JPH07166152A - Viscosity increase-suppressive agent for hydrocarbon - Google Patents
Viscosity increase-suppressive agent for hydrocarbonInfo
- Publication number
- JPH07166152A JPH07166152A JP31669793A JP31669793A JPH07166152A JP H07166152 A JPH07166152 A JP H07166152A JP 31669793 A JP31669793 A JP 31669793A JP 31669793 A JP31669793 A JP 31669793A JP H07166152 A JPH07166152 A JP H07166152A
- Authority
- JP
- Japan
- Prior art keywords
- salt
- hydrocarbons
- viscosity
- oil
- sulfonic acid
- 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.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、オレフィン製造プロセ
スにおけるオイルクエンチ塔塔底の炭化水素類の粘度上
昇を抑制することにより、製品収率の向上，熱効率向
上、運転の安定化等を目的とした、前記炭化水素類の粘
度上昇抑制剤および粘度上昇抑制方法に関する。BACKGROUND OF THE INVENTION The present invention aims to improve product yield, improve thermal efficiency, and stabilize operation by suppressing an increase in the viscosity of hydrocarbons at the bottom of an oil quench tower in an olefin production process. And a method for suppressing viscosity increase of the above hydrocarbons.
【０００２】[0002]
【従来の技術】石油化学工業におけるオレフィン類の製
造は、通常、ナフサの熱分解によって行われる。ナフサ
は熱分解炉で希釈スチームと共に８００〜８５０℃で熱
分解され、分解炉出口で３５０〜４００℃まで急冷され
た後、オイルクエンチ塔（ガソリンフラクショネータ
ー、ガソリン精留塔ともいわれる）へ送られ、ここで炭
素数９以下の軽質分と、それ以上の重質分とに分けられ
る。オイルクエンチ塔のフィード油中には、スチレン，
メチルスチレン、 ジビニルベンゼン，インデン等の芳香
族不飽和化合物が含まれており、これら化合物がオイル
クエンチ塔内、あるいは塔底部で熱により重合して、塔
底油の粘度が上昇、あるいは塔内での重合物による汚れ
等の原因となる。従来、塔内での汚れを防止するため
に、重合禁止剤の添加が専ら行われていたが、これは単
に重合抑制による汚れ防止であり、ある程度の効果が認
められるものの、塔底油の粘度上昇を抑制するまでには
至らない。従って、塔底油の粘度上昇を抑えるために
は、塔底部温度を低く抑えてこれに対処するのが一般的
であつた。The production of olefins in the petrochemical industry is usually carried out by the thermal decomposition of naphtha. Naphtha is pyrolyzed with dilution steam at 800 to 850 ° C in a thermal decomposition furnace, rapidly cooled to 350 to 400 ° C at the decomposition furnace outlet, and then sent to an oil quench tower (also called a gasoline fractionator or a gasoline rectification tower). Here, it is divided into a light component having 9 or less carbon atoms and a heavy component having more than 9 carbon atoms. In the feed oil of the oil quench tower, styrene,
Contains aromatic unsaturated compounds such as methylstyrene, divinylbenzene, and indene.These compounds are polymerized by heat in the oil quench tower or at the bottom of the tower, increasing the viscosity of the bottom oil, or in the tower. This may cause stains and the like due to the polymer. Conventionally, in order to prevent fouling in the tower, the addition of a polymerization inhibitor has been exclusively performed, but this is simply the prevention of fouling due to the inhibition of polymerization, and although some effect is observed, the viscosity of the bottom oil It is not enough to control the rise. Therefore, in order to suppress the increase in the viscosity of the bottom oil, it is common to keep the bottom temperature low and deal with this.
【０００３】[0003]
【発明が解決しようとする課題】解決しようとする問題
点は、オレフィン類製造プロセスにおいて、オイルクエ
ンチ塔塔底の炭化水素類の粘度上昇を抑制させることが
可能な薬剤およびその方法を提供することである。The problem to be solved is to provide a chemical agent capable of suppressing an increase in the viscosity of hydrocarbons at the bottom of an oil quench column in an olefin production process, and a method therefor. Is.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、オイルク
エンチ塔塔底の炭化水素類の粘度上昇は、フィード油中
に含まれるスチレン，メチルスチレン、ジビニルベンゼ
ン，インデン等の芳香族不飽和化合物の熱重合に起因す
るという推定から、重合抑制および粘度上昇機構につい
て鋭意研究を行った結果、該塔底の炭化水素類の粘度上
昇に対する抑制可能な化合物を見いだし、本発明を完成
するに至った。The inventors of the present invention have found that the increase in the viscosity of hydrocarbons at the bottom of an oil quench column is caused by the aromatic unsaturation of styrene, methylstyrene, divinylbenzene, indene, etc. contained in the feed oil. From the presumption that it is due to thermal polymerization of the compound, as a result of intensive research on the mechanism of suppressing polymerization and increasing viscosity, a compound capable of suppressing increase in viscosity of hydrocarbons at the bottom of the column was found, and the present invention was completed. It was
【０００５】すなわち、本発明は、下記一般式（I）で
表されるスルフォン酸、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あるいはアルキル
置換ナフタレン核で、置換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、ある
いは炭素数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、あるい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。）の一種以上を有効
成分として含有することを特徴とする、オイルクエンチ
塔塔底の炭化水素類の粘度上昇抑制剤である。これにさ
らに芳香族アミン系重合禁止剤、フェノール系重合禁止
剤、ジアルキルヒドロキシルアミン系重合禁止剤から選
ばれた一種以上を，下記一般式（I）の化合物に、配合
することよりなる前記炭化水素類の粘度上昇抑制剤であ
る。That is, the present invention provides a sulfonic acid represented by the following general formula (I) or a salt thereof (wherein R 1 is an alkyl group having a straight chain or branched structure having 4 to 32 carbon atoms; or an alkyl group). A substituted benzene nucleus or an alkyl-substituted naphthalene nucleus in which at least one of the substituted alkyl groups has a linear or branched structure having 4 to 32 carbon atoms, X is hydrogen, an alkali metal, an alkaline earth metal, or 1 carbon atom. To 22 primary, secondary, or tertiary amine salts having a linear or branched structure, which may have a hydroxyl group or an alkoxyl group in the molecule, n is 1 or 1/2). A viscosity increase suppressor for hydrocarbons at the bottom of an oil quench tower, which contains the above as an active ingredient. The above-mentioned hydrocarbon, which further comprises one or more selected from an aromatic amine-based polymerization inhibitor, a phenol-based polymerization inhibitor, and a dialkylhydroxylamine-based polymerization inhibitor to the compound of the following general formula (I). It is a viscosity increase inhibitor of a class.
【０００６】Ｒ1−ＳＯ3［Ｘ]n ．．．（I） また、ナフサ，軽油，天然ガス、液化天然ガス等の炭化
水素類を原料として、これらを熱分解することによりオ
レフィン類を製造するプロセスでのオイルクエンチ塔に
おいて、塔底油量に対し、上記一般式（I）のスルフォ
ン酸、あるいはその塩の有効成分を１０ｐｐｍ〜１万ｐ
ｐｍに保つように、当該薬剤を塔底油に添加することに
よる、オイルクエンチ塔塔底の炭化水素類の粘度上昇抑
制方法を提供するものである。R 1 -SO 3 [X] n . ． ． (I) In addition, in the oil quench tower in the process of producing olefins by pyrolyzing hydrocarbons such as naphtha, light oil, natural gas, and liquefied natural gas as raw materials, , 10 ppm to 10,000 p of the active ingredient of the sulfonic acid of the general formula (I) or a salt thereof.
(EN) A method for suppressing an increase in the viscosity of hydrocarbons at the bottom of an oil quench column by adding the chemical to the column bottom oil so as to maintain pm.
【０００７】本発明の有効成分は上記一般式（I）で表
されるスルフォン酸、あるいはその塩類であり、Ｒ
1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。The active ingredient of the present invention is a sulfonic acid represented by the above general formula (I) or a salt thereof, wherein R
1 is nonyl, dodecyl, octadecyl, petroleum sulfonic acid residue, dodecylbenzene, tri-decylbenzene, dibutylbenzene, octylbenzene, nonylbenzene,
It is nonylnaphthalene. X is hydrogen; alkali metal such as lithium, sodium and potassium; alkaline earth metal such as magnesium, barium and calcium; propylamine salt, dipropylamine salt, butylamine salt, dibutylamine salt, 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, palm alkylamine salt, monoethanolamine Alkylamine salts such as emission salts. Specific examples thereof include sodium dodecylbenzene sulfonate, sodium petroleum sulfonate, dodecylbenzene sulfonate coconut alkylamine salt, dodecylbenzene sulfonate monoethanolamine salt and the like. These sulfonic acids or salts thereof may be used alone or in combination of two or more, and the present invention does not limit the mixed use thereof.
【０００８】また本発明の重合禁止剤は、一般にラジカ
ル連鎖禁止作用に基づく酸化防止剤と同意義に定義され
るもので、芳香族アミン系重合禁止剤としては、ｐ−フ
ェニレンジアミン、Ｎ，Ｎ’−ジ−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、Ｎ−（１−メチルヘプチル）−
ｐ−フェニレンジアミン等のｐ−フェニレンジアミン
類；４，４´−ジクミル−ジフェニルアミン、４，４´
−ジオクチル−ジフェニルアミン、ｐ−メトキシフェニ
ルメチルアミン、４，４´−ジノニルジフェニルアミ
ン、ジフェニルアミン、フェニル−α−ナフチルアミ
ン、フェニル−β−ナフチルアミン等の二級アミン類が
挙げられる。フェノール系重合禁止剤としては、フェノ
ール、２−メチルフェノール、４−メチルフェノール、
２，６−ジメチルフェノール、２，４，６−トリメチル
フェノール、２，６−ジ−tert−ブチルフェノール、
２，４−ジ−tert−ブチルフェノール、２−メチル−４
−ｔｅｒｔ−ブチルフェノール、２，６−ジイソプロピ
ルフェノール、２，６−ジメチル−４−ｔｅｒｔ−ブチ
ルフェノール、４−メトキシフェノール等のフェノール
類；４−tert−ブチルカテコール等のカテコール類；ハ
イドロキノン、２−メチルハイドロキノン、２−ｔｅｒ
ｔ−ブチルハイドロキノン、２，５−ジ−tert−ブチル
ハイドロキノン、２，５−ジ−tert−アミルハイドロキ
ノン等のハイドロキノン類等が挙げられる。ジアルキル
ヒドロキシルアミン系重合禁止剤としては、 ジエチルヒ
ドロキシルアミン、 ジプロピルヒドロキシルアミン等
が挙げられる。Further, the polymerization inhibitor of the present invention is generally defined in the same meaning as an antioxidant based on a radical chain inhibition action, and as the aromatic amine polymerization inhibitor, p-phenylenediamine, N, N is used. '-Di-diisopropyl-p
-Phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-diphenyl-p
-Phenylenediamine, N- (1-methylheptyl)-
p-phenylenediamines such as p-phenylenediamine; 4,4′-dicumyl-diphenylamine, 4,4 ′
Secondary amines such as -dioctyl-diphenylamine, p-methoxyphenylmethylamine, 4,4'-dinonyldiphenylamine, diphenylamine, phenyl-α-naphthylamine, phenyl-β-naphthylamine and the like can be mentioned. Phenol-based polymerization inhibitors include phenol, 2-methylphenol, 4-methylphenol,
2,6-dimethylphenol, 2,4,6-trimethylphenol, 2,6-di-tert-butylphenol,
2,4-di-tert-butylphenol, 2-methyl-4
-Phenols such as tert-butylphenol, 2,6-diisopropylphenol, 2,6-dimethyl-4-tert-butylphenol and 4-methoxyphenol; catechols such as 4-tert-butylcatechol; hydroquinone and 2-methylhydroquinone , 2-ter
Hydroquinones such as t-butyl hydroquinone, 2,5-di-tert-butyl hydroquinone, and 2,5-di-tert-amyl hydroquinone are exemplified. Examples of the dialkylhydroxylamine-based polymerization inhibitor include diethylhydroxylamine and dipropylhydroxylamine.
【０００９】これら重合禁止剤は、１種類単独で用いる
こと、もしくは２種以上を組み合わせて用いることもあ
り、本発明はこれら重合禁止剤の混合使用になんら制限
を加えるものではない。本発明の重合禁止剤をスルフォ
ン酸あるいはその塩類に配合使用する場合、その配合比
は、上記一般式（I）のスルフォン酸、あるいはその塩
類に対し、１０（重量）倍以下である。本発明の粘度上
昇抑制剤の添加量は、オイルクエンチ塔塔底油量に対
し、上記一般式（I）のスルフォン酸、あるいはその塩
の有効成分を１０ｐｐｍ〜１万ｐｐｍ、好ましくは１０
ｐｐｍ〜２０００ｐｐｍに保つようにする。１０ｐｐｍ
未満では、充分な効果が期待出来ず、また１万ｐｐｍよ
り多いと、効果としては充分あるが、添加量の割りには
効果が上がらず、経済的にみて好ましくはない。These polymerization inhibitors may be used alone or in combination of two or more, and the present invention does not impose any limitation on the mixed use of these polymerization inhibitors. When the polymerization inhibitor of the present invention is used in combination with sulfonic acid or a salt thereof, the mixing ratio is 10 (weight) times or less with respect to the sulfonic acid of the general formula (I) or a salt thereof. The addition amount of the viscosity increase inhibitor of the present invention is 10 ppm to 10,000 ppm, preferably 10 parts by weight of the active ingredient of the sulfonic acid of the general formula (I) or a salt thereof with respect to the oil bottom of the oil quench tower.
Try to keep it between ppm and 2000 ppm. 10 ppm
When the amount is less than the above, a sufficient effect cannot be expected, and when it is more than 10,000 ppm, the effect is sufficient, but the effect does not increase relative to the added amount, which is not economically preferable.
【００１０】本発明の粘度上昇抑制剤の注入箇所は、特
に限定されるものではないが、通常オイルクエンチ塔フ
ィード油，還流油に添加、または直接オイルクエンチ塔
塔底液に添加される。また、本発明の粘度上昇抑制剤の
添加にあたっては、各有効成分をそれぞれ別個に添加す
る、もしくは所定量の割合で混合しておき添加する。し
かし、取り扱い易さなどから、各有効成分をそれぞれ計
量し、適当な溶剤等に溶解して添加するのが良い。The injection location of the viscosity increase inhibitor of the present invention is not particularly limited, but it is usually added to the oil quench tower feed oil, reflux oil, or directly added to the oil quench tower bottom liquid. In addition, when adding the viscosity increase inhibitor of the present invention, each active ingredient is added individually or mixed in a predetermined ratio and then added. However, for ease of handling, it is preferable that each active ingredient be weighed, dissolved in a suitable solvent or the like and added.
【００１１】[0011]
【作用】オイルクエンチ塔より留出する塔底油の粘度上
昇は、フィード油中に含まれるスチレン，メチルスチレ
ン、ジビニルベンゼン，インデン等、芳香族不飽和化合
物の重合に起因すると推定されることから、この重合を
抑制できれば、粘度の上昇を抑制可能と考えられる。し
かし、従来の重合禁止剤のみでは、効果的な抑制は行え
なかった。本発明の粘度上昇抑制剤は、生成した初期重
合物に吸着し、これを分散させることにより、重合の進
行および生成重合物の分岐，架橋を防止し、粘度の上昇
を抑制すると考えられる。[Action] The increase in the viscosity of the bottom oil distilled from the oil quench tower is presumed to be due to the polymerization of aromatic unsaturated compounds such as styrene, methylstyrene, divinylbenzene and indene contained in the feed oil. However, if this polymerization can be suppressed, it is considered that the increase in viscosity can be suppressed. However, effective suppression could not be achieved only by the conventional polymerization inhibitor. It is considered that the viscosity increase suppressor of the present invention is adsorbed to the generated initial polymerization product and dispersed therein to prevent the progress of polymerization and the branching and crosslinking of the generated polymerization product, thereby suppressing the increase in viscosity.
【００１２】[0012]
【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。 ［テストに用いた薬品］ Ａ，スルフォン酸；ドデシルベンゼンスルフォン酸（分
岐型）遊離酸 Ｂ，スルフォン酸塩；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。 Ｃ，スルフォン酸塩；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 Ｄ，スルフォン酸塩；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 Ｅ，スルフォン酸塩；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 Ｆ，スルフォン酸塩；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 Ｇ，スルフォン酸塩；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 Ｈ，スルフォン酸塩；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 Ｉ，スルフォン酸塩；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 Ｊ，スルフォン酸塩；ｔert−ブチルベンゼンスルフォ
ン酸／ｎ−ブチルアミン塩 Ｋ，スルフォン酸塩；石油スルフォン酸／ナトリウム塩 Ｌ，スルフォン酸塩；ｐ−エチルベンゼンスルフォン酸
／ｎ−ブチルアミン塩４−ｔｅｒｔ−ブチルカテコール
（ＴＢＣ）：大日本インキ化学工業株式会社製、ＤＩＣ
−ＴＢＣ（商標名） ２，６−ジメチル−ｐ−クレゾール（ＢＨＴ）：川口化
学工業株式会社製、アンテージＢＨＴ（商標名） 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） ジエチルヒドロキシルアミン：東海電化工業株式会社
製、ＤＥＨＡ（商標名） ジフェニルアミン（ＤＰＡ）：精工化学株式会社製、 ポリメタクリレート系分散剤：分子量１５万〜２０万、
テキサコカンパニー製、ＴＣ−８１０３（商標名）EXAMPLES The present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples. [Chemicals used in the test] A, sulfonic acid; dodecylbenzene sulfonic acid (branched type) free acid B, sulfonate; dodecylbenzene sulfonic acid (branched type) / tetradecylamine salt dodecylbenzene sulfonic acid (branched type) Tetradecylamine was dissolved in equimolar xylene and kept at 60 ° C. for 2 hours to form a salt. For the test, the xylene solution was added as it was. Thereafter, a salt was obtained in the same manner. C, sulfonate; dodecylbenzene sulfonic acid (branched type) / coconut alkylamine salt D, sulfonate; dodecylbenzene sulfonic acid (branched type) / 2-ethylhexylamine salt E, sulfonate; dodecylbenzene sulfonic acid ( (Branched type) / dibutylamine salt F, sulfonate; dodecylbenzenesulfonic acid (branched type) / ethylenediamine salt G, sulfonate; dodecylbenzenesulfonic acid (branched type) / monoethanolamine salt H, sulfonate; dodecyl Benzenesulfonic acid (linear type) / tetradecylamine salt I, sulfonate; tridecylbenzenesulfonic acid (branched type) / tetradecylamine salt J, sulfonate; tert-butylbenzenesulfonic acid / n-butylamine salt K, sulfonate; petroleum Rufon acid / sodium salt L, sulfonates; p-ethylbenzene sulfonic acid / n-butylamine salt 4-tert-butylcatechol (TBC): manufactured by Dainippon Ink and Chemicals, Inc., DIC
-TBC (trade name) 2,6-dimethyl-p-cresol (BHT): manufactured by Kawaguchi Chemical Co., Ltd., Antage BHT (trade name) N, N'-di-sec-butyl-p-phenylenediamine: Sumitomo Chemical Industrial Co., Ltd., Sumilizer BPA (trade name) Diethyl hydroxylamine: Tokai Denka Kogyo Co., Ltd., DEHA (trade name) Diphenylamine (DPA): Seiko Chemical Co., Ltd., Polymethacrylate-based dispersant: Molecular weight 150,000 to 200,000 ,
TC-8103 (trade name) manufactured by Texaco Company
【００１３】［粗原料］ ドデシルベンゼンスルフォン酸（分岐型）：テイカ株式
会社製、テイカパワーＢ−１２０（商標名） ドデシルベンゼンスルフォン酸（直鎖型）：テイカ株式
会社製、テイカパワーＬ−１２０（商標名） トリデシルベンゼンスルフォン酸（分岐型）：テイカ株
式会社製、テイカパワー Ｂ−１３０（商標名） 石油スルフォン酸ナトリウム塩：株式会社松村石油研究
所製、スルホール ５００（商標名） テトラデシルアミン：日本油脂株式会社製、アミン Ｍ
Ｂ（商標名） ヤシアルキルアミン：日本油脂株式会社製、アミン Ｆ
Ｂ（商標名） ２−エチルヘキシルアミン、ジブチルアミン、エチレン
ジアミン、モノエタノールアミン、ｎ−ブチルアミン：
東京化成株式会社製の試薬を用いた。[Crude Raw Material] Dodecylbenzenesulfonic acid (branched type): manufactured by Teika Co., Ltd., Takeca Power B-120 (trade name) Dodecylbenzene sulfonic acid (linear type): manufactured by Teika Co., Ltd., Takeca Power L-120 (Trade name) Tridecyl benzene sulfonic acid (branched type): manufactured by Teika Co., Ltd., Teika Power B-130 (trade name) Petroleum sulfonic acid sodium salt: manufactured by Matsumura Oil Research Institute Co., Ltd., Sulhol 500 (trade name) tetradecyl Amine: Amine M manufactured by NOF CORPORATION
B (trade name) Palm alkylamine: Amine F manufactured by NOF CORPORATION
B (trade name) 2-ethylhexylamine, dibutylamine, ethylenediamine, monoethanolamine, n-butylamine:
A reagent manufactured by Tokyo Kasei Co., Ltd. was used.
【００１４】[粘度上昇抑制テスト]２００ｍｌガラス容
器に、 試験油１００ｍｌを入れ、所定量の粘度上昇抑制
剤を添加した後、恒温槽（１８０℃）に１５時間静置し
た。冷却後、ＢＬ型回転粘度計（株式会社東京計器社
製）により２５℃における粘度の測定を行った。試験油
として、実機オイルクエンチ塔塔底油（スチレン ０．
１％以下、メチルスチレン ０．１％以下、ジビニルベ
ンゼン ０．１％以下、インデン ０．１％以下含有）
と、 塔底油とオイルクエンチ塔リフラックス油（スチレ
ン ３０％、メチルスチレン １４．５％、ジビニルベ
ンゼン ０．２％、インデン ９％含有）の９：１（容
積比）混合油とをそれぞれ用いた。それらのテスト結果
を表１と表２に示す。[Viscosity increase suppression test] 100 ml of test oil was placed in a 200 ml glass container, a predetermined amount of viscosity increase suppression agent was added, and the mixture was allowed to stand in a thermostat (180 ° C) for 15 hours. After cooling, the viscosity was measured at 25 ° C. with a BL type rotational viscometer (manufactured by Tokyo Keiki Co., Ltd.). As the test oil, the bottom oil of the actual equipment oil quench tower (styrene 0.
1% or less, methylstyrene 0.1% or less, divinylbenzene 0.1% or less, indene 0.1% or less)
And a 9: 1 (volume ratio) mixture of bottom oil and oil quench tower reflux oil (containing 30% styrene, 14.5% methylstyrene, 0.2% divinylbenzene, 9% indene). I was there. The test results are shown in Tables 1 and 2.
【００１５】これらの結果より、本発明のスルフォン酸
あるいはその塩、さらに重合禁止剤を加えて用いること
により、オイルクエンチ塔塔底の炭化水素類の粘度上昇
を効率よく抑制できることが認められた。From these results, it was confirmed that the viscosity increase of the hydrocarbons at the bottom of the oil quench column can be efficiently suppressed by using the sulfonic acid or its salt of the present invention and the polymerization inhibitor.
【００１６】 [0016]
【００１７】[0017]
【発明の効果】本発明により、オイルクエンチ塔塔底の
炭化水素類の粘度上昇を抑制することができ、ガソリン
収率の向上，ボトムポンプの負荷の軽減、配管内各所で
の閉塞抑制、オイルクエンチ塔での還流量の削減が可能
となる。また、塔底部の温度を上げることが可能となる
ことから、後続プロセスにおける加熱スチーム使用量の
削減等、様々な経済的効果が期待できる。EFFECTS OF THE INVENTION According to the present invention, it is possible to suppress an increase in the viscosity of hydrocarbons at the bottom of an oil quench tower, improve the gasoline yield, reduce the load on the bottom pump, suppress clogging at various points in the pipe, and oil. It is possible to reduce the amount of reflux in the quench tower. In addition, since it is possible to raise the temperature of the bottom of the column, various economic effects such as reduction of the amount of heating steam used in the subsequent process can be expected.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 谷崎 青磁 三重県四日市市別名６−６−９ 伯東株式 会社四日市研究所内 (72)発明者 熊澤 信光 三重県四日市市生桑町1940−10 (72)発明者 竹内 豊 三重県四日市市別名３−４−１ ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tanizaki Celadon Yokkaichi City, Mie Prefecture 6-6-9 Inside Yokkaichi Research Institute, Hakuto Co., Ltd. Yutaka Takeuchi Yokkaichi, Mie aka 3-4-1
Claims (3)
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、置換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。）の化合物の少なくとも一種
を有効成分として含有することを特徴とする、炭化水素
類の粘度上昇抑制剤。1. The general formula (I) R 1 —SO 3 [X] n . ． ． (I) Sulfonic acid or a salt thereof (wherein R 1 is an alkyl group having a linear or branched structure having 4 to 32 carbon atoms; or an alkyl-substituted benzene nucleus or an alkyl-substituted naphthalene nucleus, and a substituted alkyl group At least one has a linear 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 amine salt having a linear or branched structure having 1 to 22 carbon atoms, and having a hydroxyl group or an alkoxyl group in the molecule. Good. n is 1 or 1/2. A viscosity increase inhibitor for hydrocarbons, which comprises at least one of the compounds of 1) as an active ingredient.
系重合禁止剤、 ジアルキルヒドロキシルアミン系重合禁
止剤の群から選ばれた一種以上を、１０（重量）倍以下
の割合で請求項１記載の一般式（I）に配合することを
特徴とする炭化水素類の粘度上昇抑制剤。2. The one or more selected from the group consisting of an aromatic amine-based polymerization inhibitor, a phenol-based polymerization inhibitor and a dialkylhydroxylamine-based polymerization inhibitor in a proportion of 10 (weight) times or less. A viscosity increase inhibitor for hydrocarbons, which is contained in the general formula (I).
フィン類を製造するプロセスでのオイルクエンチ塔にお
いて、塔底油量に対し、請求項１記載の一般式（I）で
表されるスルフォン酸、あるいはその塩の有効成分を１
０ｐｐｍ〜１万ｐｐｍに保つように、請求項１と２記載
の粘度上昇抑制剤を塔底油に添加することを特徴とす
る、オイルクエンチ塔塔底の炭化水素類の粘度上昇抑制
方法。3. The sulfonic acid represented by the general formula (I) according to claim 1, in the oil quench tower in the process of producing olefins by thermally decomposing hydrocarbons, relative to the amount of bottom oil. , Or the active ingredient of its salt 1
A method for suppressing the increase in viscosity of hydrocarbons at the bottom of an oil quench tower, which comprises adding the viscosity increase suppressor according to claim 1 or 2 to the bottom oil so as to maintain the viscosity at 0 ppm to 10,000 ppm.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31669793A JP3545440B2 (en) | 1993-12-16 | 1993-12-16 | Viscosity increase inhibitor for aromatic unsaturated compound and method thereof |
| US08/861,922 US5824829A (en) | 1993-12-16 | 1997-05-22 | Hydrocarbon viscosity inhibitor and inhibiting method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31669793A JP3545440B2 (en) | 1993-12-16 | 1993-12-16 | Viscosity increase inhibitor for aromatic unsaturated compound and method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07166152A true JPH07166152A (en) | 1995-06-27 |
| JP3545440B2 JP3545440B2 (en) | 2004-07-21 |
Family
ID=18079899
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31669793A Expired - Lifetime JP3545440B2 (en) | 1993-12-16 | 1993-12-16 | Viscosity increase inhibitor for aromatic unsaturated compound and method thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3545440B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0908505A1 (en) * | 1997-10-06 | 1999-04-14 | Chimec S.P.A. | Anti-aging additive composition for a quench oil circuit in an ethylene production plant and method for operating the circuit |
| JP2003040813A (en) * | 2001-07-31 | 2003-02-13 | Hakuto Co Ltd | Method for preventing polymerization of aromatic vinyl compound |
| JP2006500439A (en) * | 2002-09-20 | 2006-01-05 | ジーイー・ベッツ・インコーポレイテッド | Suppression of viscosity increase and fouling in hydrocarbon streams containing unsaturated bonds. |
| WO2007111237A1 (en) | 2006-03-24 | 2007-10-04 | Hakuto Co., Ltd. | Method of inhibiting polymerization of aromatic vinyl compound |
| JP2008530269A (en) * | 2005-02-04 | 2008-08-07 | 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 |
| JP2010275233A (en) * | 2009-05-28 | 2010-12-09 | Hakuto Co Ltd | Method of preventing growth of stain in gas phase part in oil quenching column |
| JP2014530934A (en) * | 2011-10-19 | 2014-11-20 | ナルコ カンパニー | Circulation assistance for primary fractional quenching loop |
| KR20190091450A (en) * | 2016-12-07 | 2019-08-06 | 에코랍 유에스에이 인코퍼레이티드 | Antifouling Compositions for Petroleum Process Streams |
-
1993
- 1993-12-16 JP JP31669793A patent/JP3545440B2/en not_active Expired - Lifetime
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0908505A1 (en) * | 1997-10-06 | 1999-04-14 | Chimec S.P.A. | Anti-aging additive composition for a quench oil circuit in an ethylene production plant and method for operating the circuit |
| JP2003040813A (en) * | 2001-07-31 | 2003-02-13 | Hakuto Co Ltd | Method for preventing polymerization of aromatic vinyl compound |
| JP2006500439A (en) * | 2002-09-20 | 2006-01-05 | ジーイー・ベッツ・インコーポレイテッド | Suppression of viscosity increase and fouling in hydrocarbon streams containing unsaturated bonds. |
| JP2008530269A (en) * | 2005-02-04 | 2008-08-07 | 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 |
| 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 |
| WO2007111237A1 (en) | 2006-03-24 | 2007-10-04 | Hakuto Co., Ltd. | Method of inhibiting polymerization of aromatic vinyl compound |
| KR101103158B1 (en) * | 2006-03-24 | 2012-01-04 | 하쿠토 가부시키가이샤 | Method of inhibiting polymerization of aromatic vinyl compound |
| EP2995601A1 (en) | 2006-03-24 | 2016-03-16 | Hakuto Co., Ltd | Method of inhibiting polymerization of aromatic vinyl compound |
| JP2010275233A (en) * | 2009-05-28 | 2010-12-09 | Hakuto Co Ltd | Method of preventing growth of stain in gas phase part in oil quenching column |
| JP2014530934A (en) * | 2011-10-19 | 2014-11-20 | ナルコ カンパニー | Circulation assistance for primary fractional quenching loop |
| KR20190091450A (en) * | 2016-12-07 | 2019-08-06 | 에코랍 유에스에이 인코퍼레이티드 | Antifouling Compositions for Petroleum Process Streams |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3545440B2 (en) | 2004-07-21 |
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