JPS5911635B2 - Catalytic dewaxing method for gas oil - Google Patents

Catalytic dewaxing method for gas oil

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Publication number
JPS5911635B2
JPS5911635B2 JP49041825A JP4182574A JPS5911635B2 JP S5911635 B2 JPS5911635 B2 JP S5911635B2 JP 49041825 A JP49041825 A JP 49041825A JP 4182574 A JP4182574 A JP 4182574A JP S5911635 B2 JPS5911635 B2 JP S5911635B2
Authority
JP
Japan
Prior art keywords
dewaxing
catalyst
zsm
pour point
sulfur
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.)
Expired
Application number
JP49041825A
Other languages
Japanese (ja)
Other versions
JPS5017401A (en
Inventor
リ− ゴ−リング ロバ−ト
フレデリツク シツプマン ジヨ−ジ
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Oil Corp
Original Assignee
Mobil Oil Corp
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Filing date
Publication date
Application filed by Mobil Oil Corp filed Critical Mobil Oil Corp
Publication of JPS5017401A publication Critical patent/JPS5017401A/ja
Publication of JPS5911635B2 publication Critical patent/JPS5911635B2/en
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
    • C10G65/043—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a change in the structural skeleton
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/06—Gasoil

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Description

【発明の詳細な説明】 この発明は石油処理法に関する。[Detailed description of the invention] This invention relates to a method for processing petroleum.

更に詳しくはこの発明はある種の軽油ガスオイル留分を
低流動点燃料に品質向上することに関する。More particularly, this invention relates to the upgrading of certain light oil gas oil fractions into low pour point fuels.

２０４℃〜４５４℃（４００’）’〜８５０°Ｆ）の沸
点範囲の液体炭化水素には灯油、ディーゼル燃料および
／１６２すなわち家庭暖房燃料が含まれる。Liquid hydrocarbons in the boiling range of 204°C to 454°C (400' to 850°F) include kerosene, diesel fuel, and /162 or home heating fuel.

この沸点範囲の石油留分はしばしばかなりの長鎖パラフ
ィン含有物を含み、この長鎖パラフィンは前記留分の高
流動点の原因となる。Petroleum fractions in this boiling range often contain significant long chain paraffin content, which accounts for the high pour point of said fractions.

この型の留分にとって１０℃〜３８℃（５０°Ｆ〜１０
０°Ｆ）の流動点を持つことは珍らしいことではない。For this type of distillate, 10°C to 38°C (50°F to 10°C)
It is not uncommon to have a pour point of 0°F.

／Ｉ６２油の一つの重要な規格の一つは−１７，８℃（
０’Ｆ）またはそれ以下の流動点を持つことである。/ One of the important specifications for I62 oil is -17,8℃ (
0'F) or lower.

こうして流動点の降下は脱ロウすなわちこの性質に主た
る責任があるように見える長鎖パラフィンを除去するこ
とによって達成される。Pour point lowering is thus achieved by dewaxing, or removing the long chain paraffins that appear to be primarily responsible for this property.

この脱ロウは伝統的に軽油を適当な溶媒、しばしばメチ
ルエチルケトンと充分に混合して溶媒中にロウを溶解す
る溶媒膜ロウ技術によって達成されてきた。This dewaxing has traditionally been accomplished by solvent membrane waxing techniques in which the gas oil is thoroughly mixed with a suitable solvent, often methyl ethyl ketone, to dissolve the wax in the solvent.

過去においては溶媒例えば前記ケトンを蒸発することに
よって溶媒からロウを回収し、精製し、封ロウ、ロウそ
くおよび他の用途に販売された。In the past, the wax was recovered from the solvent by evaporating the solvent, such as the ketone, purified and sold for sealing wax, candles and other uses.

より最近は石油工業はこの市場で顕著な退潮を見せ、従
ってこの成分のより有利な、より経費を要しない販路を
探究していた。More recently, the petroleum industry has experienced a marked decline in this market and has therefore sought more lucrative and less expensive outlets for this component.

これまでも形状選択性ゼオライト触媒を使用してこれら
のパラフィン成分をクランキング好適には水素化分解し
、それらをより小さい適当にパラフィン性の分解物に変
え、これを軽質ガスまたは分子が大きくても非ロウ質パ
ラフィン性物質（処理される軽油の沸点範囲内にある）
として捕集し、従って脱ロウ操作の収量を増大すること
が提唱された。Previously, shape-selective zeolite catalysts have been used to crank, preferably hydrocrack, these paraffinic components, converting them into smaller suitably paraffinic decomposition products, which can be converted into light gases or larger molecules. Also non-waxy paraffinic substances (within the boiling range of the gas oil being processed)
It has been proposed to collect as much as possible and thus increase the yield of the dewaxing operation.

上記によるクランキングしてより小さくした分解生成物
は燃料として使用でき、燃料として販売されるか或は成
分毎に分離して処分していた。The decomposition products made smaller by cranking can be used as fuel, and are either sold as fuel or separated into their components and disposed of.

最も最近新規なＺＳＭ−５型のゼオライトをりラッキン
グまたは水素化分解脱ロウ触媒として使用することが提
唱された。Most recently, novel ZSM-5 type zeolites have been proposed for use as re-racking or hydrocracking dewaxing catalysts.

その理由はＺ Ｓ Ｍ−５型ゼオライトは正パラフィン
だけでなく僅かに枝分れしたパラフィンも同様に従来達
成されていたのよりも効率よく流動点の低下した生成物
に、よりよい収率で転化するからである（米国特許第３
．７００，５８５号参照）。The reason is that the ZS M-5 type zeolite can convert not only normal paraffins but also slightly branched paraffins as well into products with lower pour points more efficiently and in better yields than previously achieved. (U.S. Patent No. 3)
．． 700,585).

ＺＳＭ−５系のゼオライトは一群の小孔をもつゼオライ
トであり、その最も注目に値するゼオライトはＺＳＭ−
５、ＺＳＭ−８およびＺＳＭ−１１である。ZSM-5 series zeolites are zeolites with a group of small pores, the most notable of which is ZSM-5.
5, ZSM-8 and ZSM-11.

米国特許第３，７０２，８８６号はゼオライトＺＳＭ−
５それ自体に関し、英国特許第１３３４２４３号はゼオ
ライトＺＳＭ−８、米国特許第３７０９９７９号はＺＳ
Ｍ−１１に関するものである。U.S. Patent No. 3,702,886 describes zeolite ZSM-
5 As for themselves, British Patent No. 1,334,243 describes the zeolite ZSM-8, and US Pat. No. 3,709,979 describes the ZS
This is related to M-11.

これらの特許明細書の記載はそれらを参照することによ
ってこの明細書に加入される。The contents of these patent specifications are incorporated herein by reference.

ＺＳＭ−５系のゼオライトは添加水素の不在において正
パラフィンまたはわずかに枝分れしたパラフィンのクラ
ンキングを促進するのに使用でき、或は添加水素の存在
において上記のようなパラフィンの水素化分解を促進す
るのに使用できる。ZSM-5 series zeolites can be used to promote the cranking of normal paraffins or slightly branched paraffins in the absence of added hydrogen, or to promote the hydrocracking of paraffins as described above in the presence of added hydrogen. Can be used to promote.

代表的なりラッキング条件には約０．２５〜２００ＬＨ
８Ｖの空間速度、約２０４℃〜５９３℃（４００′Ｐ〜
１１００’Ｆ）の温度、大気圧以下の圧力から数百気圧
までの圧力が含まれる。Approximately 0.25-200LH for typical racking conditions
8V space velocity, approximately 204°C to 593°C (400'P to
1100'F) and pressures from subatmospheric to hundreds of atmospheres.

代表的な水素化分解条件には約０．１〜１０ＬＨ８Ｖの
空間速度、約１〜２０対１の水素対炭化水素モル比、約
３４．３℃〜５３８℃（６５０′Ｆ〜１００００Ｆ）の
温度および約７〜２１０にしを一計器圧（１００〜３０
００Ｐｓｉｇ）の圧力（米国特許第３，７００，５８５
号参照）が含まれる。Typical hydrocracking conditions include a space velocity of about 0.1 to 10 LH8V, a hydrogen to hydrocarbon molar ratio of about 1 to 20 to 1, and a temperature of about 650'F to 10,000F. and about 7 to 210 meter pressure (100 to 30
00 Psig) pressure (U.S. Patent No. 3,700,585
(see issue).

大抵の石油処理においては、仕込原料を転化しおよび品
質向上処理する前に仕込原料から硫黄および（または）
金属および（または）窒素を除去するように計算した操
作方法で仕込原料を予備処理することが慣習である。In most petroleum processes, sulfur and/or
It is customary to pre-treat the feedstock with a method of operation designed to remove metals and/or nitrogen.

すなわち接触水素化脱硫処理は石油精製において広く使
用されている単位操作である。That is, catalytic hydrodesulfurization treatment is a unit operation widely used in petroleum refining.

仕込原料中に存在する硫黄、窒素および（または）金属
は往々にして炭化水素転化触媒上に有害な作用を及ぼす
から、前述の接触水素化脱硫処理は改質操作および他の
転化操作に先行して行われる。Since sulfur, nitrogen and/or metals present in the feed often have a deleterious effect on the hydrocarbon conversion catalyst, the catalytic hydrodesulfurization process described above should precede reforming and other conversion operations. will be carried out.

金属、硫黄および窒素は重質の石油留分中に濃縮される
傾向があるから、このような重質の石油留分を使用する
転化操作は慣用の脱硫処理続いて接触転化処理を行う手
順における脱硫処理の主たる使用者である。Because metals, sulfur, and nitrogen tend to concentrate in heavy petroleum fractions, conversion operations using such heavy petroleum fractions are difficult to perform in conventional desulfurization followed by catalytic conversion procedures. It is the main user of desulfurization treatment.

こうして２０４℃〜４８２℃（４００’Ｆ 〜９００下
）で沸騰し、硫黄を含有する軽油またはその任意の部分
の脱ロウ処理において、当業者はそのような軽油を脱ロ
ウ処理前に接触水素化脱硫処理することを考えるだろう
。Thus, in the dewaxing treatment of gas oils or any portion thereof boiling between 204°C and 482°C (below 400'F and 900°C) and containing sulfur, one skilled in the art would catalytically hydrogenate such gas oils prior to dewaxing. I would consider desulfurization treatment.

事実これか「慣用」のエリオナイト型の形状選択性触媒
を使用する軽油の脱ロウ処理に対する望ましい処理手順
である。In fact, this is the preferred procedure for dewaxing gas oils using "conventional" erionite-type shape-selective catalysts.

ところが今ここに全く意外にもＺＳＭ−５型ゼオライト
脱ロウ触媒を使用してこの手順に従って操作すれば誰も
が予期するだろう活性に比して著しく活性が減少するこ
とを見出した（以下の例１および２参照）。However, we have now, quite unexpectedly, discovered that when operating according to this procedure using a ZSM-5 type zeolite dewaxing catalyst, the activity is significantly reduced compared to what one would expect (see below). (see Examples 1 and 2).

このＺＳＭ−５触媒を使用する軽油の脱硫／脱ロウ処理
にあたってＺＳＭ−５型ゼオライトはＨ２Ｓによっても
或は多くの炭化水素原料に存在する硫黄含有汚染物によ
っても悪影響を受けないことがわかった。In the desulfurization/dewaxing process of gas oil using this ZSM-5 catalyst, it has been found that the ZSM-5 type zeolite is not adversely affected by H2S or by sulfur-containing contaminants present in many hydrocarbon feedstocks.

この特性はＺＳＭ−５型ゼオライトが慣用の脱硫／脱ロ
ウ手順を使用する高硫黄含量軽油の脱硫／脱ロウ手順に
おける理想重膜ロウ触媒であるだろうことを示唆した。This property suggested that the ZSM-5 type zeolite would be an ideal heavy membrane wax catalyst in the desulfurization/dewaxing procedure of high sulfur content gas oils using conventional desulfurization/dewaxing procedures.

このことは例えば１０係〜９０係の留出温度範囲が２６
７℃〜４１７℃（５１２下〜７８３’Ｆ）、硫黄含量２
．４７係、流動点４．４℃（４０’Ｆ）の軽油を水素供
給速度０．４４５ ｍ３Ｈｖ／ｌ軽油［２５００標準立
方フイート（ＳＣＦ）／バレル〕、空間速度２．０ＬＨ
８Ｖ、圧力１４Ｋｙ／ｃｖｔ’ （２００ｐｓｉ ）、
温度３２１℃〜４５４℃（６１０°Ｆ〜８５０’Ｆ）（
テストの始めから終りに対して）の範囲でＮｉＨｚＳＭ
−５ゼオライトを使って３０日間水素化脱膜ウしたテス
トにより明らかである。This means, for example, that the distillation temperature range from 10 to 90 is 26
7°C to 417°C (512 below to 783'F), sulfur content 2
．． Section 47, gas oil with pour point 4.4°C (40'F), hydrogen supply rate 0.445 m3Hv/l gas oil [2500 standard cubic feet (SCF)/barrel], space velocity 2.0LH
8V, pressure 14Ky/cvt' (200psi),
Temperature 321°C to 454°C (610°F to 850'F) (
NiHzSM in the range (from the beginning to the end of the test)
This is clear from a 30-day hydrogen demembrane test using -5 zeolite.

これらの試験のデータを下記に示す。Data from these tests are shown below.

表中のＨ２Ｓ含量（ｐｐｍ）は水素含有ガス中のＨ２Ｓ
の含量を示し、流動点は水素脱税ロウ処理から取ったサ
ンプルの軽油の流動点を示す；これらの結果はＨ２Ｓの
存在は水素脱膜ロウにおけるＺ Ｓ Ｍ −５の触媒活
性に悪影響はないことを明確に証明するものである。The H2S content (ppm) in the table is H2S in hydrogen-containing gas.
and the pour point indicates the pour point of the sample gas oil taken from the hydrogen dewaxing process; these results indicate that the presence of H2S has no negative effect on the catalytic activity of ZSM-5 in the hydrodewaxing process. This clearly proves that

これらのテ゛−夕にも拘らず例２に示したデータは慣用
の脱硫／脱ロウ手順ではＺＳＭ−５触媒はＣ０−Ｍｏ−
Ａｌ２Ｏ３触媒を使用する脱硫段階からの全流出流をＺ
ＳＭ−５脱ロウ触媒上に通ずとＺＳＭ−５脱ロウ触媒が
著しく失活したことを示した。Despite these considerations, the data presented in Example 2 show that in conventional desulfurization/dewaxing procedures, the ZSM-5 catalyst
The total effluent from the desulfurization stage using Al2O3 catalyst is Z
The results showed that the ZSM-5 dewaxing catalyst was significantly deactivated when passed over the SM-5 dewaxing catalyst.

このことは結局のところ、ＺＳＭ−５は脱硫工程で発生
するＨ２Ｓによっては悪影響を受けないにも拘らず慣用
の脱硫／脱ロウ操作では中間の洗浄操作なしには脱ロウ
触媒として満足には働かないことを明らかに示すもので
あった。This ultimately means that although ZSM-5 is not adversely affected by the H2S generated during the desulfurization process, it cannot work satisfactorily as a dewaxing catalyst in conventional desulfurization/dewaxing operations without an intermediate cleaning operation. It clearly showed that there was no such thing.

しかし、この脱ロウ操作の結果最終的に製造した生成物
は硫黄および（または）窒素含量が減少していなければ
ならず、或は好適には実質上全熱硫黄または窒素を含ま
ないものでなければならない。However, the final product produced as a result of this dewaxing operation must have a reduced sulfur and/or nitrogen content, or preferably be substantially free of total hot sulfur or nitrogen. Must be.

このことがこの生成物が窒素および硫黄の発生が厳密に
制御されねばならないジェット燃料、ディーゼル燃料お
よび家庭暖房市場に主として販路を伸ばしてゆく理由で
ある。This is why this product is primarily marketed to the jet fuel, diesel fuel and home heating markets where nitrogen and sulfur emissions must be strictly controlled.

上述のテストに鑑みて、種々研究の結果、原料中に窒素
含有汚染物が存在することこそ、例２で説明する慣用の
脱硫／脱ロウ手順における脱ロウ触媒としてのＺＳＭ−
５の劣悪な性能の原因であることを知見した。In view of the above-mentioned tests, various studies have shown that the presence of nitrogen-containing contaminants in the feedstock is the reason why ZSM-
It was found that this was the cause of the poor performance of 5.

従ってこの発明の重要な目的は効率的な軽油脱ロウ、脱
硫および脱窒素処理法を提供するにある。Therefore, an important object of the present invention is to provide an efficient process for dewaxing, desulfurization and denitrification of light oil.

この発明の他の目的はＺＳＭ−５型のゼオライト脱ロウ
触媒を利用できる方法を提供するにある。Another object of the present invention is to provide a method that can utilize a ZSM-5 type zeolite dewaxing catalyst.

この発明の更に他の目的は約−１７，８℃（Ｏ″Ｆ”）
の流動点を持つ腐２燃料油を高収率で製造する方法を提
供するにある。Still another object of the invention is to
The object of the present invention is to provide a method for producing high-yield fuel oil having a pour point of .

この発明の他の付加的な目的は特許請求の範囲を含む全
明細書を考慮すれば明らかとなるであろう。Other additional objects of the invention will become apparent upon consideration of the entire specification, including the claims.

これらの目的を達成するために、この発明の重要な一面
は約２０４℃〜４８２℃（４００°Ｆ〜９００’Ｆ）の
沸点範囲をもち、硫黄および窒素を含有する軽油を接触
的に脱ロウし、次いで前記脱ロウ処理から得られた少く
とも液状生成物を脱硫および脱窒素することから本質的
に成る処理手順にある。To achieve these objectives, an important aspect of the present invention is to catalytically dewax gas oils having a boiling range of about 204°C to 482°C (400°F to 900'F) and containing sulfur and nitrogen. and then desulfurizing and denitrifying at least the liquid product obtained from said dewaxing process.

この発明の好適な一面においては、この発明が関与する
軽油はそれぞれ少くとも０．１重量％および１０ｐｐｍ
の全硫黄含量および全窒素含量を含み、かつ少くとも−
６，７°Ｃ（＋２０’Ｆ）の流動点をもつ。In a preferred aspect of the invention, the light oil to which this invention relates is at least 0.1% by weight and 10ppm, respectively.
containing a total sulfur content and a total nitrogen content of at least -
It has a pour point of 6.7°C (+20'F).

この発明における脱ロウ処理にはＺＳＭ−５型のゼオラ
イト触媒を使用し、この発明の方法における処理工程を
約１４９°Ｃ〜５３８℃（３００〜１０００°Ｆ）、大
気圧１４０Ｋｙ／ｃｒＩｉ２計器圧（０〜２０００ Ｐ
ｓｉｇ）、０．１〜１０ＬＨ８Ｖおよび水素対炭化水素
比を約０〜２５対１で実施するのが好適である。The dewaxing treatment in this invention uses a ZSM-5 type zeolite catalyst, and the treatment steps in the method of this invention are carried out at a temperature of about 149°C to 538°C (300 to 1000°F) and an atmospheric pressure of 140 Ky/crIi2 instrument pressure ( 0~2000P
sig), 0.1 to 10 LH8V and a hydrogen to hydrocarbon ratio of about 0 to 25:1.

この発明の方法における脱ロウ工程が水素化膜ロウ型で
ある場合にはＺＳＭ−５型ゼオライトに脱ロウ触媒の全
重量を基準として約０．５〜５重量重量制合のニッケル
、パラジウムまたは白金のような水素移動能をもつ成分
を配合する。When the dewaxing step in the method of this invention is of the hydrogenated membrane wax type, ZSM-5 type zeolite is coated with nickel, palladium or platinum in an amount of about 0.5 to 5% by weight based on the total weight of the dewaxing catalyst. Blend components with hydrogen transfer ability such as

脱ロウ触媒はこれを所望に応じ固定床または流動床の形
で使用できる。The dewaxing catalyst can be used in the form of a fixed bed or a fluidized bed, as desired.

固定床操作にお１ いては触媒粒子はこれヲ０．８〜３．２ ” （ａ ２
／／ ｓ ）の間の粒度となすべきである。In fixed bed operation, the catalyst particles range from 0.8 to 3.2" (a2
// s ).

流動床では触媒粒子は約８０〜４００メツシユとすべき
である。In a fluidized bed, the catalyst particles should be about 80 to 400 mesh.

触媒はアルミナ、シリカ、シリカ−アルミナまたは他の
既知の母材を使用する母材担持型であってもよい。The catalyst may be matrix supported using alumina, silica, silica-alumina or other known matrix materials.

この母材担持型の実施例においてはＺＳＭ−５型ゼオラ
イトは全触媒母材の約５〜９５重量係を構成すべきであ
る。In this matrix-supported embodiment, the ZSM-5 type zeolite should constitute about 5 to 95 weight percent of the total catalyst matrix.

接触膜ロウ操作の生成物はこれを所定の圧力で所定の温
度に冷却することによって液−ガス分離を行い、液体部
分とガス部分とに分割する。The product of the catalytic membrane waxing operation undergoes liquid-gas separation by cooling it to a predetermined temperature at a predetermined pressure and is divided into a liquid portion and a gas portion.

液体はこれを次に脱硫および脱窒素操作に付する。The liquid is then subjected to desulfurization and denitrification operations.

しかし上記のように中間生成物の分割を行わないで金膜
ロウ生成物を脱硫および脱窒素処理するのが好適である
。However, it is preferred to desulfurize and denitrify the gold film wax product without splitting the intermediate product as described above.

中間生成物を分割しないことによってエネルギー特に熱
の著大な節減が行われる。Significant savings in energy, especially heat, are achieved by not splitting up intermediate products.

その理由はこの分割処理は中間生成物を冷却し、続いて
行う脱硫および脱窒素処理は再加熱を必要とするからで
ある。This is because this splitting process cools the intermediate product and subsequent desulfurization and denitrification processes require reheating.

脱硫と脱窒素とは通常同時に達成され、一つの処理で送
給中間原料から硫黄と窒素との双方を遊離させる。Desulfurization and denitrification are usually accomplished simultaneously, liberating both sulfur and nitrogen from the feed intermediate in one process.

この処理は所望する任意の仕方で例えば普通的２８８℃
〜４２７℃（５５０〜８００°Ｆ）、１４〜７０Ｋｙ／
ｊメ計器圧（２００〜１０００ Ｐｓｉｇ） 、０．５
〜４．０ ＬＨ８Ｖ、２〜１０モル添加水素対１モルの
送給中間原料の条件で、コバルト−モリブデン−アルミ
ナ触媒と効果的な接触において行うことができる。This treatment can be carried out in any desired manner, for example at 288°C.
~427℃ (550-800°F), 14-70Ky/
Instrument pressure (200-1000 Psig), 0.5
It can be carried out in effective contact with a cobalt-molybdenum-alumina catalyst at conditions of ~4.0 LH8V, 2-10 moles of added hydrogen to 1 mole of feed intermediate feed.

この操作は送給中間原料中の硫黄および窒素を硫化水素
およびアンモニアに変え、硫化水素およびアンモニアは
それらを後で最終生成物のガス部分から回収する。This operation converts sulfur and nitrogen in the feed intermediate to hydrogen sulfide and ammonia, which are later recovered from the gaseous portion of the final product.

上記の操作態様および手順で操作すれば約８０係以上の
液体収率をもって許容しうる程度にすぐれた脱ロウおよ
び流動点降下を生じ、且つ触媒活性の再生操作期間が約
２０〜４００日で全触媒寿命が約６〜６０カ月に亘る脱
ロウ触媒寿命を達成できるが、上記操作の手順を逆にす
れば、すなわち上記と同じ条件の下で脱硫および脱窒素
し、こうして生じた中間生成物を直接税ロウして同じ規
格の最終生成物となせば、脱ロウ触媒として可能な操作
は再生操作間に約１〜２４時間実施できるにすぎない。The operating mode and procedure described above will produce acceptably excellent dewaxing and pour point depression with a liquid yield of about 80% or higher, and the catalyst activity will be completely regenerated in about 20 to 400 days. Although dewaxing catalyst lifetimes with catalyst lifetimes of about 6 to 60 months can be achieved, if the above operating procedure is reversed, i.e., desulfurization and denitrification are carried out under the same conditions as above, and the intermediate products thus formed are If directly waxed to the same specification final product, the possible operations for the dewaxing catalyst can only be carried out for about 1 to 24 hours between regeneration operations.

次に例を掲げてこの発明を説明するが、これら例はこの
発明の範囲または適用性を制限するものと考えるべきで
はない。The invention will now be illustrated by examples, which should not be considered as limiting the scope or applicability of the invention.

以下の例において部または係は特に他の基準に基ずくも
のであると記述しない限り重量部および重量部である。In the following examples, parts and parts are by weight unless specifically stated otherwise.

例１ （先行技術） 沸点範囲２６０℃〜４２７℃（５００°Ｆ〜８００’Ｆ
）、流動点１０℃（＋５０′Ｆ）、硫黄含量３重量部以
下および窒素含量３０００ｐｐｍ以下め軽油を３７１℃
（７００下）、２８に２Δゴ計器圧（４００Ｐｓｉｇ）
、５．０対１の水素対炭化水素モル比および３．０ＬＨ
８ＶでＺ Ｓ Ｍ−５ゼオライトと接触させた。Example 1 (Prior Art) Boiling Point Range 260°C to 427°C (500°F to 800'F
), pour point 10°C (+50'F), sulfur content 3 parts by weight or less and nitrogen content 3000 ppm or less. Light oil at 371°C.
(700 below), 2Δgo meter pressure at 28 (400Psig)
, 5.0 to 1 hydrogen to hydrocarbon molar ratio and 3.0LH
Contacted with Z SM-5 zeolite at 8V.

１６６℃（３３０″Ｆ）以上の沸点の液体への転化率は
８４％で、流動点は−１７，８℃（０′Ｆ）に低下した
。Conversion to liquids boiling above 166°C (330″F) was 84% and the pour point decreased to -17.8°C (0′F).

触媒再生操作間の期間は２０日間であった。The period between catalyst regeneration operations was 20 days.

例２ （先行技術） 沸点範囲２６０℃〜４２７℃（５００’Ｆ〜８００’Ｆ
）、流動点１０℃（＋５０″Ｆ）、硫黄含量２．５係お
よび窒素含量０．０２％の軽油を３７１℃（７００’Ｆ
）、２８Ｋｐ／ｄ計器圧（４００Ｐｓｉω、５．０対１
の水素対炭化水素比および１．０ＬＨ８Ｖでコバルト−
モリブデン−アルミナ触媒と接触させた。Example 2 (Prior Art) Boiling Point Range 260°C to 427°C (500'F to 800'F
), pour point 10°C (+50″F), sulfur content 2.5%, and nitrogen content 0.02%, at 371°C (700′F).
), 28Kp/d instrument pressure (400Psiω, 5.0 to 1
cobalt at a hydrogen-to-hydrocarbon ratio of and 1.0LH8V
Contacted with molybdenum-alumina catalyst.

こうして生成した生成物を直接そして中間生成物の分割
なしに３７１℃（７００°Ｆ）、２８ＫＰ／ａ相土器圧
（４００Ｐｓｉｇ）、５．０対１の水素対炭化水素モル
比、および３゜０ＬＨ８ＶでＺＳＭ−５ゼオライトと接
触させた。The product thus produced was directly and without partitioning of intermediate products at 371°C (700°F), 28 KP/a phase earthen pressure (400 Psig), a hydrogen to hydrocarbon molar ratio of 5.0 to 1, and 3°0 LH8V. with ZSM-5 zeolite.

１６６℃（３３０°Ｆ）以上の沸点の液体の収率は９６
％であった。The yield of liquids boiling above 166°C (330°F) is 96
%Met.

しかしその流動点は１０℃（＋５０°Ｆ）から−３，９
℃（−＋２５’Ｆ）に低下したのにすぎず、ＺＳＭ−５
脱ロウ触媒が著しく脱活性されたことを示した。However, its pour point ranges from 10°C (+50°F) to -3.9
℃ (-+25'F), ZSM-5
It showed that the dewaxing catalyst was significantly deactivated.

例３ 例２の操作手順を逆にした以外は例２を正確にくり返し
た。Example 3 Example 2 was repeated exactly, except that the operating procedure was reversed.

１６６℃（３３０″Ｆ）以上の沸点をもつ液体の収率は
８４係で、流動点は１０℃（５０６Ｆ）から−１７，８
℃（ｏ′Ｆ）へ低下シタ。The yield of liquids with a boiling point above 166°C (330″F) is 84%, and the pour point is -17.8° from 10°C (506°F).
The temperature drops to °C (o'F).

Ｚ Ｓ Ｍ −５触媒再生操作問の期間は２０日間であ
った。The duration of the ZSM-5 catalyst regeneration operation was 20 days.

例４ 英国特許第１１６７８６９号（特公昭４８−３８８７号
公報に対応、）の例１に記載のようにして造ったモルデ
ナイト白金触媒を３１６℃〜３９９℃（６００下〜７５
０”Ｆ）の沸点をもつミツドーコンチネント軽油を使用
して脱ロウ能をＺｎ／Ｈ／ＺＳＭ−５触媒と比較した。Example 4 A mordenite platinum catalyst prepared as described in Example 1 of British Patent No. 1167869 (corresponding to Japanese Patent Publication No. 48-3887) was heated at 316°C to 399°C (600°C to 75°C).
Dewaxing performance was compared to the Zn/H/ZSM-5 catalyst using Mido Continental gas oil with a boiling point of 0''F).

この比較は両方の触媒の定常状態の活性、すなわち少く
とも１週間の連続期間にわたって軽油の流動点が５５．
６℃（１００”Ｆ）またはそれ以上だけ低下する最大Ｌ
Ｈ８Ｖ（軽油／触媒比）を測定することによって行った
。This comparison reflects the steady-state activity of both catalysts, i.e., a gas oil pour point of 55.5% over a continuous period of at least one week.
Maximum L reduced by 6°C (100”F) or more
This was done by measuring H8V (light oil/catalyst ratio).

得られた結果及び生成物の分析値は下記の通りであった
： 経済面を考慮すると定常状態の活性は少くとも１．０で
あるから、Ｐｉ１モルデナイト触媒は完全に非活性触媒
である。The results obtained and the analytical values of the product were as follows: Considering the economic aspects, the steady state activity is at least 1.0, so the Pi1 mordenite catalyst is a completely inactive catalyst.

Claims (1)

【特許請求の範囲】[Claims] １２０４℃〜４８２℃の温度範囲で沸とうする硫黄及び
窒素を含有する軽油を１４９°Ｃ〜５３８℃の温度で最
初に接触脱ロウ処理してその流動点を下げ、次いで流動
点が低下した全生成物を脱硫脱窒素処理することからな
る、２０４℃〜４８２℃の温度で沸とうする硫黄及び窒
素を含有する軽油の流動点を低下させる方法において、
脱ロウ触媒がＺＳＭ−５型ゼオライトであることを特徴
とする方法。Gas oil containing sulfur and nitrogen, which boils in the temperature range of 1204°C to 482°C, is first treated with catalytic dewaxing at a temperature of 149°C to 538°C to lower its pour point, and then the pour point is lowered. A method for lowering the pour point of sulfur- and nitrogen-containing light oil boiling at a temperature of 204°C to 482°C, comprising subjecting the product to a desulfurization and denitrification treatment,
A method characterized in that the dewaxing catalyst is ZSM-5 type zeolite.
JP49041825A 1973-06-15 1974-04-16 Catalytic dewaxing method for gas oil Expired JPS5911635B2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US370265A US3894938A (en) 1973-06-15 1973-06-15 Catalytic dewaxing of gas oils
US370265 1973-06-15

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JPS5017401A JPS5017401A (en) 1975-02-24
JPS5911635B2 true JPS5911635B2 (en) 1984-03-16

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CA (1) CA1024091A (en)
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FR (1) FR2233384B1 (en)
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TR17826A (en) 1976-04-13
DE2428463C2 (en) 1990-02-15
FR2233384A1 (en) 1975-01-10
GB1443877A (en) 1976-07-28
BE816234A (en) 1974-12-12
DE2428463A1 (en) 1975-01-09
ZA742111B (en) 1975-11-26
US3894938A (en) 1975-07-15
IT1015078B (en) 1977-05-10
AU6929674A (en) 1975-11-27
JPS5017401A (en) 1975-02-24
NL7407870A (en) 1974-12-17
CA1024091A (en) 1978-01-10
FR2233384B1 (en) 1979-10-12

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