JPS6348249B2 - - Google Patents
Info
- Publication number
- JPS6348249B2 JPS6348249B2 JP17688280A JP17688280A JPS6348249B2 JP S6348249 B2 JPS6348249 B2 JP S6348249B2 JP 17688280 A JP17688280 A JP 17688280A JP 17688280 A JP17688280 A JP 17688280A JP S6348249 B2 JPS6348249 B2 JP S6348249B2
- Authority
- JP
- Japan
- Prior art keywords
- butene
- reaction
- isobutylene
- column
- fraction
- 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
Links
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 120
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 59
- 229930195733 hydrocarbon Natural products 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 27
- 239000004215 Carbon black (E152) Substances 0.000 claims description 26
- -1 C 4 hydrocarbon Chemical class 0.000 claims description 23
- KOYGZROXUOTUEE-UHFFFAOYSA-N butane;but-1-ene Chemical compound CCCC.CCC=C KOYGZROXUOTUEE-UHFFFAOYSA-N 0.000 claims description 23
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 230000002378 acidificating effect Effects 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 7
- 238000005336 cracking Methods 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 5
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 75
- 238000004821 distillation Methods 0.000 description 29
- 239000002994 raw material Substances 0.000 description 17
- 239000012530 fluid Substances 0.000 description 15
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 14
- 239000007788 liquid Substances 0.000 description 13
- 150000002430 hydrocarbons Chemical class 0.000 description 12
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 10
- 239000003729 cation exchange resin Substances 0.000 description 10
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical class CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 239000001282 iso-butane Substances 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 4
- 235000013844 butane Nutrition 0.000 description 4
- 239000003456 ion exchange resin Substances 0.000 description 4
- 229920003303 ion-exchange polymer Polymers 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 4
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 229940044654 phenolsulfonic acid Drugs 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical group CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Description
【発明の詳細な説明】
本発明はイソブチレンおよびブテン―１を含む
ブタン―ブテン留分から高収率で高純度のブテン
―１を分離回収する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for separating and recovering high-yield, high-purity butene-1 from a butane-butene fraction containing isobutylene and butene-1.
イソブチレンおよびブテン―１を含むブタン―
ブテン留分からブテン―１を分離するためにはブ
テン―１以外のC4留分を精密蒸留によつて分離
除去しなければならないが、その際イソブチレン
はブテン―１と比揮発度が酷似しているために単
に蒸留操作では高純度のブテン―１を分離回収す
ることができない。 Butanes, including isobutylene and butene-1
In order to separate butene-1 from the butene fraction, the C4 fraction other than butene-1 must be separated and removed by precision distillation, but in this case, isobutylene has a specific volatility that is very similar to butene-1. Therefore, high purity butene-1 cannot be separated and recovered simply by distillation.
したがつて、イソブチレンおよびブテン―１を
含むブタン―ブテン留分から高純度のブテン―１
を分離回収するためにまずこの留分からイソブチ
レンをほぼ完全に除去することが要求される。 Therefore, high purity butene-1 can be obtained from the butane-butene fraction containing isobutylene and butene-1.
In order to separate and recover isobutylene, it is first required to almost completely remove isobutylene from this fraction.
従来、ブタン―ブテン留分からイソブチレンを
分離する方法として硫酸抽出法がある。しかしこ
の方法は硫酸の腐食性のために高級な材質を使用
しなければならないために経済的負担が大きい。
イソブチレンを分離する他の方法としてゼオライ
トによる吸着方法もあるが、この方法ではブテン
―１およびブテン―２との分離が不十分である。 Conventionally, a sulfuric acid extraction method has been used to separate isobutylene from a butane-butene fraction. However, this method requires the use of high-grade materials due to the corrosive nature of sulfuric acid, which imposes a heavy economic burden.
Another method for separating isobutylene is adsorption using zeolite, but this method does not sufficiently separate butene-1 and butene-2.
一般に酸性触媒を用いることによりイソブチレ
ンを２量化又は多量化して、この多量体を蒸留で
ブタン―ブテン留分から除去することが考えられ
るが、通常この反応の際にブテン―１が異性化し
てブテン―２となる傾向が強い。またブテン―１
がイソブチレンと共低量重合反応を起こす。 Generally, it is considered to dimerize or polymerize isobutylene by using an acidic catalyst and remove this polymer from the butane-butene fraction by distillation, but usually during this reaction, butene-1 is isomerized and butene-1 is There is a strong tendency for it to be 2. Also butene-1
causes a low amount copolymerization reaction with isobutylene.
したがつて、ブテン―１を高収率で分離回収す
るためにはこれらの副反応を極力抑制してイソブ
チレンを多量化する必要がある。 Therefore, in order to separate and recover butene-1 in high yield, it is necessary to suppress these side reactions as much as possible and increase the amount of isobutylene.
本発明はイソブチレン、ブテン―１を含むブタ
ン―ブテン留分をそれぞれ特別な反応条件を有す
る二段の反応によりブテン―１の損失をできるだ
け抑えてイソブチレンを低重合させ、しかる後蒸
留操作を施すことを特徴とする高収率で高純度の
ブテン―１を分離回収する方法に関するものであ
る。 The present invention involves low-polymerizing isobutylene and butane-butene fractions containing butene-1 through a two-stage reaction with special reaction conditions, respectively, with the loss of butene-1 being suppressed as much as possible, followed by distillation. The present invention relates to a method for separating and recovering butene-1 with high yield and high purity.
すなわち本願発明はイソブチレン0.1〜15wt％、
ブテン―１ 10〜50wt％を含むブタン―ブテン
留分を平均粒径0.2〜10mmの強酸型陽イオン交換
樹脂粒子を充填した第１反応器に温度30〜100℃、
液空間速度0.1〜50（１／hr）、圧力１〜50気圧で
連続的に通過させ、この反応塔出口混合物を流量
比１〜15：１の２つの流れに分割し、流量比１〜
15の１つの流れを該イオン交換樹脂を充填した第
一反応塔に循環供給し、流量比１の他の流れを平
均粒径0.2〜10mmの強酸型陽イオン交換樹脂粒子
を充填した第二反応塔に温度30〜100℃、液空間
速度0.1〜50（１／hr）、圧力１〜50気圧で通過さ
せ、第二反応器からの流れを蒸留し、主にイソブ
チレンの低重合体を含む重質炭化水素とブタン―
ブテンを主に含む軽質炭化水素を得、さらに該軽
質炭化水素を精密蒸留することによりブテン―１
を他のC4炭化水素と分離しブテン―１を得るこ
とを特徴とする高純度ブテン―１を高収率で分離
回収する方法に関するものである。 That is, the present invention contains 0.1 to 15 wt% of isobutylene,
A butane-butene fraction containing 10 to 50 wt% of butene-1 was placed in a first reactor filled with strong acid type cation exchange resin particles with an average particle size of 0.2 to 10 mm at a temperature of 30 to 100°C.
It is passed continuously at a liquid hourly space velocity of 0.1 to 50 (1/hr) and a pressure of 1 to 50 atm, and the reaction column outlet mixture is divided into two streams with a flow rate ratio of 1 to 15:1;
One stream of 15 is circulated and supplied to the first reaction column filled with the ion exchange resin, and the other stream with a flow rate ratio of 1 is fed to the second reaction column filled with strong acid type cation exchange resin particles with an average particle size of 0.2 to 10 mm. The stream from the second reactor is distilled by passing through the column at a temperature of 30 to 100°C, a liquid hourly space velocity of 0.1 to 50 (1/hr), and a pressure of 1 to 50 atm. Hydrocarbons and butane
Butene-1 is obtained by obtaining light hydrocarbons mainly containing butene, and then precision distilling the light hydrocarbons.
The present invention relates to a method for separating and recovering high-purity butene-1 in a high yield, which is characterized by separating butene-1 from other C 4 hydrocarbons to obtain butene-1.
本発明で使用される出発原料はイソブチレン
0.1〜15wt％、ブテン―１ 10〜50wt％を含むブ
タン―ブテン留分である。この原料は通常石油類
を熱分解、水蒸気分解、接触分解する際に生成す
るC4留分から得られるもので、ブタジエンをほ
ぼ完全に、たとえば0.1wt％以下に除去したもの
が通常使用される。 The starting material used in the present invention is isobutylene.
It is a butane-butene fraction containing 0.1 to 15 wt% and 10 to 50 wt% of butene-1. This raw material is usually obtained from the C4 fraction produced when petroleum is thermally cracked, steam cracked, or catalytically cracked, and it is usually used that has almost completely removed butadiene, for example, to 0.1 wt% or less.
これらには通常イソブチレン、ブテン―１の他
にブテン―２、イソブタン、ｎ―ブタンが含有さ
れる。イソブチレンが15wt％より多量に含有さ
れている場合には有効に使用されない。イソブチ
レン１〜10wt％、ブテン１ 20〜40wt％が好ま
しい。 These usually contain isobutylene, butene-1, butene-2, isobutane, and n-butane. If isobutylene is contained in an amount greater than 15 wt%, it will not be used effectively. 1 to 10 wt% of isobutylene and 20 to 40 wt% of butene are preferred.
本発明においては、原料ブタン―ブテン留分と
して石油類を分解することにより得られるC4炭
化水素留分からブタジエンを分離除去したC4炭
化水素混合物を塩化アルミニウム触媒により重合
させ液状又は半固体状重合体を製造する際の未反
応のC4炭化水素混合物を用いることが好ましく
採用される。従来からブタジエンを除去したC4
炭化水素混合物原料として塩化アルミニウム触媒
でこれを重合処理し主にC4炭化水素混合物中の
イソブチレンを重合させて液状又は半固体状の重
合物（ポリブテン）を製造することは公知で、こ
の重合反応後の未反応C4炭化水素混合物はイソ
ブチレン含有量は減少しているものの依然約１〜
10wt％特に２〜6wt％含有されている。この未反
応C4炭化水素混合物をそのまま蒸留しても高純
度のブテン―１が得られず、この混合物は燃料と
して使用されるのが一般的であつた。本発明にお
いてはこの未反応C4炭化水素混合物を出発原料
とすることがきわめて好ましく採用される。 In the present invention, a C 4 hydrocarbon mixture obtained by separating butadiene from a C 4 hydrocarbon fraction obtained by cracking petroleum as a raw material butane-butene fraction is polymerized with an aluminum chloride catalyst to form a liquid or semi-solid polymer. It is preferably employed to use an unreacted C 4 hydrocarbon mixture in producing the coalescence. Conventional C 4 with butadiene removed
It is known that a hydrocarbon mixture raw material is polymerized using an aluminum chloride catalyst to polymerize mainly isobutylene in a C4 hydrocarbon mixture to produce a liquid or semi-solid polymer (polybutene), and this polymerization reaction The subsequent unreacted C4 hydrocarbon mixture, although reduced in isobutylene content, still contains approximately 1 to
The content is 10wt%, especially 2 to 6wt%. Distilling this unreacted C 4 hydrocarbon mixture as it is does not yield highly pure butene-1, and this mixture has generally been used as a fuel. In the present invention, it is very preferable to use this unreacted C 4 hydrocarbon mixture as a starting material.
また本発明においては出発原料のブタン―ブテ
ン留分として、石油類を分解することにより得ら
れるC4炭化水素留分よりブタジエンを分離除去
したC4炭化水素混合物とメタノールを酸性触媒
の存在化で反応させてメチル―ターシヤリーブチ
ルエーテルを製造する際の未反応のC4炭化水素
混合物も有効に使用できる。ブタジエンを分離除
去したC4炭化水素混合物とメタノールを酸性触
媒たとえば本願で用いると同種の後述する強酸型
陽イオン交換樹脂の存在下で反応させ混合物中の
イソブチレンとメタノールの反応によりメチル―
ターシヤリーブチルエーテルを製造することは公
知であり、この反応後の未反応のC4炭化水素混
合中にはイソブチレンが依然１〜10wt％程度含
まれており、通常燃料として用いられるものであ
る。本発明においてはこの未反応C4炭化水素混
合物も有効に使用される。 In addition, in the present invention, as a butane-butene fraction as a starting material, a C 4 hydrocarbon mixture obtained by separating butadiene from a C 4 hydrocarbon fraction obtained by cracking petroleum and methanol in the presence of an acidic catalyst is used. The unreacted C 4 hydrocarbon mixture that is reacted to produce methyl-tert-butyl ether can also be effectively used. A C 4 hydrocarbon mixture from which butadiene has been separated and methanol are reacted in the presence of an acidic catalyst, such as a strong acid type cation exchange resin described below when used in the present application, and the reaction between isobutylene and methanol in the mixture causes methyl-
It is known to produce tertiary butyl ether, and the unreacted C4 hydrocarbon mixture after this reaction still contains about 1 to 10 wt% of isobutylene, which is commonly used as a fuel. This unreacted C 4 hydrocarbon mixture is also effectively used in the present invention.
本発明においてはさらに原料のブタン―ブテン
留分として、石油類を分解することにより得られ
るC4炭化水素留分よりブタジエンを分離除去し
たC4炭化水素混合物と水とを酸性触媒の存在下
に反応させてターシヤリーブチルアルコールを製
造する際の未反応のC4炭化水素混合物も有効に
使用することができる。ブタジエンを除去した
C4炭化水素留分と水とを酸性触媒たとえば硫酸、
塩酸、本願で使用するのと同種の後述する陽イオ
ン交換樹脂等を用いて反応させ該留分中のイソブ
チレンを水和し、ターシヤリーブチルアルコール
を製造することは公知である。この反応における
未反応混合物中には同様に１〜10wt％のイソブ
チレンが含有されており、通常燃料として使用さ
れていたものである。本願においてはこの未反応
C4炭化水素混合物も有効に使用することができ
る。 In the present invention, a C 4 hydrocarbon mixture obtained by separating butadiene from a C 4 hydrocarbon fraction obtained by cracking petroleum and water is further used as a butane-butene fraction as a raw material in the presence of an acidic catalyst. The unreacted C 4 hydrocarbon mixture that is reacted to produce tertiary butyl alcohol can also be effectively used. butadiene removed
The C4 hydrocarbon fraction and water are treated with an acidic catalyst such as sulfuric acid,
It is known to produce tertiary butyl alcohol by hydrating isobutylene in the fraction by reacting it with hydrochloric acid, a cation exchange resin similar to that used in the present application, which will be described later. The unreacted mixture in this reaction also contains 1 to 10 wt% of isobutylene, which is normally used as a fuel. In this application, this unresponsive
C4 hydrocarbon mixtures can also be used effectively.
本発明においては前述した原料ブタン―ブテン
留分を用いて、これを下記する強酸型陽イオン交
換樹脂をそれぞれ充填した２段の反応に供する。 In the present invention, the above-mentioned raw material butane-butene fraction is used and subjected to a two-stage reaction each filled with the following strong acid type cation exchange resin.
すなわち本発明においては反応塔を二段に分
け、第一反応塔に前記原料をまず供する。第一反
応塔を通過した反応混合物を２つの流れに分割
し、１つの流れを後続する第二反応塔に供給し、
他の流れを第一反応塔に循環供給する循環供給方
式が採用される。この場合各流れの量は前者の量
に対して後者の量（循環する量）は１〜15（重量
倍）、好ましくは３〜７である。第二反応塔は通
常の一回通過方式である。 That is, in the present invention, the reaction tower is divided into two stages, and the raw material is first supplied to the first reaction tower. dividing the reaction mixture that has passed through the first reaction column into two streams and feeding one stream to the subsequent second reaction column;
A circulation supply system is adopted in which the other streams are circulated to the first reaction column. In this case, the amount of each flow is 1 to 15 (by weight), preferably 3 to 7 times the amount of the latter (the amount to be circulated) relative to the former amount. The second reaction column is of the usual one-pass type.
本発明において反応塔を二段に分け第一反応塔
においては循環供給方式が、第二反応塔において
は一回通過方式が採用されるのは以下の理由によ
る。すなわち本発明におけるイソブチレンの低重
合反応は発熱反応であるために循環方式によらな
い場合には第一反応塔の入口と出口の間の温度差
が大となり、特に出口近傍ではかなりの高温にな
る。このような高温になることは原料中のブテン
―１の異性化・重合損失量の増大と触媒の劣化の
点で厳密に回避せねばならない。したがつてこの
場合、反応器内にたとえば特別の冷却器等を装備
する必要が生ずるが、イオン交換樹脂の伝熱が悪
いために多管冷却反応型にしなければならず、こ
のような方法を採用すると触媒の取り替えが煩雑
となる。しかもこの場合でも局部的な高温部分の
存在が往々生じて不利となる。循環方式の場合は
反応塔内の温度は十分均一に保持される。しかし
ながら一段循環方式では、これと等温の一回通過
方式（ピストンフロー方式）に比べてイソブチレ
ンの低重合反応が抑制される。すなわち原料中の
イソブチレンに対する反応後のイソブチレンの残
存量が増してくる。そのために反応条件を過酷
（反応温度を上げたり、液空間速度を小とする。）
にしなければならない。しかしこのように過酷な
条件にするとブテン―１の異性化・重合による損
失量が増加してブテン―１の残存量が減少するこ
とになる。そこで一段目ではイソブチレンの低重
合をある程度抑えた条件（たとえばイソブチレン
の反応率70〜90wt％好ましくは75〜85wt％）に
おいて循環方式を採用し、残りのイソブチレンの
大部分たとえば75wt％以上特に85wt％以上を二
段目の反応塔で反応させる。二段目においては、
二段目に供給されるものの中のイソブチレンはよ
り低減されており、反応熱の蓄積も少ないために
反応塔内の入口と出口の間の温度差が小さいこ
と、およびブテン―１の異性化反応をできるだけ
抑制する目的で二段目の反応塔は一回通過方式が
採用される。 In the present invention, the reaction tower is divided into two stages, and the first reaction tower uses a circulating feed system, and the second reaction tower uses a single-pass system for the following reason. That is, since the isobutylene low polymerization reaction in the present invention is an exothermic reaction, if the circulation method is not used, the temperature difference between the inlet and outlet of the first reaction column will be large, and the temperature will be considerably high, especially near the outlet. . Such high temperatures must be strictly avoided from the viewpoint of increasing the isomerization and polymerization loss of butene-1 in the raw material and deteriorating the catalyst. Therefore, in this case, it is necessary to equip the reactor with, for example, a special cooler, but due to the poor heat transfer of the ion exchange resin, a multi-tube cooling reaction type must be used. If this method is adopted, replacing the catalyst becomes complicated. Moreover, even in this case, the presence of localized high-temperature parts often occurs, which is disadvantageous. In the case of a circulation system, the temperature within the reaction tower is maintained sufficiently uniform. However, in the one-stage circulation system, the low polymerization reaction of isobutylene is suppressed compared to this and the isothermal one-pass system (piston flow system). That is, the amount of isobutylene remaining after the reaction with isobutylene in the raw material increases. To achieve this, the reaction conditions are harsh (e.g., raising the reaction temperature and reducing the liquid hourly space velocity).
must be done. However, under such harsh conditions, the amount of loss due to isomerization and polymerization of butene-1 increases, and the remaining amount of butene-1 decreases. Therefore, in the first stage, a circulation method is adopted under conditions that suppress the low polymerization of isobutylene to some extent (for example, the reaction rate of isobutylene is 70 to 90 wt%, preferably 75 to 85 wt%), and most of the remaining isobutylene is, for example, 75 wt% or more, especially 85 wt%. The above is reacted in the second stage reaction tower. In the second stage,
The isobutylene in the second stage is reduced, and the accumulation of reaction heat is also small, so the temperature difference between the inlet and outlet in the reaction column is small, and the isomerization reaction of butene-1. In order to suppress this as much as possible, a single-pass system is adopted for the second stage reaction tower.
本発明においては、反応温度は第一反応塔、第
二反応塔いずれにおいても30〜100℃で行う。好
ましくは45〜75℃で行ういずれの反応塔において
も反応温度が30℃よりも低いと反応速度が小さい
ためにイソブチレンの分離が不十分となる。また
100℃より高いとブテン―１の反応が過激となり
ブテン―１の損失量が増加する。 In the present invention, the reaction temperature is 30 to 100°C in both the first reaction tower and the second reaction tower. In any reaction column, preferably conducted at a temperature of 45 to 75°C, if the reaction temperature is lower than 30°C, the reaction rate will be low and separation of isobutylene will be insufficient. Also
When the temperature is higher than 100°C, the reaction of butene-1 becomes radical and the loss of butene-1 increases.
本発明における反応圧力は第一反応塔、第二反
応塔ともに１〜50気圧、好ましくは５〜30気圧で
ある。反応圧力が1atmより低いと反応系内が気
相となり反応が十分に達せられず、50atmより大
とすることは反応容器及びその付属装置を堅固な
耐圧装置とせねばならず工業的に不利となる。 The reaction pressure in the present invention is 1 to 50 atm, preferably 5 to 30 atm in both the first reaction column and the second reaction column. If the reaction pressure is lower than 1 atm, the reaction system will be in a gas phase and the reaction will not be sufficiently achieved, and if it is higher than 50 atm, the reaction vessel and its attached equipment must be made into solid pressure-resistant equipment, which is industrially disadvantageous. .
本発明でいう強酸型陽イオン交換樹脂とは、強
酸性を示す陽イオン交換樹脂であり、スチレン系
スルホン酸型樹脂あるいはフエノールスルホン酸
型樹脂等がそれらの代表である。スチレン系スル
ホン酸型イオン交換樹脂はスチレンとジビニルベ
ンゼンなどの多不飽和化合物を共重合させて得ら
れる樹脂をスルホン化したものであり通常次式で
示される。 The strong acid type cation exchange resin as used in the present invention is a cation exchange resin exhibiting strong acidity, and representative examples thereof include styrene sulfonic acid type resin and phenolsulfonic acid type resin. A styrene-based sulfonic acid type ion exchange resin is a sulfonated resin obtained by copolymerizing styrene and a polyunsaturated compound such as divinylbenzene, and is generally represented by the following formula.
また、フエノールスルホン酸型樹脂は通常フエ
ノールスルホン酸をホルムアルデヒドで縮合した
ものであり通常次式で示される。 Furthermore, the phenolsulfonic acid type resin is usually obtained by condensing phenolsulfonic acid with formaldehyde, and is usually represented by the following formula.
上述の強酸型陽イオン交換樹脂は本発明におい
て触媒として用いられ、平均粒径0.2〜10mmの球
形又は円柱形の粒子として用いられる。 The above-mentioned strong acid type cation exchange resin is used as a catalyst in the present invention, and is used in the form of spherical or cylindrical particles with an average particle size of 0.2 to 10 mm.
この触媒粒子は第一および第二の耐圧の円筒状
反応容器に充填され、固定床のベツドを形成す
る。 The catalyst particles are packed into first and second pressure-resistant cylindrical reaction vessels to form a fixed bed bed.
固定床の大きさはいずれも特に限定されない。
通常高さ0.2m〜20mである。 The size of the fixed bed is not particularly limited.
Usually 0.2m to 20m in height.
固定床の上端又は下端から、好ましくは上端か
らイソブチレンおよびブテン―１を含むブタン―
ブテン留分を連続的に供給する。供給量は液空間
速度が0.1〜50（Kg／Kg×１／hr＝１／hr）、好ましく
は0.5
〜15（１／hr）となる量で行う。ここで言う液空
間速度は第一反応塔の場合は毎時（hr）、触媒１
Kg当り第一反応塔に供給される流れの重量（Kg）
（前記第一反応塔を循環する流れを除く）で示す
ものとし、第二反応塔の場合は毎時（hr）、触媒
１Kg当り第二反応塔を通過する流れの重量（Kg）
で示すものとする。ブタン―ブテン留分の供給量
が0.1（hr）より小であると、イソブチレン分離後
のブタン―ブテン留分の収量が少なく工業的に不
利である。また供給量が50（１／hr）より大であ
るとイソブチレンの分離が十分達成されない。 Butane-containing isobutylene and butene-1 from the upper or lower end of the fixed bed, preferably from the upper end.
Continuously feed the butene fraction. The amount supplied is such that the liquid hourly space velocity is 0.1 to 50 (Kg/Kg x 1/hr = 1/hr), preferably 0.5 to 15 (1/hr). The liquid space velocity referred to here is per hour (hr) in the case of the first reaction column, and
Weight of stream fed to the first reaction column per kg (Kg)
(excluding the flow circulating through the first reactor), and in the case of the second reactor, the weight of the flow passing through the second reactor per hour (hr) per kilogram of catalyst (Kg).
shall be shown as If the feed rate of the butane-butene fraction is less than 0.1 (hr), the yield of the butane-butene fraction after isobutylene separation will be small, which is industrially disadvantageous. Furthermore, if the feed rate is greater than 50 (1/hr), sufficient separation of isobutylene will not be achieved.
本発明においては第一反応塔で原料のブタン―
ブテン留分中のイソブチレンの約70〜90wt％を
低重合させ残りのイソブチレンの大部分を第二反
応塔で低重合させることによつてイソブチレンの
二量化・低重合化が達成される。 In the present invention, the raw material butane-
Dimerization and underpolymerization of isobutylene are achieved by underpolymerizing about 70 to 90 wt% of isobutylene in the butene fraction and underpolymerizing most of the remaining isobutylene in the second reaction column.
前記反応を経た反応混合物を蒸留塔に供し、イ
ソブチレンの二量体・低重合体を主に含む重質炭
化水素を塔底から得、塔頂からブタン―ブテンを
主に含む軽質炭化水素を得る。この蒸留は通常の
蒸留で段数約３〜30段たとえば10〜20段程度で充
分である。 The reaction mixture that has undergone the above reaction is subjected to a distillation column, and heavy hydrocarbons containing mainly isobutylene dimers and low polymers are obtained from the bottom of the column, and light hydrocarbons containing mainly butane-butene are obtained from the top of the column. . For this distillation, it is sufficient to carry out ordinary distillation using about 3 to 30 stages, for example, about 10 to 20 stages.
次に前記蒸留から得られる軽質炭化水素をさら
に精密蒸留に供する。通常この精密蒸留は２段で
行なわれ、初めの精密蒸留においては塔頂から主
にイソブタンを分離除去する。塔底流をさらに精
密蒸留に供し塔底から主にｎ―ブタン、ブテン―
２を除去し、塔頂から高純度の製品のブテン―１
を分離回収する。精密蒸留はいずれも通常30〜
150段特に90〜140段程度のものが用いられる。 The light hydrocarbons obtained from the distillation are then further subjected to precision distillation. Usually, this precision distillation is carried out in two stages, and in the first precision distillation, isobutane is mainly separated and removed from the top of the column. The bottom stream is further subjected to precision distillation, and mainly n-butane and butene are extracted from the bottom of the column.
Butene-2 is removed and high-purity product Butene-1 is extracted from the top of the column.
Separate and collect. Precision distillation usually takes 30~
Those with 150 stages, especially around 90 to 140 stages, are used.
本発明の方法による場合は純度99％以上さらに
は純度99.5％以上の製品イソブチレンを得ること
ができる。製品純度がこのようにより高いものを
必要としない場合は前記の反応条件をより温和に
すること、蒸留操作条件を緩和させることにより
行なうことができることはもちろんである。 When using the method of the present invention, it is possible to obtain product isobutylene with a purity of 99% or higher, and even 99.5% or higher. Of course, if higher product purity is not required, this can be achieved by making the reaction conditions milder or by relaxing the distillation operating conditions.
また本発明において、原料中のブテン―１の回
収率（製品中の残存率）が80％以上さらには85％
以上とすることが可能できわめて高収率でブテン
―１が分離回収できる。 In addition, in the present invention, the recovery rate of butene-1 in the raw material (residual rate in the product) is 80% or more, and even 85%.
It is possible to do the above, and it is possible to separate and recover butene-1 with an extremely high yield.
次に本発明の方法をさらに具体的に説明するた
めに図面にしたがつてプロセスの一例を説明す
る。 Next, in order to explain the method of the present invention in more detail, an example of the process will be explained with reference to the drawings.
図において管路１を経て原料のブタン―ブテン
留分が送入され管路２を経て加熱器E1で加熱さ
れ所定の温度に保たれ、強酸型陽イオン交換樹脂
粒子が充填されている固定床の反応塔R1に入る。
反応塔R1を出た流体は二つの流れに分けられ、
一つの流れは冷却器E2で冷却された後循環ポン
プＰで循環されて管路３を経て管路１から送入さ
れる原料と合流して反応塔R1に循環される。反
応塔R1を出た流体の他の流れは管路４を経て熱
交換器E3によつて所定の温度に保たれ強酸型陽
イオン交換樹脂が充填されている固定床の反応塔
R2に入る。反応塔R1およびR2まわりの圧力は圧
力コントロールバルブPCVで所定の圧力でコン
トロールされている。反応塔R2を出た流体は管
路５を経てPCVで圧力が減じられ、必要に応じ
て熱交換器E4で温度コントロールされて蒸留塔
D1に入る。蒸留塔D1の塔底管６からイソブチレ
ンの低重合体が分離され、塔頂からイソブチレン
低重合体の除去されたブタン―ブテン留分が留出
し、これは管路７を経て蒸留塔D2に入る。D2の
塔頂から主にイソブタンが管８から分離除去さ
れ、塔底留分は管路９を経て蒸留塔D3に入る。
D3の塔頂から管１０を経て高純度のブテン―１
が分離回収され、D3の塔底から管１１を経て残
りのC4留分が除去される。 In the figure, the raw material butane-butene fraction is fed through pipe 1, passed through pipe 2, heated by heater E 1 , and kept at a predetermined temperature, and fixed with strong acid type cation exchange resin particles. Enter bed reaction column R1 .
The fluid leaving the reactor R1 is divided into two streams,
One stream is cooled by a cooler E 2 and then circulated by a circulation pump P, where it joins with the raw material fed from the pipe 1 through a pipe 3 and is circulated to the reaction tower R 1 . The other stream of fluid leaving the reaction column R1 passes through line 4 to a fixed bed reaction column which is maintained at a predetermined temperature by a heat exchanger E3 and is filled with a strong acid type cation exchange resin.
Enter R2 . The pressure around the reaction towers R1 and R2 is controlled at a predetermined pressure by a pressure control valve PCV. The fluid exiting the reaction tower R2 passes through pipe 5, where the pressure is reduced in the PCV, and if necessary, the temperature is controlled by the heat exchanger E4 , and then the fluid is transferred to the distillation tower.
Enter D 1 . The isobutylene low polymer is separated from the bottom pipe 6 of the distillation column D1 , and a butane-butene fraction from which the isobutylene low polymer has been removed is distilled from the top of the column, and this is passed through the pipe 7 to the distillation column D2. to go into. Mainly isobutane is separated off from the top of D 2 via line 8, and the bottom fraction enters distillation column D 3 via line 9.
High purity butene-1 is passed from the top of D 3 through pipe 10.
is separated and recovered, and the remaining C 4 fraction is removed from the bottom of the D 3 column via pipe 11.
次に実施例をあげて本発明の特徴をさらに具体
的に記載する。 Next, the features of the present invention will be described in more detail with reference to Examples.
実施例 １
図面にしたがつて反応プロセスにより、反応塔
R1およびR2にスチレン系スルホン酸型イオン交
換樹脂（ジビニルベンゼン約20％含有、酸量
4.7meq／ｇ、平均粒径0.5mmφ）触媒をそれぞれ
50Kgおよび29.2Kg充填する。管路１を経てブタン
―ブテン留分（組成：イソブチレン3.5％（重量
％、以下同じ）、ブテン―１ 30.1％、ブテン―
２ 25.8％、イソブタン9.5％、ｎ―ブタン31.1
％）を350Kg／hrの流速で送入する。原料の液空
間速度は7.0（１／hr）である。反応系内の圧力は
PCVの作動により18Kg／cm2Ｇに保持される。こ
の原料は循環管路３を経て流れてきた流体と合流
して管路２を経て反応塔R1に送入される。反応
塔R1の入口温度50℃になるように熱交換器E1で
制御される。反応塔R1を出た流体は二つの流体
に分けられ、一つの流れは原料張込み流量の10倍
（循環比10）となるように循環ポンプＰで制御さ
れ、管路３を経て新原料と合流する。反応塔R1
を出た他の流れは管路４を経て反応塔R2に送入
される。この流体中のイソブチレンの残存率は
20.2％、ブテン―１の残存率は90.0％（残存率と
は原料中に含まれていたイソブチレン又はブテン
―１に対する割合を云う）であり、反応塔R2の
入口温度は50℃になるように熱交換器E3によつ
て制御される。R2における液空間速度は12（１／
hr）である。反応塔R2を出た流体中のイソブチ
レン残存率は2.8％、ブテン―１の残存率は85.5
％であり、この流体は管路５を経てPCVで圧力
が減じられて、蒸留塔D1に送入される。塔頂か
らイソブチレン含有量0.098％、ブテン―１含有
25.7％のブタン―ブテン留分が留出し、塔底から
イソブチレンのオリゴマー類が分離除去される。
蒸留塔D1の塔頂から留出した留分は理論段数100
段の精密蒸留塔D2およびD3によつて精密蒸留さ
れ、D3の塔頂から管路１０を経て純度99.6％のブ
テン―１が90Kg／hrの流速で分離される。Example 1 A reaction tower was constructed according to the reaction process according to the drawings.
R 1 and R 2 are styrene-based sulfonic acid type ion exchange resin (contains about 20% divinylbenzene, acid content
4.7meq/g, average particle size 0.5mmφ) catalyst, respectively.
Fill 50Kg and 29.2Kg. Butane-butene fraction (composition: isobutylene 3.5% (wt%, same below), butene-1 30.1%, butene-1 through pipe 1)
2 25.8%, isobutane 9.5%, n-butane 31.1
%) at a flow rate of 350Kg/hr. The liquid hourly space velocity of the raw material is 7.0 (1/hr). The pressure inside the reaction system is
It is maintained at 18Kg/cm 2 G by PCV operation. This raw material joins the fluid flowing through the circulation pipe 3 and is sent to the reaction tower R 1 through the pipe 2. The inlet temperature of reaction column R 1 is controlled by heat exchanger E 1 to be 50°C. The fluid exiting the reaction tower R1 is divided into two fluids, one flow is controlled by a circulation pump P so that the flow rate is 10 times the raw material charging flow rate (circulation ratio 10), and the new raw material is transferred through pipe 3. join with. Reaction tower R 1
The other stream leaving the reactor column R 2 is sent via line 4 to the reaction column R 2 . The residual rate of isobutylene in this fluid is
20.2%, the residual rate of butene-1 was 90.0% (residual rate refers to the ratio to isobutylene or butene-1 contained in the raw material), and the inlet temperature of reaction tower R 2 was set to 50°C. controlled by heat exchanger E 3 . The liquid hourly space velocity at R 2 is 12 (1/
hr). The residual rate of isobutylene in the fluid exiting the reaction tower R2 is 2.8%, and the residual rate of butene-1 is 85.5.
%, and this fluid passes through line 5, has its pressure reduced in the PCV, and is sent to distillation column D1 . Isobutylene content from the top of the column: 0.098%, butene-1 content
A 25.7% butane-butene fraction is distilled out, and isobutylene oligomers are separated and removed from the bottom of the column.
The fraction distilled from the top of distillation column D 1 has 100 theoretical plates.
Precise distillation is carried out by precision distillation columns D 2 and D 3 in stages, and butene-1 with a purity of 99.6% is separated from the top of D 3 via line 10 at a flow rate of 90 Kg/hr.
実施例 ２
反応塔R1およびR2のいずれに対しても、実施
例１と同様の触媒を30Kg充填する。管路１を経て
実施例１の同一組成のブタン―ブテン留分を300
Kg／hrの流速（液空間速度10.0）で送入する。反
応塔R1の入口温度は55℃、循環比は５とし、反
応塔R2の入口温度は50℃とする。以上の他は実
施例１と同じである。管路４を通過する流体のイ
ソブチレン残存率は25％、ブテン―１残存率は92
％であり、管路５を通過する流体中のイソブチレ
ン残存率は2.4％、ブテン―１残存率は86.0％で
ある。この流体は管路５を経て蒸留塔D1に送入
される。塔頂からイソブチレン含有量0.08％、ブ
テン―１含有量25.9％のブタン―ブテン留分が留
出し、塔底からイソブチレンのオリゴマー類が分
離除去される。精密蒸留塔D3の塔頂から管路１
０を経て純度99.7％のブテン―１が77Kg／hrの流
速で分離される。Example 2 30 kg of the same catalyst as in Example 1 was packed into both reaction towers R 1 and R 2 . 300 ml of the butane-butene fraction with the same composition as in Example 1 was passed through pipe 1.
Deliver at a flow rate of Kg/hr (liquid space velocity 10.0). The inlet temperature of the reaction tower R1 is 55°C, the circulation ratio is 5, and the inlet temperature of the reaction tower R2 is 50°C. Other than the above, this embodiment is the same as the first embodiment. The residual rate of isobutylene in the fluid passing through pipe 4 is 25%, and the residual rate of butene-1 is 92%.
%, the residual rate of isobutylene in the fluid passing through the pipe 5 is 2.4%, and the residual rate of butene-1 is 86.0%. This fluid is fed via line 5 to distillation column D1 . A butane-butene fraction with an isobutylene content of 0.08% and a butene-1 content of 25.9% is distilled from the top of the column, and isobutylene oligomers are separated and removed from the bottom of the column. Pipe 1 from the top of precision distillation column D 3
Butene-1 with a purity of 99.7% is separated at a flow rate of 77 kg/hr.
実施例 ３
反応塔R1およびR2に実施例１と同様の触媒を
それぞれ50Kgおよび20Kg充填する。管路１を経て
石油類の分解により得られるC4留分からブタジ
エンを抽出除去したものを塩化アルミニウム触媒
により重合反応に供し、液状重合体を生成させて
分離した未反応C4留分であるブタン―ブテン留
分（組成；イソブチレン5.4％、ブテン―１
37.0％、ブテン―２ 31.0％、イソブタン5.9％、
ｎ―ブタン20.3％）を200Kg／hrの流速（反応塔
R1での液空間速度４、R2での液空間速度10）で
送入する。反応塔R1の入口温度は47℃、循環比
は10とし、反応塔R2の入口温度は50℃とする。
以上の他は実施例１と同じである。管路４を通過
する流体中のイソブチレン残存率は14.8％、ブテ
ン―１残存率は88.5％であり、管路５を通過する
流体中のイソブチレン残存率は1.5％、ブテン―
１残存率は82.4％である。蒸留塔D1の塔頂からイ
ソブチレン含有量0.08％、ブテン―１含有量30.5
％のブタン―ブテン留分が留出し、塔底からイソ
ブチレンのオリゴマー類が分離除去される。精密
蒸留塔D3の塔頂から管路１０を経て純度99.8％の
ブテン―１が61Kg／hrの流速で分離される。Example 3 Reaction towers R 1 and R 2 are charged with 50 Kg and 20 Kg of the same catalyst as in Example 1, respectively. Butadiene is extracted and removed from the C4 fraction obtained by cracking petroleum through pipe 1, and subjected to a polymerization reaction using an aluminum chloride catalyst to produce a liquid polymer and separate the unreacted C4 fraction, butane. -Butene fraction (composition: isobutylene 5.4%, butene-1
37.0%, butene-2 31.0%, isobutane 5.9%,
n-butane 20.3%) at a flow rate of 200 Kg/hr (reaction tower
The liquid hourly velocity at R 1 is 4, and the liquid hourly velocity at R 2 is 10). The inlet temperature of the reaction tower R1 is 47°C, the circulation ratio is 10, and the inlet temperature of the reaction tower R2 is 50°C.
Other than the above, this embodiment is the same as the first embodiment. The residual rate of isobutylene in the fluid passing through pipe 4 is 14.8% and the residual rate of butene-1 is 88.5%, and the residual rate of isobutylene in the fluid passing through pipe 5 is 1.5% and butene-1.
1 survival rate is 82.4%. Isobutylene content 0.08% and butene-1 content 30.5 from the top of distillation column D 1
% of butane-butene fraction is distilled out, and isobutylene oligomers are separated and removed from the bottom of the column. Butene-1 with a purity of 99.8% is separated from the top of precision distillation column D 3 via line 10 at a flow rate of 61 kg/hr.
図は本発明のプロセスの一例を示す流れ概要図
である。
R1；第一反応塔、E1；熱交換器、E2：熱交換
器、Ｐ；ポンプ、E3；熱交換器、R2；第二反応
塔、E4；熱交換器、D1；蒸留塔、D2；精密蒸留
塔、D3；精密蒸留塔、１〜１１；管路。
The figure is a flow diagram showing an example of the process of the present invention. R 1 ; first reaction column, E 1 ; heat exchanger, E 2 : heat exchanger, P; pump, E 3 ; heat exchanger, R 2 ; second reaction column, E 4 ; heat exchanger, D 1 ; Distillation column, D 2 ; Precision distillation column, D 3 ; Precision distillation column, 1 to 11; Pipe line.
１ 高温にてプロピレンと塩素とを反応させて生
ずるガス状反応生成物を冷却して、未反応プロピ
レン、副生塩化水素、軽質留分、重質残渣および
アリルクロライドに各々分離することから成るア
リルクロライドの製造方法において、少なくとも
該ガス状反応生成物が約300〜150℃に冷却される
装置の内面を、ニツケル又はニツケル含有量30重
量％以上のニツケル合金製の部材で構成したこと
を特徴とするアリルクロライドの製造方法。
２ ガス状反応生成物が約300〜150℃に冷却され
る装置の内面を、ニツケル又はニツケル含有量45
重量％以上のニツケル合金製の部材で構成したこ
とを特徴とする特許請求の範囲第１項記載のアリ
ルクロライドの製造方法。
1. Allyl chloride, which consists of cooling the gaseous reaction product produced by reacting propylene and chlorine at high temperature and separating each into unreacted propylene, by-product hydrogen chloride, light fraction, heavy residue, and allyl chloride. The method for producing chloride is characterized in that at least the inner surface of the device in which the gaseous reaction product is cooled to about 300 to 150°C is made of a member made of nickel or a nickel alloy having a nickel content of 30% by weight or more. A method for producing allyl chloride. 2 The inner surface of the apparatus in which the gaseous reaction products are cooled to approximately 300-150°C is made of nickel or nickel containing 45
The method for producing allyl chloride according to claim 1, characterized in that the member is made of a nickel alloy of at least % by weight.
Claims (1)
許請求の範囲１記載のブテン―１の分離回収方
法。 ３ イソブチレン0.1〜15wt％、ブテン―１ 10
〜50wt％を含む前記ブタン―ブテン留分として、
石油類を分解することにより得られるC4炭化水
素留分よりブタジエンを分離除去したC4炭化水
素混合物とメタノールを酸性触媒の存在下で反応
させてメチル―ターシヤリ―ブチルエーテルを製
造する際の未反応のC4炭化水素混合物を用いる
ことを特徴とする特許請求の範囲１記載のブテン
―１の分離回収方法。 ４ イソブチレン0.1〜15wt％、ブテン―１ 10
〜50wt％を含む前記ブタン―ブテン留分として、
石油類を分解することにより得られるC4炭化水
素留分よりブタジエンを分離除去したC4炭化水
素混合物と水とを酸性触媒の存在下に反応させて
ターシヤリ―ブチルアルコールを製造する際の未
反応のC4炭化水素混合物を用いることを特徴と
する特許請求の範囲１記載のブテン―１の分離回
収方法。The method for separating and recovering butene-1 according to claim 1, characterized in that a C 4 hydrocarbon mixture is used. 3 Isobutylene 0.1-15wt%, butene-1 10
As the butane-butene fraction containing ~50wt%,
Unreacted when producing methyl tert-butyl ether by reacting a C 4 hydrocarbon mixture obtained by separating butadiene from the C 4 hydrocarbon fraction obtained by cracking petroleum and methanol in the presence of an acidic catalyst. The method for separating and recovering butene-1 according to claim 1, characterized in that a C 4 hydrocarbon mixture of: 4 Isobutylene 0.1-15wt%, butene-1 10
As the butane-butene fraction containing ~50wt%,
Unreacted when producing tert-butyl alcohol by reacting a C 4 hydrocarbon mixture obtained by separating butadiene from the C 4 hydrocarbon fraction obtained by cracking petroleum with water in the presence of an acidic catalyst. The method for separating and recovering butene-1 according to claim 1, characterized in that a C 4 hydrocarbon mixture of:
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17688280A JPS5799534A (en) | 1980-12-15 | 1980-12-15 | Separating and recovering method of high-purity butene-1 |
| US06/328,317 US4356339A (en) | 1980-12-15 | 1981-12-07 | Process for isolating and recovering butene-1 of high purity |
| GB8136917A GB2092171B (en) | 1980-12-15 | 1981-12-08 | Butene-1 recovery |
| CA000391809A CA1164481A (en) | 1980-12-15 | 1981-12-09 | Process for isolating and recovering butene-1 of high purity |
| FR8123402A FR2496096A1 (en) | 1980-12-15 | 1981-12-15 | PROCESS FOR ISOLATING AND RECOVERING HIGH-PURITY BUTENE-1 |
| DE19813149738 DE3149738A1 (en) | 1980-12-15 | 1981-12-15 | METHOD FOR SEPARATING BUTEN-1 FROM BUTANE-BUTEN FRACTIONS |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17688280A JPS5799534A (en) | 1980-12-15 | 1980-12-15 | Separating and recovering method of high-purity butene-1 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5799534A JPS5799534A (en) | 1982-06-21 |
| JPS6348249B2 true JPS6348249B2 (en) | 1988-09-28 |
Family
ID=16021410
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17688280A Granted JPS5799534A (en) | 1980-12-15 | 1980-12-15 | Separating and recovering method of high-purity butene-1 |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5799534A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5810527A (en) * | 1981-07-11 | 1983-01-21 | Nippon Oil Co Ltd | Separation and recovery of high-purity butene-1 |
-
1980
- 1980-12-15 JP JP17688280A patent/JPS5799534A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5799534A (en) | 1982-06-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7026519B2 (en) | Obtaining tert-butanol | |
| TWI444364B (en) | Process for preparing 1-butene from technical mixtures of c4 hydrocarbons | |
| US7002053B2 (en) | Method for preparing high-purity diisobutene | |
| CN107473917B (en) | Process for producing diisobutylene by mixing C4 | |
| GB2092171A (en) | Butene-1 recovery | |
| JPS6250453B2 (en) | ||
| CN111073690B (en) | Process for oligomerizing olefins using a reduced olefin content stream | |
| JP2021031494A (en) | Process for oligomerization of olefins with optimized distillation | |
| CN107778123B (en) | Method for preparing isobutene | |
| JPH08245433A (en) | Method of decomposing t-butyl alcohol | |
| EP0717022B1 (en) | Process for producing isopropyl alcohol by hydrating propylene | |
| JPS6348249B2 (en) | ||
| JP3344594B2 (en) | Reaction method | |
| JPH0136447B2 (en) | ||
| JPH0257525B2 (en) | ||
| JPS60204730A (en) | Continuous manufacture and apparatus for alkylate from olefin and paraffin | |
| JPS59212438A (en) | Separation and recovery of high purity butene-1 | |
| JPS6363254B2 (en) | ||
| JPS5951224A (en) | Separation of isobutylene from 4c hydrocarbon fraction | |
| EP4001248B1 (en) | Olefin trimerization | |
| JPH0216291B2 (en) | ||
| KR0127863B1 (en) | Process for diisobutene with high purity | |
| CN216472988U (en) | High-purity MTBE preparation system capable of efficiently removing isobutene | |
| RU2177930C1 (en) | Alkene oligomers production process | |
| JPH0245607B2 (en) |