JP3673292B2 - Method for preventing fouling in processes handling vinyl compounds - Google Patents
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- JP3673292B2 JP3673292B2 JP17521994A JP17521994A JP3673292B2 JP 3673292 B2 JP3673292 B2 JP 3673292B2 JP 17521994 A JP17521994 A JP 17521994A JP 17521994 A JP17521994 A JP 17521994A JP 3673292 B2 JP3673292 B2 JP 3673292B2
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Description
【０００１】
【産業上の利用分野】
本発明はビニル化合物の製造、精製、反応、貯蔵、あるいは輸送時に発生するファウリング（汚れ）防止方法に関するものである。
【０００２】
【従来の技術】
アクリル酸、アクリル酸エステル、メタクリル酸、メタクリル酸エステル、アクリロニトリル、メタクリロニトリル、アクリルアミド、メタクリルアミド、スチレン、マレイン酸、酢酸ビニルなどのビニル化合物は極めて重合しやすく、その製造、精製、反応、貯蔵、あるいは輸送工程では、熱が加わり、更に鉄錆等の混入等があって重合が一層加速され、蒸溜塔、反応塔、リボイラーなどの関連装置、あるいは配管等に重合物が堆積する。これら装置、配管内に重合物が堆積すると、プロセスの流れが悪くなり、又熱伝導が悪くなるなど運転上多くの支障を来すことになる。このように装置、配管などに発生する重合物の堆積は所謂「ファウリング」と総称されており、その防止対策は運転担当者にとって極めて大きな問題である。
【０００３】
従来このファウリングを防止する為に重合防止剤、例えば、tert−ブチルフェノールなどのフェノール類、 tert−ブチルカテコールなどのカテコール類、ハイドロキノンなどのキノン類、ニトロソフェノール、ニトロソフェニルアミン、ニトロソベンゼンなどのニトロソ類、ｐ−フェニレンジアミンなどのアミン類などを添加する方法が行われてきた。しかし、これら重合防止剤の添加にも拘わらず重合防止効果は充分でなく、また、多量に添加すると、毒性が高く、高価であるなどの問題を有し、改善が強く望まれている。
【０００４】
ビニル化合物の重合は、線上に長く進むばかりでなく、三次元網目構造に進み、不溶性ポリマー（ポップコーン重合体）を生成する性質を有している。このポップコーン重合体は、重合のシード（ポリマーの核となる種）が発生するとそこが核となって爆発的に成長を続け、重合防止剤を添加しても抑制しきれず、装置、特に蒸留塔、反応塔内及びリボイラー、あるいは配管等にファウリングとなってくる。ファウリングが成長して装置を閉塞することさえあり、極めて好ましくないものである。
【０００５】
【発明が解決しようとする課題】
従来、重合防止剤を用いる方法によってその解決が図られ、その使用量を増やすことによってある程度の効果がみられている。しかし、その使用量にも実際上限界があり、さらに効率のよい解決策が望まれている。本発明の目的は、ビニル化合物に重合防止剤を添加して処理する工程において、重合防止剤の効果を増大させることによりその添加量を低く抑えて、蒸留塔、反応塔、リボイラー、貯蔵タンク、配管等に発生するファウリングを防止する方法を提供する。
【０００６】
【課題を解決する為の手段】
本発明者らは、ビニル化合物の製造、精製、反応、貯蔵、輸送などの工程で発生するファウリングは、その重合体、特にポップコーン重合体の核となるシードを可溶化、分散化せしめればかなり抑えられるという観点から、該シードの可溶、分散機構について鋭意研究を行った結果、重合防止剤と同時に特定のスルフォン酸を併用することによっその目的が達せられることを見い出し本発明を完成するに至った。
【０００７】
すなわち、本発明は、ビニル化合物に重合防止剤を添加して処理する工程において、一般式（I）
Ｒ1−ＳＯ3［Ｘ]n （I）
のスルフォン酸、 あるいはその塩類（式中Ｒ1は炭素数４〜３２の直鎖，もしくは分岐構造を有するアルキル基、又はアルキル置換ベンゼン核、もしくはアルキル置換ナフタレン核でアルキル基のうち少なくとも１つは炭素数４〜３２の直鎖、もしくは分岐構造を有する。Ｘは水素、アルカリ金属、アルカリ土類金属、又は炭素数１〜２２の直鎖，もしくは分岐構造を有する一級、二級、もしくは三級アミン塩で、分子中にヒドロキシル基、もしくはアルコキシル基をもっていてもよい。ｎは１あるいは１/２である）で表される化合物の少なくとも一種を添加することを特徴とするビニル化合物工程のファウリング防止方法である。
【０００８】
本発明のビニル化合物は、アクリル酸、アクリル酸エステル、メタクリル酸、メタクリル酸エステル、アクリロニトリル、メタクリロニトリル、アクリルアミド、メタクリルアミド、スチレン、マレイン酸、酢酸ビニルなどである。アクリル酸エステル、メタクリル酸エステルにおけるエステル成分は、メチル、エチル、プロピル、ブチルなどの低級炭化水素基である。
【０００９】
本発明のスルフォン酸、あるいはその塩は、一般式（I）にて表されるものであり、Ｒ1の例は、ノニル、ドデシル、オクタデシル、石油スルホン酸残基、ドデシルベンゼン、トリ−デシルベンゼン、ジブチルベンゼン、オクチルべンゼン、ノニルベンゼン、ノニルナフタレンである。また、Ｘの例としては、水素、リチウム、 ナトリウム、カリウム等のアルカリ金属、マグネシウム、バリウム、カルシウム等のアルカリ土類金属、プロピルアミン塩、ジプロピルアミン塩、ブチルアミン塩、ジブチルアミン塩、トリブチルアミン塩、イソブチルアミン塩、ジイソブチルアミン塩、ｓｅｃ−ブチルアミン塩、ジ−ｓｅｃ−ブチルアミン塩、１，２−ジメチルプロピルアミン塩、ヘキシルアミン塩、シクロヘキシルアミン塩、ヘプチルアミン塩、２−エチルヘキシルアミン塩、ジ−（２−エチルヘキシル）アミン塩、オクチルアミン塩、ノニルアミン塩、デシルアミン塩、ウンデシルアミン塩、ドデシルアミン塩、テトラデシルアミン塩、ヘキサデシルアミン塩、オクタデシルアミン塩、ヤシアルキルアミン塩、 モノエタノールアミン塩等のアルキルアミン塩が挙げられる。具体的な例としては、 ドデシルベンゼンスルフォン酸ナトリウム、 石油スルフォン酸ナトリウム、 ドデシルベンゼンスルフォン酸ヤシアルキルアミン塩、 ドデシルベンゼンスルフォン酸モノエタノールアミン塩等がある。これらスルフォン酸、あるいはその塩類は、 一種類単独で用いること、もしくは二種以上を組み合わせて用いることもあり、本発明はこれら混合使用になんら制限を加えるものではない。
【００１０】
本発明のスルフォン酸、あるいはその塩の添加量は、ビニル化合物に対して好ましくは１０ｐｐｍ〜１０万ｐｐｍ、さらに好ましくは２０〜１万ｐｐｍである。１０ｐｐｍより少なくては、添加効果が小さく、１０万ｐｐｍより多いと、それなりの効果は充分あるが、添加量の割りには効果が大きくなく、経済的にみて好ましいとはいえない。
【００１１】
ビニル化合物の製造、精製、反応、貯蔵、輸送などの工程で使用される重合防止剤は、本発明で特に限定するものではないが、従来から使用されている一般的な物で良く、キノン類、ハイドロキノン類及びその誘導体、ニトロソ類、フェニレンジアミン等のアミン類、フェノチアヂン、金属キレート化合物、銅塩、カテコール類、メチレンブルー等であり具体的には、アントラキノン、ハイドロキノン、ハイドロキノンモノメチルエーテル、ｐ−ニトロソフェノール、ニトロソジフェニルアミン、ニトロソベンゼン、α−ニトロソ−β−ナフトール、パラフェニレンジアミン、Ｎ，Ｎ’−ジ−イソプロピル−ｐ−フェニレンジアミン、Ｎ，Ｎ’−ジ−ｓｅｃ−ブチル−ｐ−フェニレンジアミン、Ｎ，Ｎ’−ジフェニル−Ｐ−フェニレンジアミン、フェノチアヂン、 ２−メチル−フェノチアジン、２−オクチルフェノチアジン、酢酸銅、ジブチルジチオカルバミン酸銅等が挙げられる。又、これら重合防止剤の添加量についても、本発明で限定するものでない。通常これらのプロセスに添加される量は、ビニル化合物の重量基準に対して１０〜１０万ｐｐｍである。この範囲より少ない添加量は充分な効果は望めず、逆にこの範囲より多い添加量は添加量に見合った効果が出ず、経済的メリットは得られない。
【００１２】
本発明のスルフォン酸、あるいはその塩の添加方法は、特に限定されるものではないが、予め原料に所定量添加するか、蒸留塔、反応塔の塔頂部、もしくは塔底部、あるいは貯蔵タンクに直接添加する。添加にあたっては、本発明のスルフォン酸、あるいはその塩をそのまま、あるいは適当な溶剤に溶解して添加する。また、本発明のスルフォン酸、あるいはその塩を重合防止剤と一緒に添加するも、また別々に添加するのも何ら制限するものではない。
【００１３】
【作用】
ビニル化合物の前記処理工程で発生するファウリングはシード重合によるものが大きいと推定されることから、このシードの活性を鈍く抑えることができれば、ファウリングの生成を抑えられる。従来の重合防止剤はシードの発生そのものを少なく抑え込もうとするものであり、それなりの効果は認められるものも、それだけでは充分な効果が得られなかった。本発明のスルフォン酸、あるいはその塩は、生成したシード、あるいはシードからの初期重合物に吸着し、これを可溶化、分散させることにより、シードの重合活性を鈍らせ、重合反応の進行を抑制し、重合物の分岐、 架橋を防止することにより、ファウリングの生成を抑制することができる。
【００１４】
【実施例】
実施例によって、本発明をさらに詳細に説明するが、本発明は以下の実施例に限定されるものではない。
【００１５】
［テストに用いた薬品］
＊ スルフォン酸−ａ；ドデシルベンゼンスルフォン酸（分岐型）遊離酸
＊ スルフォン酸塩−ｂ；ドデシルベンゼンスルフォン酸（分岐型）／テトラデシルアミン塩
＊ ドデシルベンゼンスルフォン酸（分岐型）とテトラデシルアミンを等モルキシレンに溶解し、６０℃にて２時間保ち塩を形成させた。テストにはキシレン溶液そのまま添加した。
以下同様にして塩を得た。
＊ スルフォン酸塩−ｃ；ドデシルベンゼンスルフォン酸（分岐型）／ヤシアルキルアミン塩
＊ スルフォン酸塩−ｄ；ドデシルベンゼンスルフォン酸（分岐型）／２−エチルヘキシルアミン塩
＊ スルフォン酸塩−ｅ；ドデシルベンゼンスルフォン酸（分岐型）／ジブチルアミン塩
＊ スルフォン酸塩−ｆ；ドデシルベンゼンスルフォン酸（分岐型）／エチレンジアミン塩
【００１６】
＊ スルフォン酸塩−ｇ；ドデシルベンゼンスルフォン酸（分岐型）／モノエタノールアミン塩
＊ スルフォン酸塩−ｈ；ドデシルベンゼンスルフォン酸（直鎖型）／テトラデシルアミン塩
＊ スルフォン酸塩−ｉ；トリデシルベンゼンスルフォン酸（分岐型）／テトラデシルアミン塩
＊ スルフォン酸塩−ｊ；ｔert−ブチルベンゼンスルフォン酸／ｎ−ブチルアミン塩
＊ スルフォン酸塩−ｋ；石油スルフォン酸／ナトリウム塩
＊ スルフォン酸塩−ｌ；ｐ−エチルベンゼンスルフォン酸／ｎ−ブチルアミン塩
＊ ハイドロキノン：精工化学株式会社製
＊ フェノチアヂン：精工化学株式会社製
＊ Ｎ，Ｎ’−ジ−Ｓｅｃ−ブチル−Ｐ−フェニレンジアミン：住友化学工業株式会社製、スミライザーＢＰＡ（商標名）
＊ コハク酸イミド系分散剤：テキサコケミカル社製、ＴＣ−９５９６Ａ（商標名）
＊ ポリメタクリレート系分散剤：テキサコケミカル社製、ＴＣ−８１０３（商標名）
【００１７】
（参考例１）
アクリル酸製造装置蒸留塔塔底液（アクリル酸を８５重量％以上含み、重合防止剤としてハイドロキノン ０．３重量％、 Ｎ，Ｎ’−ジ−ｓｅｃ−ブチル−ｐ−フェニレンジアミン ０．２重量％を含有)に本発明のスルフォン酸−ａ、あるいはその塩−ｂ〜ｋを添加し、及び比較例として無添加あるいは比較化合物を添加し、 一定時間加熱後の不溶性物質の生成量及び容器への付着程度によってその効果を確認した。その操作は以下の通りである。
【００１８】
〔不溶性物質生成量の測定〕
２００ｍｌ共栓付き三角フラスコに試料液５０ｇを入れ、９０℃にて６００時間保った後、試験液中の不溶性物質生成量を求めると共に、三角フラスコの底及び壁に付着した不溶性物質の付着程度を観察した。
１） １．０μテフロン製メンブレンフィルターの重量を測定、Ｗｏ（ｇ）
２） 上記三角フラスコ内試験液を、１）のメンブレンフィルターを用いて吸引口過する。
３） アセトンで三角フラスコとメンブレンフィルターを十分洗浄する。
４） ３）で得られたメンブレンフィルターを１０５℃で２時間乾燥させ、デシケーター中で放冷する。
５） ４）で得られたメンブレンフィルターの重量を測定、Ｗ（ｇ）
６） （Ｗ−Ｗｏ）より不溶性物質の生成量を求め、試験液１，０００ｇ中の量に換算する。
【００１９】
〔不溶性物質の付着状態〕
又、３）で得られた、三角フラスコについて、アセトン洗浄前の不溶性物質の付着程度を観察した。なお付着程度は、その小さい順序にＡ、Ｂ、Ｃ、及びＤのアルファベットによって表示した。
不溶性物質の付着状態は、次の基準で視覚判定した。
Ａ：付着が認められない。Ｂ：わずかに付着が認められる。Ｃ：付着が認められる。Ｄ：多量の付着が認められる。
結果を表１に示す。
【００２０】
（参考例２）
ビニル化合物の混合液（アクリル酸９０重量％、アクリル酸ダイマー０．５重量％、マイレン酸０．２重量％、キシレン８．３重量％、フルフラール０．２重量％、酢酸０．２重量％、水０．１重量％、メチルハイドロキン０．２重量％、Ｎ，Ｎ’−ジ−ｓｅｃ−ブチル−ｐ−フェニレンジアミン０．３重量％）を試料とし，本発明のスルフォン酸−ａ、あるいはその塩−ｂ〜ｆを添加し、及び比較例として無添加あるいは比較化合物を添加し、参考例１と同様にして９０℃にて、６００時間保った後の不溶性物質の生成量及び容器への付着程度を観察した。この結果を表２に示す。
【００２１】
（参考例３)
〔ガラスチューブ閉塞時間の測定〕
１ｌビンを試料ビンとし、 そこからホットブロックに収めたガラスチューブ（内径１ｍｍ、加熱部分の長さ１ｍ）を循環して再び試料ビンに戻る循環系を作った。この評価装置を用い、試料ビンに試料２００ｇを入れ系内を窒素置換した後、試料を定量ポンプにて流量０．２ｍｌ／分で、１８０℃に加熱したガラスチューブに送り込み循環させた。ガラスチューブに重合物が付着し、閉塞する迄の時間を比較した。閉塞する迄の時間が長い程、ファウリング防止効果が高いことを示す。
この評価装置を用いて、 参考例１と同じアクリル酸製造装置蒸留塔塔底液を試料とし、本発明のスルフォン酸−ａ、あるいはその塩−ｂ〜ｃを添加し、及び比較例として無添加あるいは比較化合物を添加し、ガラスチューブが閉塞する迄の時間を比較した。この結果を表３に示す。
【００２２】
（実施例１）
アクリロニトリル製造装置蒸留塔塔底液（アクリロニトリルを９０重量％以上含み、重合防止剤としてハイドロキノン ０．０２重量％を含有)を用いて行った。
この蒸留塔底液３０ｇに本発明のスルフォン酸−ａ、あるいはその塩−ｂ〜ｆを添加し、及び比較例として無添加あるいは比較化合物を添加し、 １００ｍｌステンレス製オートクレーブ中、１２０℃、４８時間保った。不溶性物質の生成量を参考例１と同様にして求めた。結果を表４に示す。
【００２３】
（実施例２）
スチレン製造装置蒸留塔塔底液（スチレンを９０重量％以上含み、重合防止剤としてｐ−ニトロソフェノール ０．０１重量％を含有)３０ｇに本発明のスルフォン酸−ａ、あるいはその塩−ｂ〜ｆを添加し、及び比較例として無添加あるいは比較化合物を添加し、 １００ｍｌ耐圧ガラス製オートクレーブ中、１００℃、２時間保った。参考例１と同様にして、不溶性物質の生成量、及びガラス壁面への付着状況を求めた。結果を表５に示す。
【００２４】
【発明の効果】
本発明方法により、ビニル化合物を扱う製造、精製、反応、貯蔵、輸送などの工程におけるファウリングの発生が防止でき、装置中でのプロセスの流れ良くなり、又熱伝導も良好に保たれ、操作の範囲が広くなり、長期連続運転の可能化、 安全操業、製品の収率向上、さらには製品品質の向上も達成できるなど様々な経済的効果が期待できる。[0001]
[Industrial application fields]
The present invention relates to a method for preventing fouling (dirt) that occurs during production, purification, reaction, storage, or transportation of vinyl compounds.
[0002]
[Prior art]
Vinyl compounds such as acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, styrene, maleic acid, vinyl acetate are extremely easy to polymerize, and their production, purification, reaction, and storage Alternatively, in the transportation process, heat is applied, and iron rust or the like is further mixed to further accelerate the polymerization, and a polymer is deposited on related equipment such as a distillation tower, a reaction tower, a reboiler, or piping. If a polymer is deposited in these devices and pipes, the flow of the process is deteriorated and heat conduction is deteriorated, resulting in many troubles in operation. As described above, the accumulation of the polymer generated in the apparatus, the piping and the like is collectively referred to as so-called “fouling”, and the preventive measure thereof is a very big problem for the operator.
[0003]
Conventionally, in order to prevent this fouling, polymerization inhibitors such as phenols such as tert-butylphenol, catechols such as tert-butylcatechol, quinones such as hydroquinone, nitrosophenols such as nitrosophenol, nitrosophenylamine and nitrosobenzene are used. And methods for adding amines such as p-phenylenediamine have been performed. However, despite the addition of these polymerization inhibitors, the effect of preventing polymerization is not sufficient, and when added in a large amount, there are problems such as high toxicity and high cost, and improvement is strongly desired.
[0004]
The polymerization of the vinyl compound not only proceeds for a long time on the line, but also proceeds to a three-dimensional network structure to generate an insoluble polymer (popcorn polymer). This popcorn polymer continues to grow explosively when a polymerization seed (a seed that becomes the core of the polymer) is generated, and cannot be controlled even by adding a polymerization inhibitor. Fouling occurs in the reaction tower, reboiler, or piping. Fouling can grow and even block the device, which is highly undesirable.
[0005]
[Problems to be solved by the invention]
Conventionally, the solution has been achieved by a method using a polymerization inhibitor, and a certain amount of effect has been observed by increasing the amount used. However, there is a practical limit on the amount of use, and a more efficient solution is desired. The object of the present invention is to reduce the addition amount by increasing the effect of the polymerization inhibitor in the step of adding a polymerization inhibitor to the vinyl compound and treating it, and a distillation column, a reaction column, a reboiler, a storage tank, Provided is a method for preventing fouling generated in piping or the like.
[0006]
[Means for solving the problems]
The inventors of the present invention have found that fouling generated in the steps of production, purification, reaction, storage, transportation, etc. of vinyl compounds can be achieved by solubilizing and dispersing the seeds that form the core of the polymer, particularly popcorn polymer. As a result of earnest research on the solubilization and dispersion mechanism of the seed from the viewpoint of being considerably suppressed, it was found that the object can be achieved by using a specific sulfonic acid in combination with the polymerization inhibitor, and the present invention was completed. It came to do.
[0007]
That is, the present invention is a process of adding a polymerization inhibitor to a vinyl compound and treating it with a general formula (I)
R 1 —SO 3 [X] n (I)
Or a salt thereof (wherein R 1 is a linear or branched alkyl group having 4 to 32 carbon atoms, or an alkyl-substituted benzene nucleus or an alkyl-substituted naphthalene nucleus, and at least one of the alkyl groups is It has a straight chain or branched structure having 4 to 32 carbon atoms, X is hydrogen, an alkali metal, an alkaline earth metal, or a primary, secondary, or tertiary structure having a straight chain or branched structure having 1 to 22 carbon atoms. Fouling of vinyl compound process characterized by adding at least one compound represented by the following formula: an amine salt, which may have a hydroxyl group or an alkoxyl group in the molecule, and n is 1 or 1/2. It is a prevention method.
[0008]
Examples of the vinyl compound of the present invention include acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, styrene, maleic acid, and vinyl acetate. The ester component in acrylic acid ester and methacrylic acid ester is a lower hydrocarbon group such as methyl, ethyl, propyl, and butyl.
[0009]
The sulfonic acid of the present invention or a salt thereof is represented by the general formula (I), and examples of R 1 are nonyl, dodecyl, octadecyl, petroleum sulfonic acid residue, dodecylbenzene, tri-decylbenzene. Dibutylbenzene, octylbenzene, nonylbenzene, nonylnaphthalene. Examples of X include alkali metals such as hydrogen, lithium, sodium and potassium, alkaline earth metals such as magnesium, barium and calcium, propylamine salts, dipropylamine salts, butylamine salts, dibutylamine salts, tributylamine Salt, isobutylamine salt, diisobutylamine salt, sec-butylamine salt, di-sec-butylamine salt, 1,2-dimethylpropylamine salt, hexylamine salt, cyclohexylamine salt, heptylamine salt, 2-ethylhexylamine salt, di -(2-ethylhexyl) amine salt, octylamine salt, nonylamine salt, decylamine salt, undecylamine salt, dodecylamine salt, tetradecylamine salt, hexadecylamine salt, octadecylamine salt, cocoalkylamine salt, monoethanol Alkylamine salts such as amine salts. Specific examples include sodium dodecylbenzenesulfonate, sodium petroleum sulfonate, coconut alkylamine salt of dodecylbenzenesulfonate, monoethanolamine salt of dodecylbenzenesulfonate, and the like. These sulfonic acids or salts thereof may be used singly or in combination of two or more, and the present invention does not impose any restrictions on the mixed use.
[0010]
The addition amount of the sulfonic acid of the present invention or a salt thereof is preferably 10 ppm to 100,000 ppm, more preferably 20 to 10,000 ppm with respect to the vinyl compound. If it is less than 10 ppm, the effect of addition is small, and if it is more than 100,000 ppm, the effect is sufficient, but the effect is not large for the amount of addition, and it cannot be said that it is economically preferable.
[0011]
The polymerization inhibitor used in the steps of production, purification, reaction, storage, transport, etc. of the vinyl compound is not particularly limited in the present invention, but may be a conventional one that has been used conventionally, and quinones , Hydroquinones and derivatives thereof, amines such as nitroso, phenylenediamine, phenothiazine, metal chelate compounds, copper salts, catechols, methylene blue and the like, specifically, anthraquinone, hydroquinone, hydroquinone monomethyl ether, p-nitrosophenol , Nitrosodiphenylamine, nitrosobenzene, α-nitroso-β-naphthol, paraphenylenediamine, N, N′-di-isopropyl-p-phenylenediamine, N, N′-di-sec-butyl-p-phenylenediamine, N , N′-diphenyl-P-phenylenediamine, fluoro Examples include enothiazine, 2-methyl-phenothiazine, 2-octylphenothiazine, copper acetate, copper dibutyldithiocarbamate and the like. Further, the addition amount of these polymerization inhibitors is not limited by the present invention. Usually the amount added to these processes is 100,000 to 100,000 ppm based on the weight of the vinyl compound. If the addition amount is less than this range, a sufficient effect cannot be expected. Conversely, if the addition amount is more than this range, an effect commensurate with the addition amount cannot be obtained, and an economic merit cannot be obtained.
[0012]
The addition method of the sulfonic acid or its salt of the present invention is not particularly limited, but a predetermined amount is added to the raw material in advance, or it is directly added to the distillation tower, the top of the reaction tower, the bottom of the tower, or the storage tank. Added. In the addition, the sulfonic acid of the present invention or a salt thereof is added as it is or dissolved in an appropriate solvent. Further, there is no limitation to adding the sulfonic acid of the present invention or a salt thereof together with the polymerization inhibitor or adding them separately.
[0013]
[Action]
Since it is presumed that the fouling generated in the treatment step of the vinyl compound is largely caused by seed polymerization, generation of fouling can be suppressed if the activity of the seed can be suppressed dull. Conventional polymerization inhibitors are intended to suppress the generation of seeds to a small extent, and although a certain effect is recognized, a sufficient effect cannot be obtained by itself. The sulfonic acid of the present invention or a salt thereof is adsorbed on the seed or the initial polymer from the seed, solubilized and dispersed to slow down the polymerization activity of the seed and suppress the progress of the polymerization reaction. In addition, fouling can be suppressed by preventing branching and crosslinking of the polymer.
[0014]
【Example】
The present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples.
[0015]
[Chemicals used for testing]
* Sulphonic acid-a; Dodecylbenzene sulfonic acid (branched) free acid * Sulfonate-b; Dodecylbenzene sulfonic acid (branched) / tetradecylamine salt * Dodecylbenzene sulfonic acid (branched) and tetradecylamine It was dissolved in equimolar xylene and kept at 60 ° C. for 2 hours to form a salt. In the test, the xylene solution was added as it was.
In the same manner, a salt was obtained.
* Sulfonate-c; dodecylbenzene sulfonic acid (branched) / coconut alkylamine salt * Sulfonate-d; dodecylbenzene sulfonic acid (branched) / 2-ethylhexylamine salt * sulfonate-e; dodecylbenzene Sulfonic acid (branched) / dibutylamine salt * sulfonate-f; dodecylbenzene sulfonic acid (branched) / ethylenediamine salt
* Sulfonate-g; dodecylbenzene sulfonic acid (branched) / monoethanolamine salt * Sulfonate-h; dodecylbenzene sulfonic acid (straight chain) / tetradecylamine salt * sulfonate-i; tridecyl Benzene sulfonic acid (branched) / tetradecylamine salt * sulfonate-j; tert-butylbenzene sulfonic acid / n-butylamine salt * sulfonate-k; petroleum sulfonic acid / sodium salt * sulfonate-l; p-Ethylbenzenesulfonic acid / n-butylamine salt * Hydroquinone: Seiko Chemical Co., Ltd. * Phenothiazine: Seiko Chemical Co., Ltd. * N, N′-di-Sec-butyl-P-phenylenediamine: Sumitomo Chemical Co., Ltd. Sumilyzer BPA (trade name)
* Succinimide-based dispersant: manufactured by Texaco Chemical Co., Ltd., TC-9596A (trade name)
* Polymethacrylate dispersant: TC-8103 (trade name), manufactured by Texaco Chemical Co., Ltd.
[0017]
( Reference Example 1 )
Acrylic acid production apparatus distillation tower bottom liquid (containing 85% by weight or more of acrylic acid, hydroquinone 0.3% by weight as a polymerization inhibitor, N, N′-di-sec-butyl-p-phenylenediamine 0.2% by weight Sulphonic acid-a of the present invention, or a salt thereof -b to k, and no added or comparative compound as a comparative example, and the amount of insoluble material produced after heating for a certain period of time and The effect was confirmed by the degree of adhesion. The operation is as follows.
[0018]
(Measurement of insoluble substance production)
Place 50 g of sample solution in a 200 ml Erlenmeyer flask with a stopper and keep it at 90 ° C. for 600 hours. Then, determine the amount of insoluble material produced in the test solution and determine the degree of adhesion of insoluble material adhering to the bottom and wall of the Erlenmeyer flask. Observed.
1) Measure the weight of 1.0μ Teflon membrane filter, Wo (g)
2) The Erlenmeyer flask test solution is passed through the suction port using the membrane filter of 1).
3) Wash the Erlenmeyer flask and membrane filter thoroughly with acetone.
4) The membrane filter obtained in 3) is dried at 105 ° C. for 2 hours and allowed to cool in a desiccator.
5) Measure the weight of the membrane filter obtained in 4), W (g)
6) Obtain the amount of insoluble material produced from (W-Wo) and convert it to the amount in 1,000 g of the test solution.
[0019]
[Adhesion state of insoluble substances]
Moreover, about the conical flask obtained by 3), the adhesion degree of the insoluble substance before acetone washing | cleaning was observed. The degree of adhesion was indicated by the alphabets A, B, C, and D in the small order.
The adhesion state of the insoluble substance was visually judged according to the following criteria.
A: Adhesion is not recognized. B: Slight adhesion is observed. C: Adhesion is recognized. D: A large amount of adhesion is observed.
The results are shown in Table 1.
[0020]
( Reference Example 2 )
Mixture of vinyl compounds (acrylic acid 90% by weight, acrylic acid dimer 0.5% by weight, maleic acid 0.2% by weight, xylene 8.3% by weight, furfural 0.2% by weight, acetic acid 0.2% by weight, Water 0.1% by weight, methylhydroquine 0.2% by weight, N, N′-di-sec-butyl-p-phenylenediamine 0.3% by weight) and the sulfonic acid-a of the present invention, or The salt-b to f was added, and no additive or a comparative compound was added as a comparative example, and in the same manner as in Reference Example 1 , the amount of insoluble material produced and maintained in a container at 90 ° C. for 600 hours was added. The degree of adhesion was observed. The results are shown in Table 2.
[0021]
( Reference Example 3 )
[Measurement of glass tube closing time]
A 1 l bottle was used as a sample bottle, and a circulation system was circulated through the glass tube (inner diameter 1 mm, heated portion length 1 m) housed in a hot block and returned to the sample bottle. Using this evaluation apparatus, 200 g of a sample was placed in a sample bottle and the inside of the system was purged with nitrogen. Then, the sample was fed into a glass tube heated to 180 ° C. at a flow rate of 0.2 ml / min and circulated. The time until the polymer adhered to the glass tube and closed was compared. It shows that the longer the time until closing, the higher the fouling prevention effect.
Using this evaluation apparatus, the same acrylic acid production apparatus distillation tower bottom liquid as in Reference Example 1 was used as a sample, the sulfonic acid-a of the present invention or its salt -b to c was added, and there was no addition as a comparative example. Alternatively, a comparison compound was added, and the time until the glass tube was blocked was compared. The results are shown in Table 3.
[0022]
( Example 1 )
It was carried out using an acrylonitrile production apparatus distillation column bottom liquid (containing 90% by weight or more of acrylonitrile and 0.02% by weight of hydroquinone as a polymerization inhibitor).
The sulfonic acid-a of the present invention or salts -b to f of the present invention are added to 30 g of this distillation column bottom liquid, and no additive or comparative compound is added as a comparative example. Kept. The amount of insoluble material produced was determined in the same manner as in Reference Example 1 . The results are shown in Table 4.
[0023]
( Example 2 )
Styrene production apparatus distillation tower bottom liquid (containing 90% by weight or more of styrene and 0.01% by weight of p-nitrosophenol as a polymerization inhibitor) As a comparative example, no additive or a comparative compound was added, and the mixture was kept at 100 ° C. for 2 hours in a 100 ml pressure-resistant glass autoclave. In the same manner as in Reference Example 1 , the amount of insoluble material produced and the state of adhesion to the glass wall surface were determined. The results are shown in Table 5.
[0024]
【The invention's effect】
By the method of the present invention, fouling can be prevented in production, purification, reaction, storage, transportation, etc. handling vinyl compounds, the process flow in the apparatus is improved, heat conduction is also kept good, and operation As the range of products is widened, various economic effects such as enabling long-term continuous operation, safe operation, improving product yield, and improving product quality can be expected.
Claims (3)
Ｒ１−ＳＯ３［Ｘ］ｎ （Ｉ）
のスルフォン酸、あるいはその塩類（式中Ｒ１ は炭素数４〜３２の直鎖、もしくは分岐構造を有するアルキル基、又はアルキル置換ベンゼン核、もしくはアルキル置換ナフタレン核でアルキル基のうち少なくとも１つは炭素数４〜３２の直鎖、もしくは分岐構造を有する。Ｘは水素、アルカリ金属、アルカリ土類金属、又は炭素数１〜２２の直鎖，もしくは分岐構造を有する一級、二級、もしくは三級アミン塩で、分子中にヒドロキシル基、もしくはアルコキシル基をもっていてもよい。ｎは１あるいは１/２である）で表される化合物の少なくとも一種を添加することを特徴とするビニル化合物の前記工程におけるファウリング防止方法。In the step of producing, purifying, storing or transporting a vinyl compound selected from the group consisting of acrylonitrile, methacrylonitrile, acrylamide, methacrylamide and styrene by adding a polymerization inhibitor, the compound represented by the general formula (I)
R 1 —SO 3 [X] n (I)
Or a salt thereof (wherein R 1 is a linear or branched alkyl group having 4 to 32 carbon atoms, or an alkyl-substituted benzene nucleus or an alkyl-substituted naphthalene nucleus, and at least one of the alkyl groups is It has a straight chain or branched structure having 4 to 32 carbon atoms, X is hydrogen, an alkali metal, an alkaline earth metal, or a primary, secondary, or tertiary structure having a straight chain or branched structure having 1 to 22 carbon atoms. An amine salt, which may have a hydroxyl group or an alkoxyl group in the molecule, wherein n is 1 or 1/2), Anti-fouling method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17521994A JP3673292B2 (en) | 1994-07-27 | 1994-07-27 | Method for preventing fouling in processes handling vinyl compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17521994A JP3673292B2 (en) | 1994-07-27 | 1994-07-27 | Method for preventing fouling in processes handling vinyl compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0834748A JPH0834748A (en) | 1996-02-06 |
| JP3673292B2 true JP3673292B2 (en) | 2005-07-20 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17521994A Expired - Lifetime JP3673292B2 (en) | 1994-07-27 | 1994-07-27 | Method for preventing fouling in processes handling vinyl compounds |
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| JP (1) | JP3673292B2 (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5746924A (en) * | 1997-04-15 | 1998-05-05 | Nalco/Exxon Energy Chemicals, L.P. | Antifoulant for acrylonitrile purification |
| JP2001172224A (en) * | 1999-12-21 | 2001-06-26 | Idemitsu Petrochem Co Ltd | Method for preventing polymerization of vinyl compound |
| JP3788950B2 (en) * | 2001-04-25 | 2006-06-21 | 伯東株式会社 | Method for inhibiting polymerization of aromatic vinyl compound |
| JP4068886B2 (en) * | 2001-05-01 | 2008-03-26 | 株式会社日本触媒 | Acrylic acid (salt) polymer, production method thereof and use thereof |
| JP2002371034A (en) * | 2001-06-15 | 2002-12-26 | Tosoh Corp | Method for producing para-acetoxystyrene |
| JP4834250B2 (en) * | 2001-07-31 | 2011-12-14 | 伯東株式会社 | Method for inhibiting polymerization of aromatic vinyl compound |
| US6770219B2 (en) * | 2002-10-15 | 2004-08-03 | Nalco Energy Services | Composition and method for preventing fouling in (meth)acrylic acid processes |
| US6984749B2 (en) * | 2002-12-04 | 2006-01-10 | Bp Corporation North America Inc. | Method for inhibiting polymerization during the recovery and purification of unsaturated mononitriles |
| EP1604965A4 (en) * | 2003-03-17 | 2010-01-06 | Hakuto Kk | Polymerization inhibitor for aromatic vinyl compounds and method for inhibiting the polymerization of the compounds |
| JP4743822B2 (en) * | 2004-03-30 | 2011-08-10 | 伯東株式会社 | Method for inhibiting polymerization of aromatic vinyl compound |
| JP4686550B2 (en) * | 2005-02-04 | 2011-05-25 | ケムチュア コーポレイション | Means for controlling the exothermic reaction between styrenic monomers and sulfonic acids |
| JP2006282541A (en) * | 2005-03-31 | 2006-10-19 | Hakuto Co Ltd | Polymerization retarding agent composition and method for inhibiting polymerization of aromatic vinyl compound |
| JP4883928B2 (en) * | 2005-04-08 | 2012-02-22 | ダイヤニトリックス株式会社 | Amides composition |
| JP4959158B2 (en) * | 2005-08-05 | 2012-06-20 | 旭化成ケミカルズ株式会社 | Method for separating and recovering acrylonitrile |
| TWI400252B (en) * | 2006-03-08 | 2013-07-01 | Hakuto Kk | A process for inhibiting polymerization of an aromatic vinyl compound |
| US8246858B2 (en) * | 2006-03-24 | 2012-08-21 | Hakuto Co., Ltd. | Process for inhibiting polymerization of an aromatic vinyl compound |
| US8067629B2 (en) * | 2008-11-19 | 2011-11-29 | Nalco Company | Dispersant antifoulant for acrylonitrile |
| EP4132904A4 (en) * | 2020-04-08 | 2023-12-27 | Ecolab USA, Inc. | Compositions and methods to inhibit fouling of ammonium salts |
-
1994
- 1994-07-27 JP JP17521994A patent/JP3673292B2/en not_active Expired - Lifetime
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