JP5314546B2 - Method for pyrolysis of heavy oil - Google Patents
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- JP5314546B2 JP5314546B2 JP2009212635A JP2009212635A JP5314546B2 JP 5314546 B2 JP5314546 B2 JP 5314546B2 JP 2009212635 A JP2009212635 A JP 2009212635A JP 2009212635 A JP2009212635 A JP 2009212635A JP 5314546 B2 JP5314546 B2 JP 5314546B2
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- 238000000034 method Methods 0.000 title claims description 45
- 238000000197 pyrolysis Methods 0.000 title claims description 40
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- 238000004519 manufacturing process Methods 0.000 claims description 25
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 24
- 239000006227 byproduct Substances 0.000 claims description 9
- 125000003367 polycyclic group Chemical group 0.000 claims description 9
- 238000004231 fluid catalytic cracking Methods 0.000 claims description 8
- 125000002619 bicyclic group Chemical group 0.000 claims description 4
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- 238000006243 chemical reaction Methods 0.000 description 12
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- 125000003118 aryl group Chemical group 0.000 description 11
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- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 6
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- 239000011593 sulfur Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 238000005979 thermal decomposition reaction Methods 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- -1 bicyclic aromatic hydrocarbons Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000004508 fractional distillation Methods 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 238000012643 polycondensation polymerization Methods 0.000 description 2
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- 239000002002 slurry Substances 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- 238000005054 agglomeration Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
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- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
本発明は、エチレンクラッカーなどのオレフィン製造プロセスで副生する重質油の熱分解方法に関する。 The present invention relates to a method for pyrolyzing heavy oil by-produced in an olefin production process such as ethylene cracker.
ナフサなどの石油留分を熱分解してエチレンを製造する、いわゆるエチレンクラッカーなどのオレフィン製造プロセスで副生する重質油は、石炭乾留タールや石油留分の接触分解の塔底油と比較すると、硫黄、窒素、重金属分が少なく、各種炭素材料の原料物質として適した性状を有しているが、これらの重質油（ボトム油又はエチレンヘビーエンド）は、もっぱら石油化学プロセス内での自家用燃料として利用するに留まっていた。
本出願人は、この自家用燃料としてしか利用されてこなかったオレフィン製造プロセスで副生する重質油を熱分解処理して、より付加価値の高い自動車用燃料油、暖房用燃料油といったガソリン、灯油、軽油等の中間留分や、高品質コークス燃料や加炭材、アルミニウム精錬用電極、二次電池電極等の炭素材として好適な高純度の石油コークスを製造する方法を提案した（特許文献１及び２）。
Heavy oil produced as a by-product in the olefin production process such as so-called ethylene cracker, which produces ethylene by thermally cracking petroleum fractions such as naphtha, is compared with bottom oil of catalytic cracking of coal dry distillation tar and petroleum fractions. It has low sulfur, nitrogen and heavy metal content, and has suitable properties as a raw material for various carbon materials, but these heavy oils (bottom oil or ethylene heavy end) are exclusively for private use within petrochemical processes. It was only used as fuel.
The present applicant thermally decomposes heavy oil produced as a by-product in the olefin production process, which has been used only as a private fuel, to provide gasoline, kerosene such as high-value automobile fuel oil and heating fuel oil. A method for producing high-purity petroleum coke suitable as carbon materials such as middle distillates such as light oil, high-quality coke fuel, carburized material, aluminum refining electrode, and secondary battery electrode has been proposed (Patent Document 1). And 2).
しかしながら、このオレフィン製造プロセスで副生する重質油を熱分解すると、熱分解装置の加熱炉チューブにコーキングが発生し、ひいてはチューブが閉塞し、熱分解装置を長期間、連続して運転ができなくなるという問題があった。
一方、重質油の熱分解処理などにおいて、コーク生成を抑制する方法として、凝集緩和処理剤の存在下に、予め１５０〜３５０℃の温度でアスファルテンの凝集緩和処理を行うことが提案されている（特許文献３）。しかし、この方法は、有機溶媒や有用な石油留分等を凝集緩和剤として用いる必要があり、また新たに加熱設備を設ける必要などがあり、好ましいものではない。
However, when the heavy oil by-produced in this olefin production process is pyrolyzed, coking occurs in the furnace tube of the pyrolysis device, which eventually closes the tube, allowing the pyrolysis device to operate continuously for a long period of time. There was a problem of disappearing.
On the other hand, as a method for suppressing the formation of coke in the pyrolysis treatment of heavy oil, etc., it has been proposed to perform the asphaltene aggregation relaxation treatment at a temperature of 150 to 350 ° C. in the presence of an aggregation relaxation treatment agent in advance. (Patent Document 3). However, this method is not preferable because an organic solvent, a useful petroleum fraction or the like needs to be used as an agglomeration mitigating agent, and a heating facility needs to be newly provided.
本発明は、上記課題を解決するもので、本発明の目的は、新たな加熱設備などを設けることなく、低コストで、重質油を熱分解する際に、加熱炉チューブでのコーキングを抑制し、連続して、安定的に熱分解装置を長期間に亘って運転する方法の提供にある。 The present invention solves the above problems, and the object of the present invention is to suppress coking in a heating furnace tube when pyrolyzing heavy oil at low cost without providing new heating equipment. In addition, the present invention provides a method for continuously and stably operating a thermal decomposition apparatus over a long period of time.
上記課題を解決するために、本発明者は鋭意検討した結果、この重質油中では、アスファルテンは、一環、二環の芳香族炭化水素に覆われて安定して分散しているが、加熱によって、重質油中の一環、二環の芳香族炭化水素の含有量が変化することにより、特にアスファルテン分が２％以上あると、このアスファルテン分が会合してスラッジとなって沈降してコーキングを生じるが、驚くべきことに、三環以上の芳香族炭化水素が所定量以上存在すると、このアスファルテン分の分離、会合が防止され、コーキングの発生を抑制できることを見出した。
本発明は、かかる知見に基づきなされたもので、本発明は次のとおりである。
（１）芳香族分の含有量が８０重量％以上であり、かつ三環以上の多環芳香族分の含有量が２５重量％以上、アスファルテン分が２〜２０％である原料重質油を、温度４００〜６００℃、圧力０.０１〜１.０MPaで熱分解する重質油の熱分解方法。
（２）前記原料重質油が、オレフィン製造プロセスで副生する重質油に、一環芳香族分と二環芳香族分の合計含有量が６０重量％以下で、三環以上の多環芳香族分が４０重量％以上の第２の重質油を混合したものである上記（１）に記載の重質油の熱分解方法。
（３）前記第２の重質油が、流動接触分解残渣油及び／又は重質熱分解油である上記（１）又は（２）に記載の重質油の熱分解方法。
In order to solve the above-mentioned problems, the present inventor has intensively studied. As a result, in this heavy oil, asphaltenes are partly covered with bicyclic aromatic hydrocarbons and stably dispersed. As a result of the change in the content of bicyclic aromatic hydrocarbons as part of heavy oil, the asphaltene content, especially when it is 2% or more, aggregates and settles into sludge and coking. Surprisingly, it has been found that when a predetermined amount or more of an aromatic hydrocarbon having three or more rings is present, the separation and association of the asphaltenes are prevented and the occurrence of coking can be suppressed.
The present invention has been made based on such findings, and the present invention is as follows.
(1) A raw material heavy oil having an aromatic content of 80% by weight or more, a tricyclic or higher polycyclic aromatic content of 25% by weight or more, and an asphaltene content of 2 to 20%. , A method for thermally decomposing heavy oil that is thermally decomposed at a temperature of 400 to 600 ° C. and a pressure of 0.01 to 1.0 MPa.
(2) A heavy oil produced as a by-product of the olefin production process, wherein the raw heavy oil has a total aromatic content and bicyclic aromatic content of 60% by weight or less, and a tricyclic or higher polycyclic aroma. The method for pyrolyzing heavy oil according to (1) above, wherein the second heavy oil having a group content of 40% by weight or more is mixed.
(3) The heavy oil pyrolysis method according to (1) or (2), wherein the second heavy oil is fluid catalytic cracking residue oil and / or heavy pyrolysis oil.
本発明は、新たな加熱設備などを設けることなく、低コストで、重質油を熱分解する際に、熱分解装置の加熱炉チューブでのコーキング発生を抑制し、連続して、安定的に熱分解装置を長期間に亘って運転できるという効果を奏する。 The present invention suppresses the occurrence of coking in the heating furnace tube of the pyrolysis device when pyrolyzing heavy oil at low cost without providing new heating equipment and the like, continuously and stably. There is an effect that the thermal decomposition apparatus can be operated for a long period of time.
本発明の原料重質油は、芳香族分の含有量が８０重量％以上、好ましくは８５重量％、より好ましくは９０重量％以上のものである。芳香族分が８０重量％未満であると加熱炉でのコーキングが生じやすくなる。また、三環以上の多環芳香族分の含有量が２５重量％以上、好ましくは３０重量％以上のものである。三環以上の多環芳香族分の含有量が２５重量％未満であると加熱炉でのコーキングが生じやすくなる。
この芳香族分は、ＴＬＣ法（Thin Layer Chromatography）により測定されるものである。このＴＬＣ法は、例えば、クロマトロッド（株式会社三菱化学ヤトロン社製、クロマロッド−ＳIII）に、試料をチャージし、まずノルマルヘキサンで展開してサチュレート分を分離し、次いでトルエンで展開してアロマ分を分離し、さらにジクロロメタン／メタノール（９５：５）でレジン分を展開し、３つのブロックに分離する。その後、薄層自動検出装置（株式会社三菱化学ヤトロン社製、new ＭＫ−５）により３つのそれぞれのブロックを水素炎イオン化検出器で定量してサチュレート分、アロマ分、レジン分として測定することができる。また、多環芳香族分はイギリス石油協会規格ＩＰ３９１に準じて測定されるものである。
The raw material heavy oil of the present invention has an aromatic content of 80% by weight or more, preferably 85% by weight, more preferably 90% by weight or more. If the aromatic content is less than 80% by weight, coking in a heating furnace tends to occur. Further, the content of the tricyclic or higher polycyclic aromatic component is 25% by weight or more, preferably 30% by weight or more. When the content of the tricyclic or higher polycyclic aromatic component is less than 25% by weight, coking in a heating furnace tends to occur.
This aromatic content is measured by the TLC method (Thin Layer Chromatography). In this TLC method, for example, a sample is charged on a chromatorod (manufactured by Mitsubishi Chemical Yatron Co., Ltd., Chromarod-SIII), first developed with normal hexane to separate the saturate, and then developed with toluene to obtain an aroma. Separate the minutes and develop the resin with dichloromethane / methanol (95: 5) and separate into three blocks. Then, each of the three blocks can be quantified with a flame ionization detector using a thin-layer automatic detector (manufactured by Mitsubishi Chemical Yatron Co., Ltd., new MK-5) and measured as a saturating component, aroma component, and resin component. it can. The polycyclic aromatic component is measured according to British Petroleum Institute Standard IP391.
さらに、本発明の原料重質油はアスファルテン分が２〜２０％、好ましくは４〜１２％のものである。アスファルテン分が２０％より多くなると加熱炉でのコーキングが生じやすくなる。アスファルテン分が２％未満だと、コーキングの問題は生じないが、オレフィン製造プロセスで副生する重質油の処理量が減少するため好ましくない。また、加熱炉でのコーキングの発生を抑制するためには、アスファルテン分／三環以上の多環芳香族分の比（重量比）を０.０５〜０.５にすることが好ましく、より好ましく０.０７〜０.４とするとよい。なお、アスファルテン分は、イギリス石油協会規格ＩＰ１４３に準拠して測定（トルエンに可溶で、ｎ−ヘプタンに不溶な物質の割合）されるものである。 Furthermore, the raw heavy oil of the present invention has an asphaltene content of 2 to 20%, preferably 4 to 12%. When the asphaltene content exceeds 20%, coking in a heating furnace tends to occur. If the asphaltene content is less than 2%, the problem of coking does not occur, but it is not preferable because the amount of heavy oil produced as a by-product in the olefin production process decreases. In order to suppress the occurrence of coking in a heating furnace, the ratio (weight ratio) of asphaltenes / tricyclic or higher polycyclic aromatics is preferably 0.05 to 0.5, and more preferably. It is good to set it as 0.07-0.4. The asphaltene content is measured in accordance with British Petroleum Institute Standard IP143 (a ratio of a substance soluble in toluene and insoluble in n-heptane).
また、この原料重質油は、蒸留性状の５％留出温度が１５０〜２５０℃が好ましく、１７０〜２３０℃がより好ましく、特には１８０〜２１０℃が好ましい。９５％留出温度は４５０〜６５０℃が好ましく、５００〜６１０℃がより好ましく、特には５１５〜６００℃が好ましい。５％留出温度が１５０℃より低いと熱分解処理した際に低級炭化水素留分（常温常圧でガス状の炭化水素）が多くなり、また、２５０℃より大きいと原料油の動粘度が高くなるので、流動性を持たせるために加熱する必要が生じ、消費熱量が大きくなり、あまり好ましくない。また、９５％留出温度が４５０℃より低いと熱分解処理した際に得られる３６０℃以下の中間留分の生成量が低くなり、また、６５０℃より大きいと残留炭素分が増加し、コークドラム前段の加熱炉でコーキングをおこし易くなるので、あまり好ましいものではない。さらに、５０％留出温度は３００〜４００℃が好ましく、３３０〜３８０℃がより好ましい。なお、この蒸留性状は、ＪＩＳＫ２２５４（ガスクロ法）に規定する方法で測定されるものである。 Further, this raw material heavy oil has a distillation property of 5% distillation temperature of preferably 150 to 250 ° C, more preferably 170 to 230 ° C, and particularly preferably 180 to 210 ° C. The 95% distillation temperature is preferably 450 to 650 ° C, more preferably 500 to 610 ° C, and particularly preferably 515 to 600 ° C. When the 5% distillation temperature is lower than 150 ° C., the lower hydrocarbon fraction (gaseous hydrocarbon at normal temperature and normal pressure) increases during pyrolysis, and when it is higher than 250 ° C., the kinematic viscosity of the feedstock oil increases. Since it becomes high, it is necessary to heat in order to have fluidity, and the amount of heat consumption increases, which is not preferable. Also, if the 95% distillation temperature is lower than 450 ° C, the amount of middle distillate of 360 ° C or less obtained when pyrolyzing is reduced, and if it is higher than 650 ° C, the residual carbon content increases and coke. Since it becomes easy to perform coking in the heating furnace in front of the drum, it is not so preferable. Furthermore, the 50% distillation temperature is preferably 300 to 400 ° C, more preferably 330 to 380 ° C. In addition, this distillation property is measured by the method prescribed | regulated to JISK2254 (gas chromatography method).
この原料重質油中の硫黄分、窒素分は低いほど望ましいが、硫黄分は好ましくは０.５重量％以下、より好ましくは０.３重量％以下である。同様に、窒素分は好ましくは０.２重量％以下で、より好ましくは０.１重量％以下である。なお、この硫黄分は、ＪＩＳ Ｋ２５４１（放射線式励起法、紫外蛍光法）に、窒素分はＪＩＳＫ２６０９（化学発光法）に規定する方法で測定されるものである。 The lower the sulfur content and nitrogen content in the raw material heavy oil, the better. However, the sulfur content is preferably 0.5% by weight or less, more preferably 0.3% by weight or less. Similarly, the nitrogen content is preferably 0.2% by weight or less, more preferably 0.1% by weight or less. This sulfur content is measured by the method defined in JIS K2541 (radiation excitation method, ultraviolet fluorescence method), and the nitrogen content is defined in JIS K2609 (chemiluminescence method).
また、原料重質油の動粘度は、ハンドリング性及び流動性を持たせるための加熱にエネルギーを投入しなければならなくなることなどから、５０℃における動粘度が、好ましくは５〜５００mm２/sであり、より好ましくは１０〜１００mm２/s、特には２０〜７０mm２/sである。なお、この動粘度は、ＪＩＳ Ｋ２２８３に規定する方法で、５０℃で測定されるものである。 In addition, the kinematic viscosity of the raw material heavy oil has a kinematic viscosity at 50 ° C. of preferably 5 to 500 mm 2 / s because energy must be input for heating to provide handling and fluidity. More preferably, it is 10-100 mm < 2 > / s, Especially 20-70 mm < 2 > / s. This kinematic viscosity is measured at 50 ° C. by the method specified in JIS K2283.
上記原料重質油は、オレフィン製造プロセスで副生する重質油に、一環芳香族と二環芳香族の合計含有量が５０重量％以下で、三環以上の多環芳香族分が５０重量％以上の第２の重質油を混合することで調製できる。 The raw heavy oil is a heavy oil produced as a by-product in the olefin production process. The total content of aromatics and bicyclic aromatics is 50% by weight or less, and the polycyclic aromatic content of three or more rings is 50% by weight. % Or more of the second heavy oil can be prepared.
オレフィン製造プロセスで副生する重質油は、特に限定するものではなく、公知の任意のオレフィン製造プロセスを所定の運転条件下で稼動して得られた重質油を用いることができる。オレフィン製造プロセスでは、炭化水素の熱分解により目的とするオレフィン分（エチレン、プロピレン）やバイプロダクトのＬＰＧ、芳香族炭化水素（ベンゼン、トルエン、キシレン）等のガソリン留分、水素、メタン等のガス分とともに、重質油が生成される。重質油の物性は、オレフィン製造プロセスで処理される原料炭化水素によって異なるが、本発明の重質油は、プロパン、ブタン等のＬＰＧ、ナフサ、灯軽油、あるいは減圧軽油などの炭化水素を処理するオレフィン製造プロセスから副生する、いずれの重質油も用いることができる。より好ましくはエチレンクラッカーに代表されるオレフィン製造プロセスから得られる、いわゆるエチレンボトムあるいはエチレンヘビーエンドと称される重質油である。
なお、オレフィン製造プロセスとしては、Lummus法オレフィンプロセスやStone & Webster Eng．社、Kinetics Technology International社、M. W. Kellogg社のプロセスなどが知られており（例えば、石油学会編「石油化学プロセス」、講談社サイエンティフィク、２５〜２７頁、２００１年出版）、これらのいずれのプロセスからの重質油でもあっても好適に用いることができる。
The heavy oil by-produced in the olefin production process is not particularly limited, and a heavy oil obtained by operating any known olefin production process under predetermined operating conditions can be used. In the olefin production process, the target olefins (ethylene, propylene), biproduct LPG, gasoline fractions such as aromatic hydrocarbons (benzene, toluene, xylene), hydrogen, methane, and other gases by thermal decomposition of hydrocarbons Over time, heavy oil is produced. The physical properties of heavy oil differ depending on the raw material hydrocarbons processed in the olefin production process, but the heavy oil of the present invention treats hydrocarbons such as LPG such as propane and butane, naphtha, kerosene, or vacuum gas oil. Any heavy oil by-produced from the olefin production process can be used. More preferred is a heavy oil called so-called ethylene bottom or ethylene heavy end, which is obtained from an olefin production process represented by ethylene cracker.
The olefin production process includes the Lummus olefin process and Stone & Webster Eng. The processes of the company, Kinetics Technology International, and MW Kellogg are known (for example, “The Petrochemical Process” edited by the Japan Petroleum Institute, Kodansha Scientific, 25-27 pages, published in 2001). Even heavy oils from can be suitably used.
オレフィン製造プロセスから得られる、いわゆるエチレンボトムあるいはエチレンヘビーエンドと称される重質油は、芳香族分の含有量は８０重量％以上、好ましくは８５重量％、であり、一環芳香族と二環芳香族の合計含有量が５０重量％以上、好ましくは６０重量％以上、特には７０重量％以上、三環以上の多環芳香族分の含有量が２５重量％以下、好ましくは５〜２０重量％のものである。蒸留性状としては５％留出温度が１５０〜２３０℃が好ましく、１７０〜２１０℃がより好ましく、９５％留出温度は５５０〜７００℃が好ましく、６００〜６５０℃がより好ましい。 The heavy oil obtained from the olefin production process, so-called ethylene bottom or ethylene heavy end, has an aromatic content of 80% by weight or more, preferably 85% by weight. The total aromatic content is 50% by weight or more, preferably 60% by weight or more, particularly 70% by weight or more, and the content of tricyclic or more polycyclic aromatics is 25% by weight or less, preferably 5 to 20% by weight. %belongs to. As distillation properties, 5% distillation temperature is preferably 150 to 230 ° C, more preferably 170 to 210 ° C, and 95% distillation temperature is preferably 550 to 700 ° C, more preferably 600 to 650 ° C.
アスファルテンは、ベンゼン環が５〜６個縮合した縮合環とパラフィン側鎖とからなり、縮合環部分は芳香族炭化水素と、側鎖部分はパラフィン系炭化水素とミセル構造を形成して、油中に分散している。ところで、オレフィン製造プロセスで副生する重質油は、アスファルテン分の含有量が高い割には、三環以上の多環芳香族分が少なく、一環、二環に芳香族分が多いので、縮合環とミセル構造を形成しているのは、比較的軽い一環、二環の芳香族分と考えられる。この比較的軽い一環、二環の芳香族分は、加熱により、容易にミセル構造が解体して、スラッジとして析出し、コーキングが生じるものと推測される。 Asphaltenes consist of a condensed ring in which 5 to 6 benzene rings are condensed and a paraffin side chain. The condensed ring portion forms an aromatic hydrocarbon and the side chain portion forms a micellar structure with paraffinic hydrocarbons. Are distributed. By the way, the heavy oil produced as a by-product in the olefin production process has a high content of asphaltenes, but has a low polycyclic aromatic content of three or more rings. It is considered that the formation of the micelle structure with the ring is a relatively light part and a bicyclic aromatic component. As a relatively light part of this, it is assumed that the bicyclic aromatic component easily disassembles the micelle structure and precipitates as sludge by heating, resulting in coking.
本発明者は、この推測に基づき、アスファルテン分が比較的少なく、三環以上の多環芳香族分の多い重質油を混合した結果、加熱によるスラッジの析出が抑制され、コーキングの発生を防ぐことができたものである。したがって、上記オレフィン製造プロセスで副生する重質油に混合される第２の重質油は、一環と二環芳香族分の合計含有量が少なく、三環以上の多環芳香族分の含有量が多い、すなわち、一環芳香族分と二環芳香族分の合計含有量は６０重量％以下が好ましく、より好ましくは５０重量％以下、特には４０重量％以下で、三環以上の多環芳香族分は４０重量％以上が好ましく、より好ましくは５０重量％以上、特には６０重量％以上の重質油が好ましい。 Based on this assumption, the present inventor mixed heavy oil with a relatively small amount of asphaltenes and a large amount of tricyclic or higher polycyclic aromatics. As a result, precipitation of sludge due to heating was suppressed and coking was prevented. Was able to. Therefore, the second heavy oil mixed with the heavy oil produced as a by-product in the above olefin production process has a small total content of one part and two ring aromatics, and contains three or more polycyclic aromatics. A large amount, that is, the total content of aromatic and bicyclic aromatics is preferably 60% by weight or less, more preferably 50% by weight or less, particularly 40% by weight or less, and a tricyclic or more polycyclic ring. The aromatic content is preferably 40% by weight or more, more preferably 50% by weight or more, and particularly preferably 60% by weight or more heavy oil.
このような第２の重質油としては、流動接触分解残渣油や熱分解重質油が好適である。
流動接触分解残渣油は、通常、重質軽油、減圧軽油、常圧蒸留残渣油を、流動する触媒と約４３０〜５５０℃で接触させて分解し、ガソリン留分や軽油留分を生成する流動接触分解装置から副生するスラリーオイル或いはデカンテッドオイルである。このほか、水素化脱硫を経た原料油、例えば、間接脱硫留出油、直脱留出油などを流動接触分解装置で処理して得られたスラリーオイル或いはデカンテッドオイルなども流動接触分解残渣油に含まれる。この流動接触分解残渣油には、一般に、アスファルテン分は数％以下と少なく、一環及び二環芳香族分は合計で２０〜４０重量％程度、三環以上の多環芳香族分が５０重量％以上含まれている。
As such second heavy oil, fluid catalytic cracking residue oil and pyrolysis heavy oil are suitable.
Fluid catalytic cracking residue oil is usually a fluid that generates heavy gas oil, vacuum gas oil, or atmospheric distillation residue oil by contacting it with a flowing catalyst at about 430-550 ° C. to produce a gasoline fraction or a light oil fraction. It is slurry oil or decanted oil by-produced from the catalytic cracking device. In addition, slurry oil or decanted oil obtained by processing a hydrodesulfurized raw material oil, for example, indirect desulfurized distillate oil, direct destilled distillate oil, etc. with a fluid catalytic cracking apparatus is also fluid catalytic cracking residual oil. include. This fluid catalytic cracking residue oil generally has a low asphaltene content of a few percent or less, a total of about 1 to 40% by weight of mono- and bicyclic aromatics, and 50% by weight of tricyclic or higher polycyclic aromatics. Included.
熱分解重質油とは、常圧蒸留残渣油や減圧蒸留残渣油に熱を加えてラジカル反応を主体とした分解反応により得られる留出分のうち、ガス、ガソリン・ナフサ、灯・軽油留分を回収した後の分留温度３６０℃以上の留出残油である。例えば、ビスブレーキングプロセス、フルードコーキングプロセス、フレキシコーキングプロセス、ディレードコーキングプロセス、ユリカプロセス、ＨＳＣプロセス（例えば、石油学会編「石油精製プロセス」、講談社サイエンティフィク、１９７〜２０５頁、１９９８年出版参照）などのプロセスから得られるものが好適である。この熱分解重質油には、一般に、アスファルテン分は数％以下と少なく、一環及び二環芳香族分は合計で１０〜３０重量％程度、三環以上の多環芳香族分が６０重量％以上含まれている。 Pyrolysis heavy oil is gas, gasoline / naphtha, kerosene / light oil distillate among distillates obtained by cracking reaction mainly consisting of radical reaction by heating atmospheric distillation residue oil or vacuum distillation residue oil. This is a distillation residual oil having a fractionation temperature of 360 ° C. or higher after the fraction is collected. For example, visbreaking process, fluid coking process, flexi coking process, delayed coking process, yurika process, HSC process (see, for example, “The Petroleum Society” “Oil Refinery Process”, Kodansha Scientific, pp. 197-205, 1998 publication. And the like obtained from processes such as In general, the pyrolysis heavy oil has a low asphaltene content of a few percent or less, a total of about 10 to 30% by weight of monocyclic and bicyclic aromatic components, and 60% by weight of polycyclic aromatic components having three or more rings. Included.
オレフィン製造プロセスで副生する重質油と第２の重質油の混合割合は、それぞれの重質油中の芳香族分、三環以上の多環芳香族分及びアスファルテン分の含有量が、プロセスの種類や処理原料、条件より変動するため、一概には決めることができないが、通常は、オレフィン製造プロセスで副生する重質油を２０〜８０重量％、第２の重質油を８０〜２０重量％の範囲で適宜選定でき、混合後の原料重質油中の芳香族分が８０重量％以上、三環以上の多環芳香族分が２５重量％以上、アスファルテン分が２〜２０％になるような割合で混合して調製するとよい。 The mixing ratio of the heavy oil and the second heavy oil by-produced in the olefin production process is such that the aromatic content, the polycyclic aromatic content of three or more rings, and the asphaltene content in each heavy oil, Since it varies depending on the type of process, processing raw materials, and conditions, it cannot be determined unconditionally, but usually 20 to 80% by weight of heavy oil produced as a by-product in the olefin production process and 80% of second heavy oil are used. Can be appropriately selected in the range of ˜20% by weight, the aromatic content in the raw heavy oil after mixing is 80% by weight or more, the polycyclic aromatic content of three or more rings is 25% by weight or more, and the asphaltene content is 2 to 20%. It is good to mix and prepare in the ratio which becomes%.
本発明においては、上記原料重質油を熱分解するが、この熱分解は、例えば、ビスブレーキングプロセス、フルードコーキングプロセス、フレキシコーキングプロセス、ディレードコーキングプロセス、ユリカプロセス、ＨＳＣプロセスなどのプロセスを用いて行うことができる。
なかでもディレードコーキングプロセスを用いることが好ましい。この場合、ディレードコーキングプロセスの装置構成、運転条件は特に限定されるものではなく、公知の任意の製造装置、運転条件を採用できる。ディレードコーキングプロセスは加熱炉で原料油を加熱してコークドラムに張り込み、そこで蒸し焼き状態で熱分解縮重合反応が行われ、より付加価値の高いガス、分解ガソリン、灯油軽油などの石油留分（熱分解処理油）を生成すると同時に、コークスを製造する装置である。コークスはコークドラム中に堆積していくので、いっぱいになったコークドラムは系から切り離して堆積したコークスを切り出す。空になったコークドラムは、再び加熱された原料油を受け入れて熱分解縮重合反応を行う。ディレードコーキングプロセスは、通常、複数基のコークドラムを備えていて、上記の操作を順繰りに繰り返すことが行われる。
In the present invention, the raw heavy oil is pyrolyzed. For this pyrolysis, for example, a process such as a visbreaking process, a fluid coking process, a flexi coking process, a delayed coking process, a yurika process, or an HSC process is used. Can be done.
Among these, it is preferable to use a delayed coking process. In this case, the apparatus configuration and operating conditions of the delayed coking process are not particularly limited, and any known manufacturing apparatus and operating conditions can be adopted. In the delayed coking process, the feedstock oil is heated in a heating furnace and placed on a coke drum, where the pyrolysis condensation polymerization reaction is performed in a steamed state, and petroleum fractions such as higher value-added gas, cracked gasoline, kerosene gas oil, etc. This is an apparatus for producing coke at the same time as producing cracked oil. Since coke accumulates in the coke drum, the full coke drum separates from the system and cuts the deposited coke. The emptied coke drum receives the heated raw material oil again and performs a thermal decomposition condensation polymerization reaction. The delayed coking process is usually provided with a plurality of coke drums, and the above operations are repeated in order.
上記原料重質油は、反応温度４００〜６００℃、より好ましくは４５０〜５５０℃、反応圧力０.０１〜１.０MPa、より好ましくは０.０５〜０.５MPaで熱分解される。これらの反応条件は、この範囲内で適宜設定することができるが、熱分解処理油の収率が５０重量％以上、特には６０重量％以上になるように設定することが好ましい。熱分解の反応温度は、４００℃より低いと、熱分解処理油の収率が低くなり、好ましくなく、また６００℃を超えると分解ガスの生成量が増加し、好ましくない。反応圧力が、１.０MPaより高いと、熱分解処理油の収率が低くなり、好ましくない。 The raw heavy oil is thermally decomposed at a reaction temperature of 400 to 600 ° C., more preferably 450 to 550 ° C., a reaction pressure of 0.01 to 1.0 MPa, more preferably 0.05 to 0.5 MPa. These reaction conditions can be appropriately set within this range, but are preferably set so that the yield of the pyrolysis oil is 50% by weight or more, particularly 60% by weight or more. If the reaction temperature for pyrolysis is lower than 400 ° C., the yield of the pyrolysis oil will be low, which is not preferred. When the reaction pressure is higher than 1.0 MPa, the yield of the pyrolysis oil is lowered, which is not preferable.
液空間速度は装置の大きさやコークスの生成量を考慮して設定して構わないが、好ましくは０.０１〜０.５ｈ−１であり、より好ましくは０.１〜０.３ｈ−１である。
なお、ここで熱分解処理油の収率（wt％）は、次の式（１）によって得られる値を意味する。
熱分解処理油の収率＝熱分解油の重量／原料供給量×１００ （１）
上記式中、熱分解油の重量は、熱分解実験装置の空冷式コンデンサに回収された油の重量であり、原料供給量は、熱分解装置への原料重質油の供給量（重量）である。
Liquid hourly space velocity may be set in consideration of the production of the size and coke device, preferably 0.01～0.5H -1, more preferably 0.1～0.3H -1 is there.
Here, the yield (wt%) of the pyrolysis oil means a value obtained by the following equation (1).
Yield of pyrolysis oil = weight of pyrolysis oil / feed amount of raw material × 100 (1)
In the above formula, the weight of the pyrolysis oil is the weight of the oil recovered in the air-cooled condenser of the pyrolysis experimental device, and the feed rate of raw material is the feed amount (weight) of the feed heavy oil to the pyrolysis device. is there.
前記熱分解は、熱分解処理油の収率が３０重量％以上、特には５０重量％以上となるようにすることが好ましく、また、得られた熱分解処理油に含まれる３６０℃以下の留分の比率が６５重量％以上となるようにすることが好ましく、８０重量％以上であることがより好ましい。また、２７０℃以下の留分が５０容量％以上にすることが好ましく、６０容量％以上がより好ましい。さらに、１５０〜２７０℃の留分が３０容量％以上になるようにすることが好ましく、４０容量％以上がより好ましく、１５０〜３６０℃の留分は６０容量％以上となるようにすることが好ましく、７０容量％以上がより好ましい。 The pyrolysis is preferably performed so that the yield of the pyrolysis-treated oil is 30% by weight or more, particularly 50% by weight or more, and the temperature of 360 ° C. or less contained in the obtained pyrolysis-treated oil. The ratio of the minute is preferably 65% by weight or more, and more preferably 80% by weight or more. Moreover, it is preferable to make a fraction of 270 degreeC or less into 50 volume% or more, and 60 volume% or more is more preferable. Further, it is preferable that the fraction at 150 to 270 ° C. is 30% by volume or more, more preferably 40% by volume or more, and the fraction at 150 to 360 ° C. is 60% by volume or more. Preferably, 70% by volume or more is more preferable.
前記熱分解により得た熱分解処理油は、分留、抽出など種々の方法により分画処理することにより、ガソリン、灯油、軽油など各種の燃料油や、又はそれらを製造するための調合用基材等を得ることができる。
熱分解処理油は、蒸留性状の５％留出温度が１２０〜２３０℃、特には１４０〜２１０℃のものが好ましく、また９５％留出温度が、２９０〜５２０℃、特には３１０〜５００℃のものが好ましい。この熱分解処理油のうち、３６０℃以下の留分は、分留をはじめとするその他各種の石油精製手段を用いて上記の各種燃料油、あるいはそれらの基材として分離、調製することができる。また、３６０℃以上の留分は、上記第２の重質油として、再利用することができる。
The pyrolysis oil obtained by the above pyrolysis is subjected to fractionation treatment by various methods such as fractional distillation, extraction, etc., so that various fuel oils such as gasoline, kerosene, light oil, or a preparation base for producing them. Materials etc. can be obtained.
The pyrolysis-treated oil preferably has a distillation property of 5% distillation temperature of 120 to 230 ° C., particularly 140 to 210 ° C., and 95% distillation temperature of 290 to 520 ° C., particularly 310 to 500 ° C. Are preferred. Of this pyrolysis-treated oil, a fraction of 360 ° C. or lower can be separated and prepared as the above-mentioned various fuel oils or their base materials using various other petroleum refining means including fractional distillation. . Moreover, a fraction of 360 ° C. or higher can be reused as the second heavy oil.
すなわち、得られた熱分解処理油を分留することにより、例えば、３０〜２２０℃の留分はガソリン基材として、１５０〜２７０℃の留分は灯油基材として、また、１５０〜３６０℃の留分が軽油基材として、それぞれ回収することができる。また、熱分解処理油の硫黄分は、０.５重量％以下が好ましく、より好ましくは０.２重量％以下であり、また、窒素分は１０００重量ppm以下が好ましく、より好ましくは２００重量ppm以下である。プロダクト中の硫黄分、窒素分は、原料の重質油の性状に依存するが、含有する不純物量は少ないほど好ましい。 That is, by fractionating the obtained pyrolysis-treated oil, for example, a fraction of 30 to 220 ° C. is used as a gasoline base, a fraction of 150 to 270 ° C. is used as a kerosene base, and 150 to 360 ° C. Can be recovered as a light oil base. Further, the sulfur content of the pyrolysis oil is preferably 0.5% by weight or less, more preferably 0.2% by weight or less, and the nitrogen content is preferably 1000 ppm by weight or less, more preferably 200 ppm by weight. It is as follows. The sulfur content and nitrogen content in the product depend on the properties of the raw heavy oil, but the smaller the amount of impurities contained, the better.
以下に、実施例に基づき、本発明をより詳細に説明するが、この実施例は本発明を限定するものではない。
各原料油基材としては次のものを用いた。
エチレンボトム油は、原油由来のナフサを熱分解してエチレンを製造するオレフィン製造プロセス（Lummus社、オレフィンプロセス）から得られたエチレンボトム油を用いた。接触分解残渣油Ａは、脱硫減圧軽油を原料とし、これをゼオライト触媒を用いて、接触分解して得られた接触分解残渣油を用いた。接触分解残渣油Ｂは、直留残渣油を原料とし、これをゼオライト触媒を用いて、接触分解して得られた接触分解残渣油を用いた。また、重質熱分解油は、流動接触分解残渣油を中心とする混合油を原料とするディレードコーカープロセスから得られた重質熱分解油を用いた。表１に各種原料油基材の性状を示す。
これらを表２に示す割合で混合した原料重質油を用い、熱分解実験装置により反応圧力０.５０MPa、反応温度５００℃の条件下で３０分間熱分解した。
反応終了後、装置内の熱分解油及び固形分を回収し、目開き０.１μmのフィルターで濾過した。固形分の回収及び固形物の洗浄にはトルエンを使用した。フィルター上の固形分は、乾燥後、測定し、熱分解に供した原料重質油に対する割合として求め、この結果を表２に示した。
なお、熱分解実験装置は、加熱部と冷却部からなる金属製の反応装置であり、加熱部には最大５０gの試料を仕込むことが可能な装置であり、冷却部は空冷式のコンデンサである。圧力の調整は窒素によって行った。
Hereinafter, the present invention will be described in more detail based on examples, but the examples do not limit the present invention.
The followings were used as each raw material base material.
As the ethylene bottom oil, an ethylene bottom oil obtained from an olefin production process (Lummus, olefin process) in which naphtha derived from crude oil was pyrolyzed to produce ethylene was used. As the catalytic cracking residue oil A, desulfurized vacuum gas oil was used as a raw material, and the catalytic cracking residual oil obtained by catalytic cracking using a zeolite catalyst was used. As the catalytic cracking residual oil B, a direct cracking residual oil was used as a raw material, and a catalytic cracking residual oil obtained by catalytic cracking using a zeolite catalyst was used. Moreover, the heavy pyrolysis oil used the heavy pyrolysis oil obtained from the delayed coker process which uses the mixed oil centering on fluid catalytic cracking residue oil as a raw material. Table 1 shows the properties of various raw material base materials.
The raw material heavy oil mixed at the ratio shown in Table 2 was used, and pyrolysis was performed for 30 minutes under the conditions of a reaction pressure of 0.50 MPa and a reaction temperature of 500 ° C. using a thermal decomposition experimental apparatus.
After completion of the reaction, pyrolyzed oil and solid content in the apparatus were collected and filtered through a filter having an opening of 0.1 μm. Toluene was used for solids recovery and solids washing. The solid content on the filter was measured after drying and obtained as a ratio to the raw material heavy oil subjected to thermal decomposition. The results are shown in Table 2.
The pyrolysis experimental apparatus is a metal reaction apparatus composed of a heating part and a cooling part. The heating part is an apparatus capable of charging a sample of up to 50 g, and the cooling part is an air-cooled condenser. . The pressure was adjusted with nitrogen.
この結果から、原料重質油中にアスファルテン分を２％以上含有していても、芳香族分の含有量が８０重量％以上であり、かつ三環以上の多環芳香族分の含有量が２５重量％以上であれば、生成する固形分が少なく、コーキングが抑制されていることが分かる。 From this result, even if the raw material heavy oil contains 2% or more of asphaltenes, the content of aromatics is 80% by weight or more, and the content of tricyclic or more polycyclic aromatics is If it is 25 weight% or more, it turns out that there is little solid content to produce | generate and coking is suppressed.
本発明は、エチレンクラッカーなどのオレフィン製造プロセスで副生する重質油の熱分解に利用することができる。 The present invention can be used for pyrolysis of heavy oil by-produced in an olefin production process such as ethylene cracker.
Claims (2)
The heavy oil pyrolysis method according to claim 1, wherein the second heavy oil is fluid catalytic cracking residue oil and / or heavy pyrolysis oil.
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