JPH08217427A - Purification of phosphorus oxychloride - Google Patents
Purification of phosphorus oxychlorideInfo
- Publication number
- JPH08217427A JPH08217427A JP4143795A JP4143795A JPH08217427A JP H08217427 A JPH08217427 A JP H08217427A JP 4143795 A JP4143795 A JP 4143795A JP 4143795 A JP4143795 A JP 4143795A JP H08217427 A JPH08217427 A JP H08217427A
- Authority
- JP
- Japan
- Prior art keywords
- phosphorus oxychloride
- gas
- phosphorus
- ozone gas
- impurities
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000000746 purification Methods 0.000 title claims description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000007789 gas Substances 0.000 claims abstract description 21
- 239000012535 impurity Substances 0.000 claims abstract description 14
- 238000007664 blowing Methods 0.000 claims abstract description 8
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 claims abstract description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 13
- 239000000463 material Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000009835 boiling Methods 0.000 abstract description 3
- 238000004821 distillation Methods 0.000 abstract description 3
- 239000012264 purified product Substances 0.000 abstract 2
- 238000011084 recovery Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はオキシ塩化燐の製造にお
いて原料黄燐中の不純物、特に含有硫黄や砒素等から副
生する不純物にオゾンガスを吹き込んで処理して除去す
る方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for removing impurities by blowing ozone gas into impurities in raw material yellow phosphorus in the production of phosphorus oxychloride, especially impurities by-produced from sulfur and arsenic contained therein.
【０００２】[0002]
【従来の技術】オキシ塩化燐は一般的に黄燐に塩素ガス
と酸素ガスを吹き込んで製造するが、原料黄燐中の不純
物から副生する不純物が製品中に混入するため、精製方
法は重要な問題である。2. Description of the Related Art Phosphorus oxychloride is generally produced by blowing chlorine gas and oxygen gas into yellow phosphorus. However, impurities by-produced from the impurities in the raw material yellow phosphorus are mixed into the product, so the purification method is an important issue. Is.
【０００３】従来、オキシ塩化燐の精製方法は低沸物を
ストリップして分離する方法や還流比をとって精留する
方法等が一般的に行われている。しかし、この様な方法
は比較的不純物の含有量が多いときは有効であるが、含
有量が少ない場合にあまり効果がない欠点があった。Conventionally, as a purification method of phosphorus oxychloride, a method of stripping and separating a low boiling point material, a method of rectifying at a reflux ratio, etc. are generally performed. However, although such a method is effective when the content of impurities is relatively large, it has a drawback that it is not very effective when the content of impurities is small.
【０００４】[0004]
【課題を解決するための手段】本発明者等は精製方法に
ついて種々検討し、オキシ塩化燐中へオゾンガスを吹き
込むことによって不純物、特にオキシ塩化燐製造の一原
料である黄燐中の硫黄等から副生するＰＳＣｌ3 等が除
去できることを見出し本発明を完成するに至った。Means for Solving the Problems The inventors of the present invention have made various studies on purification methods, and by blowing ozone gas into phosphorus oxychloride, impurities such as sulfur in yellow phosphorus, which is one of the raw materials for producing phosphorus oxychloride, are added as secondary substances. The inventors have found that the PSCl 3 and the like produced can be removed, and completed the present invention.
【０００５】即ち、本発明は黄燐に塩素ガスと酸素ガス
を吹き込むオキシ塩化燐の製造において不純物をオゾン
ガスで処理して除去することを特徴とするオキシ塩化燐
の精製方法である。That is, the present invention is a method for purifying phosphorus oxychloride, which comprises removing impurities by treating them with ozone gas in the production of phosphorus oxychloride in which chlorine gas and oxygen gas are blown into yellow phosphorus.
【０００６】本発明を遂行するには使用されるオゾンガ
スはオゾン発生装置で発生させＰＳＣｌ3 等を含むオキ
シ塩化燐中に吹き込まれる。オゾンガスの濃度は特に限
定されないが、１〜７０ｇ／ｍ3 、好ましくは１０〜６
０ｇ／ｍ3 である。余り高濃度の場合、材料、特に樹脂
系材質は使用できないこと、漏洩した場合に人体に危険
等の問題があり、また、オキシ塩化燐の二量体であるＰ
2 Ｏ3 Ｃｌ4 の副生量が増加するので好ましくない。オ
ゾンガスの濃度が薄くても反応には問題ないが、ガス量
が多くなりガスに伴って逃げるオキシ塩化燐を捕集する
ため大型の冷却装置が必要となり経済的に好ましくな
い。反応は常温でもよいがオキシ塩化燐の沸点または沸
点近辺でオゾンガスを導入する方が好ましい。オゾンガ
スの導入量はＳの含有量の２〜４倍モルの使用で充分で
ある。導入量がこれより多くても反応に影響ないが経済
的に有用でない。The ozone gas used to carry out the present invention is generated by an ozone generator and blown into phosphorus oxychloride containing PSCl 3 and the like. The concentration of ozone gas is not particularly limited, but is 1 to 70 g / m 3 , preferably 10 to 6
It is 0 g / m 3 . If the concentration is too high, there is a problem that materials, especially resin materials, cannot be used, and there is a danger to the human body in the case of leakage, and it is a dimer of phosphorus oxychloride.
It is not preferable because the amount of 2 O 3 Cl 4 by-product increases. Even if the concentration of ozone gas is low, there is no problem in the reaction, but since a large amount of gas is collected and phosphorus oxychloride that escapes with the gas is collected, a large cooling device is required, which is not economically preferable. The reaction may be carried out at room temperature, but it is preferable to introduce ozone gas at or near the boiling point of phosphorus oxychloride. It is sufficient to use ozone gas in an amount of 2 to 4 times the mol of the S content. If the amount introduced is larger than this, it does not affect the reaction, but it is not economically useful.
【０００７】[0007]
【実施例】次に実施例を挙げて本発明を更に詳細に説明
する。 実施例１ ３００ｍｌ四頚フラスコにバリテール型コンデンサー、
温度計と攪拌翼をセットし更にオゾンガス吹き込み管を
セットした。次いでＰＳＣｌ3 を１０ｗｔ％含んでいる
オキシ塩化燐１０２．３ｇをフラスコに仕込み攪拌しな
がら加温し沸騰させた。次にオゾン発生装置を運転し吹
き込んだ。オゾンガス濃度は１．０５×１０-3ｍｏｌ／
リットルで５時間吹き込んだ。オゾン吹き込み量は０．
１５８ｍｏｌであった。反応液がガス同伴するのを防止
するため、−３０℃のブラインをコンデンサーに循環さ
せた。排ガスは２０％のＮａＯＨ溶液でトラップした。
反応終了後常温まで冷却したら極く少量の白色沈澱が析
出した。反応液の回収率は９９．７ｗｔ％であった。反
応液中の残存ＰＳＣｌ3 をＩＣＰ分析で確認したら０．
０２ｍｏｌ％であった。 実施例２ ３００ｍｌ四頚フラスコに実施例１と同様なセットを
し、ブライン冷却してコンデンサーを−２５℃に冷却し
た。一方、オゾン発生装置に酸素ガスを３０Ｎｌ／Ｈｒ
で流しオゾンガスを１．０×１０-3ｍｏｌ／リットルの
濃度になる様に調節した。一方、フラスコにＳとして７
５ｐｐｍを含んでいるオキシ塩化燐２９５．２ｇを仕込
んだ。加温し還流させてからパージさせておいたオゾン
ガスを吹き込んで３時間反応を行った。ガスの吹き込み
を中止し冷却してから全重量を計量した。回収率は９
９．３ｗｔ％であった。反応液の一部をサンプリングし
ＩＣＰ分析したら、Ｓ：１０ｐｐｍであった。また、Ｐ
2 Ｏ3 Ｃｌ4 が０．２ｍｏｌ％／ＰＯＣｌ3 副生してい
た。 実施例３ ３００ｍｌフラスコに実施例１と同様な反応方法で５．
１ｗｔ％のＰＳＣｌ3が含まれているオキシ塩化燐３０
１．２ｇを仕込んだ。酸素流量３０Ｎｌ／Ｈｒ、オゾン
濃度１．１２×１０-3ｍｏｌ／リットルで４時間反応し
た。反応液の回収率は９８．６ｗｔ％であった。実施例
１と同様に後処理してＩＣＰ分析したらＰＳＣｌ3 濃度
は０．０８１ｗｔ％であった。また、Ｐ2 Ｏ3 Ｃｌ4 が
０．２ｍｏｌ％／ＰＯＣｌ3 副生していた。 実施例４ 実施例１と同様な反応装置を用いてＰＳＣｌ3 濃度が
４．８ｍｏｌ％オキシ塩化燐２２０ｇを仕込んだ。酸素
流量７５Ｎｌ／Ｈｒ、オゾン濃度５．１３ｍｏｌ／リッ
トルで５時間反応した。液重量回収率は９８．４ｗｔ％
であった。冷却後、反応液中のＰＳＣｌ3 濃度を測定し
たら未検出であった。また、副生物として０．６ｍｏｌ
％／ＰＯＣｌ3 のＰ2 Ｏ3 Ｃｌ4 がＮＭＲで確認され
た。 比較例１ オキシ塩化燐の反応液７１０ｇ（Ｓ：１０００ｐｐｍを
含む）を５００ｍｌナス型蒸留器に仕込み６段相当の精
留塔を用い、還流比４で７時間かけて留出させた。本流
分の一部をサンプリングしＩＣＰで分析したら、Ｓとし
て５６０ｐｐｍの値を得た。回収率：９８．２ｗｔ％。Next, the present invention will be described in more detail with reference to examples. Example 1 A 300 ml four-necked flask equipped with a variter condenser.
A thermometer and a stirring blade were set, and an ozone gas blowing tube was set. Next, 102.3 g of phosphorus oxychloride containing 10% by weight of PSCl 3 was charged into the flask and heated and boiled while stirring. Next, the ozone generator was operated and blown. Ozone gas concentration is 1.05 × 10 -3 mol /
Blown in liters for 5 hours. The amount of ozone blown is 0.
It was 158 mol. Brine at -30 ° C was circulated through the condenser to prevent gas entrainment of the reaction. The exhaust gas was trapped with a 20% NaOH solution.
After completion of the reaction, when cooled to room temperature, a very small amount of white precipitate was deposited. The reaction liquid recovery rate was 99.7 wt%. After confirming the residual PSCl 3 in the reaction solution by ICP analysis,
It was 02 mol%. Example 2 A 300 ml four-necked flask was set in the same manner as in Example 1, brine-cooled, and the condenser was cooled to -25 ° C. On the other hand, 30 Nl / Hr of oxygen gas was supplied to the ozone generator.
And ozone gas was adjusted so as to have a concentration of 1.0 × 10 −3 mol / liter. On the other hand, 7 as S in the flask
295.2 g of phosphorus oxychloride containing 5 ppm was charged. After heating and refluxing, ozone gas which had been purged was blown thereinto to carry out a reaction for 3 hours. The total amount was weighed after stopping the gas blowing and cooling. Recovery rate is 9
It was 9.3 wt%. When a part of the reaction solution was sampled and analyzed by ICP, it was S: 10 ppm. Also, P
2 O 3 Cl 4 was produced as a byproduct of 0.2 mol% / POCl 3 . Example 3 The same reaction method as in Example 1 was performed in a 300 ml flask.
Phosphorus oxychloride containing 1 wt% PSCl 3 30
1.2g was charged. The reaction was carried out for 4 hours at an oxygen flow rate of 30 Nl / Hr and an ozone concentration of 1.12 × 10 −3 mol / liter. The reaction liquid recovery rate was 98.6 wt%. When post-treatment was performed and ICP analysis was performed in the same manner as in Example 1, the PSCl 3 concentration was 0.081 wt%. In addition, P 2 O 3 Cl 4 was produced as a byproduct of 0.2 mol% / POCl 3 . Example 4 Using the same reactor as in Example 1, 220 g of phosphorus oxychloride having a PSCl 3 concentration of 4.8 mol% was charged. The reaction was carried out for 5 hours at an oxygen flow rate of 75 Nl / Hr and an ozone concentration of 5.13 mol / liter. Liquid weight recovery rate is 98.4 wt%
Met. After cooling, the PSCl 3 concentration in the reaction solution was measured and was not detected. As a by-product, 0.6 mol
% / POCl 3 of P 2 O 3 Cl 4 was confirmed by NMR. Comparative Example 1 710 g (containing S: 1000 ppm) of a reaction solution of phosphorus oxychloride was charged in a 500 ml eggplant-type distillation apparatus and distilled at a reflux ratio of 4 for 7 hours using a rectification column corresponding to 6 stages. When a part of the main stream was sampled and analyzed by ICP, a value of S of 560 ppm was obtained. Recovery rate: 98.2 wt%.
【０００８】[0008]
【発明の効果】本発明の精製方法は比較例からも明らか
な様に分離することが困難な不純物を蒸留などの化学工
学的な分離操作をすることなく容易に分離除去して高品
位のオキシ塩化燐をほぼ定量的に得ることができるので
工業的に非常に優れた方法である。As is apparent from the comparative examples, the purification method of the present invention can easily separate and remove impurities that are difficult to separate without performing a chemical engineering separation operation such as distillation to obtain a high-grade oxidant. Since phosphorus chloride can be obtained almost quantitatively, it is an industrially excellent method.
Claims (2)
キシ塩化燐の製造において不純物をオゾンガスで処理し
て除去することを特徴とするオキシ塩化燐の精製方法。1. A method for purifying phosphorus oxychloride, which comprises removing impurities by treating them with ozone gas in the production of phosphorus oxychloride by blowing chlorine gas and oxygen gas into yellow phosphorus.
０ｇ／ｍ3 である請求項１の精製方法。2. The concentration of ozone gas is 1.0 g / m 3 to 7
The purification method according to claim 1, which is 0 g / m 3 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4143795A JPH08217427A (en) | 1995-02-07 | 1995-02-07 | Purification of phosphorus oxychloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4143795A JPH08217427A (en) | 1995-02-07 | 1995-02-07 | Purification of phosphorus oxychloride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08217427A true JPH08217427A (en) | 1996-08-27 |
Family
ID=12608359
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4143795A Pending JPH08217427A (en) | 1995-02-07 | 1995-02-07 | Purification of phosphorus oxychloride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08217427A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0891942A1 (en) * | 1997-07-15 | 1999-01-20 | Bayer Ag | Process for purifying phosphorus oxychloride |
| EP0900762A1 (en) * | 1997-09-03 | 1999-03-10 | DSM Chemie Linz GmbH | Process for purifying phosphorus oxychloride |
-
1995
- 1995-02-07 JP JP4143795A patent/JPH08217427A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0891942A1 (en) * | 1997-07-15 | 1999-01-20 | Bayer Ag | Process for purifying phosphorus oxychloride |
| EP0900762A1 (en) * | 1997-09-03 | 1999-03-10 | DSM Chemie Linz GmbH | Process for purifying phosphorus oxychloride |
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