JPS62238227A - Production of tertiary alkyl ether - Google Patents
Production of tertiary alkyl etherInfo
- Publication number
- JPS62238227A JPS62238227A JP61079856A JP7985686A JPS62238227A JP S62238227 A JPS62238227 A JP S62238227A JP 61079856 A JP61079856 A JP 61079856A JP 7985686 A JP7985686 A JP 7985686A JP S62238227 A JPS62238227 A JP S62238227A
- Authority
- JP
- Japan
- Prior art keywords
- tertiary
- reaction
- tertiary alkyl
- alkyl ether
- reactor
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 125000005011 alkyl ether group Chemical group 0.000 title 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000001179 sorption measurement Methods 0.000 claims abstract description 27
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000004821 distillation Methods 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000005215 alkyl ethers Chemical group 0.000 claims abstract description 15
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 14
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 14
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011541 reaction mixture Substances 0.000 claims abstract description 11
- 239000003463 adsorbent Substances 0.000 claims abstract description 9
- 150000001336 alkenes Chemical group 0.000 claims abstract description 9
- 239000004927 clay Substances 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 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 abstract description 7
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 7
- 230000002378 acidificating effect Effects 0.000 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 14
- 230000005484 gravity Effects 0.000 claims description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- 150000001721 carbon Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000006266 etherification reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- RYYVLZVUVIJVGH-UHFFFAOYSA-N caffeine Chemical compound CN1C(=O)N(C)C(=O)C2=C1N=CN2C RYYVLZVUVIJVGH-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- LPHGQDQBBGAPDZ-UHFFFAOYSA-N Isocaffeine Natural products CN1C(=O)N(C)C(=O)C2=C1N(C)C=N2 LPHGQDQBBGAPDZ-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229960001948 caffeine Drugs 0.000 description 1
- VJEONQKOZGKCAK-UHFFFAOYSA-N caffeine Natural products CN1C(=O)N(C)C(=O)C2=C1C=CN2C VJEONQKOZGKCAK-UHFFFAOYSA-N 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 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
- 238000009434 installation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
発明の目的
［産業上の利用分野１
本発明は、第三級アルキルエーテルの製造、とくにイソ
ブチレンを含むＣ４炭化水素をメタノールと反応させて
］ニーチル化し、メヂルーｔｃｒ’ｔ−ブチルエーテル
（以下、ｒＭＴＢＥＪという。）の製造をづる方法の改
良に関し、外観が無色透明で製品価値の高いＭＴＢＥを
、低減されたコストで製造できるようにしたものである
。DETAILED DESCRIPTION OF THE INVENTION Purpose of the invention [Industrial field of application 1] The present invention relates to the production of tertiary alkyl ethers, particularly by reacting C4 hydrocarbons including isobutylene with methanol. - Regarding the improvement of the method for producing butyl ether (hereinafter referred to as rMTBEJ), it is possible to produce MTBE, which has a colorless and transparent appearance and high product value, at a reduced cost.
［従来の技術］
イソブチレンを含有するＣ４炭化水素をメタノールと反
応させてＭＴＢＥを製造する方法は、従来、カチオン交
換樹脂を充填した固定床反応器に原料を供給し、冑ｔう
れた反応混合物を蒸留分離して、塔底からＭＴＢＥを央
き出し、塔頂からはＭＴＢＥを含まないＣ４炭化水素を
留出させる方法をとっている。[Prior Art] Conventionally, a method for producing MTBE by reacting a C4 hydrocarbon containing isobutylene with methanol involves supplying a raw material to a fixed bed reactor filled with a cation exchange resin, and draining the resulting reaction mixture. A method is adopted in which MTBE is distilled and separated from the bottom of the column, and C4 hydrocarbons not containing MTBE are distilled from the top of the column.
ところが、塔底から扱き出（）たＭＴＢＥは、とくにブ
ロック運転を行なった場合、反応停止後において４色が
多くみられ、製品価値が低下する。However, the MTBE discharged from the bottom of the column, especially when block operation is performed, often shows four colors after the reaction has stopped, reducing the product value.
着色の原因は不明であるが、イソブチレンの三量化、三
量化やエーテル合成の際に一部生成するオレフィン、エ
ーテルの低分子量重合体の存在が、その−因と考えられ
る。The cause of the coloration is unknown, but it is thought to be due to the presence of low molecular weight polymers of olefins and ethers, which are partially produced during isobutylene trimerization and ether synthesis.
この対策として、着色した缶出液を再度塔留塔を使用し
て蒸留精製することを試みたが、本来のプロレスどは別
の蒸留塔が必要となり、余分な設備費がかかるうえに、
新たな熱源を要し、コストアップとなるので適切といえ
ない。As a countermeasure to this problem, an attempt was made to distill and purify the colored bottoms again using a distillation column, but this required a separate distillation column for traditional professional wrestling, which required extra equipment costs.
This is not appropriate as it requires a new heat source and increases costs.
［発明が解決しようとする問題点１
本発明の目的は、上記の問題を解決し、無色透明で製品
価値の高いＭＴＢＥなどの第三級アルキルエーテルを、
低減されたコストで製造できる方法を提供することにあ
る。[Problem to be Solved by the Invention 1] The purpose of the present invention is to solve the above-mentioned problems, and to solve the above problems by using a tertiary alkyl ether such as MTBE, which is colorless and transparent and has high product value.
The object of the present invention is to provide a method that can be manufactured at reduced costs.
発明の構成
［問題点を解決づるための手段１
本発明の第三級アルキルエーテルの製造方法は、第三級
炭素原子上に二重結合を４１する炭素原子数３〜５の第
三級オレフィンを含む炭化水素と炭素原子数１〜３の低
級アルコールとを、強酸型カチオン交換樹脂を充填した
反応器へ供給して反応させ、得られる反応混合物を蒸留
塔へ送って蒸留分離することからなる第三級アルキルエ
ーテルを製造する方法において、第１図に示ずように、
前記反応器１および（または）蒸留塔２の後流に活性炭
、活性白土等の吸着剤を充填した吸着塔３Ａ３３よび（
または＞３Ｂを設置して、反応混合物または第三級アル
キルエーテルの全部または一部を通過させることを特徴
とする。Structure of the Invention [Means for Solving the Problems 1] The method for producing a tertiary alkyl ether of the present invention is directed to the production of a tertiary olefin having 3 to 5 carbon atoms and having 41 double bonds on a tertiary carbon atom. A hydrocarbon containing 1 to 3 carbon atoms and a lower alcohol having 1 to 3 carbon atoms are supplied to a reactor filled with a strong acid type cation exchange resin to react, and the resulting reaction mixture is sent to a distillation column for distillation separation. In the method for producing tertiary alkyl ether, as shown in Figure 1,
Adsorption tower 3A33 and (
or >3B to allow all or part of the reaction mixture or tertiary alkyl ether to pass through.
（作 用１
反応器１から出た反応混合物または蒸留塔２の塔底から
央き出された第三級アルキルエーテルは、その後流に設
置した吸着塔３Ａまたは３Ｂを通過して、そこに充填さ
れた吸着剤と接触することによって、着色原因物質を含
む不純物が吸着除去される。 その結果、無色透明でか
つ純度の高いエーテル製品が得られるわけである。(Function 1 The reaction mixture discharged from the reactor 1 or the tertiary alkyl ether discharged from the bottom of the distillation column 2 passes through the adsorption column 3A or 3B installed at its downstream side and is filled therein. By contacting the adsorbent, impurities including color-causing substances are adsorbed and removed.As a result, a colorless, transparent and highly pure ether product is obtained.
吸着塔３Ａを反応器１の後流に設置した場合には、蒸留
塔２に送られる反応混合物中の不純物が減少するか１う
、塔頂からの炭化水素留出液中の不純物含イー■吊も低
下する。If the adsorption column 3A is installed downstream of the reactor 1, the impurities in the reaction mixture sent to the distillation column 2 will be reduced or the impurity-containing ions in the hydrocarbon distillate from the top of the column will be reduced. The suspension also decreases.
吸着塔は固定床式で十分である。 その設置は、既存の
装置にバイパスを設け、シリーズまたはパラレルに簡単
に取１→けることができ、少ない設備費で湾む。A fixed bed type adsorption tower is sufficient. Its installation can be easily installed in series or parallel by providing a bypass to existing equipment, resulting in low equipment costs.
［実施態様］
本発明の第三級アルキルエーテルの製造方法にａ３いて
、強酸性カチオン交換樹脂を充填した反応器は、通常は
固定床式であって１〜１０塁備えられて４５す、さらに
未反応の第三ｔｉ＆オレフィンを完全に転化させるため
に第二段の固定床反応器を設置する場合がある。[Embodiment] In the method for producing a tertiary alkyl ether of the present invention, the reactor filled with the strongly acidic cation exchange resin is usually a fixed bed type and is equipped with 1 to 10 bases, and further A second stage fixed bed reactor may be installed to completely convert unreacted tertiary ti&olefins.
第三級オレフィンの転化率を高くするうえで好ましい固
定床反応器およびその反応条件は、つぎのどおりである
。 なお、反応圧力は反応液を液相に保持するために必
要な圧力（Ｋｇ／ＣＭ−Ｇ）である。Preferred fixed bed reactors and reaction conditions for increasing the conversion rate of tertiary olefins are as follows. Note that the reaction pressure is the pressure (Kg/CM-G) required to maintain the reaction solution in a liquid phase.
強酸性カチオン交換樹脂 ；０．１〜５ｍ径アルコアル
コール／第三フィン
（供給モル比）： １へ−１０
反応温度二 〇へ−１２５”Ｃ
液空間速度： ０．０１−３０／ｈｒ反応圧カニ
１〜３０ＫＦＩ／ｃｎｉ ・Ｇまた、製品第
三級アルキル１−デルおよび炭化水素留出分の純度を一
定品位に保つために必要な、蒸留塔にＪ３ける操作条件
はつざのと（１３ゆである。Strongly acidic cation exchange resin; 0.1-5m diameter alcohol alcohol/third fin (supplied molar ratio): 1 to 10 Reaction temperature 20 to 125"C Liquid hourly space velocity: 0.01-30/hr Reaction pressure Crab 1 to 30KFI/cni ・G In addition, the operating conditions in J3 of the distillation column necessary to maintain the purity of the product tertiary alkyl 1-del and hydrocarbon distillate at a constant level are as follows (13 It's boiled.
操作圧力＝ ２〜１０に！７／Ｃｌｌ１−Ｇ温
度： ２０〜２００℃
これらの反応条件および操作条件は、反応に使用する原
料、目的生成物および要求される製品のＩＴ！度などに
応じて、適宜変更することができる。Operation pressure = 2 to 10! 7/Cll1-G temperature
Temperature: 20-200°C These reaction and operating conditions are based on the IT conditions of the raw materials used in the reaction, the desired product and the required product. It can be changed as appropriate depending on the degree.
本発明で使用する吸着剤としては、活性炭、活性白土、
活性アルミナ、ケイソウ土、ゼオライト等が挙げられる
。 通過させる液との接触および吸着効率がよく、液空
間速度を所定の範囲に保つうえで、平均粒子径０．０１
〜１０＃が要求される。 これらの吸着剤のうち、性能
がよく、入手が容易であることから、とくに活性炭およ
び活性白土が好ましい。 高い脱色効果を示す吸着剤の
物性は、つざのと４３ゆであることがわかった。Adsorbents used in the present invention include activated carbon, activated clay,
Examples include activated alumina, diatomaceous earth, and zeolite. In order to have good contact and adsorption efficiency with the liquid to be passed through and to maintain the liquid hourly space velocity within a specified range, an average particle size of 0.01
~10# is required. Among these adsorbents, activated carbon and activated clay are particularly preferred because they have good performance and are easily available. It was found that the physical properties of the adsorbent exhibiting a high decolorizing effect are Tsuzanoto 43YU.
活性炭活性白土
真比重＜’Ｊ／ｃｍ３） １．８〜２．３ ２．０
〜２．８かさ比重（’；Ｊ／ｃｍ３） ０．３〜０．
７ ０．２〜０．７空間率 ０．３〜０．８０．３〜
Ｏ，８細孔容積（ｃｍ３ 、”ｙ） ０．４〜Ｌ５
０．４〜１．０比表面積（洸／ｇ＞ ４００〜１．
８００ ５０〜４００以下、イソブチレンとメタノール
からＭＴＢＥを製造した場合を例にとって実施データを
示し、本発明の詳細な説明する。Activated carbon activated clay true specific gravity <'J/cm3) 1.8-2.3 2.0
~2.8 Bulk specific gravity ('; J/cm3) 0.3~0.
7 0.2~0.7 Space ratio 0.3~0.80.3~
O,8 Pore volume (cm3,"y) 0.4~L5
0.4-1.0 specific surface area (Ko/g>400-1.
800 50 to 400 Below, the present invention will be described in detail by showing practical data by taking as an example the case where MTBE was produced from isobutylene and methanol.
［実施例１］
図面に示ず措成の装置を用い、原料Ｃ４炭化水素として
、
イソブチレン ： ８重量％
ブテン−１： ３５
その他のＣ： ５７
の組成のものを使い、下記の操作条件でメタノールによ
るエーテル化反応を行なった。[Example 1] Using a device not shown in the drawings (not shown in the drawings), using a raw C4 hydrocarbon having a composition of isobutylene: 8% by weight butene-1: 35 and other C: 57, methanol was added under the following operating conditions. The etherification reaction was carried out by
（エーテル化反応条件）
固定床反応器数 ・・・・・・・・・・・
・１塁メタノール／イソブチレン供給モル比・・・２反
応器度 ・・・・・・・・・・・・・・・・・・・・・
６０″Ｃ反応圧力 ・・・・・・・・・・・・８に３／
ｃｒＡ・Ｃ液空間速度 ・・・・・・・・・・
・・・・・・・・・・・４／ｈ「（蒸 留 条 件）
操作圧力 ・・・・・・・・・・・・５Ｋｇ／ＣＩＪｌ
−Ｇ操 作 温 度： トップ ・・・・・・・・・５
２゛Ｃ回収部中段・・・・・・１２３°Ｃ
ボトム ・・・・・・１２５°Ｃ
Ｍ留塔理論段数 ・・・・・・・・・・・・・・・
・・・・・・３５段固定床吸着塔を通過させる処理をし
た結果は、それぞれつぎのとＪ３りである。(Etherification reaction conditions) Number of fixed bed reactors ・・・・・・・・・・・・
・1st base methanol/isobutylene supply molar ratio...2 reactor degree ・・・・・・・・・・・・・・・・・・・・・
60″C reaction pressure ・・・・・・・・・・・・8 to 3/
crA・C liquid space velocity ・・・・・・・・・・・・
・・・・・・・・・・・・4/h (distillation conditions) Operating pressure ・・・・・・・・・5Kg/CIJl
-G operation Temperature: Top ・・・・・・・・・5
2゛C recovery section middle stage...123°C Bottom...125°C M distillation column theoretical plate number......
...The results of passing through a 35-stage fixed bed adsorption tower are as follows.
ａ） 活性炭の固定床吸着塔をエーテル化反応器の後流
に設置した場合：
（イ）固定床吸着塔の操作条件：
液空間速度゛ ・・・・・・・・・１２／ｈｒ
操作温度 ・・・・・・・・・４０℃
操作圧力 ・・・・・・・・・８にぴ／ｃｔｒｔ・Ｇ（
ロ）活性炭の性状：
平均粒子径 ・・・・・・・・・１．０Ｍ真比重
・・・・・・・・・２．０ （’Ｊ／ｃｍ３）カサ
比重 ＝０．４５ （ＡＪ／ｃｍ３）空 間
率 ・・・・・・０．３８細孔容積 ・・・・・・
０．９５ｃｍ３／ｇ比表面積 ・・・・・・１１００尻
／Ｊ蒸留塔のＩＩｊ出液どして１ｑられた製品ＭＴＢＥ
の品質は下記のとおりで、製品規格」二の問題は全くな
かった。 なお、吸着塔入口液（反応生成物）の外観は
着色していた（ＡＰＨΔ１５０）。a) When an activated carbon fixed bed adsorption tower is installed downstream of the etherification reactor: (a) Operating conditions of the fixed bed adsorption tower: Liquid hourly space velocity ゛ ・・・・・・・・・12/hr
Operating temperature: 40℃ Operating pressure: 8 Nippi/ctrt・G (
b) Properties of activated carbon: Average particle diameter: 1.0M True specific gravity: 2.0 ('J/cm3) Bulk specific gravity: 0.45 (AJ/ cm3) space
Rate...0.38 Pore volume...
0.95cm3/g Specific surface area...1100 butts/J 1q product MTBE from IIj effluent of distillation column
The quality is as shown below, and there were no problems with the product standards. The appearance of the adsorption tower inlet liquid (reaction product) was colored (APHΔ150).
ＭＴＢＥ純度 ・・・・・・９９．９重量％以上メタノ
ール濃度・・・・・・１００重Φｐｐｍ以下外 観（Ａ
ＰＨＡ５以下）・・・・・・無色透明ｂ） 活性炭の固
定床吸着塔を蒸留塔の塔底の後流に設置した場合：
（イ）固定床吸着塔の操作条件：
液空間速度 ・・・・・・２０／ｈｒ操作温度・・
・・・・３５°Ｃ
操作圧カー ７ 、５Ｋｇ／ｃｔＡ−Ｇ（［コ）活性炭
の性状：
上記と同じ
この場合も、蒸留塔の缶出液（吸着塔後流）１夕）とし
て得られた製品ＭＴＢＥの晶質はε１）の場合と同じで
、品質に問題は全くなかった。 な、４３、吸着塔入口
液の外１１！は着色していた（ Ａ Ｐ Ｉ−１Ａ ２
５０＞。。MTBE purity: 99.9% by weight or more Methanol concentration: 100 ppm or less Appearance (A
(PHA 5 or less)...Colorless and transparentb) When an activated carbon fixed bed adsorption tower is installed downstream of the bottom of the distillation tower: (a) Operating conditions for the fixed bed adsorption tower: Liquid hourly space velocity... ...20/hr operating temperature...
...35°C Operating pressure car 7, 5Kg/ctA-G ([Co) Properties of activated carbon: Same as above In this case, it is obtained as the bottoms of the distillation column (after the adsorption column). The crystallinity of the product MTBE was the same as that of ε1), and there was no problem with the quality. What, 43, 11 outside the adsorption tower inlet liquid! was colored (AP I-1A 2
50>. .
［実施例２］
実施例１の条イ！［に従って］゛ニーデル化反応および
蒸留を行ない、蒸留塔の塔底の後流【こ活性白土の固定
床吸着塔を設置して、通過さｌだ。 その処理条件は、
つぎのとおりである。[Example 2] The article of Example 1! [According to] Niederization reaction and distillation are carried out, and a fixed bed adsorption tower of activated clay is installed at the downstream of the bottom of the distillation column. The processing conditions are
It is as follows.
（イ）固定床吸着塔の操作条イ′１：
液空間速度 ・・・・・・・・・２０／ｈｒ操作
温度 ・・・・・・・・・４０℃
操作圧力 ・・・・・・・・−７Ｋｇ／ｃｔｔｔ・Ｇ（
ロ）活性白土の性状：
平均粒子径 ・・・・・・・・・０１８ｔｒｖｎ
真 比 重 ・・・・・・・・・２゜２Ｃ
ｇ／ｃｍ３ ）カサ比重 ・・・・・・・・・０．３
＜’Ｊ／ｃｍ” ）空 間 率 ・・・・
・・・・・０．３５細孔容積 ・・・・・・・・・０．
６０ｃｍ３／９比表面積 ・・・・・・・・・２５０ｄ
／’Ｊその結果、蒸留塔の缶出液（吸着塔後流液）とし
てｊＨられた製品ＭＴＢＥの品質は下記のとおりで、品
質の問題はなかった。 なお、吸着塔入口液の外観は着
色していた（ＡＰＩ−ＩＡ２５０）。(a) Operation of fixed bed adsorption tower A'1: Liquid hourly space velocity: 20/hrOperating temperature: 40°C Operating pressure: 40°C ...-7Kg/cttt・G(
b) Properties of activated clay: Average particle size...018trvn
True specific gravity 2゜2C
g/cm3) Bulk specific gravity ・・・・・・・・・0.3
＜'J/cm'') Space ratio...
・・・・・・0.35 Pore volume ・・・・・・・・・0.
60cm3/9 Specific surface area ・・・・・・・・・250d
/'JAs a result, the quality of the product MTBE, which was collected as the distillation column bottoms (adsorption column downstream liquid), was as follows, and there were no quality problems. The appearance of the adsorption tower inlet liquid was colored (API-IA250).
ＭＴＢＥ純１宴 ・・・・・・９９．９重量％以上メタ
ノール濃度・・・・・・１００重吊ｐｐｆｆＩ以下外
ｖ；１．（ＡＰＨΔ５）・・・・・・無色透明［比較例
］
実施例］において、反応器および蒸留塔のいずれの後流
にも本発明に従う固定床吸着塔を設置しないときの、製
品ＭＴＢＥの品質は下記のとおりであった。MTBE pure 1 party...99.9% by weight or more Methanol concentration...100 heavy lifting ppffI or less
v;1. (APHΔ5)...Colorless and transparent [Comparative Example] In Example], the quality of the product MTBE is It was as follows.
ＭＴＢＥ純度 ・・・・・・９９．９重量％以上メタノ
ール濃度・・・・・・１００単ｆｆｉｐｐｍ以下外 観
（八Ｐ ｌ−Ｉ Ａ ２５０ ＞・・・・・・着色あり
ＭＴＢＥの純度およびメタノール含イｊ瀧度は実施例１
〜２の結果と変るところがないが、外観は着色しており
、品質規格を満足（〕ないため、再処理を要する。 着
色物を分析した結果、ブテン類の二〜三行１体およびエ
ーテル類の重合物が主であった。MTBE purity: 99.9% by weight or more Methanol concentration: 100 ppm or less Appearance (8 Pl-I A 250 > Colored MTBE purity and methanol The degree of water content is Example 1
The results are the same as those in ~2, but the appearance is colored and does not meet the quality standards, so reprocessing is required.As a result of analyzing the colored material, it was found that it was found to be 2-3 groups of butenes and 1 group of ethers. The main polymer was .
発明の効果
本発明の製造方法により、ブ］コック運転による停止後
においても、無色透明で高品位の第三級アルキルエーテ
ルを再蒸留によらないで得られるようになった。 代表
的な適用例であるＭＴＢＥの製造では、無色透明で高純
度のＭ Ｔ Ｂ Ｅとイソブチレンを含まないＣ４炭化
水素留分が得られ、製品ＭＴＢＥは、ガソリンのオクタ
ン価向上剤、洗浄溶剤、種々の反応溶剤、およびカフェ
インやイーストの抽出用など、広い用途がある。 また
、ＭＴＢＥを分解して、高純度イソブチレンを製造する
ことも可能となる。Effects of the Invention According to the production method of the present invention, a colorless and transparent high-grade tertiary alkyl ether can be obtained without redistillation even after the operation is stopped due to Bucock operation. In the production of MTBE, which is a typical application example, a colorless and transparent, highly pure MTBE and a C4 hydrocarbon fraction that does not contain isobutylene are obtained. It has a wide range of uses, including as a reaction solvent and for the extraction of caffeine and yeast. It also becomes possible to produce high purity isobutylene by decomposing MTBE.
本発明の別の大きな効果どして、吸着塔で反応混合物ま
たは缶出液の中の不純物が吸着除去されるから、未反応
原料を反応系に循環して転化率を高める場合にも、これ
が反応器に戻ることがなく、強酸性カブＡン交換樹脂の
活性の低下が防止され、スを命を−長く使用することが
できる。Another major effect of the present invention is that impurities in the reaction mixture or bottoms are adsorbed and removed in the adsorption tower, which is also useful when circulating unreacted raw materials into the reaction system to increase the conversion rate. There is no return to the reactor, the activity of the strongly acidic Kab A exchange resin is prevented from decreasing, and the life of the resin can be used for a long time.
図面は、本発明の製造方法を示すフローヂｉ’ −１〜
である。
１・・・固定床反応器
２・・・蒸留塔The drawings are flowcharts i'-1 to 1 showing the manufacturing method of the present invention.
It is. 1... Fixed bed reactor 2... Distillation column
Claims (7)
３〜５の第三級オレフィンを含む炭化水素と炭素原子数
１〜３の低級アルコールとを、強酸性カチオン交換樹脂
を充填した反応器へ供給して反応させ、得られる反応混
合物を蒸留塔へ送って蒸留分離することからなる第三級
アルキルエーテルを製造する方法において、前記反応器
および（または）蒸留塔の後流に活性炭、活性白土等の
吸着剤を充填した吸着塔を設置して、反応混合物または
第三級アルキルエーテルの全部または一部を通過させる
ことを特徴とする製造方法。(1) A strongly acidic cation exchange resin is filled with a hydrocarbon containing a tertiary olefin having 3 to 5 carbon atoms and a lower alcohol having 1 to 3 carbon atoms and having a double bond on a tertiary carbon atom. A method for producing a tertiary alkyl ether, which comprises supplying the reactor to a reactor for reaction, and sending the resulting reaction mixture to a distillation column for distillation separation. A production method characterized by installing an adsorption tower filled with an adsorbent such as activated carbon or activated clay, and allowing all or part of the reaction mixture or tertiary alkyl ether to pass therethrough.
ィンとしてイソブチレンを０．１〜８０重量％含むＣ＿
４炭化水素留分を使用し、第三級アルキルエーテルとし
てメチル−ｔｅｒｔ−ブチルエーテルを製造する特許請
求の範囲第１項に記載の製造方法。(2) C_ containing methanol as a lower alcohol and 0.1 to 80% by weight of isobutylene as a tertiary olefin
The method according to claim 1, wherein methyl tert-butyl ether is produced as a tertiary alkyl ether using four hydrocarbon fractions.
粒径が０．１〜５ｍｍであり、アルコール／オレフィン
の供給モル比が１〜１０、反応温度が０〜１２５℃、液
空間速度が０．０１〜３０／ｈｒで、かつ反応圧力を系
を液相に保持するのに必要な１〜３０ｋｇ／ｃｍ＾２・
Ｇとした反応条件下で、低級アルコールと第三級オレフ
ィンとを反応させる特許請求の範囲第１項に記載の製造
方法。(3) The average particle size of the strongly acidic cation exchange resin filled in the reactor is 0.1 to 5 mm, the alcohol/olefin molar ratio is 1 to 10, the reaction temperature is 0 to 125°C, and the liquid hourly space velocity is 0.01 to 30/hr, and the reaction pressure is 1 to 30 kg/cm^2 required to maintain the system in the liquid phase.
The manufacturing method according to claim 1, wherein a lower alcohol and a tertiary olefin are reacted under the reaction conditions specified in G.
平均粒子径が０．０１〜１０ｍｍであり、液空間速度が
１〜３００／ｈｒ、温度が０〜１２０℃で、かつ反応圧
力を系を液相に保持するのに必要な１〜３０ｋｇ／ｃｍ
＾２・Ｇとした条件下で、反応生成物または第三級アル
キルエーテルを吸着塔に通過させる特許請求の範囲第１
項に記載の方法。(4) The average particle diameter of the adsorbent such as activated carbon or activated clay filled in the adsorption tower is 0.01 to 10 mm, the liquid hourly space velocity is 1 to 300/hr, the temperature is 0 to 120°C, and the reaction pressure is 1 to 30 kg/cm required to maintain the system in the liquid phase.
Claim 1 in which the reaction product or tertiary alkyl ether is passed through an adsorption tower under the conditions of ^2・G.
The method described in section.
・Ｇ、操作温度２０〜２００℃の条件下に蒸留し、未反
応炭化水素および（または）未反応炭化水素と低級アル
コールとの共沸混合物を留出液として回収し、第三級ア
ルキルエーテルは缶出液として回収する特許請求の範囲
第１項に記載の製造方法。(5) The reaction product is subjected to an operating pressure of 2 to 10 kg/cm^2
・G, distillation is carried out under the operating temperature of 20 to 200°C to recover unreacted hydrocarbons and/or an azeotropic mixture of unreacted hydrocarbons and lower alcohols as a distillate, and tertiary alkyl ethers are The manufacturing method according to claim 1, wherein the bottom liquid is recovered.
〜２．３、カサ比重が０．３〜０．７、空間率が０．３
〜０．８、細孔容積が０．４〜１．５ｃｍ＾３／ｇで、
かつ比表面積が４００〜１，８００ｍ＾２／ｇである活
性炭を使用する特許請求の範囲第１項に記載の製造方法
。(6) The true specific gravity of the adsorbent packed in the adsorption tower is 1.8.
~2.3, bulk specific gravity 0.3~0.7, porosity 0.3
~0.8, pore volume is 0.4-1.5 cm^3/g,
The manufacturing method according to claim 1, which uses activated carbon having a specific surface area of 400 to 1,800 m^2/g.
〜２．８、カサ比重が０．２〜０．７、空間率が０．３
〜０．８、細孔容積が０．４〜１．０ｃｍ＾３／ｇで、
かつ比表面積が５０〜４００ｍ＾２／ｇである活性白土
を使用する特許請求の範囲第１項に記載の製造方法。(7) The true specific gravity of the adsorbent packed in the adsorption tower is 2.0.
~2.8, bulk specific gravity 0.2~0.7, porosity 0.3
~0.8, pore volume is 0.4-1.0 cm^3/g,
The manufacturing method according to claim 1, which uses activated clay having a specific surface area of 50 to 400 m^2/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61079856A JPH0699351B2 (en) | 1986-04-07 | 1986-04-07 | Method for producing tertiary alkyl ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61079856A JPH0699351B2 (en) | 1986-04-07 | 1986-04-07 | Method for producing tertiary alkyl ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62238227A true JPS62238227A (en) | 1987-10-19 |
| JPH0699351B2 JPH0699351B2 (en) | 1994-12-07 |
Family
ID=13701837
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61079856A Expired - Lifetime JPH0699351B2 (en) | 1986-04-07 | 1986-04-07 | Method for producing tertiary alkyl ether |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0699351B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006507343A (en) * | 2002-11-21 | 2006-03-02 | アルコ ケミカル テクノロジィ， エル．ピー． | Purification of methyl-t-butyl ether |
| CN105085198A (en) * | 2014-05-16 | 2015-11-25 | 上海星可高纯溶剂有限公司 | Purification method of chromatographic grade methyl tert-butyl ether |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57212127A (en) * | 1981-06-19 | 1982-12-27 | Erdoelchemie Gmbh | Manufacture of pure alkyl tertiary-alkyl ethers and hydrocarbon raffinates |
-
1986
- 1986-04-07 JP JP61079856A patent/JPH0699351B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57212127A (en) * | 1981-06-19 | 1982-12-27 | Erdoelchemie Gmbh | Manufacture of pure alkyl tertiary-alkyl ethers and hydrocarbon raffinates |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006507343A (en) * | 2002-11-21 | 2006-03-02 | アルコ ケミカル テクノロジィ， エル．ピー． | Purification of methyl-t-butyl ether |
| CN105085198A (en) * | 2014-05-16 | 2015-11-25 | 上海星可高纯溶剂有限公司 | Purification method of chromatographic grade methyl tert-butyl ether |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0699351B2 (en) | 1994-12-07 |
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