JP4048549B1 - Method for producing tertiary butanol - Google Patents
Method for producing tertiary butanol Download PDFInfo
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- JP4048549B1 JP4048549B1 JP2006244252A JP2006244252A JP4048549B1 JP 4048549 B1 JP4048549 B1 JP 4048549B1 JP 2006244252 A JP2006244252 A JP 2006244252A JP 2006244252 A JP2006244252 A JP 2006244252A JP 4048549 B1 JP4048549 B1 JP 4048549B1
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- tertiary butanol
- isobutylene
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- butene
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- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 112
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000000243 solution Substances 0.000 claims abstract description 58
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000007864 aqueous solution Substances 0.000 claims abstract description 46
- 238000006703 hydration reaction Methods 0.000 claims abstract description 30
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 21
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 17
- 230000036571 hydration Effects 0.000 claims abstract description 13
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 12
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000004821 distillation Methods 0.000 claims description 32
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 230000003197 catalytic effect Effects 0.000 claims description 13
- 238000000354 decomposition reaction Methods 0.000 claims description 7
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 230000000887 hydrating effect Effects 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 10
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 10
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 8
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000010992 reflux Methods 0.000 description 6
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 239000001282 iso-butane Substances 0.000 description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 238000001944 continuous distillation Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical group CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
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- 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
-
- 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
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/94—Use of additives, e.g. for stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/02—Monohydroxylic acyclic alcohols
- C07C31/12—Monohydroxylic acyclic alcohols containing four carbon atoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
【課題】少なくともイソブチレンと１−ブテンとを含有する炭化水素混合物から高濃度の第３級ブタノールを高収率で得ると同時に、その残渣から分離される１−ブテン中のイソブチレンの含量を最少にして品位を向上し、しかも使用した水和触媒中の第３級ブタノールを事実上完全に除去して反復使用可能にする第３級ブタノールの製造方法を提供する。
【解決手段】ヘテロポリ酸の水溶液をイソブチレンの水和触媒として使用した上で、加圧、加熱下、向流的に複数段階で炭化水素混合物と接触反応させて得られた第３級ブタノールを含有する触媒水溶液層から高濃度の第３級ブタノールを直列に配置された二個の蒸留器で完全に回収するか、または一個の蒸留器で残された触媒水溶液中の第３級ブタノールを昇温分解して、触媒水溶液を反復使用可能にする事を特徴とする第３級ブタノールの製造方法である。
【選択図】なしTo obtain a high concentration of tertiary butanol in a high yield from a hydrocarbon mixture containing at least isobutylene and 1-butene, while minimizing the content of isobutylene in 1-butene separated from the residue. Thus, the present invention provides a method for producing tertiary butanol which can be used repeatedly by removing the tertiary butanol from the used hydration catalyst virtually completely.
A solution containing tertiary butanol obtained by using an aqueous solution of a heteropoly acid as a hydration catalyst for isobutylene, and contacting and reacting with a hydrocarbon mixture in multiple stages countercurrently under pressure and heating. The high concentration of tertiary butanol is recovered from the aqueous catalyst solution layer by two distillers arranged in series, or the temperature of the tertiary butanol in the aqueous catalyst solution left by one distiller is increased. It is a method for producing tertiary butanol, characterized in that it is decomposed so that an aqueous catalyst solution can be used repeatedly.
[Selection figure] None
Description
本発明は第３級ブタノールの製造方法に関する。さらに詳細にはナフサの分解反応の生成物から分離された炭素数が４からなる炭化水素群から１，３−ブタジエンを選択的に分離除去した残渣中に含有されるイソブチレンを触媒存在下に効率的に水和させて、さらにこの炭化水素残渣中のイソブチレン含量を最少にする事の出来る第３級ブタノールの製造方法に関する。 The present invention relates to a method for producing tertiary butanol. More specifically, the isobutylene contained in the residue obtained by selectively separating and removing 1,3-butadiene from the hydrocarbon group having 4 carbon atoms separated from the product of the naphtha decomposition reaction is efficiently produced in the presence of the catalyst. The present invention relates to a process for producing tertiary butanol which can be hydrated and minimize the isobutylene content in the hydrocarbon residue.
ナフサの分解生成物から分離された炭素数が４である炭化水素混合物には多種類の炭化水素類が含有されている。その中で産業上、殊に化学工業上有用なものとしては１，３−ブタジエン、イソブチレンおよび１−ブテンが挙げられる。ここで、１，３−ブタジエンは合成ゴムまたはプラスチックスの原料として既に古くから利用されてきた。また、イソブチレンからはブチルゴム、プラスチックの安定剤類、ガソリンのオクタン価向上剤、第３級ブタノール、メタクリル酸、メタクリル酸エステル類などが誘導され、広く利用されている。さらに、１−ブテンは２−ブテンと共に第２級ブタノールまたはメチルエチルケトンなどに誘導され利用されていたが、最近、これがポリオレフィンと称されるプラスチックスの原料として使用されるようになって、特に注目され、需要が漸次拡大されつつある状況である。しかし、この分野に使用される１−ブテンには比較的に高純度の品位が要求され、殊にイソブチレンの混在は嫌われている。従って、炭素数が４である炭化水素混合物から１−ブテンを高純度で分離回収する事は新しい課題となり、とりわけ、炭化水素混合物からイソブチレンを触媒の存在下で水和して第３級ブタノールに変換して分離除去する方法においては、その後で分離される１−ブテン中に混入するイソブチレンの量が特に多く、この課題が重要視されるようになっている。 The hydrocarbon mixture having 4 carbon atoms separated from the decomposition product of naphtha contains many kinds of hydrocarbons. Among them, those useful in industry, particularly in chemical industry, include 1,3-butadiene, isobutylene and 1-butene. Here, 1,3-butadiene has been used for a long time as a raw material for synthetic rubber or plastics. In addition, butyl rubber, plastic stabilizers, gasoline octane number improvers, tertiary butanol, methacrylic acid, methacrylic esters and the like are derived from isobutylene and widely used. Furthermore, 1-butene has been derived and used as a secondary butanol or methyl ethyl ketone together with 2-butene, but recently, it has been used as a raw material for plastics called polyolefin, and has attracted particular attention. This is a situation where demand is gradually expanding. However, the 1-butene used in this field is required to have a relatively high purity grade, and in particular, mixing of isobutylene is hated. Therefore, separation and recovery of 1-butene with high purity from a hydrocarbon mixture having 4 carbon atoms is a new issue. In particular, isobutylene is hydrated from a hydrocarbon mixture in the presence of a catalyst to form tertiary butanol. In the method of converting and separating and removing, the amount of isobutylene mixed in 1-butene separated thereafter is particularly large, and this problem is regarded as important.
ナフサの分解生成物から分離された炭素数が４である炭化水素混合物からは順次有用な炭化水素類が分離回収される。先ず、１，３−ブタジエンが分離回収される。これはジメチルホルムアミドなどの溶剤による選択的な抽出法が採用されていて、１，３−ブタジエンが分離除去された残渣には殆ど１，３−ブタジエンは含有されない。この残渣は当業界ではスペントＢＢまたはＲａｆｆｉｎａｔｅ−Ｉ（以下、本明細書においてはＲ−Ｉと称する。）と称されている。続いて、Ｒ−Ｉからはイソブチレンが除去される。イソブチレンはアルコール類、特にメタノールと反応させて第３級ブチルエーテルに変換してから分離除去されるか、これを水和させて第３級ブタノールにして分離除去されるかの二つの方法が取られている。イソブチレンが回収除去された残渣はＲａｆｆｉｎａｔｅ−II（以下、本明細書においてはＲ−IIと称する。）と称されていて１−ブテンが多く含有されている。既に説明した通り、高純度の１−ブテンはポリオレフィン類の原料として最近、需要を伸ばしつつあって重要である。これは通常、蒸留法によってＲ−IIから回収分離される。ただし、Ｒ−II中に含有されているイソブチレンは蒸留法では１−ブテンと分離する事が困難である。そして、Ｒ−Ｉ中のイソブチレンを第３級ブタノールに変換して除去する方法においては最終、１−ブテン中に残存するイソブチレンの量が比較的に多く、これを効率的に減少させる事は従来、さらに困難であった。 Useful hydrocarbons are sequentially separated and recovered from the hydrocarbon mixture having 4 carbon atoms separated from the decomposition product of naphtha. First, 1,3-butadiene is separated and recovered. This employs a selective extraction method using a solvent such as dimethylformamide, and the residue from which 1,3-butadiene has been separated and removed hardly contains 1,3-butadiene. This residue is referred to in the art as Spent BB or Raffinate-I (hereinafter referred to as R-I in this specification). Subsequently, isobutylene is removed from R-I. Isobutylene can be converted into tertiary butyl ether by reacting with alcohols, especially methanol, and then separated and removed, or it can be hydrated to form tertiary butanol and separated and removed. ing. The residue from which isobutylene has been recovered and removed is called Raffinate-II (hereinafter referred to as R-II in the present specification) and contains a large amount of 1-butene. As already explained, high-purity 1-butene is important as a raw material for polyolefins, which has recently been growing in demand. This is usually recovered and separated from R-II by distillation. However, isobutylene contained in R-II is difficult to separate from 1-butene by the distillation method. In the method of removing isobutylene in R-I by converting it to tertiary butanol, the amount of isobutylene remaining in 1-butene is relatively large. It was even more difficult.
Ｒ−Ｉ中のイソブチレンを水和させて第３級ブタノールを製造するに際して使用される触媒としては、大別して二種類が知られている。その一つは硫酸またはスルホン酸類であり、これは特許文献１または特許文献２などの各公報に詳しい。他の一つはりんモリブデン酸またはりんタングステン酸などのヘテロポリ酸と称される強酸性物質であって、特許文献３、特許文献４または特許文献５などの各公報に詳しい。特に、特許文献６にはモリブデン、タングステンまたはバナジウムを縮合配位元素としたヘテロポリ酸のイソブチレンに対する水和触媒としての利点が詳述されていて、さらに、高価なヘテロポリ酸水溶液の反復使用についての説明もあるが、触媒の反復使用におけるＲ−II中のイソブチレン含量を減少させる対策に付いては認識されていない。また、特許文献７には連続蒸留法による第３級ブタノールの蒸留についての説明があるが、この方法によれば、蒸留塔頂から取り出す第３級ブタノールの濃度を充分に保ちながら、蒸留塔底から取り出す触媒水溶液中に残存する第３級ブタノール含量を０．２重量％以下にする事は困難であるとされている。そして、この方法によって回収された触媒水溶液を反復使用する時、Ｒ−II中のイソブチレン含有量を３重量％以下に保つ事の困難性は既に知られている。
ナフサ分解反応の生成物から分離された炭素数が４である炭化水素混合物から１，３−ブタジエンを選択的に回収除去した残渣すなわちＲ−Ｉ中に存在するイソブチレンを反復使用可能な水和触媒を反復使用し効率的に水和して第３級ブタノールを含有する触媒水溶液を蒸留する事によって、化学合成原料として有用な高濃度の第３級ブタノールを高収率で製造すると同時に、その炭化水素残渣すなわちＲ−II中に残存するイソブチレン量を最少にして、これから引き続き分離回収される１−ブテンの品位をポリオレフィン類の原料として好ましい程度に向上させる事が第一の課題であり、高濃度の第３級ブタノールの濃度は８０重量％以上である事が好ましい。次に、反復使用される触媒水溶液に含有される第３級ブタノール量を第一の課題を満足させる事の出来る程度にまで減少させる事が第二の課題である。 A residue obtained by selectively recovering and removing 1,3-butadiene from a hydrocarbon mixture having 4 carbon atoms separated from the product of the naphtha decomposition reaction, that is, a hydration catalyst capable of repeatedly using isobutylene present in RI Is used to repeatedly hydrate the catalyst aqueous solution containing tertiary butanol efficiently, thereby producing high-concentration tertiary butanol useful as a chemical synthesis raw material in high yield, and at the same time, carbonizing it. The first problem is to minimize the amount of isobutylene remaining in the hydrogen residue, that is, R-II, and to improve the quality of 1-butene that is subsequently separated and recovered to a preferable level as a raw material for polyolefins. The concentration of tertiary butanol is preferably 80% by weight or more. Next, the second problem is to reduce the amount of tertiary butanol contained in the aqueous catalyst solution repeatedly used to such an extent that the first problem can be satisfied.
本発明は、モリブデンまたはタングステンを縮合配位元素とするヘテロポリ酸水溶液を水和触媒として使用した上で、触媒水溶液を加圧、加熱下、向流的に複数段階で、少なくともイソブチレンと１−ブテンとを含有する炭化水素類と接触反応させて得られる第３級ブタノールを含有する触媒水溶液から、直列的に配置された二個の連続蒸留器を使用することによって、高濃度の第３級ブタノールを取得すると同時に、第３級ブタノールを事実上完全に蒸留除去した触媒水溶液を反復使用する事を特徴とする第３級ブタノールの製造方法である。 The present invention uses a heteropoly acid aqueous solution containing molybdenum or tungsten as a condensed coordination element as a hydration catalyst, and then at least isobutylene and 1-butene at a plurality of countercurrents under pressure and heating in multiple stages. By using two continuous distillers arranged in series from an aqueous catalyst solution containing tertiary butanol obtained by catalytic reaction with hydrocarbons containing a high concentration of tertiary butanol Is obtained, and at the same time, a catalyst aqueous solution in which tertiary butanol has been distilled off completely completely is repeatedly used.
発明の実施態様、実施例、比較例および参考例から理解されるように、本発明は反復使用可能な触媒を使用して、Ｒ−Ｉから効率的に高濃度第３級ブタノールが製造されると同時に副生するＲ−II中のイソブチレンの含有量を最少にして、続いてこれから分離される１−ブテンの品位が向上される効果を有している。 As will be understood from the embodiments, examples, comparative examples and reference examples of the invention, the present invention efficiently produces a high concentration of tertiary butanol from R-I using a reusable catalyst. At the same time, it has the effect of minimizing the content of isobutylene in the by-produced R-II, and subsequently improving the quality of 1-butene separated therefrom.
反復使用可能な触媒を反復使用して、Ｒ−Ｉ中のイソブチレンを選択的に水和させ、その結果、Ｒ−IIに残存するイソブチレンの含有量を最少にする事が本発明の第一の課題である。ここで、イソブチレンの最少の含有量とはＲ−IIに対して１重量％以下、より好ましくは０．７重量％以下、最も好ましくは０．５重量％以下である。ちなみに、Ｒ−Ｉの代表的な組成はイソブチレン４２重量％（以下、重量を省略する。）、１−ブテン３０％、２−ブテン１５％、ｎ−ブタン７％、イソブタン２％およびその他合計で４％である。従って、この組成のＲ−Ｉを水和処理して、Ｒ−II中のイソブチレンの残存量を０．５％にしたと仮定すれば、このＲ−IIの組成はイソブチレン０．５％、１−ブテン５１．５％、２−ブテン２５．７％、ｎ−ブタン１２％、イソブタン３．４％およびその他合計で６．９％であると算出される。実験結果もこれと相似であって、このＲ−IIから蒸留法によって分離回収される１−ブテンの純度は９９％以上が保たれる。 The first use of the present invention is to repeatedly hydrate the isobutylene in R-I by repeatedly using a reusable catalyst so that the content of isobutylene remaining in R-II is minimized. It is a problem. Here, the minimum content of isobutylene is 1% by weight or less, more preferably 0.7% by weight or less, and most preferably 0.5% by weight or less based on R-II. Incidentally, the typical composition of R-I is 42% by weight of isobutylene (hereinafter, weight is omitted), 30% of 1-butene, 15% of 2-butene, 7% of n-butane, 2% of isobutane and other totals. 4%. Therefore, assuming that RI of this composition is hydrated and the residual amount of isobutylene in R-II is 0.5%, the composition of R-II is 0.5% isobutylene, -Butene 51.5%, 2-butene 25.7%, n-butane 12%, isobutane 3.4% and other total 6.9%. The experimental result is similar to this, and the purity of 1-butene separated and recovered from this R-II by distillation is maintained at 99% or more.
イソブチレンの水和反応によって第３級ブタノールを生成させる反応は可逆反応であり、触媒の種類の如何に関わらず、平衡関係は一定である。その化学量論的な平衡点は反応温度に支配される。そして、この反応は発熱反応であり、反応温度の低い方が平衡点は生成系側に移動する。ただ、低過ぎる温度での反応は反応速度が小さいので工業的な採用は困難である。本発明の実施においての好ましい反応温度は３０ないし８０℃さらに好ましくは、４０ないし７０℃の範囲である。反応温度が３０℃未満の時は水和反応速度が極めて緩慢であり、８０℃を超える時には少量の第２級ブタノールの生成が認められ、さらに触媒寿命が短縮される傾向があり、不利である。 The reaction for generating tertiary butanol by the hydration reaction of isobutylene is a reversible reaction, and the equilibrium relationship is constant regardless of the type of catalyst. Its stoichiometric equilibrium point is governed by the reaction temperature. This reaction is an exothermic reaction, and the lower the reaction temperature, the more the equilibrium point moves to the production system side. However, the reaction at a temperature that is too low is difficult to employ industrially because the reaction rate is small. The preferred reaction temperature in the practice of the present invention is in the range of 30 to 80 ° C, more preferably 40 to 70 ° C. When the reaction temperature is less than 30 ° C., the hydration reaction rate is extremely slow, and when it exceeds 80 ° C., a small amount of secondary butanol is observed, and the catalyst life tends to be shortened, which is disadvantageous. .
通常、Ｒ−Ｉと触媒水溶液との水和反応は複数段階で向流接触的に行なわれる。ここで、反復再使用される触媒水溶液中の第３級ブタノールの残存量が多い時には、Ｒ−Ｉと触媒水溶液との量比の如何、向流的接触反応の段数の如何に関わらず、本発明が課題としているＲ−II中のイソブチレンの量を最少にする事は困難である。反復使用される触媒水溶液の第３級ブタノールの望ましい含有量は０．２ないし０．０１重量％、さらに好ましくは０．１ないし０．０１重量％である。またＲ−Ｉと触媒水溶液の向流的接触反応の実効段数は３段階以上、好ましくは４段階以上である。実効段数が３段階未満である時、Ｒ−II中のイソブチレンの量を最少にしようとするにはＲ−Ｉに対する触媒水溶液の使用量を過大にする必要があって、実際的ではない。 Usually, the hydration reaction between R-I and the aqueous catalyst solution is carried out countercurrently in a plurality of stages. Here, when there is a large amount of tertiary butanol remaining in the aqueous catalyst solution that is repeatedly reused, the present ratio is not limited regardless of the quantity ratio of RI to the aqueous catalyst solution and the number of countercurrent catalytic reactions. It is difficult to minimize the amount of isobutylene in R-II, which is the subject of the invention. The desirable content of tertiary butanol in the aqueous catalyst solution used repeatedly is 0.2 to 0.01% by weight, more preferably 0.1 to 0.01% by weight. Further, the effective number of counter-current contact reactions between R-I and the aqueous catalyst solution is 3 or more, preferably 4 or more. When the number of effective stages is less than 3, in order to minimize the amount of isobutylene in R-II, it is necessary to excessively use the aqueous catalyst solution relative to R-I, which is not practical.
本発明の実施に好ましい水和触媒はヘテロポリ酸と称されるもののすべてが包含され得るが、実際にはりんモリブデン酸またはりんタングステン酸の二種類が安定性が良く最も好ましく使用される。そしてこの水和触媒として使用されるヘテロポリ酸水溶液の濃度は２０ないし７５重量％の範囲である事が好ましく、さらに触媒活性の安定性を向上させると共に、反応機器の腐食を防止する目的で少量のりん酸を加える事は好ましい。 Preferred hydration catalysts for the practice of this invention can include all of the so-called heteropolyacids, but in practice, two types of phosphomolybdic acid or phosphotungstic acid are most preferred because of their good stability. The concentration of the aqueous heteropolyacid solution used as the hydration catalyst is preferably in the range of 20 to 75% by weight. Further, a small amount is used for the purpose of improving the stability of the catalytic activity and preventing corrosion of the reaction equipment. It is preferable to add phosphoric acid.
Ｒ−Ｉと触媒水溶液との向流的な接触水和反応において、イソブチレンの最終水和段階、つまり回収再使用触媒水溶液中の第３級ブタノール含有量とＲ−II中のイソブチレンとの量的な関係は簡単に割り出せそうではあるが、反応の平衡論的な議論は反応系が均一である時にのみ正確であって、本発明の実施形態のように油層と水層とに分離する反応系では、多くの実験結果からしか正確には知りえない事である。本発明者等の多くの実験によれば、向流的な複数段階の水和反応において、Ｒ−Ｉからのイソブチレンの最終水和段階、すなわち回収触媒水溶液の最初の使用段階で回収触媒水溶液中に残存する第３級ブタノールの量が０．２重量％を超える時には、複数段階の向流的な水和反応の段数の多さに関わらず、本発明が目指しているＲ−II中のイソブチレンの含量を１重量％以下、つまり、Ｒ−II中の１−ブテン１００重量部に対して、イソブチレンを１．５重量部以下に保つのは困難である。本発明が目指しているＲ−II中の残存イソブチレンの含有量は１重量％以下、さらに好ましくは０．５重量％以下、最も好ましくは０．３重量％以下であって、これを実現するには反復使用する触媒水溶液中に残存する第３級ブタノールの量は０．２重量％以下、さらに好ましくは０．１重量％以下、最も好ましくは０．０５重量％以下であるべきである。これは、多くの実験結果によって判明した平衡関係に関わる量的な関係である。 In the counter-current catalytic hydration reaction between R-I and aqueous catalyst solution, the final hydration stage of isobutylene, that is, the amount of tertiary butanol in the recovered reused aqueous catalyst solution and the amount of isobutylene in R-II However, the reaction equilibrium theory is accurate only when the reaction system is uniform, and the reaction system is separated into an oil layer and an aqueous layer as in the embodiment of the present invention. Then, it can only be known accurately from many experimental results. According to many experiments by the present inventors, in the countercurrent multi-stage hydration reaction, the final hydration stage of isobutylene from R-I, that is, in the recovered catalyst aqueous solution at the first use stage of the recovered catalyst aqueous solution. When the amount of tertiary butanol remaining in the water exceeds 0.2% by weight, the isobutylene in R-II aimed by the present invention is used regardless of the number of countercurrent hydration reactions in multiple stages. It is difficult to keep isobutylene at 1.5 parts by weight or less with respect to 100 parts by weight of 1-butene in R-II. The content of residual isobutylene in R-II targeted by the present invention is 1% by weight or less, more preferably 0.5% by weight or less, and most preferably 0.3% by weight or less. The amount of tertiary butanol remaining in the aqueous catalyst solution to be used repeatedly should be 0.2% by weight or less, more preferably 0.1% by weight or less, and most preferably 0.05% by weight or less. This is a quantitative relationship related to the equilibrium relationship found by many experimental results.
以上の理由から、本発明の第一の課題と第二の課題は不可分であり、本発明の第二の課題は効率的に高濃度の第３級ブタノールを採取すると同時に、回収触媒水溶液に残存する第３級ブタノールの量を最少にする事である。 For the above reasons, the first and second problems of the present invention are inseparable, and the second problem of the present invention is to efficiently collect a high concentration of tertiary butanol and at the same time remain in the recovered catalyst aqueous solution. To minimize the amount of tertiary butanol.
この課題の解決方法の一つは蒸留方法の工夫である。水和反応の完結した触媒水溶液から一挙に蒸留して高濃度の第３級ブタノールを得ると同時に触媒水溶液に残存する第３級ブタノールの量を第一の課題を満足させる程度迄に減少させる事は困難である。その理由は、この課題を満足させるには過大な精留塔とこれを運転するための過大な還流比とが必要であって、装置の建設コストおよび運転の熱効率の二点で得策でないからである。故に、本発明では触媒水溶液からの第３級ブタノールの蒸留を二段階に分けて行なう事によって、この課題を解決する方法を見い出した。すなわち、最初の蒸留器では蒸留塔頂から高濃度の第３級ブタノールが得られる範囲の蒸留を行い、塔底から排出される触媒水溶液に残存する少々の第３級ブタノールは次の蒸留器に導いて蒸留し、この蒸留塔頂から得られる比較的に低濃度の第３級ブタノールは最初の蒸留器に返して、塔底から排出される触媒水溶液に残存する第３級ブタノールの量を最少にする方法である。この二段階の蒸留設備は連続式にも回分式にも設計する事が出来るが、大規模な工業生産では連続式である事が好ましい。また、この課題の解決方法の他の一つは、第３級ブタノールを含有する触媒水溶液から得られる第３級ブタノールが高濃度である範囲に蒸留をとどめ、塔底から排出される触媒水溶液中に残存する第３級ブタノールは加熱してイソブチレンに変換する事によって、第一の課題の解決に適した反復使用可能な第３級ブタノールの含有量が最少である触媒水溶液を得る方法であるが、この方法では更に一つの工程が必要であり、第３級ブタノールのロスもあって好ましくない。大規模な工業生産に最も好ましい方法は、向流的な連続接触水和反応に連結して直列的に配置された二個の連続蒸留器を使用して、高濃度の第３級ブタノールを取得すると同時に、触媒水溶液中の第３級ブタノールを事実上完全に蒸留除去して、触媒水溶液を反復使用可能にする事である。 One solution to this problem is to devise a distillation method. A high concentration of tertiary butanol is obtained by distilling from the aqueous catalyst solution after the hydration reaction is completed, and at the same time, the amount of the tertiary butanol remaining in the aqueous catalyst solution is reduced to the extent that the first problem is satisfied. It is difficult. The reason for this is that an excessive rectification column and an excessive reflux ratio for operating the rectification column are necessary to satisfy this problem, and it is not a good idea in terms of the construction cost of the apparatus and the thermal efficiency of the operation. is there. Therefore, in the present invention, a method for solving this problem has been found by carrying out distillation of tertiary butanol from an aqueous catalyst solution in two stages. That is, in the first distiller, distillation is performed in such a range that a high concentration of tertiary butanol can be obtained from the top of the distillation column, and a small amount of tertiary butanol remaining in the aqueous catalyst solution discharged from the bottom of the column is transferred to the next distiller. The relatively low concentration of tertiary butanol obtained from the top of the distillation column is returned to the first distiller to minimize the amount of tertiary butanol remaining in the aqueous catalyst solution discharged from the bottom of the column. It is a method to make. This two-stage distillation facility can be designed either continuously or batchwise, but is preferably continuous for large-scale industrial production. Another solution to this problem is that the distillation of the tertiary butanol obtained from the aqueous catalyst solution containing tertiary butanol is stopped in a high concentration range and the catalyst aqueous solution discharged from the bottom of the column is discharged. by tertiary butanol the remaining possible to convert heat to isobutylene, although the content of tertiary butanol repeatable available suitable for solving the first problem is how to obtain a catalyst solution is minimal This method requires one more step and is not preferable because of the loss of tertiary butanol. The most preferred method for large-scale industrial production is to obtain a high concentration of tertiary butanol using two continuous distillers arranged in series connected to a countercurrent continuous catalytic hydration reaction At the same time, the tertiary butanol in the catalyst aqueous solution is virtually completely distilled off, so that the catalyst aqueous solution can be used repeatedly .
既に述べたように、Ｒ−Ｉ中に含有されるイソブチレンを触媒水溶液を使用して、複数段階での向流的水和反応で得られた第３級ブタノールは蒸留によって触媒水溶液から分離回収される。蒸留は通常、１００ないし５００ヘクトパスカルの減圧下で実施される。１００ヘクトパスカル未満の圧力での蒸留ではその操作温度も低く逆反応による第３級ブタノールのイソブチレンへの分解反応が防止されて好ましいが、過度の減圧による蒸留設備の精留塔やコンデンサーが過大となって、必ずしも得策とは言えない。また、５００ヘクトパスカルを超える圧力での蒸留では操作温度も高く、第３級ブタノールのイソブチレンへの分解反応が促進されると同時に触媒寿命を短縮させる傾向があって、好ましくない。 As described above, the tertiary butanol obtained by the countercurrent hydration reaction in multiple stages using the aqueous solution of isobutylene contained in R-I is separated and recovered from the aqueous catalyst solution by distillation. The The distillation is usually carried out under a reduced pressure of 100 to 500 hectopascals. Distillation at a pressure of less than 100 hectopascals is preferable because the operation temperature is low and the decomposition reaction of tertiary butanol to isobutylene due to the reverse reaction is prevented, but the rectifying column and condenser of the distillation facility due to excessive decompression become excessive. This is not always a good idea. Further, distillation at a pressure exceeding 500 hectopascals is not preferable because the operation temperature is high, and the decomposition reaction of tertiary butanol to isobutylene is promoted and the catalyst life tends to be shortened.
本発明の工業的な実施においては、触媒水溶液とＲ−Ｉとの複数段階での向流的接触水和反応の設備および第３級ブタノールを含有した触媒水溶液からの高濃度の第３級ブタノールの蒸留設備の二つが必要である。これらは非連続式または連続式の二様に設計する事が出来るが、運転の経済性の見地からは両設備共に連続式である事が好ましく、さらにこの二つの設備は連結して運転されるように、その処理能力を同等に設計される事が好ましい。故に、この見地に立てば触媒水溶液からの第３級ブタノールの連続蒸留は二段階で直列的に連結されている事が最も好ましい。ちなみに、向流的接触水和反応の設備およびそれに続いた直列的に配置された二個の連続蒸留器の概略図は図１で示される。図中、１は向流的接触水和反応の設備、２および３は直列的に配置された二個の連続蒸留器、ａはＲ−Ｉの入り口、ｂはＲ−IIの出口、ｃは第３級ブタノールを含有した触媒水溶液の入り口、ｄは高濃度第３級ブタノールの出口、ｅは少し第３級ブタノールを含有した触媒水溶液の入り口、ｆは希薄な第３級ブタノールの入り口、ｇは反復使用される触媒水溶液の入り口そしてｈは補充する純水の入り口である。 In the industrial practice of the present invention, a multi-stage counter-current catalytic hydration reaction equipment of an aqueous catalyst solution and R-I and a high concentration of tertiary butanol from an aqueous catalyst solution containing tertiary butanol Two distillation facilities are required. These can be designed in two ways, discontinuous or continuous, but from the standpoint of economics of operation, it is preferable that both facilities are continuous, and the two facilities are operated in conjunction. Thus, it is preferable to design the processing capacity equally. Therefore, from this viewpoint, it is most preferable that the continuous distillation of the tertiary butanol from the aqueous catalyst solution is connected in series in two stages. Incidentally, a schematic diagram of a countercurrent catalytic hydration reaction facility followed by two serial stills arranged in series is shown in FIG. In the figure, 1 is a counter-current catalytic hydration equipment, 2 and 3 are two continuous distillers arranged in series, a is the inlet of R-I, b is the outlet of R-II, c is Inlet of catalyst aqueous solution containing tertiary butanol, d is outlet of high concentration tertiary butanol, e is inlet of aqueous catalyst solution containing a little tertiary butanol, f is inlet of diluted tertiary butanol, g Is the inlet of the re-used catalyst aqueous solution and h is the inlet of pure water to be replenished.
触媒水溶液とＲ−Ｉとの複数段階での向流的接触水和反応では実効段数が３以上、より好ましくは４以上である事が求められる。これは、本発明がＲ−Ｉからイソブチレンを水和抽出した残渣、すなわちＲ−II中のイソブチレンの含有量を最少にする課題を掲げている特殊性に原因している。ちなみに、従来この課題は無視されていて、通常、二段階の向流的接触水和反応が実施されていて、Ｒ−II中のイソブチレンの含量を３重量％以下に抑える事は困難であった。さらに、この課題を無視すれば、回収反復使用される触媒水溶液中の第３級ブタノールの含有量についても問題視する必要はなく、引いては触媒水溶液からの第３級ブタノールの蒸留にも特別の配慮の必要がなかった。向流的接触水和反応の実効段数が３未満である時には、通常実施されるＲ−Ｉと触媒水溶液の量比および反応条件の範囲内ではＲ−II中に残存するイソブチレンの含有量を本発明が求めている範囲内に収める事は出来ない。 In the countercurrent catalytic hydration reaction of the catalyst aqueous solution and R-I in a plurality of stages, the effective number of stages is required to be 3 or more, more preferably 4 or more. This is due to the particularity that the present invention addresses the problem of minimizing the content of isobutylene in the residue obtained by hydrating and extracting isobutylene from R-I, that is, R-II. Incidentally, this problem has been ignored in the past, and usually a two-stage countercurrent catalytic hydration reaction has been carried out, and it has been difficult to keep the isobutylene content in R-II below 3% by weight. . Furthermore, if this problem is ignored, there is no need to consider the content of tertiary butanol in the aqueous catalyst solution that is repeatedly used for recovery, and in particular, the distillation of tertiary butanol from the aqueous catalyst solution is also special. There was no need for consideration. When the effective number of counter-current catalytic hydration reactions is less than 3, the amount of isobutylene remaining in R-II within the range of the ratio of the R-I and aqueous catalyst solution and the reaction conditions that are usually carried out is It cannot be kept within the range required by the invention.
触媒水溶液とＲ−Ｉとの向流的接触水和反応は両者が共に液体である必要から加圧出来る設備内で行なわれる。触媒はヘテロポリ酸と称されるもので、りんモリブデン酸またはりんタングステン酸が使用されるが、触媒の回収反復使用においてりんタングステン酸がより長寿命であり最も好ましい。この触媒水溶液の濃度は３０ないし７５重量％であり、より好ましくは４０ないし７０重量％の範囲である。そして、接触するＲ−Ｉと触媒水溶液の量比は１対１ないし１対５の範囲である事が好ましい。接触を密にする目的で両者は充分にかきまぜられる。反応温度は３０ないし８０℃より好ましくは４０ないし７０℃の範囲である。各段階でのＲ−Ｉと触媒水溶液との接触時間はイソブチレン量と第３級ブタノールがほぼ平衡値に達する事が好ましく、反応温度がより高い程短時間であり、より低い程長時間が必要であって、０．５ないし６時間である事が好ましい。Ｒ−ＩまたはＲ−IIと触媒水溶液は静置すれば二層に分離するので、それぞれを採取する事は容易である。連続式の向流的接触水和反応装置は二つの方式が採用しうる。その一つは攪拌機付きの反応器と静置分離槽とを交互に必要な段数だけ組み合わせた設備であり、Ｒ−Ｉと触媒水溶液とを向流的に接触反応させる事が出来る。他の一つは連続向流抽出器と類似の装置であって、その装置上部から重液である触媒水溶液を注入し、下部から軽液であるＲ−Ｉを注入して、途中二液が充分に接触するようにかきまぜられる。こうして、装置上部からはイソブチレンが除去されたＲ−ＩつまりＲ−IIが排出され、装置下部からは、第３級ブタノールを含有した触媒水溶液が排出される。二液の排出はその比重差を利用して自動的に行なわれ、且つ装置内に滞留するＲ−Ｉと触媒水溶液の量比を一定に保つ事が出来る。前者は装置の設計が容易であり、さらに各段階の水和反応温度が変えられる利点があるが、その運転はやや複雑である。一方、後者は設備の設計がやや複雑ではあるが、その運転は一旦その条件を設定すれば容易である。 The counter-current catalytic hydration reaction between the aqueous catalyst solution and R-I is carried out in a facility that can be pressurized because both must be liquid. The catalyst is referred to as a heteropolyacid, and phosphomolybdic acid or phosphotungstic acid is used, but phosphotungstic acid has the longer life and is most preferred for repeated use of the catalyst. The concentration of the catalyst aqueous solution is 30 to 75% by weight, more preferably 40 to 70% by weight. And it is preferable that the quantity ratio of R-I and catalyst aqueous solution to contact is the range of 1: 1 to 1: 5. Both are sufficiently agitated for the purpose of close contact. The reaction temperature is in the range of 30 to 80 ° C, more preferably 40 to 70 ° C. The contact time between RI and the aqueous catalyst solution at each stage is preferably such that the amount of isobutylene and tertiary butanol reach an equilibrium value. The higher the reaction temperature, the shorter the time, and the lower, the longer the time required. It is preferable that the time is 0.5 to 6 hours. Since R-I or R-II and the catalyst aqueous solution are separated into two layers when allowed to stand, it is easy to collect each of them. Two types of continuous countercurrent catalytic hydration reactors can be employed. One of them is equipment in which a reactor equipped with a stirrer and a stationary separation tank are alternately combined in a necessary number of stages, and R-I and an aqueous catalyst solution can be reacted counter-currently. The other is a device similar to a continuous countercurrent extractor, in which a catalyst aqueous solution that is a heavy liquid is injected from the upper part of the apparatus, and RI that is a light liquid is injected from the lower part. Stir to ensure full contact. Thus, R-I from which isobutylene has been removed, that is, R-II, is discharged from the upper part of the apparatus, and an aqueous catalyst solution containing tertiary butanol is discharged from the lower part of the apparatus. The discharge of the two liquids is automatically performed using the difference in specific gravity, and the ratio of the amount of RI and the catalyst aqueous solution staying in the apparatus can be kept constant. The former has the advantage that the design of the apparatus is easy and the hydration reaction temperature of each stage can be changed, but its operation is somewhat complicated. On the other hand, the latter is a little complicated in equipment design, but its operation is easy once the conditions are set.
設備の運転に際しては高濃度の第３級ブタノールを蒸留して残った触媒水溶液には、イソブチレンの水和に消費された水と高濃度の第３級ブタノールに含有されている水とが不足している。触媒水溶液を反復使用するには不足した水を補給する事が必要である。水の補給は触媒水溶液の比重を測定しながら、正確に行なう事が出来る。ちなみに、６５重量％のりんタングステン酸の比重は２．２２である。 During the operation of the equipment, the aqueous catalyst solution remaining after distillation of the high concentration of tertiary butanol lacks the water consumed for the hydration of isobutylene and the water contained in the high concentration of tertiary butanol. ing. In order to repeatedly use the catalyst aqueous solution, it is necessary to replenish the insufficient water. Water can be replenished accurately while measuring the specific gravity of the catalyst aqueous solution. Incidentally, the specific gravity of 65% by weight of phosphotungstic acid is 2.22.
本発明をさらに明確にするために、具体的な実施例、比較例および参考例を挙げて説明する。ただし、実施例は説明の明確さと理解の容易さに資するために非連続的な方法についてのみ説明するが、これは本発明を限定するものではない。なお、例中、「％」は重量％を表すものとする。 In order to further clarify the present invention, specific examples, comparative examples, and reference examples will be described. However, in order to contribute to clarity of explanation and ease of understanding, the examples will be described only for a discontinuous method, but this does not limit the present invention. In the examples, “%” represents weight%.
（実施例１）
（実施例１−１）
かきまぜ機、温度計、圧力計、液体注入口および底部に排出口の付いた内容積２０，０００ｍｌのステンレススチール製のオートクレーブにその組成がイソブチレン：４２％、１−ブテン：３０％、２−ブテン：１５％、ｎ−ブタン：７％、イソブタン：２％およびその他：４％であるＲ−Ｉを４，３３８ｇ圧入した。これをかきまぜながら、反応機内の温度を６０℃にした。この中にりんタングステン酸９，１００ｇ、８５％りん酸９１ｇおよび水４，８０９ｇからなる触媒水溶液を毎分６７３．９ｇの速度で機内の温度を６０℃に保ちながら圧入した。その後３０分間かきまぜてから、かきまぜ機を停止して３０分間静置した。分離した触媒水溶液層だけを注意深く底部から排出して、これを３回使用済みの触媒水溶液として密閉出来る内容積１０，０００ｍｌの容器に保存した。反応機の中にはＲ−Ｉからイソブチレンが１回水和除去されたＲ−Ｉ’と仮称する炭化水素が残されている。これをかきまぜながら、反応機を６０℃に保ちつつ、先に調製したのと同じ触媒水溶液を同じ速度で圧入した。その後、同様に３０分間かきまぜてから、３０分間静置して、下層の触媒水溶液を排出して、これを２回使用済みの触媒水溶液として別の内容積１０，０００ｍｌの容器に保存した。反応機の中にはＲ−Ｉ’からイソブチレンがさらに１回水和除去されたＲ−Ｉ’’と仮称する炭化水素が残されている。再びこれをかきまぜながら、反応機を４０℃に保ちつつ、先に調製したのと同じ触媒水溶液を同じ速度で圧入した。その後、９０分かきまぜてから、３０分間静置した。下層の触媒水溶液を排出して、これを１回使用済みの触媒水溶液として内容積１０，０００ｍｌの容器に保存した。反応機内に残された炭化水素はＲ−IIとして、−１０℃に冷却した容器に取出し、その組成の分析に供した。分析の結果はイソブチレン：０．２８％、１−ブテン：５１％、２−ブテン：２６％、ｎ−ブタン：１２％、イソブタン：３．６％そしてその他：７％であった。
Example 1
(Example 1-1)
The composition is isobutylene: 42%, 1-butene: 30%, 2-butene in a 20,000 ml stainless steel autoclave with a stirrer, thermometer, pressure gauge, liquid inlet and outlet at the bottom. 4,338 g of R-I, which was 15%, n-butane: 7%, isobutane: 2%, and others: 4%, were injected. While stirring this, the temperature in the reactor was set to 60 ° C. A catalyst aqueous solution consisting of 9,100 g of phosphotungstic acid, 91 g of 85% phosphoric acid and 4,809 g of water was injected into this at a rate of 673.9 g / min while maintaining the temperature inside the apparatus at 60 ° C. After stirring for 30 minutes, the agitator was stopped and allowed to stand for 30 minutes. Only the separated aqueous catalyst solution layer was carefully discharged from the bottom and stored in a container with an internal volume of 10,000 ml that can be sealed as a used aqueous catalyst solution three times. In the reactor, a hydrocarbon temporarily named RI ′ from which isobutylene is dehydrated once from RI is left. While stirring this, while keeping the reactor at 60 ° C., the same aqueous catalyst solution prepared previously was injected at the same rate. Thereafter, the mixture was stirred for 30 minutes in the same manner, and then allowed to stand for 30 minutes. The lower layer catalyst aqueous solution was discharged, and this was stored twice as a used catalyst aqueous solution in another 10,000 ml container. In the reactor, there remains a hydrocarbon temporarily named RI ″ in which isobutylene is further hydrated once from RI ′. While stirring this again, while keeping the reactor at 40 ° C., the same aqueous catalyst solution prepared previously was injected at the same rate. Then, after stirring for 90 minutes, it left still for 30 minutes. The lower layer catalyst aqueous solution was discharged and stored as a used catalyst aqueous solution in a container having an internal volume of 10,000 ml. The hydrocarbon remaining in the reactor was taken out as R-II into a container cooled to −10 ° C. and subjected to analysis of its composition. The results of the analysis were isobutylene: 0.28%, 1-butene: 51%, 2-butene: 26%, n-butane: 12%, isobutane: 3.6%, and others: 7%.
温度計および実効段数が約２０段の充填式蒸留塔の付いた内容積１５，０００ｍｌの硬質ガラス製の蒸留器に保存していた３回使用済みの触媒水溶液および純水１，２５０ｇを仕込んだ。蒸留塔の上部には精密温度計、冷却器および還流比が変化されるような装置を取り付けた。また冷却器は真空器につないで、蒸留操作を２００ヘクトパスカルの減圧下で確実に実施されるようにした。還流比を１対７にして蒸留を開始して、蒸留塔頂の温度が最初から７℃だけ上昇した点で第３級ブタノールのレシーバーを切り替えた。続いて第二のレシーバーに同じ還流比で蒸留塔頂の温度が５９℃になるまでの留分を採取した。但し、第二段階の蒸留では、触媒水溶液の濃度の上昇と共に蒸留器内の温度が上昇したので、適宜純水を補った。最初のレシーバーの第３級ブタノールの濃度は８２％であり、約２，５００ｇが得られた。第二のレシーバーの第３級ブタノールの濃度は２３％であって約１，１００ｇが得られた。これを希薄第３級ブタノールとして、容器に保存した。蒸留器に残留した触媒水溶液は余分に濃縮されていたので、純水を補充して最初に調製した触媒水溶液と同じ比重に調整して、再生触媒水溶液として容器に保存した。この第３級ブタノール含有量は０．０３９％であった。 The catalyst aqueous solution used three times and 1,250 g of pure water stored in a 15,000 ml hard glass distiller with a thermometer and a packed distillation column having an effective number of plates of about 20 were charged. . At the top of the distillation column, a precision thermometer, a condenser, and a device for changing the reflux ratio were attached. The cooler was connected to a vacuum chamber to ensure that the distillation operation was performed under a reduced pressure of 200 hectopascals. Distillation was started at a reflux ratio of 1: 7, and the tertiary butanol receiver was switched at the point where the temperature at the top of the distillation column rose by 7 ° C. from the beginning. Subsequently, a fraction from the second receiver until the temperature at the top of the distillation column reached 59 ° C. was collected at the same reflux ratio. However, in the second stage distillation, the temperature in the distiller increased as the concentration of the aqueous catalyst solution increased, so pure water was appropriately supplemented. The concentration of tertiary butanol in the first receiver was 82%, yielding about 2,500 g. The concentration of tertiary butanol in the second receiver was 23%, resulting in about 1,100 g. This was stored in a container as dilute tertiary butanol. Since the catalyst aqueous solution remaining in the distiller was excessively concentrated, it was adjusted to the same specific gravity as the catalyst aqueous solution prepared first by replenishing pure water and stored in a container as a regenerated catalyst aqueous solution. The tertiary butanol content was 0.039%.
（実施例１−２）
実施例１−１で使用した反応機にＲ−Ｉを４，３３８ｇ圧入した。これをかきまぜながら反応機内の温度を６０℃にした。ここで、実施例１−１で保存していた２回使用済みの触媒水溶液に純水８６ｇを加えてから、実施例１−１と同様に毎分６７３．９ｇの速度で６０℃の温度を保ちながら反応機に圧入した。その後３０分かきまぜ、３０分静置した。触媒水溶液だけを排出して３回使用済みの触媒水溶液として保存した。続いて、反応機内を６０℃に保って、実施例１−１の１回使用済み触媒水溶液を同じ速度で圧入してから３０分かきまぜ、３０分静置した。触媒水溶液だけを排出して２回使用済みの触媒水溶液として保存した。反応機内の温度を４０℃に保ちながら、実施例１−１の再生触媒水溶液を実施例１−１と同様に圧入して、その後、６０分かきまぜ、３０分静置した。触媒水溶液を排出して、１回使用済みの触媒水溶液として保存した。反応機に残されたＲ−II中のイソブチレン含量は０．３２％であった。
(Example 1-2)
4,338 g of R-I was injected into the reactor used in Example 1-1. While stirring this, the temperature in the reactor was set to 60 ° C. Here, 86 g of pure water was added to the twice-used catalyst aqueous solution stored in Example 1-1, and then a temperature of 60 ° C. was applied at a rate of 673.9 g / min as in Example 1-1. While maintaining, it was press-fitted into the reactor. Thereafter, the mixture was stirred for 30 minutes and allowed to stand for 30 minutes. Only the aqueous catalyst solution was discharged and stored as a used aqueous catalyst solution three times. Subsequently, while maintaining the inside of the reactor at 60 ° C., the once-used catalyst aqueous solution of Example 1-1 was injected at the same speed, stirred for 30 minutes, and allowed to stand for 30 minutes. Only the aqueous catalyst solution was discharged and stored as a used aqueous catalyst solution twice. While maintaining the temperature in the reactor at 40 ° C., the regenerated catalyst aqueous solution of Example 1-1 was injected in the same manner as in Example 1-1, and then stirred for 60 minutes and allowed to stand for 30 minutes. The aqueous catalyst solution was discharged and stored as an aqueous catalyst solution once used. The isobutylene content in R-II remaining in the reactor was 0.32%.
ここの３回使用済みの触媒水溶液に実施例１−１の希薄第３級ブタノールおよび純水４００ｇを加えて、実施例１−１の蒸留操作と全く同様にして８２％の高濃度第３級ブタノールが約２，９００ｇおよび２５％の希薄第３級ブタノールが約１，０００ｇ得られた。なお、８２％の第３級ブタノール約２，９００ｇは使用したＲ−Ｉから得られる理論量にほぼ同じであった。蒸留器に残された触媒水溶液には純水を加えて濃度を調整して、再生触媒水溶液として保存した。なお、この第３級ブタノール含量は０．０４３％であった。 The diluted aqueous tertiary butanol of Example 1-1 and 400 g of pure water were added to the aqueous catalyst solution used three times here, and the 82% high-concentration tertiary was exactly the same as the distillation operation of Example 1-1. About 2,900 g of butanol and about 1,000 g of 25% dilute tertiary butanol were obtained. In addition, about 2,900 g of 82% tertiary butanol was almost the same as the theoretical amount obtained from R-I used. Pure water was added to the catalyst aqueous solution remaining in the distiller to adjust the concentration, and the solution was stored as a regenerated catalyst aqueous solution. The tertiary butanol content was 0.043%.
（実施例１−３）
実施例１−２と全く同様にして、実施例１−２で得られた２回使用済みの触媒水溶液に純水８６ｇを加えてから、実施例１−２と同じ反応機に仕込まれたＲ−Ｉ中に温度６０℃で圧入した。以降、実施例１−２と同じく、１回使用済みおよび再生触媒水溶液を用いて操作を行なった。ここで得られたＲ−IIのイソブチレンの含有量は０．３１％であった。３回使用済みの触媒水溶液に実施例１−２で得られた希薄第３級ブタノールおよび純水５００ｇを加えて実施例１−２と同じ条件で蒸留して、８２％の第３級ブタノールが約２，９００ｇと２５％の第３級ブタノール約１，０００ｇが得られた。蒸留器に残された触媒水溶液に純水を加えて濃度の調整を行った。この第３級ブタノールの含有量は０．０３６％であった。なお、さらに実施例１を続けたが、実施例１−３で完全に定常状態になったと認められ、同等の実験結果が得られた。
(Example 1-3)
In exactly the same manner as in Example 1-2, 86 g of pure water was added to the twice-used catalyst aqueous solution obtained in Example 1-2, and then R was charged into the same reactor as in Example 1-2. Press-fit into -I at a temperature of 60 ° C. Thereafter, the same operation as in Example 1-2 was performed using the used once-used and regenerated catalyst aqueous solution. The content of R-II isobutylene obtained here was 0.31%. The diluted aqueous tertiary butanol obtained in Example 1-2 and 500 g of pure water were added to the catalyst aqueous solution used three times and distilled under the same conditions as in Example 1-2. As a result, 82% of tertiary butanol was obtained. About 2,900 grams and about 1,000 grams of 25% tertiary butanol were obtained. The concentration was adjusted by adding pure water to the catalyst aqueous solution remaining in the distiller. The tertiary butanol content was 0.036%. In addition, although Example 1 was further continued, it was recognized that it was in a steady state in Example 1-3, and an equivalent experimental result was obtained.
（比較例１）
実施例１と同じ方法で得られた３回使用済みの触媒水溶液を実施例１で使用した蒸留器に仕込み、同じ条件で還流比１対０、つまり、還流しないで蒸留したところ、触媒水溶液中の第３級ブタノールの含有量を０．０５％以下に抑えるには大量の留出量が必要であり、蒸留途中で蒸留器にしばしば純水を補充しなければならなかった。ここで得られた第３級ブタノールの濃度は３１％であり、高濃度の第３級ブタノールを得るには再度の蒸留が必要であった。
(Comparative Example 1)
The aqueous solution of the catalyst used three times obtained in the same manner as in Example 1 was charged into the distiller used in Example 1 and distilled under the same conditions at a reflux ratio of 1 to 0, that is, distilled without reflux. In order to keep the content of the tertiary butanol to 0.05% or less, a large amount of distillate was required, and it was often necessary to replenish the distiller with pure water during the distillation. The concentration of the tertiary butanol obtained here was 31%, and a second distillation was required to obtain a high concentration of tertiary butanol.
（参考例１）
実施例１−１で使用した３段階の触媒水溶液はそれぞれ新しく調製したものであって、当然第３級ブタノールは含有されていない。故にこれを本発明の参考例として考える事が出来る。なぜなら、本発明の課題の一つは第３級ブタノールを含有している触媒水溶液から、効率的に反復使用可能な触媒水溶液を再生する事であり、実施例１の各実施例の成果はほぼ同等であり、実施例１の方法が本発明の課題解決の手段として適切である事を示している。
(Reference Example 1)
Each of the three-stage aqueous catalyst solutions used in Example 1-1 was newly prepared and naturally does not contain tertiary butanol. Therefore, this can be considered as a reference example of the present invention. This is because one of the problems of the present invention is to regenerate an aqueous catalyst solution that can be used repeatedly and efficiently from an aqueous catalyst solution containing tertiary butanol. This shows that the method of Example 1 is suitable as a means for solving the problems of the present invention.
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