect of the oxygen generation in the cylinder, can keep the purity of high-purity chloro for a long time.
Description of drawings
Fig. 1 is the schema that is used to illustrate the manufacturing process of high-purity chloro.
Fig. 2 is the schema that is used to illustrate the manufacturing process of another high-purity chloro.
Fig. 3 is the figure that is used to illustrate the difference that the pore of molecular sieve and silica gel distributes.
Embodiment
Below, the manufacture method of high-purity chloro of the present invention is elaborated.
The manufacture method of high-purity chloro of the present invention is characterised in that, it is that cylinder is filled the back and suppressed the method that oxygen produces, and it makes liquid chlorine contact with zeolite, and the chlorine after the contact that will be obtained by this contact is filled to cylinder, thereby suppresses the interior oxygen generation of this cylinder.
Above-mentioned " liquid chlorine " can prepare by manufacture method arbitrarily, for example the salt solution electrolysis can be obtained chlorine, after this with sulfuric acid with this chlorine dehydration, then compress and it liquefied obtain.
Above-mentioned " zeolite " is to be used for contacting with liquid chlorine adsorbing the material that is considered to make the oxygenous origin cause of formation material of liquid chlorine, can use in natural product, the synthetics any one.In addition, the shape of zeolite can be selected arbitrarily, for example can list particulate state, pearl, sheet, bar-shaped and tubulose etc.
And then zeolite has the structure that is formed with a large amount of pores.For bulk of molecule that can be by this pore, i.e. above-mentioned " effective diameter ", can select arbitrarily, be preferably more than the 0.3nm, also can be the mixture that the material of multiple effective diameter is arranged.For example, can list synthetic zeolite and their mixtures such as molecular sieve 3a, molecular sieve 4A, molecular sieve 5A and molecular sieve 13X for being situation more than the 0.3nm.In addition, for being situation more than the 0.4nm, can list molecular sieve 4A, molecular sieve 5A and molecular sieve 13X and their mixture.In addition, for being situation more than the 0.5nm, can list molecular sieve 5A and molecular sieve 13X and their mixture.In addition, the maximum value of effective diameter is preferably below the 10nm.
Above-mentioned " cylinder " is to be used to store by liquid chlorine is contacted and the container of the purifying liquid chlorine that purifying obtains with zeolite.The purifying liquid chlorine can be to be filled in the state delivery in the cylinder.In addition, the material of cylinder can be selected arbitrarily, for example can enumerate the metal system of tapping and iron such as stainless steel etc. etc.Wherein, on cheap and this point that is widely used, iron cylinder can be used as preferred example.
Because the liquid ground that can change in the container that accommodates zeolite when removing impurity is operated in a continuous manner, so its operation efficiency is higher than intermittent type, is preferred.When carrying out in a continuous manner, the contact conditions of zeolite and liquid chlorine can suitably be selected according to the condition of rectifying etc.With the time per unit flow, be that (following brief note is for " SV " for superficial velocity.) under the situation about defining, be preferably SV=0.1～50[1/ hour] (be preferably 1～25[1/ hour]).This be because, suppress the effect that oxygen produces if SV is excessive and reduce, can produce the needs that the equipment of removing is further maximized if SV is too small.
For liquid chlorine, can separate by rectifying and remove above-mentioned " non-condensable gases ".This non-condensable gases for example is lower than the impurity of liquid chlorine for boiling points such as oxygen and nitrogen.In addition, can separate by rectifying and remove above-mentioned " high boiling point composition impurity ".This high boiling point composition impurity for example is higher than the impurity of liquid chlorine for boiling points such as bromine and metals.
Above-mentioned each rectifying can be handled the row that advances with contacting of liquid chlorine at zeolite, also can carry out thereafter.
For example, as illustrated in Fig. 1, contacting preceding liquid chlorine with zeolite can followingly obtain: the chlorine that the salt solution electrolysis is obtained is liquefied, and the thing rectifying of after this will liquefying separates non-condensable gases, then the further rectifying of rectifying thing is separated high boiling point composition impurity, thereby obtain.And then as illustrated in Fig. 2, the purifying liquid chlorine can followingly obtain: carry out rectifying and separate non-condensable gases before contacting the back and be filled to cylinder with zeolite, after this further rectifying of rectifying thing is separated high boiling point composition impurity, thereby obtain.
Before rectification working process, carry out and under any one situation of carrying out behind the rectification working process, all can obtain to suppress the effect that the oxygen in the cylinder produces in that contacting of zeolite and liquid chlorine handled.And then, when before rectifying, carrying out,, the effusive situation of powder of the zeolite that generation is contacted sneaks into to cylinder even also can suppressing powder by rectification process, and it is preferred in this.In addition, when carrying out after the rectifying and before being charged to cylinder, change used zeolite easily, it is preferred in this.
Above-mentioned oxygen concentration for comprising in the above-mentioned purifying liquid chlorine that contacts with above-mentioned zeolite after back 25 days for example can be 0.01～1.5vol.ppm (being preferably 0.01～1.4, more preferably 0.01～1.3).And then, for example can be 0.01～1.0vol.ppm (being preferably 0.01～0.9, more preferably 0.01～0.8).
Comparing the gas phase portion that easier grasp oxygen concentration changes with liquid phase portion, above-mentioned oxygen concentration for the gas phase portion that is filled with the cylinder that contacts the above-mentioned purifying liquid chlorine after back 25 days with above-mentioned zeolite is comprised for example can be 1～220vol.ppm (being preferably 1～180, more preferably 1～100).
It is filled to the oxygen concentration Y that comprises in the liquid chlorine of cylinder after 25 days from liquid chlorine is contacted with zeolite
1 (25)With 1 day after liquid chlorine in the oxygen concentration Y that comprises
1 (1)Ratio (X
1=Y
1 (25)/ Y
1 (1)) for example be 2.3～6.0;
The oxygen concentration Y that in being filled to the purifying liquid chlorine of cylinder after 25 days, comprises
2 (25)With 1 day after the purifying liquid chlorine in the oxygen concentration Y that comprises
2 (1)Ratio (X
2=Y
2 (25)/ Y
2 (1)) can be 1.0～2.1.
In addition, X
2/ X
1Be used for representing the ratio comparing, by the contact zeolite oxygen increase of liquid chlorine suppressed when not contacting zeolite, it is can be at above-mentioned X
1And X
2The scope of value in the scope, promptly 0.2～0.4 that obtains, and X
1And X
2Can be for satisfying aforementioned X in above-mentioned scope separately
2/ X
1The value of scope.
If in above-mentioned scope, then can make effect that the oxygen that suppresses in the cylinder produces for more than to a certain degree, and can keep the purity of high-purity chloro for a long time.
In addition, the oxygen concentration that comprises in the liquid chlorine is used the oxygen concentration of measuring under the state that liquid chlorine is at room temperature all gasified.
And then, it is filled to the oxygen concentration Y of the cylinder gas phase portion of cylinder after 25 days from liquid chlorine is contacted with zeolite
3 (25)With 1 day after the oxygen concentration Y of cylinder gas phase portion
3 (1)Ratio (X
3=Y
3 (25)/ Y
3 (1)) for example be 3.1～6.0;
From the oxygen concentration Y that fills the cylinder gas phase portion of purifying liquid chlorine after 25 days
4 (25)With 1 day after the oxygen concentration Y of cylinder gas phase portion
4 (1)Ratio (X
4=Y
4 (25)/ Y
4 (1)) can be 1.0～2.1.
In addition, X
4/ X
3Be used to represent the ratio comparing, by the contact zeolite oxygen increase of cylinder gas phase portion suppressed when not contacting, can be can be at X
4And X
3The scope of value in the scope that obtains, for example be 0.2～0.7.
If in above-mentioned scope, then can make effect that the oxygen that suppresses in the cylinder produces for more than to a certain degree, and can keep the purity of high-purity chloro for a long time.
Embodiment
Below, based on Fig. 1 the manufacture method of high-purity chloro of the present invention is specifically described.
(1) manufacturing of liquid chlorine
As shown in Figure 1, the chlorine by the water generates that electrolyzes table salt is dewatered, compress with 0.7～0.8MPa then, obtain thick liquid chlorine with sulfuric acid.The liquefied fraction of the thick liquid chlorine that obtains thus is 80～95%, and it contains the chlorine more than 99.8%.In addition, because thick liquid chlorine contains the oxygen that belongs to impurity, therefore, after this remove lower boiling non-condensable gases, be oxygen etc. by carrying out rectifying.Then, for the bromine of removing high boiling point composition impurity and metal ingredient etc., carry out rectifying once more.Obtain containing the liquid chlorine of 0.6vol.ppm (liquid chlorine of gathering from liquid phase portion is at room temperature all gasified and obtain volumetric concentration) oxygen thus.
(2) with the contacting and filling of zeolite
After this, with SV=13[1/ hour] flow velocity to make the liquid chlorine with above-mentioned manufacture method manufacturing be the 3A type synthetic zeolite (molecular sieve 3a of 0.3nm at the effective diameter that is filled with 150mL, crust industry manufacturing) contacts in the adsorption tower, obtain the purifying liquid chlorine of embodiment 1.After this, in steel cylinder (capacity 10L), fill 6 one-tenth of its capacity, be the purifying liquid chlorine of 8.5kg.Then, at room temperature preserve, carry out the quantitative analysis of oxygen after through 1 day, 13 days and 25 days.Analyze by with PID as detector, with 2m " Unibeads 1S " and 3m " molecular sieve 13XS " as column packing, helium is carried out under 60 ℃ of temperature as the gas-chromatography (ProductName G3900, Hitachi's manufacturing) of carrier gas.In addition, the gas phase portion in liquid chlorine portion in the cylinder (hereinafter referred to as liquid phase portion) and the cylinder is carried out the quantitative analysis of oxygen, its concentration is shown in table 1 and table 2 respectively.
In addition,, use the 13X type synthetic zeolite (" molecular sieve 13X ", crust industrial make) of pore effective diameter, in addition use manufacture method similarly to Example 1 to obtain the purifying liquid chlorine, it is filled to the steel cylinder as 1.0nm as embodiment 2.After this, carry out the quantitative analysis of oxygen with method similarly to Example 1.
And then, as a comparative example 1, the liquid chlorine raw material is contacted with zeolite and it is filled to the steel cylinder.In addition, as a comparative example 2, use the silica gel (" Unibeads 1S ", GL Sciences Inc. makes) of mean pore size 2.5nm to replace zeolite, in addition obtain the purifying liquid chlorine with similarly to Example 1 manufacture method, it is filled to the steel cylinder.After this, carry out the quantitative analysis of oxygen with method similarly to Example 1.
[table 1]
The change procedure of the oxygen concentration of table 1 liquid phase portion
[table 2]
The change procedure of the oxygen concentration of table 2 gas phase portion
(3) cylinder is filled the oxygen concentration of the liquid phase portion after 1 day
As shown in Table 1, about from the oxygen concentration that is filled to the liquid phase portion of cylinder after 1 day, be 0.7vol.ppm in the comparative example 1 that does not contact with zeolite, relative with it, be 0.2vol.ppm among embodiment 1 that has contacted with zeolite and the embodiment 2, their oxygen contents when cylinder is filled are less than comparative example 1.
In addition we know, in the comparative example 2 that liquid chlorine has been contacted with silica gel, the oxygen concentration of liquid phase portion is 0.6vol.ppm, compares with 2 0.2vol.ppm with embodiment 1, and the effect of the oxygen content that it suppresses cylinder when filling is less.
(4) cylinder is filled the oxygen concentration of the liquid phase portion after 25 days
As shown in Table 1, about from the oxygen concentration that is filled to the liquid phase portion of cylinder after 25 days, be 2.1vol.ppm in the comparative example 1 that does not contact with zeolite, relative with it, be respectively 1.3vol.ppm and 0.2vol.ppm among embodiment 1 that has contacted with zeolite and the embodiment 2, the content of their oxygen is less than comparative example 1.
And then, in embodiment 2, after 25 days of liquid phase portion with 1 day after the ratio X of oxygen concentration
2Be 0.2/0.2=1.0, oxygen concentration does not have varied slightly in 24 days.
On the other hand as can be known, in the comparative example 1 that does not contact with zeolite, after 25 days of liquid phase portion with 1 day after the ratio X of oxygen concentration
1Be 2.1/0.7=3.0, increase to some extent.Promptly as can be known, in embodiment 2, the inhibition ratio X that the oxygen that is brought by the contact zeolite of liquid phase portion increases
2/ X
1Be 1.0/3.0=0.3, compare that its oxygen increase is obviously less with comparative example 1.
(5) cylinder is filled the oxygen concentration of the gas phase portion after 1 day
As shown in Table 2, oxygen concentration about the gas phase portion after filling 1 day to cylinder, be 92vol.ppm in the comparative example 1 that does not contact with zeolite, relative with it, be 28vol.ppm among the embodiment 1 that has contacted with zeolite, and be 26vol.ppm among the embodiment 2 that has contacted with zeolite, same with liquid phase portion, their oxygen contents when cylinder is filled are less than comparative example 1.
In addition we know, in the comparative example 2 that liquid chlorine is contacted with silica gel, the oxygen concentration of gas phase portion is 81vol.ppm, compares with the 28vol.ppm of embodiment 1 and the 26vol.ppm of embodiment 2, and the effect of the oxygen content when it suppresses the cylinder filling is less.
(6) cylinder is filled the oxygen concentration of the gas phase portion after 25 days
As shown in Table 2, about from the oxygen concentration that is filled to the gas phase portion of cylinder after 25 days, be 330vol.ppm in the comparative example 1 that does not contact with zeolite, relative with it, be respectively 169vol.ppm and 26vol.ppm among embodiment 1 that has contacted with zeolite and the embodiment 2, portion is same with liquid phase, and their oxygen content is less than comparative example 1.
And then, to the filling of embodiment 1 and comparative example 2 after back 1 day with 25 days after situation when comparing, the increasing amount of the oxygen concentration of liquid phase portion is respectively 1.3-0.2=1.1vol.ppm and 1.6-0.6=1.0vol.ppm, is roughly the same value.Yet, can observe the gas phase portion of trickleer variation, the increasing amount of the oxygen concentration of embodiment 1 is 169-28=141vol.ppm, relative with it, comparative example 2 is 245-81=164vol.ppm, demonstrate than big-difference, the effect of the inhibition oxygen content of embodiment 1 is greater than comparative example 2 as can be known.
And then, in embodiment 2, after 25 days of liquid phase portion with 1 day after the ratio X of oxygen concentration
4Be 26/26=1.0, oxygen concentration does not have varied slightly in 24 days.
On the other hand as can be known, in the comparative example 1 that does not contact with zeolite, after 25 days of gas phase portion with 1 day after the ratio X of oxygen concentration
3Be 330/92=3.6, increase to some extent.Promptly as can be known, the inhibition ratio X that the oxygen that is brought by the contact zeolite of gas phase portion increases among the embodiment 2
4/ X
3Be 1.0/3.6=0.3, portion is same with liquid phase, and its oxygen increase is significantly less than comparative example 1.
In addition, can think that the reason that the oxygen of gas phase portion increases is the release that is present in the oxygen in the liquid chlorine.
As can be known, in embodiment 2, the oxygen concentration of liquid phase portion and gas phase portion is all kept roughly certain, can make effect that the oxygen that suppresses in the cylinder produces for more than to a certain degree in the time of the common maintaining period of so enough conducts in 25 days, and can keep the purity of high-purity chloro for a long time.
In addition we know, although compare with comparative example 2, the effective diameter of embodiment 1 and 2 pore is less, and the oxygen concentration that cylinder was filled after 1 day is still less.Especially as can be known, be among the embodiment 2 of 1.0nm at effective diameter, even through 25 days such time, the effect that suppresses the oxygen increase is still bigger.
Can think that its reason is: as shown in Figure 3, the comparative example 2 of the silica gel wide with using pore size distribution is compared, and what embodiment 1 and 2 used is the extremely narrow molecular sieve of pore size distribution (zeolite).
In addition, the present invention is not limited to the embodiment shown in the previous embodiment, can form the embodiment that has carried out various changes within the scope of the invention according to purpose, purposes.For example, embodiment 1 and 2 makes liquid chlorine contact with zeolite after rectifying, but is not limited thereto, and can carry out each rectifying as shown in Figure 2 after making thick liquid chlorine and zeolite contacts, and the gained liquid chlorine is filled to cylinder.When making high-purity chloro in proper order, also can obtain to suppress the effect that the oxygen in the cylinder produces, and can keep the purity of high-purity chloro for a long time with this.
Claims (7)
1. the manufacture method of a high-purity chloro is characterized in that, liquid chlorine is contacted with zeolite, will be filled to cylinder by the purifying liquid chlorine that this contact obtains, thereby the oxygen that suppresses in this cylinder produces.
2. the manufacture method of high-purity chloro according to claim 1, wherein, to liquefy described liquid chlorine before obtaining contacting of the chlorine that the salt solution electrolysis is obtained with described zeolite;
(1) after this carry out rectifying and separate non-condensable gases, then rectifying separates high boiling point composition impurity, after this contacts with zeolite, then is filled to described cylinder;
Perhaps, (2) after this contact with zeolite and obtain described purifying liquid chlorine, then this purifying liquid chlorine rectifying are separated non-condensable gases, after this carry out rectifying and separate high boiling point composition impurity, then are filled to described cylinder.
3. the manufacture method of high-purity chloro according to claim 1 and 2, wherein, contacting the described concentration of oxygen that comprises in the described purifying liquid chlorine after back 25 days with described zeolite is 0.01～1.5vol.ppm.
4. according to the manufacture method of each the described high-purity chloro in the claim 1～3, wherein, the effective diameter of the pore of described zeolite is more than the 0.3nm.
5. according to the manufacture method of each the described high-purity chloro in the claim 1～4, wherein, contacting the described concentration of oxygen that comprises in the described purifying liquid chlorine after back 25 days with described zeolite is 0.01～1.0vol.ppm.
6. according to the manufacture method of each the described high-purity chloro in the claim 1～5, wherein, the effective diameter of the pore of described zeolite is more than the 0.4nm.
7. according to the manufacture method of each the described high-purity chloro in the claim 3～6, wherein, it is filled to the ratio X of described cylinder oxygen concentration after with 1 day, that comprise in this liquid chlorine after 25 days from described liquid chlorine is contacted with described zeolite
1Be 2.3～6.0;
From the ratio X that described purifying liquid chlorine is filled to described cylinder oxygen concentration after with 1 day, that comprise in this liquid chlorine after 25 days
2Be 1.0～2.1;
Described X
2/ described X
1Be 0.2～0.4.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008244798A JP5544696B2 (en) | 2008-09-24 | 2008-09-24 | Method for producing liquefied chlorine |
| JP2008-244798 | 2008-09-24 | ||
| PCT/JP2009/066189 WO2010035673A1 (en) | 2008-09-24 | 2009-09-16 | Process for producing high-purity chlorine |
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|---|---|
| CN102164850A true CN102164850A (en) | 2011-08-24 |
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| CN2009801376565A Pending CN102164850A (en) | 2008-09-24 | 2009-09-16 | Process for producing high-purity chlorine |
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| JP (1) | JP5544696B2 (en) |
| KR (1) | KR101609011B1 (en) |
| CN (1) | CN102164850A (en) |
| TW (1) | TWI457285B (en) |
| WO (1) | WO2010035673A1 (en) |
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| CN108290734B (en) * | 2015-12-22 | 2021-11-26 | 昭和电工株式会社 | Hydrogen chloride mixture, method for producing same, and filling container |
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|---|---|---|---|---|
| JPS5265194A (en) * | 1975-11-25 | 1977-05-30 | Tetsuo Takaishi | Method of purifying chlorine or hydrogen chloride for semiconductors |
| JP3566996B2 (en) * | 1994-10-19 | 2004-09-15 | 日本パイオニクス株式会社 | Purification method of halogen gas |
| JP2002316804A (en) * | 2001-04-19 | 2002-10-31 | Sumitomo Chem Co Ltd | Method for refining chlorine |
| WO2005044725A1 (en) * | 2003-11-05 | 2005-05-19 | Toagosei Co., Ltd. | Method for producing high purity liquid chlorine |
| WO2006035571A1 (en) * | 2004-09-29 | 2006-04-06 | Showa Denko K.K. | Method for producing high-purity liquid chlorine |
-
2008
- 2008-09-24 JP JP2008244798A patent/JP5544696B2/en active Active
-
2009
- 2009-09-16 WO PCT/JP2009/066189 patent/WO2010035673A1/en active Application Filing
- 2009-09-16 CN CN2009801376565A patent/CN102164850A/en active Pending
- 2009-09-16 KR KR1020117006747A patent/KR101609011B1/en active IP Right Grant
- 2009-09-22 TW TW098131924A patent/TWI457285B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| JP5544696B2 (en) | 2014-07-09 |
| TW201016607A (en) | 2010-05-01 |
| TWI457285B (en) | 2014-10-21 |
| JP2010076953A (en) | 2010-04-08 |
| KR101609011B1 (en) | 2016-04-04 |
| KR20110057177A (en) | 2011-05-31 |
| WO2010035673A1 (en) | 2010-04-01 |
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Application publication date: 20110824 |