JPH0137379B2 - - Google Patents
Info
- Publication number
- JPH0137379B2 JPH0137379B2 JP11044079A JP11044079A JPH0137379B2 JP H0137379 B2 JPH0137379 B2 JP H0137379B2 JP 11044079 A JP11044079 A JP 11044079A JP 11044079 A JP11044079 A JP 11044079A JP H0137379 B2 JPH0137379 B2 JP H0137379B2
- Authority
- JP
- Japan
- Prior art keywords
- isobutylene
- water
- sulfone
- tba
- hydrocarbon mixture
- 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
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 47
- 229930195733 hydrocarbon Natural products 0.000 claims description 24
- 239000004215 Carbon black (E152) Substances 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 18
- -1 C 4 hydrocarbon Chemical class 0.000 claims description 13
- 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 claims description 9
- 239000003729 cation exchange resin Substances 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 235000013844 butane Nutrition 0.000 claims description 5
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical class CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- MBDNRNMVTZADMQ-UHFFFAOYSA-N sulfolene Chemical compound O=S1(=O)CC=CC1 MBDNRNMVTZADMQ-UHFFFAOYSA-N 0.000 claims description 3
- MBDUIEKYVPVZJH-UHFFFAOYSA-N 1-ethylsulfonylethane Chemical group CCS(=O)(=O)CC MBDUIEKYVPVZJH-UHFFFAOYSA-N 0.000 claims description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 description 23
- 150000003457 sulfones Chemical class 0.000 description 19
- 150000002430 hydrocarbons Chemical class 0.000 description 16
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 230000000887 hydrating effect Effects 0.000 description 5
- 238000006703 hydration reaction Methods 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- CKGMDQVIRZYXHU-UHFFFAOYSA-N but-1-ene hydrate Chemical compound O.CCC=C CKGMDQVIRZYXHU-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 1
- HQCNSHPBVRWXGH-UHFFFAOYSA-N 2-methylprop-1-ene;hydrate Chemical group O.CC(C)=C HQCNSHPBVRWXGH-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
- C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
Description
本発明は、イソブチレンを含有するC4炭化水
素混合物から第３級ブチルアルコール（以下
TBAという）を高収率で製造する方法に関する。
さらに詳しくは、多孔性の酸型陽イオン交換樹
脂とスルホンとの存在下に、イソブチレンを含有
するC4炭化水素混合物からイソブチレンと水と
を選択的に反応させTBAを高収率で製造する方
法に関するものである。
酸性陽イオン交換樹脂および種々の溶媒の存在
下に、オレフイン系不飽和化合物を水和して対応
するアルコール類を製造する方法については多く
の提案がなされている。たとえば、イソブチレン
又はイソブチレン含有炭化水素混合物を酸性イオ
ン交換剤を触媒として有機酸水溶液で反応させる
方法（特開昭50−32116号、特公昭53−14044号公
報）、同様の触媒を用いて反応系中に１価アルコ
ールを添加して反応させる方法（特開昭50−
137906号公報）、同じく反応系中にグリコール、
グリコールエーテル、グリコールジエーテルなど
を添加して反応させる方法（特開昭51−59802号
公報、米国特許第4096194号明細書）などイソブ
チレンと水とを反応させてTBAを製造する方法、
あるいは、酸性イオン交換樹脂の触媒およびスル
ホンの存在下にオレフイン系不飽和化合物、特に
ブテン―１および／またはブテン―２と水とを
100〜220℃の温度で反応させ第２級ブチルアルコ
ール（以下SBAという）を製造する方法（特開
昭53−7605号公報）などが提案されている。
しかしながら、これら公知方法のうちイソブチ
レンを水和してTBAを製造する方法は、反応速
度的には若干の向上が認められるが、反応系に添
加して存在させる有機酸あるいは有機溶媒とイソ
ブチレンとの付加物などの副生物が生成する。ま
た、それら副生物および反応系に添加される溶媒
などは、TBAの沸点に近いかまたはそれ以下の
沸点を有するために、溶媒からTBAの分離回収
を困難あるいは経費のかかるものとしている。さ
らに、ブテン−１およびブテン−２と水とを100
〜220℃の温度で反応させてSBAを製造する方法
では、溶媒の安定性は認められるが、原料にイソ
ブチレンを含有するC4炭化水素混合物を用いイ
ソブチレンと水とを水和してTBAを製造する場
合に、SBAの生成およびイソブチレンの二量化
が起るため、イソブチレンを選択的に水和して高
収率でTBAを製造することができないという問
題がある。
本発明者らは、上記のような問題点を改善する
ために研究を重ねた結果、特定のイオン交換樹脂
と特定のスルホン類の存在下に、特定の条件下イ
ソブチレンと水を反応させることにより副反応を
抑制し、かつ反応速度と転化率を著しく促進する
ことを見出し本発明を完成したのである。
すなわち、本発明は、イソブチレンを含有する
C4炭化水素混合物からイソブチレンと水とを選
択的に反応させTBAを製造する方法において、
表面積0.5〜200m2／ｇおよび交換容量２〜
5meq／ｇのスルホン化スチレン−ジビニルベン
ゼン共重合体の多孔性の酸型陽イオン交換樹脂と
スルホレンまたは非環状スルホンの濃度が50〜97
重量％の水との混合液とを存在させ、イソブチレ
ン、ｎ−ブテン類、ブタン類を含有するC4炭化
水素混合物中のイソブチレンの水／イソブチレン
のモル比を１〜10の割合とし、温度が40〜100℃、
該C4炭化水素混合物が液状を保持する圧力で反
応させることを特徴とするTBAの製造方法であ
る。
本発明に用いるイソブチレンを含有するC4炭
化水素混合物は特に限定されるものではなく、通
常は炭素数が４の炭化水素類で、たとえば、イソ
ブチレン、ブテン−１、ブテン−２、イソブタ
ン、ｎ−ブタンなどを主体とするもので若干の
C3またはC5の炭化水素を含有していてもよい。
工業的には石油類の水蒸気分解、溶解分解などか
ら得られるイソブチレン含有のC4留分が用いら
れる。
本発明で用いられるスルホン類は、
スルホン、
または非環状のスルホンであるが、非環状のスル
ホンとしては、例えば
The present invention produces tertiary butyl alcohol (hereinafter referred to as
This invention relates to a method for producing TBA) with high yield. More specifically, a method for producing TBA in high yield by selectively reacting isobutylene and water from a C 4 hydrocarbon mixture containing isobutylene in the presence of a porous acidic cation exchange resin and sulfone. It is related to. Many proposals have been made regarding methods for producing corresponding alcohols by hydrating olefinically unsaturated compounds in the presence of acidic cation exchange resins and various solvents. For example, there is a method in which isobutylene or an isobutylene-containing hydrocarbon mixture is reacted with an aqueous organic acid solution using an acidic ion exchanger as a catalyst (Japanese Unexamined Patent Publication No. 50-32116, Japanese Patent Publication No. 53-14044), a reaction system using a similar catalyst, A method of reacting by adding monohydric alcohol to
137906), glycol is also included in the reaction system,
A method of producing TBA by reacting isobutylene with water, such as a method of adding and reacting glycol ether, glycol diether, etc. (Japanese Unexamined Patent Publication No. 51-59802, US Pat. No. 4,096,194);
Alternatively, an olefinically unsaturated compound, especially butene-1 and/or butene-2, and water in the presence of an acidic ion exchange resin catalyst and a sulfone.
A method of producing secondary butyl alcohol (hereinafter referred to as SBA) by reaction at a temperature of 100 to 220°C has been proposed (Japanese Patent Laid-Open No. 7605/1983). However, among these known methods, the method of producing TBA by hydrating isobutylene shows a slight improvement in the reaction rate, but the method of producing TBA by hydrating isobutylene has a slight improvement in the reaction rate. By-products such as adducts are produced. Furthermore, these by-products and the solvent added to the reaction system have boiling points close to or lower than the boiling point of TBA, making it difficult or expensive to separate and recover TBA from the solvent. Furthermore, butene-1 and butene-2 and water were added to 100%
In the method of producing SBA by reacting at a temperature of ~220°C, the stability of the solvent is recognized, but TBA is produced by hydrating isobutylene and water using a C 4 hydrocarbon mixture containing isobutylene as a raw material. When doing so, the formation of SBA and the dimerization of isobutylene occur, so there is a problem that it is not possible to selectively hydrate isobutylene and produce TBA in high yield. As a result of repeated research in order to improve the above-mentioned problems, the present inventors discovered that by reacting isobutylene and water under specific conditions in the presence of a specific ion exchange resin and specific sulfones. They have completed the present invention by discovering that side reactions can be suppressed and the reaction rate and conversion rate can be significantly accelerated. That is, the present invention contains isobutylene.
In a method for producing TBA by selectively reacting isobutylene and water from a C4 hydrocarbon mixture,
Surface area 0.5~ 200m2 /g and exchange capacity 2~
Porous acid type cation exchange resin of 5meq/g sulfonated styrene-divinylbenzene copolymer and sulfolene or acyclic sulfone concentration 50-97
% by weight of water is present, the water/isobutylene molar ratio of isobutylene in the C4 hydrocarbon mixture containing isobutylene, n-butenes, and butanes is from 1 to 10, and the temperature is 40~100℃,
The method for producing TBA is characterized in that the reaction is carried out at a pressure that maintains the C 4 hydrocarbon mixture in a liquid state. The C4 hydrocarbon mixture containing isobutylene used in the present invention is not particularly limited, and is usually a hydrocarbon having 4 carbon atoms, such as isobutylene, butene-1, butene-2, isobutane, n- Contains mainly butane, etc., with some
It may contain C3 or C5 hydrocarbons.
Industrially, isobutylene-containing C4 fractions obtained from steam cracking, dissolution cracking, etc. of petroleum are used. The sulfones used in the present invention include sulfone, or an acyclic sulfone, but as an acyclic sulfone, e.g.
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】などがあげられる。
また、これらスルホン類は混合物として用いるこ
ともできる。スルホン類は、通常水に溶解して使
用するが、その使用量は、水100重量部に対して
100〜3000部、特に200〜2000重量部が好ましい。
本発明において用いる多孔性の酸型陽イオン交
換樹脂は、スチレンとジビニルベンゼンとの共重
合体を母核として、これにスルホン酸基の入つた
ポリスチロールスルホン酸型樹脂であり、幾何学
的構造面からは物理的な細孔を有する多孔性（ポ
ーラス、ハイポーラス）型で、表面積が0.5m2／
ｇ〜200m2／ｇ（乾燥重量）、交換容量2.0meq／
ｇ〜5.0meq／ｇ（乾燥重量）であることを要す
る。
触媒の使用量は、触媒を懸濁状で使用する場合
と、固定床で使用する場合で異なるが、前者の場
合はスルホン類の水溶液に対して0.1〜10重量％
が好ましい。
なお、イソブチレンに対する水のモル比は１以
下になると反応率が低下し、一方モル比が大き過
ぎると反応器の効率が低下するので１〜10の範囲
とする必要がある。
反応温度は40〜100℃である。反応圧力は、反
応温度における原料炭化水素混合物の蒸気圧ない
しはそれよりも若干加圧で操作するのが好まし
い。
反応器の型式は、回分式でもよいが、通常は多
孔性の酸型陽イオン交換樹脂を固定床とした連続
式で行われる。
反応時間は、回分式の場合は通常20分〜10時間
の範囲であり、連続式の場合は通常炭化水素の液
時空間速度（LHSV）0.3〜10hr-1の範囲が適当
である。
本発明の好ましい実施の態様は、上記の条件の
うちでも特に表面積３〜200m2／ｇ、および交換
容量2.7〜5.0meq／ｇのスルホン化スチレン−ジ
ビニルベンゼン共重合体の多孔性の酸型陽イオン
交換樹脂と、スルホレン、ジエチルスルホン、ま
たはジメチルスルホンの濃度が60〜95重量％の水
との混合液で、イソブチレン、ｎ−ブテン類、ブ
タン類を含有するC4炭化水素混合物中のイソブ
チレンの水／イソブチレンのモル比が1.6〜6.0の
割合で、温度が60〜100℃で、圧力が、７〜18
Kg／cm2で反応させるものである。
なぜならば、スルホン化スチレン−ジビニルベ
ンゼン共重合体の表面積が0.5m2／ｇ以下の通常
のゲル型樹脂では交換容量が2.0meq／ｇ以上で
も触媒としての活性は低く、また、交換容量が
2.0meq／ｇ以下であれば表面積が0.5m2／ｇ以上
であつてもその触媒活性は低い。また、スルホン
類の濃度が50〜97重量％において、水／イソブチ
レンのモル比１〜10においてイソブチレンの水和
反応が促進されるが、反応温度100〜200℃におい
てはイソブチレンの二量化反応およびｎ−ブテン
類の水和反応が促進されジイソブチレンおよび
SBAが生成するために、イソブチレンと水との
選択的反応においては40〜100℃の温度が効果的
である。
原料のイソブチレン含有C4炭化水素混合物と
スルホン水溶液とを触媒充填反応器において反応
させ、得られた水和反応生成物の混合物は蒸留し
て未反応炭化水素混合物とTBAを含むスルホン
水溶液とに分離し、この水溶液分については蒸留
を行なつて粗TBA（TBA／水共沸混合物）とス
ルホン水溶液とに分離する。粗TBAは常法によ
り水を除去して実質的に純粋なTBAとし、分離
された未反応炭化水素混合物とスルホン水溶液は
反応器に再循環して水和反応に用いることができ
る。
以上、本発明の方法によるとイソブチレン含有
C4炭化水素混合物からイソブチレンを選択的に
水和する方法において、イソブチレンの反応速
度、転化率が著しく増加されるとともに副反応を
抑制して高収率でTBAを製造することができる。
さらに、スルホン類の沸点はTBAに比べて相当
に高く、蒸留分離が容易であり、再使用が簡単で
ある。
また、本発明の方法を利用するとイソブチレン
を含有するC4炭化水素混合物からイソブチレン
を単離することができる。すなわち、イソブチレ
ン含有C4炭化水素混合物中のイソブチレンを本
発明の方法により選択的にTBAに転換し、引続
きTBA含有スルホン水溶液と未反応炭化水素混
合物とを分離し、TBA含有スルホン水溶液より
蒸留によりTBAを分離した後、公知の方法によ
りTBAを脱水してイソブチレンを得る方法で、
きわめて高純度のイソブチレンを得ることができ
る。
以下に本発明をさらに具体的に説明するために
実施例および比較例を示す。なお、実施例および
比較例における％はモル％を示す。
実施例 １〜11
撹拌際つきのオートクレーブを使用して、スル
ホン化されたスチレン−ジビニルベンゼン共重合
体の多孔性（ハイポーラス）型の陽イオン交換樹
脂を触媒とし、水にスルホン類を添加した水溶液
でイソブチレン含有C4炭化水素混合物（イソブ
チレン40.0％、ｎ−ブテン類40.0％、ブタン類
20.0％）の水和反応を第１表に示す条件で行つ
た。反応終了後、急冷して反応生成物をガスクロ
マトグラフで分析し、イソブチレンおよびｎ−ブ
テンの転化率並びにTBAおよびSBAの選択率を
求めてその結果を第１表に併記した。Examples include [Formula]. Moreover, these sulfones can also be used as a mixture. Sulfones are usually used dissolved in water, but the amount used is 100 parts by weight of water.
100 to 3000 parts by weight, especially 200 to 2000 parts by weight are preferred. The porous acid type cation exchange resin used in the present invention is a polystyrene sulfonic acid type resin containing a sulfonic acid group in a core of a copolymer of styrene and divinylbenzene, and has a geometric structure. From the surface, it is a porous (porous, high porous) type with physical pores, and the surface area is 0.5 m 2 /
g~200m 2 /g (dry weight), exchange capacity 2.0meq/
g to 5.0 meq/g (dry weight). The amount of catalyst used differs depending on whether the catalyst is used in suspension or in a fixed bed, but in the former case it is 0.1 to 10% by weight based on the aqueous solution of sulfones.
is preferred. Note that if the molar ratio of water to isobutylene is less than 1, the reaction rate will decrease, while if the molar ratio is too large, the efficiency of the reactor will decrease, so it is necessary to keep it in the range of 1 to 10. The reaction temperature is 40-100°C. The reaction pressure is preferably operated at or slightly higher than the vapor pressure of the raw hydrocarbon mixture at the reaction temperature. Although the reactor type may be a batch type, it is usually a continuous type using a fixed bed of porous acid type cation exchange resin. The reaction time is usually in the range of 20 minutes to 10 hours in the case of a batch method, and in the case of a continuous method, the liquid hourly space velocity (LHSV) of the hydrocarbon is usually in the range of 0.3 to 10 hr −1 . A preferred embodiment of the present invention is a porous acid-type sulfonated styrene-divinylbenzene copolymer having a surface area of 3 to 200 m 2 /g and an exchange capacity of 2.7 to 5.0 meq/g. A mixture of ion exchange resin and water with a concentration of 60 to 95% by weight of sulfolene, diethyl sulfone, or dimethyl sulfone to remove isobutylene in a C4 hydrocarbon mixture containing isobutylene, n-butenes, and butanes. The molar ratio of water/isobutylene is 1.6-6.0, the temperature is 60-100℃, and the pressure is 7-18℃.
The reaction is carried out at Kg/ cm2 . This is because the sulfonated styrene-divinylbenzene copolymer has a surface area of 0.5 m 2 /g or less, and the catalytic activity is low even if the exchange capacity is 2.0 meq/g or more.
If it is 2.0 meq/g or less, the catalytic activity is low even if the surface area is 0.5 m 2 /g or more. Furthermore, when the concentration of sulfones is 50 to 97% by weight and the molar ratio of water/isobutylene is 1 to 10, the hydration reaction of isobutylene is promoted, but at a reaction temperature of 100 to 200°C, the dimerization reaction of isobutylene and n - The hydration reaction of butenes is promoted and diisobutylene and
Temperatures of 40-100°C are effective in the selective reaction of isobutylene and water to form SBA. The raw material isobutylene-containing C 4 hydrocarbon mixture and sulfone aqueous solution are reacted in a catalyst-packed reactor, and the resulting hydration reaction product mixture is distilled to separate the unreacted hydrocarbon mixture and the sulfone aqueous solution containing TBA. This aqueous solution is then distilled to separate it into crude TBA (TBA/water azeotrope) and an aqueous sulfone solution. Water is removed from the crude TBA by conventional methods to obtain substantially pure TBA, and the separated unreacted hydrocarbon mixture and aqueous sulfone solution can be recycled to the reactor for use in the hydration reaction. As described above, according to the method of the present invention, isobutylene-containing
In the method of selectively hydrating isobutylene from a C4 hydrocarbon mixture, the reaction rate and conversion rate of isobutylene are significantly increased, side reactions are suppressed, and TBA can be produced in high yield.
Furthermore, the boiling point of sulfones is considerably higher than that of TBA, making it easier to separate by distillation and reuse. Also, the method of the present invention can be used to isolate isobutylene from C 4 hydrocarbon mixtures containing isobutylene. That is, isobutylene in an isobutylene-containing C4 hydrocarbon mixture is selectively converted to TBA by the method of the present invention, followed by separating a TBA-containing sulfone aqueous solution from an unreacted hydrocarbon mixture, and distilling the TBA-containing sulfone aqueous solution to convert TBA into TBA. After separating, TBA is dehydrated using a known method to obtain isobutylene.
Very high purity isobutylene can be obtained. Examples and comparative examples are shown below to further specifically explain the present invention. Note that % in Examples and Comparative Examples indicates mol%. Examples 1 to 11 An aqueous solution in which sulfones were added to water using a porous cation exchange resin of sulfonated styrene-divinylbenzene copolymer as a catalyst using an autoclave with a stirring stand. C4 hydrocarbon mixture containing isobutylene (isobutylene 40.0%, n-butenes 40.0%, butanes
20.0%) was carried out under the conditions shown in Table 1. After the reaction was completed, the reaction product was rapidly cooled and analyzed by gas chromatography to determine the conversion rates of isobutylene and n-butene and the selectivity of TBA and SBA, and the results are also listed in Table 1.
【表】
比施例 １〜９
実施例と同様の反応器、触媒、原料炭化水素を
用いるイソブチレンの水和反応において、反応系
中にスルホン類を添加しない場合と、触媒の表面
積が0.5m2／ｇ以下あるいは交換容量が2.0meq／
ｇ以下の場合、反応温度が100℃以上の場合と40
℃以下の場合及びスルホン類の濃度が97重量％以
上と50重量％以下の場合について比較実験を行つ
た。実験条件並びに実験結果を第２表に併記し
た。
なお、イソブチレン、ｎ−ブテンの転化率およ
びTBA，SBAの選択率は実施例と同様にして求
めた。[Table] Comparative Examples 1 to 9 In the hydration reaction of isobutylene using the same reactor, catalyst, and raw material hydrocarbon as in the example, the case where no sulfones were added to the reaction system and the case where the surface area of the catalyst was 0.5 m 2 /g or less or exchange capacity is 2.0meq/
If the reaction temperature is 100℃ or higher,
A comparative experiment was conducted for cases where the temperature was below 0.degree. C. and when the concentration of sulfones was 97% by weight or more and 50% by weight or less. The experimental conditions and experimental results are also listed in Table 2. Incidentally, the conversion rates of isobutylene and n-butene and the selectivities of TBA and SBA were determined in the same manner as in the examples.
Claims (1)
からイソブチレンと水とを選択的に反応させ第３
級ブチルアルコールを製造する方法において、表
面積0.5〜200m2／ｇおよび交換容量２〜5meq／
ｇのスルホン化スチレン−ジビニルベンゼン共重
合体の多孔性の酸型陽イオン交換樹脂とスルホレ
ンまたは非環状スルホンの濃度が50〜97重量％の
水との混合液とを存在させ、イソブチレン、ｎ−
ブテン類、ブタン類を含有するC4炭化水素混合
物中のイソブチレンの水／イソブチレンのモル比
を１〜10の割合とし、温度が40〜100℃、該C4炭
化水素混合物が液状を保持する圧力で反応させる
ことを特徴とする第３級ブチルアルコールを製造
する方法。 ２ 非環状スルホンがジエチルスルホンまたはジ
メチルスルホンであることを特徴とする特許請求
の範囲１に記載の方法。[Claims] 1. A method of selectively reacting isobutylene with water from a C 4 hydrocarbon mixture containing isobutylene.
In the method for producing grade butyl alcohol, the surface area is 0.5 to 200 m 2 /g and the exchange capacity is 2 to 5 meq/g.
g of a porous acid type cation exchange resin of sulfonated styrene-divinylbenzene copolymer and water with a concentration of 50 to 97% by weight of sulfolene or acyclic sulfone are present, and isobutylene, n-
The water/isobutylene molar ratio of isobutylene in a C 4 hydrocarbon mixture containing butenes and butanes is set at a ratio of 1 to 10, the temperature is 40 to 100°C, and the pressure at which the C 4 hydrocarbon mixture remains liquid A method for producing tertiary butyl alcohol, which comprises reacting with. 2. The method according to claim 1, wherein the acyclic sulfone is diethyl sulfone or dimethyl sulfone.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11044079A JPS5634643A (en) | 1979-08-31 | 1979-08-31 | Preparation of tertiary butyl alcohol |
| GB8027443A GB2060616B (en) | 1979-08-31 | 1980-08-22 | Process for the production of tertiary butyl alcohol |
| DE19803031702 DE3031702A1 (en) | 1979-08-31 | 1980-08-22 | METHOD FOR PRODUCING TERT.-BUTANOL |
| CA359,042A CA1129890A (en) | 1979-08-31 | 1980-08-26 | Process for the production of tertiary butyl alcohol |
| FR8018789A FR2464241A1 (en) | 1979-08-31 | 1980-08-29 | PROCESS FOR PRODUCING TERTIARY BUTYL ALCOHOL |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11044079A JPS5634643A (en) | 1979-08-31 | 1979-08-31 | Preparation of tertiary butyl alcohol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5634643A JPS5634643A (en) | 1981-04-06 |
| JPH0137379B2 true JPH0137379B2 (en) | 1989-08-07 |
Family
ID=14535768
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11044079A Granted JPS5634643A (en) | 1979-08-31 | 1979-08-31 | Preparation of tertiary butyl alcohol |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS5634643A (en) |
| CA (1) | CA1129890A (en) |
| DE (1) | DE3031702A1 (en) |
| FR (1) | FR2464241A1 (en) |
| GB (1) | GB2060616B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3628008C1 (en) * | 1986-08-19 | 1987-11-05 | Deutsche Texaco Ag, 2000 Hamburg, De | |
| JPH11193255A (en) * | 1997-12-26 | 1999-07-21 | Mitsubishi Rayon Co Ltd | Production of tertiary butyl alcohol |
| TW200514767A (en) * | 2003-08-21 | 2005-05-01 | Mitsubishi Rayon Co | Method of producing tertiary alcohols |
| DE10338581A1 (en) | 2003-08-22 | 2005-03-17 | Oxeno Olefinchemie Gmbh | Process for producing tert-butanol |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2297196A1 (en) * | 1975-01-10 | 1976-08-06 | Chaplits Donat | Isobutylene recovery from 4C hydrocarbon fractions - by intermediate conversion to tert. butanol and dehydration of the alcohol |
| GB1518461A (en) * | 1976-05-13 | 1978-07-19 | Shell Int Research | Hydration of unsaturated compounds |
| US4180688A (en) * | 1977-07-29 | 1979-12-25 | Nippon Oil Co., Ltd. | Method for continuously producing tert-butyl alcohol |
| JPS5682580A (en) * | 1979-12-07 | 1981-07-06 | Hitachi Maxell Ltd | Manufacture of button-type battery |
-
1979
- 1979-08-31 JP JP11044079A patent/JPS5634643A/en active Granted
-
1980
- 1980-08-22 DE DE19803031702 patent/DE3031702A1/en not_active Withdrawn
- 1980-08-22 GB GB8027443A patent/GB2060616B/en not_active Expired
- 1980-08-26 CA CA359,042A patent/CA1129890A/en not_active Expired
- 1980-08-29 FR FR8018789A patent/FR2464241A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| GB2060616B (en) | 1983-10-26 |
| JPS5634643A (en) | 1981-04-06 |
| FR2464241B1 (en) | 1984-10-19 |
| GB2060616A (en) | 1981-05-07 |
| DE3031702A1 (en) | 1981-03-19 |
| FR2464241A1 (en) | 1981-03-06 |
| CA1129890A (en) | 1982-08-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5368791B2 (en) | Reactive distillation in olefin recycling | |
| US20060135823A1 (en) | Process for preparing dimethylether from methanol | |
| CS207465B2 (en) | Method of making the clean methyl-terc.butylether | |
| US4287379A (en) | Process for obtaining isobutene from C4 -hydrocarbon mixtures containing isobutene | |
| AU694889B2 (en) | Dehydration of primary alcohols | |
| EP0629601B1 (en) | Method for the removal of dimethyl ether from methyl tertiary butyl ether | |
| CA1140945A (en) | Process for preparation of high purity isobutylene | |
| KR101075381B1 (en) | 3 Process for preparing tert-butanol | |
| US2070258A (en) | Production of tertiary butyl alcohol | |
| JPS6058894B2 (en) | Manufacturing method of tertiary alcohol | |
| US4270011A (en) | Process for the production of tertiary butyl alcohol | |
| CA1086333A (en) | Hydration reactions | |
| JPH0137379B2 (en) | ||
| US5157162A (en) | One step synthesis of methyl t-butyl ether from t-butanol using fluorosulfonic acid-modified clay catalysts | |
| GB2024812A (en) | Process for producing tert-butanol from a mixture of isobutylene and n-butene | |
| NO873642L (en) | PROTON CATALYzed REACTIONS. | |
| CA1188711A (en) | Process for production of secondary alcohols | |
| JPH04225930A (en) | Process for producing alcohol or ether by hydration of olefinic material | |
| JPS6058893B2 (en) | Method for producing tertiary alcohol | |
| JPS60149535A (en) | Alcohol continuous manufacture | |
| US5157161A (en) | One-step synthesis of methyl t-butyl ether from t-butanol using hydrogen fluoride-modified montmorillonite clays | |
| US5563301A (en) | Sequential reaction of TBA and isobutylene with methanol | |
| US5214218A (en) | One step synthesis of methyl t-butyl ether from t-butanol using haloacid-modified clay catalysts | |
| US5183947A (en) | One step synthesis of methyl t-butyl ether from t-butanol using fluorophosphoric acid-modified clay catalysts | |
| EP0313905B1 (en) | Process for the direct hydration of linear olefins |