WO2013002000A1 - 混合c4留分を原料とするジイソブチレンの製造方法 - Google Patents
混合c4留分を原料とするジイソブチレンの製造方法 Download PDFInfo
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- WO2013002000A1 WO2013002000A1 PCT/JP2012/064590 JP2012064590W WO2013002000A1 WO 2013002000 A1 WO2013002000 A1 WO 2013002000A1 JP 2012064590 W JP2012064590 W JP 2012064590W WO 2013002000 A1 WO2013002000 A1 WO 2013002000A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/12—Catalytic processes with crystalline alumino-silicates or with catalysts comprising molecular sieves
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
Definitions
- the present invention relates to a process for producing diisobutylene using a mixed C4 fraction as a raw material, and more specifically, contacting a mixed C4 fraction with a solid acid catalyst, preferably a silica-alumina catalyst, to form an isobutene oligomer in a one-stage reaction.
- the present invention relates to a method for producing a high-value-added high-purity diisobutylene with a high reaction selectivity by carrying out a distillation operation after carrying out the conversion reaction.
- Diisobutylene which is a dimer of isobutene (hereinafter sometimes abbreviated as “DIB”), is a raw material for oxo alcohol, a raw material for isononanoic acid, a raw material for p-octylphenol, a raw material for rubber tackifier, and a surface activity. It is known to be useful as a raw material for chemicals, as well as gasoline fuel additives, rubber chemicals and the like.
- DIB dimer of isobutene
- isobutene is selectively reacted with sulfuric acid from a C4 fraction produced from FCC (fluid catalytic cracking) or an ethylene plant to produce 1-butene, 2-butene or butane as isobutyl sulfate.
- Diisobutylene is obtained by separating it from the like and then thermally decomposing it.
- isobutene is converted into MTBE (methyl tert-butyl ether) or TBA (tertiary butyl alcohol) from the C4 fraction, and then decomposed and dimerized to obtain diisobutylene.
- Patent Document 1 discloses a technique for an oligomerization method of isobutene using an acidic ion exchange resin having a sulfonic acid group, in which a part of protons of an acidic ion exchanger is exchanged with metal ions. .
- high-purity diisobutylene is obtained using a C4 mixed fraction as a raw material, but isobutene has only been shown to have a low conversion rate, and the oligomerization catalyst is completely different from the silica-alumina catalyst. Is different.
- Patent Document 2 discloses a technique for oligomerization of olefins that can produce a fuel such as gasoline and / or kerosene / light oil using a silica-alumina catalyst.
- oligomerization is carried out using a C4 mixed fraction as a raw material with an isobutene conversion rate of 90% or more, a 1-butene conversion rate of 90%, and a 2-butene conversion rate of about 80%.
- the conversion rate of isobutene is 97 to 100%, and the reaction is performed in a region where the conversion rate of isobutene is extremely high.
- the present invention has been made under such circumstances.
- the mixed C4 fraction is brought into contact with a polymerization catalyst to carry out isobutene oligomerization reaction in a one-stage reaction, and high purity DIB is obtained with high reaction selectivity.
- An object is to provide a method of manufacturing.
- a solid acid catalyst preferably a silica-alumina catalyst, is used as the oligomerization catalyst, and when contacting the mixed C4 fraction with this, the conversion of isobutene in the mixed C4 fraction is controlled to a predetermined range, thereby increasing the level. It has been found that DIB can be obtained with a reaction selectivity, and that high purity DIB can be obtained by subjecting the reaction product to a specific distillation operation. The present invention has been completed based on such findings.
- the present invention [1] A method for producing diisobutylene by bringing a mixed C4 fraction of a raw material into contact with a solid acid catalyst, (A) an isobutene oligomerization reaction step; (B) a step of distilling and separating an unreacted C4 fraction and an oligomer fraction containing the generated C8 fraction, and (c) a step of distilling and purifying diisobutylene in the C8 fraction, And in the step (a), the conversion of isobutene in the mixed C4 fraction is controlled in the range of 60 to 95%, and a method for producing diisobutylene, [2] The process for producing diisobutylene according to the above [1], wherein the solid acid catalyst is a silica-alumina catalyst, [3] In the step (a), the reaction conditions in the isobutene oligomerization reaction step are such that the WHSV of the mixed C4 fraction with respect to the solid acid catalyst (feed mass relative to the catalyst mass per
- a solid acid catalyst preferably a silica-alumina catalyst
- the conversion rate of isobutene in the mixed C4 fraction Is controlled within a predetermined range, and by subjecting the reaction product to a specific distillation operation, DIB having a high reaction selectivity and high purity can be obtained efficiently.
- the DIB production method of the present invention is a method for producing diisobutylene by bringing a mixed C4 fraction of a raw material into contact with a solid acid catalyst, (A) an isobutene oligomerization reaction step; (B) a step of distilling and separating an unreacted C4 fraction and an oligomer fraction containing the generated C8 fraction, and (c) a step of distilling and purifying diisobutylene in the C8 fraction, And the conversion of isobutene in the mixed C4 fraction is controlled in the range of 60 to 95% in the step (a).
- a mixed C4 fraction is used as a raw material.
- the mixed C4 fraction include an olefin fraction produced by an FCC process, an olefin fraction obtained by removing a diene component from a fraction produced by a naphtha cracker by selective hydrogenation, and the like. It may be a mixture of Furthermore, you may adjust by increasing / decreasing content of a specific fraction using well-known methods, such as distillation, with respect to them.
- a raffinate obtained by extracting butadiene from a C4 fraction produced by a naphtha cracker or an FCC-C4 fraction is distilled (or reactively distilled), and isobutene-isobutane containing a high concentration of isobutene excluding normal butenes and normal butanes.
- a fraction can be used.
- the mixed C4 fraction generally contains components such as 1-butene, trans-2-butene, cis-2-butene, isobutene, n-butane, isobutane, and butadiene.
- the mixed C4 fraction of the raw material is subjected to pretreatment as shown in (1) to (3) below to remove and purify impurities.
- Dienes such as butadiene in the mixed C4 fraction which cause a decrease in catalytic activity and diisobutylene purity, can be removed with an extraction solvent such as N, N-dimethylformamide or acetonitrile.
- an extraction solvent such as N, N-dimethylformamide or acetonitrile.
- a hydrogenation catalyst such as Pd or Ni as required.
- 1000 mass ppm or less is a standard.
- Sulfur and basic nitrogen that cause a decrease in catalytic activity can be removed by washing with water or adsorbent treatment such as activated alumina, activated carbon, and molecular sieve.
- adsorbent treatment such as activated alumina, activated carbon, and molecular sieve.
- the C3 fraction that causes a decrease in the purity of diisobutylene can be removed from the top of the column by distillation.
- the DIB production method of the present invention is a method for producing DIB by bringing a mixed C4 fraction of the above-mentioned raw material, which is preferably subjected to pretreatment, into contact with a solid acid catalyst, which comprises (a) In the isobutene oligomerization reaction step, the conversion of isobutene in the mixed C4 fraction is controlled to 60 to 95%. When the conversion of isobutene exceeds 95%, 1-butene and 2-butene are present in addition to the desired diisobutylenes 2,4,4-trimethyl-1-pentene and 2,4,4-trimethyl-2-pentene.
- the reacted C8 component and further heavy components such as trimer and tetramer increase, and diisobutylene cannot be highly purified by subsequent distillation.
- the isobutene conversion rate falls below 60%, unreacted raw materials increase, and diisobutylene cannot be produced in a high yield.
- the conversion of isobutene is preferably 65 to 90%, more preferably 70 to 90%. The control of isobutene conversion will be described in detail later.
- Solid acid catalyst examples of the solid acid catalyst used as the oligomerization reaction catalyst in the DIB production method of the present invention include silica-alumina, silica-magnesia, silica-boria, alumina-boria, chlorinated alumina, fluorinated alumina, silica gel and alumina. Hydrochloric acid, sulfuric acid, phosphoric acid, BF 3 etc.
- silica-alumina is particularly preferable.
- this silica-alumina catalyst a deposition method in which alumina is adhered to silica gel with Al 2 (SO 4 ) 3 solution and NH 4 OH, or a sodium silicate (water glass) solution is added to the Al 2 (SO 4 ) 3 solution. It can be produced by a method such as a precipitation method. What baked this gel at the temperature of about 550 degreeC has very large activity.
- this silica-alumina catalyst those having the following properties are usually used.
- the control of isobutene conversion can be performed within the following reaction conditions.
- (1) mixing to the solid acid catalyst C4 fraction WHSV (feed weight to catalyst weight per hour) is preferably 0.1 ⁇ 5 hr -1, more preferably 0.2 ⁇ 2 hr -1. When this WHSV is 0.1 hr ⁇ 1 or more, the conversion of isobutene can be maintained at 95% or less, while when it is 5 hr ⁇ 1 or less, the conversion of isobutene can be maintained at 60% or more. it can.
- (2) The reaction temperature is preferably 150 ° C. or lower, more preferably 25 to 100 ° C. When the reaction temperature is 25 ° C.
- the reaction pressure is preferably 0.2 MPa or more, as long as the raw material can be liquefied.
- an adiabatic reactor, a multitubular reactor, or the like can be used. In order to control the reaction temperature (heat removal), the reaction product liquid can be recycled to the reactor (mixed and fed with the raw material) or diluted with the diluent.
- the recycle liquid is preferably 0 to 4 mass ratio, more preferably 0 to 3 mass ratio with respect to the raw material.
- the recycling amount is 4 mass times or less, the reaction rate does not decrease due to a decrease in the raw material concentration, and a large amount of catalyst is not required.
- the flow type reactor of a fixed bed, a fluidized bed, a moving bed, a batch type by a tank type reactor, a semibatch type, a continuous flow type reaction. It is possible to employ a continuous flow type reaction by, for example.
- the step (b) is a step of distilling and separating the unreacted C4 fraction in the reaction product solution in the oligomerization reaction and the oligomer component containing the produced C8 fraction.
- the reaction product liquid is fed to a distillation column, and the distillation conditions (reflux ratio (R / D), pressure, etc.) are set so that the C4 fraction in the bottom liquid is 1% by mass or less.
- the C4 fraction that is an unreacted raw material is removed from the top of the column to obtain a polymer containing diisobutylene in the C8 fraction as the bottom liquid.
- the step (c) is a step of distilling and purifying diisobutylene in the C8 fraction obtained in the step (b), and the bottom liquid containing the diisobutylene in the step (b) is fed to a distillation column. From the top of the column, a C8 fraction mainly composed of diisobutylene is obtained, and from the bottom of the column, a component mainly composed of a polymer of trimer or higher is obtained.
- diisobutylene having a C4 fraction content of 1% by mass or less and a purity of 95% by mass or more can be obtained.
- the diisobutylene (2,4,4-trimethyl-1-pentene and 2,4,4-trimethyl-2-pentene) obtained by the DIB production method of the present invention is, for example, a raw material of oxo alcohol, a raw material of isononanoic acid , P-octylphenol raw material, rubber tackifier raw material, surfactant raw material, gasoline fuel additive, rubber chemicals and the like.
- Examples 1 to 3 and Comparative Example 1 Diene components such as butadiene in the mixed C4 fraction obtained from naphtha cracking were extracted with dimethylformaldehyde, and then selectively hydrogenated with a commercially available Pd catalyst to a diene concentration of 10 ppm by mass or less. Subsequently, the S component and the N component were removed to 5 ppm by mass or less by washing with water. Further, the C3 component was removed from the top of the tower by continuous distillation, and used as a raw material for producing diisobutylene. (Raw material composition in Table 1).
- Silica-alumina catalyst [SiO 2 / Al 2 O 3 mass ratio: 9, average pore diameter: 6 nm, total pore volume: 0.5 mL / g, BET specific surface area: 400 m 2 / g] as a polymerization catalyst
- the reactor was charged and a fixed bed continuous reaction was carried out.
- the reactor was heated with a mantle heater and the catalyst bed was controlled to be isothermal.
- the reaction conditions and reaction results are shown in Table 1. In Examples 1 to 3, the reaction pressure and WHSV were fixed, and the reaction temperature was varied so that the conversion of isobutene was less than 95%.
- a mixed C4 fraction of a raw material is brought into contact with a solid acid catalyst, preferably a silica-alumina catalyst, and an oligomerization reaction of isobutene is performed in a one-stage reaction, followed by a distillation operation.
- a solid acid catalyst preferably a silica-alumina catalyst
- an oligomerization reaction of isobutene is performed in a one-stage reaction, followed by a distillation operation.
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Abstract
Description
前者は、目的とするジイソブチレン以外に3量体や4量体以上のオリゴマーが多量に生成し、DIBの反応選択性が低い上、高価な耐食材料が必要となる。さらに、両者とも反応工程が多く煩雑であるという問題を有している。
オリゴマー化触媒として、固体酸触媒、好ましくはシリカ-アルミナ触媒を用い、これに混合C4留分を接触させるに際し、混合C4留分中のイソブテンの転化率を所定の範囲に制御することにより、高い反応選択率でDIBが得られること、そして反応生成物に特定の蒸留操作を施すことにより、高純度のDIBが得られることを見出した。
本発明は、かかる知見に基づいて完成したものである。
[1]固体酸触媒に、原料の混合C4留分を接触させることにより、ジイソブチレンを製造する方法であって、
(a)イソブテンのオリゴマー化反応工程、
(b)未反応のC4留分と生成したC8留分を含むオリゴマー留分とを蒸留分離する工程、及び
(c)C8留分中のジイソブチレンを蒸留精製する工程、
を含み、かつ前記(a)工程において、混合C4留分中のイソブテンの転化率を60~95%の範囲に制御することを特徴とするジイソブチレンの製造方法、
[2]固体酸触媒が、シリカ-アルミナ触媒である上記[1]に記載のジイソブチレンの製造方法、
[3](a)工程において、イソブテンのオリゴマー化反応工程における反応条件は、固体酸触媒に対する混合C4留分のWHSV(1時間当たりの触媒質量に対する供給原料質量)が0.1~5hr-1、反応温度が150℃以下及び反応圧力が0.2MPa以上であって、原料が液化できる圧力である上記[1]又は[2]に記載のジイソブチレンの製造方法、及び
[4](c)C8留分中のジイソブチレンを蒸留精製する工程において、C4留分の含有量が1質量%以下で、純度が95質量%以上のジイソブチレンを得る上記[1]~[3]のいずれかに記載のジイソブチレンの製造方法、
を提供するものである。
(a)イソブテンのオリゴマー化反応工程、
(b)未反応のC4留分と生成したC8留分を含むオリゴマー留分とを蒸留分離する工程、及び
(c)C8留分中のジイソブチレンを蒸留精製する工程、
を含み、かつ前記(a)工程において、混合C4留分中のイソブテンの転化率を60~95%の範囲に制御することを特徴とする。
本発明のDIBの製造方法においては、原料として混合C4留分が用いられる。
当該混合C4留分は、例えばFCCプロセスで生産されるオレフィン留分、ナフサクラッカーで生産される留分からジエン成分を抽出や選択的水素化によって除去したオレフィン留分などが挙げられ、またこれらを任意の割合で混合したものでもよい。さらに、それらに対し蒸留などの公知の方法を用いて、特定の留分の含有量を増減させて調整してもよい。例えば、ナフサクラッカーで生成するC4留分からブタジエンを抽出したラフィネートやFCC-C4留分を蒸留(または反応蒸留)し、ノルマルブテン類およびノルマルブタン類を除いたイソブテンを高濃度に含有するイソブテン-イソブタン留分を用いることができる。
当該混合C4留分中には、一般に1-ブテン、trans-2-ブテン、cis-2-ブテン、イソブテン、n-ブタン、イソブタン、ブタジエンなどの成分が含まれている。
本発明のDIBの製造方法においては、原料の混合C4留分は、下記(1)~(3)に示す前処理を施し、不純物を除去・精製しておくことが好ましい。
(1)触媒活性低下やジイソブチレン純度低下の原因となる混合C4留分中のブタジエン等のジエン類はN,N-ジメチルホルムアミドやアセトニトリル等の抽出溶剤にて除去が可能である。さらに必要に応じてPdやNiなどの水素化触媒にて選択的に水素化してジエンを低減することが可能である。一般的には1000質量ppm以下が目安となる。
(2)触媒活性低下の原因となる硫黄分・塩基性窒素分は水洗あるいは活性アルミナや活性炭、モレキュラーシーブ等の吸着剤処理によって除去が可能である。
(3)ジイソブチレン純度低下の原因となるC3留分は蒸留により塔頂より除去しておくことが可能である。
本発明のDIBの製造方法においては、固体酸触媒に、好ましくは前処理を施してなる前述した原料の混合C4留分を接触させることにより、DIBを製造する方法であって、当該(a)工程のイソブテンのオリゴマー化反応工程において、混合C4留分中のイソブテンの転化率を60~95%に制御する。
イソブテン転化率が、95%を超えると目的とするジイソブチレンである2,4,4-トリメチル-1-ペンテンと2,4,4-トリメチル-2-ペンテン以外に1-ブテンや2-ブテンが反応したC8成分、さらには3量体や4量体等の重質成分が増加し、あとに続く蒸留によりジイソブチレンを高純度化することができない。イソブテン転化率が60%より低下すると未反応原料が増加し、高収率でジイソブチレンを製造することができない。以上の観点より、イソブテンの転化率は65~90%が好ましく、70~90%がより好ましい。
なお、イソブテン転化率の制御については後で詳述する。
本発明のDIBの製造方法において、オリゴマー化反応触媒として用いる固体酸触媒としては、例えば、シリカ-アルミナ、シリカ-マグネシア、シリカ-ボリア、アルミナ-ボリア、塩素化アルミナ、フッ素化アルミナ、シリカゲルやアルミナゲルに塩酸、硫酸、リン酸、BF3などを付着させたもの、陽イオン交換樹脂、合成ゼオライト、ヘテロポリ酸、酸化モリブデン/ジルコニアや酸化タングステン/ジルコニア等のジルコニア系複合金属酸化物、さらには酸性白土、ベントナイト、カオリン、モンモリロナイトなどの粘土鉱物等を挙げることができる。これらの固体酸触媒は、一種を単独で用いてもよく、二種以上を組み合わせて用いてもよいが、これらの中で、特にシリカ-アルミナが好適である。
このシリカ-アルミナ触媒としては、通常下記の性状を有するものが用いられる。
・SiO2/Al2O3質量比:2~20
・窒素吸着法にて測定される平均細孔直径:2~10nm
・窒素吸着法にて測定される総細孔容積:0.2~1mL/g
・BET比表面積:200~600m2/g
イソブテン転化率の制御は、下記の反応条件の範囲で行うことができる。
(1)固体酸触媒に対する混合C4留分のWHSV(1時間当たりの触媒質量に対する供給原料質量)は、0.1~5hr-1が好ましく、0.2~2hr-1がより好ましい。このWHSVが0.1hr-1以上であると、イソブテンの転化率を95%以下に保持することができ、一方、5hr-1以下であるとイソブテンの転化率を60%以上に保持することができる。
(2)反応温度は150℃以下が好ましく、25~100℃がより好ましい。反応温度が25℃以上であると、適当な反応速度を有し、多量の触媒を必要としない。一方、150℃以下であるとDIBの反応選択率低下を抑えることができ、高純度のDIBを得ることができる。
(3)反応圧力は0.2MPa以上であることが好ましく、原料が液化できる圧力であればよい。
(4)反応を行うにあたっては、断熱反応器や多管式反応器などが利用できる。反応温度の制御(除熱)のために、反応生成液の反応器へのリサイクル(原料と混合してフィード)や希釈剤による原料希釈を行うこともできる。反応生成液の反応器へのリサイクルを行う場合は、リサイクル液が原料に対して0~4質量倍率であることが好ましく、0~3質量倍率であることがより好ましい。リサイクル量が4質量倍率以下であると、原料濃度低下により反応速度が小さくなることがなく、多量の触媒を必要としない。
[(b)工程]
当該(b)工程は、オリゴマー化反応における反応生成液中の未反応のC4留分と生成したC8留分を含むオリゴマー成分とを蒸留分離する工程である。
当該(b)工程においては、前記反応生成液を蒸留塔にフィードし、塔底液中のC4留分が1質量%以下になるように蒸留条件(還流比(R/D)、圧力等)を調節して、塔頂より未反応原料であるC4留分を除去し、塔底液としてC8留分中のジイソブチレンを含む重合物を得る。
当該(c)工程は、前記(b)工程で得られたC8留分中のジイソブチレンを蒸留精製する工程であり、前記(b)工程におけるジイソブチレンを含む塔底液を蒸留塔にフィードし、塔頂よりジイソブチレンを主とするC8留分、塔底より3量体以上の重合物を主とする成分を得る。
当該(c)工程においては、C4留分の含有量が1質量%以下で、純度が95質量%以上のジイソブチレンを得ることができる。
本発明のDIBの製造方法により得られたジイソブチレン(2,4,4-トリメチル-1-ペンテン及び2,4,4-トリメチル-2-ペンテン)は、例えばオキソアルコールの原料、イソノナン酸の原料、p-オクチルフェノールの原料、ゴム粘着付与剤の原料、界面活性剤の原料、さらにはガソリン燃料添加剤、ゴム薬品などとして用いられる。
ナフサのクラッキングから得られた混合C4留分中のブタジエン等のジエン成分をジメチルホルムアルデヒドにて抽出後、さらに市販のPd触媒にて選択的に水素化してジエン濃度を10質量ppm以下とした。続いて水洗によりS成分とN成分を5質量ppm以下に除去した。さらに連続蒸留によりC3成分を塔頂より除去し、ジイソブチレン製造の原料とした。(表1中の原料組成)。
重合触媒としてシリカ-アルミナ触媒[SiO2/Al2O3質量比:9、平均細孔直径:6nm、総細孔容積:0.5mL/g、BET比表面積:400m2/g]を管型反応器に充填し、固定床連続反応を実施した。反応器はマントルヒーターで加熱し、触媒床は等温となるように制御した。反応条件と反応成績を表1に示す。
実施例1~3は、反応圧力及びWHSVを固定し、反応温度を変動させてイソブテン転化率を95%未満としたものである。一方、比較例として実施例1~3と同様に、反応圧力及びWHSVを固定し、反応温度を80℃にして、イソブテン転化率を98%とした結果を記載した。
さらに、得られた反応生成液を18段、R/D:0.29、塔頂圧力0.38MPaの連続蒸留に供して未反応原料のC4成分を除去し、続いてジイソブチレンを含む塔底液をフィード液として40段、R/D:5、塔頂圧力0.65MPaの連続蒸留に供してジイソブチレンを含むC8成分を塔頂より得た。得られたC8成分中の目的とするジイソブチレンである2,4,4-トリメチル-1-ペンテンと2,4,4-トリメチル-2-ペンテン濃度を表1最下段に示す。
Claims (4)
- 固体酸触媒に、原料の混合C4留分を接触させることにより、ジイソブチレンを製造する方法であって、
(a)イソブテンのオリゴマー化反応工程、
(b)未反応のC4留分と生成したC8留分を含むオリゴマー留分とを蒸留分離する工程、及び
(c)C8留分中のジイソブチレンを蒸留精製する工程、
を含み、かつ前記(a)工程において、混合C4留分中のイソブテンの転化率を60~95%の範囲に制御することを特徴とするジイソブチレンの製造方法。 - 前記固体酸触媒が、シリカ-アルミナ触媒である請求項1に記載のジイソブチレンの製造方法。
- 前記(a)工程において、イソブテンのオリゴマー化反応工程における反応条件は、固体酸触媒に対する混合C4留分のWHSV(1時間当たりの触媒質量に対する供給原料質量)が0.1~5hr-1、反応温度が150℃以下及び反応圧力が0.2MPa以上であって、原料が液化できる圧力である請求項1又は2に記載のジイソブチレンの製造方法。
- 前記(c)C8留分中のジイソブチレンを蒸留精製する工程において、C4留分の含有量が1質量%以下で、純度が95質量%以上のジイソブチレンを得る請求項1~3のいずれかに記載のジイソブチレンの製造方法。
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KR1020137031929A KR101915336B1 (ko) | 2011-06-29 | 2012-06-06 | 혼합 c4 유분을 원료로 하는 디이소부틸렌의 제조 방법 |
CN201280032065.3A CN103619785B (zh) | 2011-06-29 | 2012-06-06 | 以混合c4馏分为原料的二异丁烯的制造方法 |
SG2013086269A SG195091A1 (en) | 2011-06-29 | 2012-06-06 | Method for producing diisobutylene using mixed c4 fraction as raw material |
US14/129,410 US20140128652A1 (en) | 2011-06-29 | 2012-06-06 | Method for producing diisobutylene using mixed c4 fraction as raw material |
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JP2011144900A JP5767875B2 (ja) | 2011-06-29 | 2011-06-29 | 混合c4留分を原料とするジイソブチレンの製造方法 |
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JP6803729B2 (ja) * | 2016-11-16 | 2020-12-23 | Eneos株式会社 | p−キシレンの製造方法 |
JP7090470B2 (ja) * | 2018-05-15 | 2022-06-24 | Eneos株式会社 | p-キシレンの製造方法 |
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EP4103571B1 (de) | 2020-02-11 | 2023-11-15 | Basf Se | Niederdruckhydroformylierung von diisobuten |
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JPS5679629A (en) * | 1979-12-05 | 1981-06-30 | Nippon Oil & Fats Co Ltd | Preparation of isobutylene oligomer |
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JP2009529528A (ja) * | 2006-03-10 | 2009-08-20 | エクソンモービル・ケミカル・パテンツ・インク | イソブテンを含む原料油のオリゴマー化 |
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FR2547830B1 (fr) * | 1983-06-22 | 1988-04-08 | Inst Francais Du Petrole | Procede de production de supercarburant par polymerisation des coupes c4 |
DE19629906A1 (de) * | 1996-07-24 | 1998-01-29 | Huels Chemische Werke Ag | Verfahren zur Herstellung von Butenoligomeren aus Fischer-Tropsch-Olefinen |
IT1318536B1 (it) | 2000-05-26 | 2003-08-27 | Snam Progetti | Procedimento per la produzione di idrocarburi altoottanici mediantedimerizzazione selettiva di isobutene con catalizzatori acidi. |
EP1388528B1 (de) * | 2002-08-06 | 2015-04-08 | Evonik Degussa GmbH | Verfahren zur Oligomerisierung von Isobuten in n-Buten-haltigen Kohlenwasserstoffströmen |
DE10302457B3 (de) * | 2003-01-23 | 2004-10-07 | Oxeno Olefinchemie Gmbh | Verfahren zur Herstellung von Butenoligomeren und tert.-Butylethern aus Isobuten-haltigen C4-Strömen |
FR2873116B1 (fr) * | 2004-07-15 | 2012-11-30 | Inst Francais Du Petrole | Procede d'oligomerisation des olefines utilisant un catalyseur a base de silice-alumine |
EP2098498A1 (en) * | 2008-03-04 | 2009-09-09 | ExxonMobil Chemical Patents Inc. | Selective oligomerization of isobutene |
US8853483B2 (en) | 2008-12-02 | 2014-10-07 | Catalytic Distillation Technologies | Oligomerization process |
FR2951164B1 (fr) * | 2009-10-08 | 2011-10-21 | Inst Francais Du Petrole | Procede d'oligomerisation d'une charge hydrocarbonee olefinique utilisant un catalyseur a base d'une silice-alumine macroporeuse |
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JPS5679629A (en) * | 1979-12-05 | 1981-06-30 | Nippon Oil & Fats Co Ltd | Preparation of isobutylene oligomer |
JP2004505008A (ja) * | 1999-12-23 | 2004-02-19 | エクソンモービル ケミカル パテンツ インコーポレイテッド | イソブテンの選択的二量化方法 |
JP2009529528A (ja) * | 2006-03-10 | 2009-08-20 | エクソンモービル・ケミカル・パテンツ・インク | イソブテンを含む原料油のオリゴマー化 |
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CN103619785B (zh) | 2016-08-17 |
CN103619785A (zh) | 2014-03-05 |
KR101915336B1 (ko) | 2018-11-05 |
JP2013010717A (ja) | 2013-01-17 |
US20140128652A1 (en) | 2014-05-08 |
SG195091A1 (en) | 2013-12-30 |
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TW201313661A (zh) | 2013-04-01 |
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