JP2008169297A - Desulfurizing agent for super-deep oxidative desulfurization and oxidative desulfurization method using the same - Google Patents
Desulfurizing agent for super-deep oxidative desulfurization and oxidative desulfurization method using the same Download PDFInfo
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Abstract
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本発明は、液状油に含まれる有機硫黄化合物を超深度酸化脱硫する脱硫剤及びその脱硫方法に関する。 The present invention relates to a desulfurization agent that desulfurizes an organic sulfur compound contained in a liquid oil, and a method for desulfurization thereof.
石油や石炭などの化石資源を原料とする燃料油中に含まれる硫黄化合物類は、燃焼に際して硫黄酸化物を生成し、大気環境汚染の原因となる。その主な原因として、軽油等を燃料とする自動車の排出ガス中に含まれる硫黄酸化物が挙げられ、近年の燃料油の硫黄分は５０ｐｐｍ以下に規制され、将来的には更なる規制の強化が見込まれている。そのため、燃料油中に含まれる硫黄化合物の脱硫技術は、積極的に開発が進められてきており、現在精油所では、触媒の存在下に水素化処理を行う水素化脱硫方法が行われている。 Sulfur compounds contained in fuel oils made from fossil resources such as oil and coal produce sulfur oxides during combustion and cause air pollution. The main cause is sulfur oxides contained in the exhaust gas of automobiles that use diesel oil as fuel. The sulfur content of fuel oil in recent years has been regulated to 50 ppm or less, and further regulations will be strengthened in the future. Is expected. Therefore, desulfurization technology for sulfur compounds contained in fuel oil has been actively developed, and at present refineries, hydrodesulfurization methods that perform hydrotreating in the presence of a catalyst are being carried out. .
ところで、このような軽油等の燃料油中には、前記水素化脱硫法において、その除去が極めて困難な有機硫黄化合物、特に硫黄原子近傍にアルキル基などの立体障害性の置換基を持つアルキル置換ジベンゾチオフェン類が含まれており、硫黄分を５０ｐｐｍ以下へと低減させるためには、これらの難脱硫性化合物を効果的に脱硫する必要がある。そこで、超深度脱硫の達成のためには、このような難分解性有機硫黄化合物を有効に除去することのできる、新たな脱硫技術の開発が急務とされている。 By the way, in such fuel oil such as light oil, in the hydrodesulfurization method, organic sulfur compounds that are extremely difficult to remove, particularly alkyl substitution having a sterically hindered substituent such as an alkyl group in the vicinity of the sulfur atom. Dibenzothiophenes are contained, and in order to reduce the sulfur content to 50 ppm or less, it is necessary to effectively desulfurize these difficult-to-desulfurize compounds. Therefore, in order to achieve ultra-deep desulfurization, there is an urgent need to develop a new desulfurization technique that can effectively remove such persistent organic sulfur compounds.
そこで様々な脱硫方法が考案されている。従来、脱硫の方法としては、金属系の触媒を使用することが一般的であり、現在もその方法が通常的に行われている。しかし、金属系の触媒だけを使用した場合、超深度の脱硫は難しく、近年、金属系の触媒に酸化剤を併用することが考えられてきた（例えば、特許文献１，２を参照）。 Various desulfurization methods have been devised. Conventionally, as a method of desulfurization, it is common to use a metal-based catalyst, and the method is usually performed at present. However, when only a metal catalyst is used, ultra-deep desulfurization is difficult, and in recent years, it has been considered to use an oxidizing agent in combination with a metal catalyst (for example, see Patent Documents 1 and 2).
しかし、こうした酸化剤を使用する方法はある程度の効果はあるものの、難分解性の有機硫黄化合物は分解されにくく、また、特許文献１のように溶剤を使用すると溶剤処理のための処理時間増及びコスト増をまねくため、更に効率の良い脱硫触媒が求められていた。 However, although the method using such an oxidizing agent has a certain effect, the hardly decomposable organic sulfur compound is difficult to be decomposed, and when a solvent is used as in Patent Document 1, the processing time for solvent treatment is increased. In order to increase the cost, a more efficient desulfurization catalyst has been demanded.
従って、本発明が解決しようとする課題は、液状油に含まれる有機硫黄化合物、特に難分解性の有機硫黄化合物を効率よく除去することのできる脱硫剤、及びその脱硫剤を用いた脱硫方法を提供することにある。 Therefore, the problem to be solved by the present invention is to provide a desulfurization agent that can efficiently remove organic sulfur compounds contained in liquid oil, particularly difficult-to-decompose organic sulfur compounds, and a desulfurization method using the desulfurization agent. It is to provide.
そこで本発明者等鋭意検討し、難分解性の有機硫黄化合物も効率よく分解できる脱硫剤を見出し、本発明に至った。
即ち、（１）以下の成分（ａ）および成分（ｂ）からなる固形触媒、
（ａ）金属の酸化物、該酸化物の酸及び該酸化物の酸の塩、金属のイソポリ酸類及びその塩、金属のヘテロポリ酸類及びその塩よりなる群から選択された少なくとも一種の成分（該金属はタングステン、モリブデン及びバナジウムよりなる群から選択される）、
（ｂ）ハイドロタルサイト、並びに
（２）過酸化尿素
を含む脱硫剤である。
Thus, the present inventors have intensively studied, and found a desulfurization agent that can efficiently decompose hardly-decomposable organic sulfur compounds, and have reached the present invention.
That is, (1) a solid catalyst comprising the following components (a) and (b),
(A) at least one component selected from the group consisting of a metal oxide, an acid of the oxide and an acid salt of the oxide, a metal isopolyacid and a salt thereof, a metal heteropolyacid and a salt thereof (the The metal is selected from the group consisting of tungsten, molybdenum and vanadium);
(B) a desulfurization agent containing hydrotalcite and (2) urea peroxide.
本発明の効果は、液状油に含まれる有機硫黄化合物、特に難分解性の有機硫黄化合物を効率よく除去することのできる脱硫剤、及びその脱硫剤を用いた脱硫方法を提供したことにある。以下、本発明をその好ましい実施形態に基づき詳細に説明する。 The effect of the present invention is to provide a desulfurization agent capable of efficiently removing an organic sulfur compound contained in a liquid oil, particularly a hardly decomposable organic sulfur compound, and a desulfurization method using the desulfurization agent. Hereinafter, the present invention will be described in detail based on preferred embodiments thereof.
まず（１）固形触媒である成分（ａ）について説明する。成分（ａ）としては、タングステン、モリブデンおよびバナジウムのいずれか一種以上を含有する金属の酸化物、該酸化物の酸または該酸化物の酸の塩を使用することができる。これらの金属の酸化物やその酸としては、例えば、三酸化タングステン、三酸化モリブデン、五酸化バナジウム、タングステン酸、モリブデン酸、バンジン酸等が挙げられるが、これらの中でも、タングステン原子を含有しているものが好ましい。また、塩の対イオンとしては、例えば、アルカリ金属類、アルカリ土類金属類、塩基性の窒素化合物等が挙げられるが、これらの中でもカリウム、ナトリウムまたはアンモニウム等の対イオンが好ましい。 First, (1) component (a) which is a solid catalyst will be described. As the component (a), an oxide of a metal containing at least one of tungsten, molybdenum, and vanadium, an acid of the oxide, or an acid salt of the oxide can be used. Examples of these metal oxides and acids thereof include tungsten trioxide, molybdenum trioxide, vanadium pentoxide, tungstic acid, molybdic acid, and bannic acid. Among these, tungsten atoms are contained. Is preferred. Examples of the counter ion of the salt include alkali metals, alkaline earth metals, basic nitrogen compounds, etc. Among them, a counter ion such as potassium, sodium or ammonium is preferable.
更に、タングステン、モリブデンおよびバナジウムよりなる群から選択された少なくとも一種の金属元素を含有するイソポリ酸類、ヘテロポリ酸類、又はその酸の塩も成分（ａ）として使用することができる。これらのポリ酸類の中でも、イソポリタングステン酸及びその塩、イソポリモリブデン酸及びその塩、ヘテロポリタングステン酸及びその塩、ヘテロポリモリブデン酸及びその塩が好ましく、ヘテロポリタングステン酸及びその塩がより好ましい。また、塩の対イオンとしては、カリウム、ナトリウムまたはアンモニウム等の対イオンが好ましい。これらのポリ酸類の構造にはケギン型や、ドーソン型も含まれる。 Furthermore, isopolyacids, heteropolyacids, or salts of the acids containing at least one metal element selected from the group consisting of tungsten, molybdenum and vanadium can also be used as component (a). Among these polyacids, isopolytungstic acid and its salt, isopolymolybdic acid and its salt, heteropolytungstic acid and its salt, heteropolymolybdic acid and its salt are preferable, and heteropolytungstic acid and its salt are more preferable. The counter ion of the salt is preferably a counter ion such as potassium, sodium or ammonium. The structures of these polyacids include Keggin type and Dawson type.
通常ポリ酸は陰イオンとして存在し、荷電を中和するためＮａ+、Ｋ+等のアルカリ金属類あるいはＭｇ2+、Ｃａ2+等のアルカリ土類金属、アンモニウムイオンさらには第四級アンモニウムイオンまたは含窒素複素環を有する第四級アンモニウム型化合物のイオンの塩よりなる群から選択された少なくとも一種の対イオンで中和されている。これらの対イオンの中でも、より好ましい例としてＮａ+、Ｋ+、アンモニウムおよびピリジン環を有する第四級アンモニウム化合物が挙げられる。また、ヘテロポリ酸におけるヘテロ原子としてはリン、ホウ素、珪素、ゲルマニウム、ランタノイド、ニッケル、鉄、コバルト、ルテニウム等が挙げられる。これらのポリ酸類は市販品を利用することができる。また、例えば特許公表２００２−５３２３７８号公報またはＭ．Ｔ．Ｐｏｐｅ らによる「インオーガニックケミストリー、第６巻 １１４７．頁（１９６７）」等に従い合成することもできる。 Polyacids usually exist as anions, and to neutralize the charge, alkali metals such as Na + and K + , alkaline earth metals such as Mg 2+ and Ca 2+ , ammonium ions, and quaternary ammonium ions Alternatively, it is neutralized with at least one counter ion selected from the group consisting of salts of ions of quaternary ammonium type compounds having a nitrogen-containing heterocycle. Among these counter ions, more preferable examples include Na + , K + , ammonium and a quaternary ammonium compound having a pyridine ring. Moreover, phosphorus, boron, silicon, germanium, a lanthanoid, nickel, iron, cobalt, ruthenium etc. are mentioned as a hetero atom in heteropoly acid. Commercially available products can be used for these polyacids. Also, for example, Japanese Patent Publication No. 2002-532378 or M.S. T.A. It can also be synthesized according to “Inorganic Chemistry, Vol. 6, 1147. (1967)” by Pope et al.
成分（ａ）としては、上記のいずれの化合物も使用できるが、触媒としての活性が高いことから、タングステンのヘテロポリ酸またはその酸の塩が特に好ましく、１２−タングストリン酸及び１２−タングストリン酸塩がより好ましい。 As the component (a), any of the above-mentioned compounds can be used. However, since the activity as a catalyst is high, a tungsten heteropolyacid or a salt of the acid is particularly preferable. 12-tungstophosphoric acid and 12-tungstophosphoric acid A salt is more preferred.
次に成分（ｂ）のハイドロタルサイト類の説明をする。ハイドロタルサイト類としては、下記一般式（１）（Ｍ2+）1-x（Ｍ3+）x（ＯＨ）2（Ａn-）x/n・ａＨ2Ｏ （１）
（式中、Ｍ2+は２価金属イオンを示し、Ｍ3+は３価金属イオンを示し、Ａn-はｎ価のアニオンを示し、ｘおよびａはそれぞれ０＜ｘ＜０．５、０≦ａ＜１の範囲を示す）で表すことができる。本発明に使用できる成分（ｂ）としては、上記一般式（１）で表される化合物の群から選択された少なくとも一種からなるハイドロタルサイト類であり、好ましくは、Ｍ2+はＭｇ、ＣａおよびＺｎよりなる群から選ばれた少なくとも一種、Ｍ3+はＡｌおよびＦｅから選ばれた少なくとも一種、Ａn-はＯＨ-、ＣｌＯ4 -、ＮＯ3 -、ＳＯ4 2-、ＣＯ3 2-、ＳｉＯ3 2-、ＨＰＯ4 2-、ＰＯ4 3-およびＣＨ3ＣＯＯ-よりなる群から選ばれた少なくとも一種からなるハイドロタルサイト類で、より好ましくはＭ2+はＭｇ、Ｍ3+はＡｌ、Ａn-はＣＯ3 2-で示されるハイドロタルサイト類が使用される。ハイドロタルサイト類の合成方法は、例えば特公昭４７−３２１９８号公報に示された合成方法が利用できる。
Next, the hydrotalcite component (b) will be described. As hydrotalcites, the following general formula (1) (M 2+ ) 1-x (M 3+ ) x (OH) 2 (A n− ) x / n · aH 2 O (1)
(Wherein, M 2+ is a divalent metal ion, M 3+ is a trivalent metal ion, A n-represents an n-valent anion, respectively x and a 0 <x <0.5, 0 ≦ a <1). The component (b) that can be used in the present invention is a hydrotalcite composed of at least one selected from the group of compounds represented by the general formula (1). Preferably, M 2+ is Mg, Ca. and at least one, at least one M 3+ is selected from Al and Fe selected from the group consisting of Zn, A n-is OH -, ClO 4 -, NO 3 -, SO 4 2-, CO 3 2- , SiO 3 2− , HPO 4 2− , PO 4 3−, and CH 3 COO − are at least one hydrotalcite, more preferably M 2+ is Mg and M 3+ is al, A n-hydrotalcite compound represented by CO 3 2- is used. As a method for synthesizing hydrotalcites, for example, a synthesis method disclosed in Japanese Patent Publication No. 47-32198 can be used.
成分（ａ）および成分（ｂ）よりなる固体触媒の調製は、両者を混合するだけで良く、例えば、予めハイドロタルサイト類の乾燥物にポリ酸類の粉末を添加し、よく粉末同士を攪拌混合する等である。成分（ｂ）であるハイドロタルサイト類に成分（ａ）をできるだけ均一に分散させることが好ましく、そのため成分（ａ）の粉末は微粒子であることが好ましい。好ましい粒子サイズとして電子顕微鏡観察による平均粒子径が１０μｍ以下、より好ましくは５〜０．０１μｍである。
他の方法としては、ハイドロタルサイト類の乾燥物に、水溶液とした成分（ａ）を添加し、攪拌混合する方法でも良い。さらにはハイドロタルサイト類を調製する際に、成分（ａ）を少量添加しておく方法や、ハイドロタルサイト類に成分（ａ）をスプレー噴霧する方法でも良い。
Preparation of the solid catalyst consisting of the component (a) and the component (b) only requires mixing them. For example, the powder of polyacids is added to the dried hydrotalcite in advance, and the powders are mixed well with stirring. Etc. It is preferable to disperse the component (a) as uniformly as possible in the hydrotalcite that is the component (b), and therefore the powder of the component (a) is preferably fine particles. As a preferable particle size, an average particle diameter by electron microscope observation is 10 μm or less, more preferably 5 to 0.01 μm.
As another method, a method of adding the component (a) as an aqueous solution to the dried hydrotalcite and stirring and mixing it may be used. Furthermore, when preparing hydrotalcite, the method of adding a small amount of component (a) or the method of spraying component (a) on hydrotalcite may be used.
成分（ｂ）のハイドロタルサイト類の粒子サイズについては特に制限は無く、例えばハイドロタルサイト類の乾燥粉末を精製水と混練した後、押し出し造粒したものから得られた乾燥粉末およびそのものを微粉砕した微粒子でも使用できる。通常の使用範囲としては５ｍｍ〜０．１μｍであり、好ましくは１ｍｍ〜５μｍ、さらに好ましくは１００μｍ〜１０μｍである。ハイドロタルサイト類の表面積にも特に制限はないが、通常はＢＥＴ法で５００ｍ2／ｇ〜５ｍ2／ｇのものが多く、好ましくは３００ｍ2／ｇ〜１０ｍ2／ｇ、より好ましくは２５０ｍ2／ｇ〜５０ｍ2／ｇである。 The particle size of the hydrotalcite of component (b) is not particularly limited. For example, the dry powder obtained by extruding and granulating the hydrotalcite dry powder after being kneaded with purified water is finely divided. Even pulverized fine particles can be used. The normal use range is 5 mm to 0.1 μm, preferably 1 mm to 5 μm, and more preferably 100 μm to 10 μm. Although there is no particular limitation to the surface area of the hydrotalcite, usually many things 500m 2 / g~5m 2 / g by the BET method, preferably 300m 2 / g~10m 2 / g, more preferably 250 meters 2 / G to 50 m 2 / g.
成分（ａ）と成分（ｂ）の混合比に制限はないが、成分（ｂ）のハイドロタルサイト類１モルあたり成分（ａ）を分子内の金属元素（タングステン、モリブデン等）として０．００１モル〜０．１モルとするのが好ましく、０．００５モル〜０．０５モルとするのがより好ましい。 Although there is no restriction | limiting in the mixing ratio of a component (a) and a component (b), 0.001 as a metal element (tungsten, molybdenum, etc.) in a molecule | numerator (a) per 1 mol of hydrotalcites of a component (b). It is preferable to set it as mol-0.1 mol, and it is more preferable to set it as 0.005 mol-0.05 mol.
混合方法については特に制限されないが、混合時の温度は２００℃を超えないほうが好ましい。より好ましい混合温度は０℃〜１００℃であり、特に成分（ａ）の塩が第四級アンモニウムイオンまたは含窒素複素環を有する第四級アンモニウム化合物の塩である場合は１００℃を超えないほうが好ましい。混合する方法としては、成分（ａ）を均一に分散させることが出来るのであればいずれの方法・装置でもよく、例えば、ヘンシェルミキサーのような高速攪拌翼のついた混合機、Ｖ型混合機、リボンブレンダー等が利用できる。 The mixing method is not particularly limited, but it is preferable that the temperature during mixing does not exceed 200 ° C. A more preferable mixing temperature is 0 ° C. to 100 ° C. Especially when the salt of the component (a) is a salt of a quaternary ammonium compound having a quaternary ammonium ion or a nitrogen-containing heterocyclic ring, it should not exceed 100 ° C. preferable. As a mixing method, any method and apparatus may be used as long as the component (a) can be uniformly dispersed. For example, a mixer having a high-speed stirring blade such as a Henschel mixer, a V-type mixer, Ribbon blenders can be used.
次に（２）過酸化尿素について説明する。過酸化尿素は、尿素と過酸化水素を原料として製造するものであり、その製造方法としては、例えば、尿素１モルに対して過酸化水素を１〜３モル、好ましくは１．１〜２モル添加し、３０〜８０℃で１〜１０時間混合させた後、冷却して過酸化尿素の結晶を析出させて分離・乾燥させればよい。過酸化水素が１モルより少ないと反応速度が遅くなり、更に未反応の尿素が大量に残存してしまう。また、過酸化水素が３モルより多いと未反応の過酸化水素が大量に残存してしまう。
過酸化水素は通常水溶液の状態で流通しているが、過酸化水素の濃度の低いものを使用すると反応系内に水が大量に入ってしまい、過酸化尿素が析出しにくくなるので、５０質量％以上の高濃度の過酸化水素水を使用するのが好ましい。
Next, (2) urea peroxide will be described. Urea peroxide is produced using urea and hydrogen peroxide as raw materials, and as a production method thereof, for example, hydrogen peroxide is 1 to 3 moles, preferably 1.1 to 2 moles per mole of urea. After adding and mixing at 30 to 80 ° C. for 1 to 10 hours, cooling is performed to precipitate urea peroxide crystals, followed by separation and drying. When the amount of hydrogen peroxide is less than 1 mole, the reaction rate becomes slow, and a large amount of unreacted urea remains. If the amount of hydrogen peroxide is more than 3 mol, a large amount of unreacted hydrogen peroxide remains.
Hydrogen peroxide usually circulates in the form of an aqueous solution, but if a low concentration of hydrogen peroxide is used, a large amount of water will enter the reaction system, making it difficult for urea peroxide to precipitate. It is preferable to use a high concentration hydrogen peroxide solution of at least%.
本発明の脱硫剤は（１）成分（ａ）および成分（ｂ）からなる固体触媒並びに（２）過酸化尿素を含有する触媒組成物であるが、過酸化水素に対する固体触媒の量が少なすぎたり多すぎたりすると、酸化反応がスムーズに進まずに反応時間が長くなる場合があるため、その混合比は、過酸化尿素１質量部に対して固体触媒０．１〜１０質量部が好ましく、０．５〜８質量部がより好ましい。２つの成分とも粉末、あるいは顆粒状の固体であり、混合方法としては２つの成分を均一になるように混合できれば特に制限はなく、例えば、ヘンシェルミキサーのような高速攪拌翼のついた混合機、Ｖ型混合機、リボンブレンダー等が利用できる。また本発明の脱硫剤は、成分（ａ）と成分（ｂ）からなる固体触媒の触媒効果と過酸化尿素の酸化剤としての効果が同時に働くことによって有機硫黄化合物を効果的に酸化させるものである。 The desulfurizing agent of the present invention is a catalyst composition containing (1) a solid catalyst comprising component (a) and component (b) and (2) urea peroxide, but the amount of solid catalyst relative to hydrogen peroxide is too small. If it is too much, the oxidation reaction may not proceed smoothly and the reaction time may become long. Therefore, the mixing ratio is preferably 0.1 to 10 parts by mass of the solid catalyst with respect to 1 part by mass of urea peroxide, 0.5-8 mass parts is more preferable. The two components are either powder or granular solid, and the mixing method is not particularly limited as long as the two components can be mixed uniformly. For example, a mixer equipped with a high-speed stirring blade such as a Henschel mixer, V-type mixers, ribbon blenders, etc. can be used. The desulfurizing agent of the present invention effectively oxidizes an organic sulfur compound by simultaneously acting as a catalytic effect of the solid catalyst comprising the component (a) and the component (b) and an oxidizing agent of urea peroxide. is there.
本発明に用いられる液状油に特に制約はなく、硫黄化合物が含有する一般的な燃料油や潤滑油等に利用することができる。こうした燃料油や潤滑油としては、例えば、ガソリン、軽油、重油、灯油、ジェット燃料、天然ガス、アルコール、ＬＰＧ、ナフサ、アスファルト油、オイルサンド油、石炭液化油、シェルオイル、廃プラスチック油、バイオフューエル、ＧＴＬ、パラフィン系鉱油、ナフテン系鉱油あるいはこれらを精製した精製鉱油類を用いることができる。これらの中でも、燃焼時の硫黄酸化物が問題となる燃料油が好ましく、ガソリン、軽油、灯油がより好ましい。 There is no restriction | limiting in particular in the liquid oil used for this invention, It can utilize for the common fuel oil, lubricating oil, etc. which a sulfur compound contains. Examples of such fuel oil and lubricating oil include gasoline, light oil, heavy oil, kerosene, jet fuel, natural gas, alcohol, LPG, naphtha, asphalt oil, oil sand oil, coal liquefied oil, shell oil, waste plastic oil, bio Fuel, GTL, paraffinic mineral oil, naphthenic mineral oil, or refined mineral oil refined from these can be used. Among these, fuel oils in which sulfur oxides during combustion are a problem are preferable, and gasoline, light oil, and kerosene are more preferable.
これらの液状油には、主に原料由来の有機硫黄化合物が含まれるが、こうした有機硫黄化合物としては、例えば、チオール類、チオエーテル類、チオフェノール類、チオアニソール類、チオフェン類、ベンゾチオフェン類、ジベンゾチオフェン類等が挙げられる。こうした有機硫黄化合物の中でも、骨格中に硫黄原子を含有する複素環化合物、特に硫黄原子周辺にアルキル基などの置換基を持つジベンゾチオフェン類は、通常の水素化脱硫方法では立体障害の影響により分解することが困難な化合物であるが、本発明ではこのような難分解性の有機硫黄化合物でも容易に酸化させて除去することができる。 These liquid oils mainly contain organic sulfur compounds derived from raw materials. Examples of such organic sulfur compounds include thiols, thioethers, thiophenols, thioanisoles, thiophenes, benzothiophenes, And dibenzothiophenes. Among these organic sulfur compounds, heterocyclic compounds containing a sulfur atom in the skeleton, especially dibenzothiophenes having a substituent such as an alkyl group around the sulfur atom, are decomposed by the effects of steric hindrance in ordinary hydrodesulfurization methods. In the present invention, even such a hardly decomposable organic sulfur compound can be easily oxidized and removed.
本発明の脱硫方法は、本発明の触媒組成物と液状油とを接触させるものであるが、接触方法としては、例えば、吸着塔に本発明の触媒組成物を充填して液状油を流通させる方法、本発明の触媒組成物を内部に固定したタンクなどの容器に液状油を入れて静置または撹拌する方法、タンクなどの容器に液状油と本発明の触媒組成物を入れて反応後に触媒組成物を除去する方法等が挙げられる。これら脱硫時の反応温度は、−４０〜１００℃が好ましく、−２０℃〜８０℃がより好ましい。反応温度が−４０℃より低いと燃料油の流動性が低下し、反応がスムーズに進まない場合があり、１００℃より高いと触媒活性が低下する上、過酸化尿素の好ましくない分解反応が優先的に進行する場合がある。また、反応時の圧力は常圧〜１ＭＰａの範囲であるのが好ましい。また本発明の触媒組成物と液状油とを接触させる時間は、１〜２０時間が好ましく、３〜１５時間がより好ましい。１時間より短いと有機硫黄化合物の酸化反応が完全に終了しない場合があり、２０時間以上の接触は反応率がほとんど変わらないため経済的な損失が大きくなる場合がある。 The desulfurization method of the present invention is a method in which the catalyst composition of the present invention and liquid oil are brought into contact. Examples of the contact method include filling the catalyst composition of the present invention into an adsorption tower and circulating the liquid oil. Method, a method in which liquid oil is placed in a container such as a tank in which the catalyst composition of the present invention is fixed, and is allowed to stand or stir. Examples thereof include a method for removing the composition. The reaction temperature at the time of desulfurization is preferably -40 to 100 ° C, and more preferably -20 to 80 ° C. If the reaction temperature is lower than −40 ° C., the fluidity of the fuel oil is lowered, and the reaction may not proceed smoothly. Sometimes progress. The pressure during the reaction is preferably in the range of normal pressure to 1 MPa. Further, the time for contacting the catalyst composition of the present invention with the liquid oil is preferably 1 to 20 hours, more preferably 3 to 15 hours. If it is shorter than 1 hour, the oxidation reaction of the organic sulfur compound may not be completed completely, and contact for 20 hours or more may cause a large economic loss because the reaction rate hardly changes.
有機硫黄化合物の酸化反応が進むと、本発明の脱硫剤の一成分である過酸化尿素に含有している過酸化水素が減少していく。過酸化水素が完全になくなってしまうと、過酸化尿素の酸化剤としての性能がなくなってしまうため、精製できる液状油の量には限界がある。液状油中の有機硫黄化合物の量にもよるが、通常、本発明の脱硫剤１質量部に対して、液状油は２０００質量部以下が好ましく、１０００質量部以下がより好ましい。 As the oxidation reaction of the organic sulfur compound proceeds, hydrogen peroxide contained in urea peroxide, which is one component of the desulfurizing agent of the present invention, decreases. When hydrogen peroxide is completely eliminated, the performance of urea peroxide as an oxidant is lost, so the amount of liquid oil that can be refined is limited. Although depending on the amount of the organic sulfur compound in the liquid oil, the liquid oil is usually preferably 2000 parts by mass or less and more preferably 1000 parts by mass or less with respect to 1 part by mass of the desulfurizing agent of the present invention.
酸化反応により生成した有機硫黄酸化物を処理するには、抽出、吸着、蒸留等の各種分離操作を用いて除去すればよい。吸着操作の吸着剤には、例えば、シリカゲル、ゼオライト、モレキュラシーブ、活性白土、イオン交換樹脂、吸着樹脂、粘度鉱物、活性炭等、分子極性吸着や分子篩い作用のある剤を挙げることができる。また、上記処理操作に加えて蒸留精製する事により、該有機硫黄酸化物は完全に除去する事ができる。 In order to treat the organic sulfur oxide generated by the oxidation reaction, it may be removed by using various separation operations such as extraction, adsorption, and distillation. Examples of the adsorbent for the adsorption operation include silica polar particles, zeolites, molecular sieves, activated clay, ion exchange resins, adsorbent resins, viscous minerals, activated carbon, and the like, which have molecular polar adsorption or molecular sieving action. In addition to the above treatment operation, the organic sulfur oxide can be completely removed by purification by distillation.
本発明の脱硫剤は過酸化尿素の酸化剤としての性能がなくなった後でも、容易に再利用することができる。過酸化尿素の酸化剤としての性能がなくなった本発明の脱硫剤は、成分（ａ）及び成分（ｂ）よりなる固体触媒並びに尿素との混合物になっている。この混合物に水を添加すると尿素だけが溶解するので、ろ過によって簡単に固体触媒と分離することができる。固体触媒はそのまま再利用でき、水に溶解した尿素は過酸化水素と反応させて過酸化尿素に再生し、再び過酸化尿素の酸化剤として再利用することができる。 The desulfurizing agent of the present invention can be easily reused even after the performance of urea peroxide as an oxidizing agent is lost. The desulfurizing agent of the present invention, which has lost the performance of urea peroxide as an oxidizing agent, is a mixture of a solid catalyst comprising components (a) and (b) and urea. When water is added to this mixture, only urea is dissolved, so that it can be easily separated from the solid catalyst by filtration. The solid catalyst can be reused as it is, and urea dissolved in water can be regenerated to urea peroxide by reacting with hydrogen peroxide and reused again as an oxidizing agent for urea peroxide.
以下本発明を実施例により、具体的に説明する。尚、以下の実施例等において％及びｐｐｍは特に記載が無い限り質量基準である。 Hereinafter, the present invention will be specifically described by way of examples. In the following examples and the like,% and ppm are based on mass unless otherwise specified.
＜固体触媒の調整＞
（固体触媒１）
化学式Ｍｇ6Ａｌ2（ＯＨ）16ＣＯ3・４Ｈ2Ｏで示される市販のハイドロタルサイト（協和化学工業（株）製 キョーワードＫＷ−５００：成分（ｂ））２５０ｇに、１２−タングストリン酸ナトリウム（成分（ａ））１０．０ｇを加え小型Ｖミキサーで３０分間混合して固体触媒１を得た。
（固体触媒２）
化学式Ｍｇ6Ａｌ2（ＯＨ）16ＣＯ3・４Ｈ2Ｏで示される市販のハイドロタルサイト（協和化学工業（株）製 キョーワードＫＷ−５００：成分（ｂ））２５０ｇに、タングステン酸ナトリウム（成分（ａ））１．０ｇを加え小型Ｖミキサーで３０分間混合して固体触媒２を得た。
<Preparation of solid catalyst>
(Solid catalyst 1)
To 250 g of commercially available hydrotalcite (Kyowa Chemical Industry Co., Ltd. Kyoward KW-500: component (b)) represented by the chemical formula Mg 6 Al 2 (OH) 16 CO 3 .4H 2 O, 12-tungstophosphoric acid 10.0 g of sodium (component (a)) was added and mixed with a small V mixer for 30 minutes to obtain a solid catalyst 1.
(Solid catalyst 2)
250 g of commercially available hydrotalcite represented by the chemical formula Mg 6 Al 2 (OH) 16 CO 3 .4H 2 O (Kyowa Chemical Industry Co., Ltd. Kyoward KW-500: component (b)) is added to sodium tungstate (component (A) 1.0 g was added and mixed with a small V mixer for 30 minutes to obtain a solid catalyst 2.
＜分析方法＞
モデル硫黄化合物として、難分解性の４，６−ジメチルジベンゾチオフェンを使用し、高速液体クロマトグラフィー（ＨＰＬＣ）によって、４，６−ジメチルジベンゾチオフェンの分解率を確認した。また液中の硫黄濃度は、ＩＣＰにて硫黄分を確認した。結果を表１に記した。なお、両分析機器の詳細は以下の通りである。
<Analysis method>
As the model sulfur compound, hardly decomposed 4,6-dimethyldibenzothiophene was used, and the decomposition rate of 4,6-dimethyldibenzothiophene was confirmed by high performance liquid chromatography (HPLC). The sulfur concentration in the liquid was confirmed by ICP. The results are shown in Table 1. The details of both analytical instruments are as follows.
（ＨＰＬＣ分析方法）
カラム ：ODSカラム(LUNA 5C18 RS,φ4.6mm×250mm)
溶離液 ：アセトニトリル／水＝７５／２５
流速 ：１．０mL／min
検出器 ：UV、３２５nm
カラムオーブン温度 ：４０℃
（ＩＣＰ（Inductively Coupled Plasma）分析方法）
分析使用機器：島津製作所製 ＩＣＰＳ−８１００
分析方法：内部標準補正法（希釈溶媒キシレン）
(HPLC analysis method)
Column: ODS column (LUNA 5C18 RS, φ4.6mm × 250mm)
Eluent: acetonitrile / water = 75/25
Flow rate: 1.0 mL / min
Detector: UV, 325nm
Column oven temperature: 40 ° C
(ICP (Inductively Coupled Plasma) analysis method)
Analytical instrument: ICPS-8100 manufactured by Shimadzu Corporation
Analysis method: Internal standard correction method (diluted solvent xylene)
実施例１
モデル軽油（４，６−ジメチルジベンゾチオフェン含有オクタン：全硫黄成分として５０ｐｐｍ）５００ｍｌに過酸化尿素（有効過酸化水素：３６．１％）０．２ｇ及び上記で調整した触媒１を０．５ｇ加え２７℃で５時間撹拌した後、ＨＰＬＣ分析によって残留する４，６−ジメチルジベンゾチオフェンの濃度を調べた。その後、得られたモデル軽油を蒸留精製し、液中の全硫黄濃度をＩＣＰ分析によって調べた。
Example 1
Add 0.5 g of urea peroxide (effective hydrogen peroxide: 36.1%) and 0.5 g of catalyst 1 prepared above to 500 ml of model light oil (4,6-dimethyldibenzothiophene-containing octane: 50 ppm as total sulfur component) After stirring for 5 hours at 27 ° C., the residual 4,6-dimethyldibenzothiophene concentration was determined by HPLC analysis. Thereafter, the obtained model light oil was purified by distillation, and the total sulfur concentration in the liquid was examined by ICP analysis.
実施例２
モデル軽油（４，６−ジメチルジベンゾチオフェン含有オクタン：全硫黄成分として５０ｐｐｍ）５００ｍｌに過酸化尿素（有効過酸化水素：３６．１％）０．２ｇ及び上記で調整した触媒２を０．５ｇ加え２７℃で５時間撹拌した後、ＨＰＬＣ分析によって残留する４，６−ジメチルジベンゾチオフェンの濃度を調べた。その後、得られたモデルを蒸留精製し、液中の全硫黄濃度を、ＩＣＰ分析によって調べた。
Example 2
Add 0.5 g of urea peroxide (effective hydrogen peroxide: 36.1%) and 0.5 g of catalyst 2 prepared above to 500 ml of model light oil (4,6-dimethyldibenzothiophene-containing octane: 50 ppm as total sulfur component) After stirring for 5 hours at 27 ° C., the residual 4,6-dimethyldibenzothiophene concentration was determined by HPLC analysis. Thereafter, the obtained model was purified by distillation, and the total sulfur concentration in the liquid was examined by ICP analysis.
実施例３
市販の軽油（全硫黄成分３５０ｐｐｍ）５００ｍｌに過酸化尿素（有効過酸化水素：３６．１％）１．３５ｇ、上記で調整した触媒１を１．０ｇ加え２７℃で５時間撹拌した後、得られたモデル軽油中にシリカゲル１０ｇを加え２７℃で１時間攪拌した後、シリカゲルを濾過除去して蒸留精製し、液中の全硫黄濃度を、ＩＣＰ分析によって調べた。
Example 3
After adding 1.35 g of urea peroxide (effective hydrogen peroxide: 36.1%) to 500 ml of commercially available light oil (total sulfur component 350 ppm) and 1.0 g of catalyst 1 prepared as described above, stirring was performed at 27 ° C. for 5 hours, and then obtained. After adding 10 g of silica gel to the obtained model light oil and stirring at 27 ° C. for 1 hour, the silica gel was removed by filtration and purified by distillation, and the total sulfur concentration in the liquid was examined by ICP analysis.
実施例４
モデルガソリン（４，６−ジメチルジベンゾチオフェン含有オクタン５０質量％／シクロヘキサン３０質量％／１−オクテン２０質量％混合液：全硫黄成分５０ｐｐｍ）５００ｍｌに過酸化尿素（有効過酸化水素：３６．１％）１．３５ｇ、上記で調整した触媒１を１．０ｇ加え５５℃で１０時間撹拌した後、ＨＰＬＣ分析によって残留する４，６−ジメチルジベンゾチオフェンの濃度を調べた。その後、得られたモデル軽油中にシリカゲル１０ｇを加え５５℃で１時間攪拌した後、シリカゲルを濾過除去して蒸留精製し、液中の全硫黄濃度をＩＣＰ分析によって調べた。
Example 4
Model gasoline (4,6-dimethyldibenzothiophene-containing octane 50% by mass / cyclohexane 30% by mass / 1-octene 20% by mass mixture: total sulfur component 50ppm) urea peroxide (effective hydrogen peroxide: 36.1%) 1.35 g, 1.0 g of the catalyst 1 prepared above was added and stirred at 55 ° C. for 10 hours, and then the concentration of 4,6-dimethyldibenzothiophene remaining was examined by HPLC analysis. Thereafter, 10 g of silica gel was added to the obtained model light oil and stirred at 55 ° C. for 1 hour, and then the silica gel was removed by filtration and purified by distillation. The total sulfur concentration in the liquid was examined by ICP analysis.
比較例１
モデル軽油（４，６−ジメチルジベンゾチオフェン含有オクタン：全硫黄成分５０ｐｐｍ）５００ｍｌに過酸化尿素（有効過酸化水素：３６．１％）１．１０９ｇ、１２−タングストリン酸１．００ｇを加え２７℃で５時間撹拌した後、ＨＰＬＣ分析によって残留する４，６−ジメチルジベンゾチオフェンの濃度を調べた。その後、得られたモデル軽油中にシリカゲル１０ｇを加え２７℃で１時間攪拌した後、シリカゲルを濾過除去して蒸留精製し、液中の全硫黄濃度をＩＣＰ分析によって調べた。
Comparative Example 1
1.109 g of urea peroxide (effective hydrogen peroxide: 36.1%) and 1.00 g of 12-tungstophosphoric acid were added to 500 ml of model light oil (4,6-dimethyldibenzothiophene-containing octane: total sulfur component 50 ppm) at 27 ° C. After stirring for 5 hours, the concentration of 4,6-dimethyldibenzothiophene remaining was determined by HPLC analysis. Thereafter, 10 g of silica gel was added to the obtained model light oil and stirred at 27 ° C. for 1 hour, and then the silica gel was removed by filtration and purified by distillation. The total sulfur concentration in the liquid was examined by ICP analysis.
比較例２
モデル軽油（４，６−ジメチルジベンゾチオフェン含有オクタン：全硫黄成分５０ｐｐｍ）５００ｍｌに市販の３５％過酸化水素水１．１１０ｇ、上記で調整した触媒１を０．５ｇ加え２７℃で５時間撹拌した後、ＨＰＬＣ分析によって残留する４，６−ジメチルジベンゾチオフェンの濃度を調べた。その後、得られたモデル軽油中にシリカゲル１０ｇを加え２７℃で１時間攪拌した後、シリカゲルを濾過除去して蒸留精製し、液中の全硫黄濃度をＩＣＰ分析によって調べた。
Comparative Example 2
To 500 ml of model light oil (4,6-dimethyldibenzothiophene-containing octane: total sulfur component 50 ppm), 1.110 g of commercially available 35% hydrogen peroxide water and 0.5 g of catalyst 1 prepared above were added and stirred at 27 ° C. for 5 hours. Thereafter, the concentration of 4,6-dimethyldibenzothiophene remaining was examined by HPLC analysis. Thereafter, 10 g of silica gel was added to the obtained model light oil and stirred at 27 ° C. for 1 hour, and then the silica gel was removed by filtration and purified by distillation. The total sulfur concentration in the liquid was examined by ICP analysis.
比較例３
モデル軽油（４，６−ジメチルジベンゾチオフェン含有オクタン：全硫黄成分５０ｐｐｍ）５００ｍｌに微粉化過硫酸ナトリウム１．１１０ｇ、上記で調整した触媒１を０．５ｇ加え２７℃で５時間撹拌した後、ＨＰＬＣ分析によって残留する４，６−ジメチルジベンゾチオフェンの濃度を調べた。その後、得られたモデル軽油中にシリカゲル１０ｇを加え２７℃で１時間攪拌した後、シリカゲルを濾過除去して蒸留精製し、液中の全硫黄濃度をＩＣＰ分析によって調べた。
Comparative Example 3
To 500 ml of model light oil (4,6-dimethyldibenzothiophene-containing octane: total sulfur component 50 ppm), 1.110 g of finely powdered sodium persulfate and 0.5 g of catalyst 1 prepared as described above were added and stirred at 27 ° C. for 5 hours. The concentration of residual 4,6-dimethyldibenzothiophene was examined by analysis. Thereafter, 10 g of silica gel was added to the obtained model light oil and stirred at 27 ° C. for 1 hour, and then the silica gel was removed by filtration and purified by distillation. The total sulfur concentration in the liquid was examined by ICP analysis.
比較例４
モデル軽油（４，６−ジメチルジベンゾチオフェン含有オクタン：全硫黄成分５０ｐｐｍ）５００ｍｌに過酸化尿素（有効過酸化水素：３６．１％）１．１０９ｇ、化学式Ｍｇ6Ａｌ2（ＯＨ）16ＣＯ3・４Ｈ2Ｏで示される市販のハイドロタルサイト（協和化学工業（株）製 キョーワードＫＷ−５００）を０．５ｇ加え２７℃で５時間撹拌した後、ＨＰＬＣ分析によって残留する４，６−ジメチルジベンゾチオフェンの濃度を調べた。その後、得られたモデル軽油中にシリカゲル１０ｇを加え２７℃で１時間攪拌した後、シリカゲルを濾過除去して蒸留精製し、液中の全硫黄濃度をＩＣＰ分析によって調べた。
Comparative Example 4
Model light oil (4,6-dimethyldibenzothiophene-containing octane: total sulfur component 50 ppm) and 1.109 g of urea peroxide (effective hydrogen peroxide: 36.1%), chemical formula Mg 6 Al 2 (OH) 16 CO 3. After adding 0.5 g of commercially available hydrotalcite (Kyowa Chemical Industry Co., Ltd. Kyoward KW-500) represented by 4H 2 O and stirring at 27 ° C. for 5 hours, 4,6-dimethyldibenzoic acid remaining by HPLC analysis was retained. The concentration of thiophene was examined. Thereafter, 10 g of silica gel was added to the obtained model light oil and stirred at 27 ° C. for 1 hour, and then the silica gel was removed by filtration and purified by distillation. The total sulfur concentration in the liquid was examined by ICP analysis.
上記の結果から、本願発明を用いると硫黄濃度だけでなく、難分解性の有機硫黄化合物を効率よく除去できることがわかる。 From the above results, it can be seen that not only the sulfur concentration but also the hard-to-decompose organic sulfur compound can be efficiently removed by using the present invention.
Claims (4)
（ａ）金属の酸化物、該酸化物の酸及び該酸化物の酸の塩、金属のイソポリ酸類及びその塩、金属のヘテロポリ酸類及びその塩よりなる群から選択された少なくとも一種の成分（該金属はタングステン、モリブデン及びバナジウムよりなる群から選択される）、
（ｂ）ハイドロタルサイト、並びに
（２）過酸化尿素
を含む脱硫剤。 (1) a solid catalyst comprising the following component (a) and component (b);
(A) at least one component selected from the group consisting of a metal oxide, an acid of the oxide and an acid salt of the oxide, a metal isopolyacid and a salt thereof, a metal heteropolyacid and a salt thereof (the The metal is selected from the group consisting of tungsten, molybdenum and vanadium);
(B) A hydrotalcite, and (2) a desulfurization agent containing urea peroxide.
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| CN102134508A (en) * | 2011-01-30 | 2011-07-27 | 山东大学 | Oxidation desulfuration method based on modified MCM-41 anchored heteropolyacid catalyst |
| WO2013035200A1 (en) * | 2011-09-09 | 2013-03-14 | Aida Tetsuo | Method for producing ultra-low sulfur fuel oil |
| KR101509137B1 (en) | 2013-10-18 | 2015-04-07 | 한국과학기술원 | Method of Removing Hydrogen Sulfide Using Heteropoly Acid |
| CN106268236A (en) * | 2016-09-30 | 2017-01-04 | 扬州大学 | A kind of compost reaction fuel gas efficient purifying, collecting device |
| WO2018205113A1 (en) * | 2017-05-08 | 2018-11-15 | Solvay Sa | Process for removing sulfur compounds from a liquid composition |
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| CN108939801A (en) * | 2018-08-13 | 2018-12-07 | 长有彬 | A kind of desulfurizing agent preparation method |
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