JPH026414A - Preparation of isobutylene - Google Patents
Preparation of isobutyleneInfo
- Publication number
- JPH026414A JPH026414A JP63157830A JP15783088A JPH026414A JP H026414 A JPH026414 A JP H026414A JP 63157830 A JP63157830 A JP 63157830A JP 15783088 A JP15783088 A JP 15783088A JP H026414 A JPH026414 A JP H026414A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- aluminum compound
- temperature
- silica
- reaction
- 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.)
- Pending
Links
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 46
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- -1 aluminum compound Chemical class 0.000 claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 22
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 19
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- 239000007789 gas Substances 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract description 6
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 abstract description 5
- 238000000354 decomposition reaction Methods 0.000 abstract description 5
- 239000012071 phase Substances 0.000 abstract description 5
- 238000001354 calcination Methods 0.000 abstract description 3
- QLJCFNUYUJEXET-UHFFFAOYSA-K aluminum;trinitrite Chemical compound [Al+3].[O-]N=O.[O-]N=O.[O-]N=O QLJCFNUYUJEXET-UHFFFAOYSA-K 0.000 abstract 1
- 239000007792 gaseous phase Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 18
- 238000010304 firing Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000002699 waste material 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
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分解〉
本発明はｔ−ブチルアルコールの脱水反応によりイソブ
チレンを製造する方法に関するものである。Detailed Description of the Invention <Industrial Decomposition> The present invention relates to a method for producing isobutylene by a dehydration reaction of t-butyl alcohol.
イソブチレンはブチルゴム、ポリブテン等の重合体の原
料として用いられる他−Ｂ Ｈ’し子−ブチルカテコー
ル等の工業薬品の原料としても使用されている。また最
近では１酸法ＭＭＡ製造の原料として注目されている。Isobutylene is used as a raw material for polymers such as butyl rubber and polybutene, and is also used as a raw material for industrial chemicals such as -B H'shishiko-butylcatechol. Recently, it has also attracted attention as a raw material for the production of MMA using the monoacid method.
〈従来の技術〉
ｔ−ブチルアルコールが酸触媒存在下脱水反応によりイ
ソブチレンを生成することはよく知られている。<Prior Art> It is well known that t-butyl alcohol produces isobutylene through a dehydration reaction in the presence of an acid catalyst.
液相下でもｔ−ブチルアルコールを脱水する方法として
は硫酸等の強酸を用いて均一系で行なうのが一般的であ
るが、高価な耐食材料を必要とするとか廃酸の処理が必
要である等の問題がある。またスルホン酸基を含有する
強酸性イオン交換樹脂を触媒として不均一系液相下で該
脱水反応を行なう方法が、特開昭５４−１３５７１０号
公報、特開昭５４−１３８５０６号公報等に開示されて
いる。しかしながら一般に液相下の反応ではｔ−ブチル
アルコールとイソブチレン、水が平衡関係にあるため、
高転化率下では水の組成比率が上がって反応速度が低下
し、むしろ副反応であるイソブチレンの多量化が進み収
率が低下する。そのため高い収率な得るためには転化率
を抑えて未反応分を回収し、該回収した未反応分を反応
系ヘリサイクルする必要があり、製造プロセスが複雑化
するという欠点を有している。A common method for dehydrating t-butyl alcohol even in a liquid phase is to use a strong acid such as sulfuric acid in a homogeneous system, but this requires expensive corrosion-resistant materials and requires treatment of waste acid. There are other problems. Furthermore, a method of carrying out the dehydration reaction in a heterogeneous liquid phase using a strongly acidic ion exchange resin containing a sulfonic acid group as a catalyst is disclosed in JP-A-54-135710, JP-A-54-138506, etc. has been done. However, in general, in liquid phase reactions, t-butyl alcohol, isobutylene, and water are in an equilibrium relationship, so
At a high conversion rate, the composition ratio of water increases and the reaction rate decreases, and rather the amount of isobutylene, which is a side reaction, increases and the yield decreases. Therefore, in order to obtain a high yield, it is necessary to suppress the conversion rate and recover the unreacted components, and then to recycle the recovered unreacted components to the reaction system, which has the disadvantage of complicating the production process. .
またｔ−ブチルアルコールを気相下、固体リン酸、活性
アルミナ、シリカ・アルミナ等の固体酸を触媒として脱
水することによりイソブチレンを製造する方法もよく知
られている（米国特許第４．０３６．９０５号公報、特
公昭５０−１２４０３号公報、特公昭４８−１０１２１
号公報等）。Furthermore, a method for producing isobutylene by dehydrating t-butyl alcohol in a gas phase using a solid acid such as solid phosphoric acid, activated alumina, or silica/alumina as a catalyst is also well known (US Pat. No. 4.036). Publication No. 905, Japanese Patent Publication No. 12403/1983, Publication No. 10121/1986
Publications, etc.).
常２５０°Ｃ以上の高い反応温度が必要であり、般に反
応温度が低温の場合は触媒活性が著しく小さく、また反
応温度が低いほどイソブチレンの選択率が低くなるとい
う欠点を有している。A high reaction temperature of 250° C. or higher is usually required, and in general, when the reaction temperature is low, the catalyst activity is extremely low, and the lower the reaction temperature, the lower the selectivity of isobutylene.
また、最近比較的低温でｔ−ブチルアルコールを気相下
で脱水し、イソブチレンを製造する方法が報告されてい
る（特開昭６１−２６号公報。Recently, a method for producing isobutylene by dehydrating t-butyl alcohol in a gas phase at a relatively low temperature has been reported (Japanese Patent Laid-Open Publication No. 1983-26).
特開昭６３−４１４３１号公報）。(Japanese Patent Application Laid-Open No. 63-41431).
しかしながらこれらの方法は触媒の調製が煩雑であると
か、反応系に非反応性ガスまたは水蒸気を混合させねば
ならない等の経済的に不利な条件を有している。However, these methods have economically disadvantageous conditions, such as the complicated preparation of the catalyst and the necessity of mixing non-reactive gas or steam into the reaction system.
〈発明が解決しようとする課題〉
そこで高活性な触媒により、より低い反応温度でイソブ
チレンを製造する経済的に有利な方法の開発が望まれて
いた。<Problems to be Solved by the Invention> Therefore, it has been desired to develop an economically advantageous method for producing isobutylene at a lower reaction temperature using a highly active catalyst.
く課題を解決するための手段〉
本発明者らはｔ−ブチルアルコールを触媒の存在下気相
で脱水反応を行なうことにより収率よ（イソブチレンを
製造する方法について検討をし、本発明に到達したもの
である。Means for Solving the Problems The present inventors have studied a method for producing isobutylene with a high yield by dehydrating t-butyl alcohol in the gas phase in the presence of a catalyst, and have arrived at the present invention. This is what I did.
すなわち本発明は。That is, the present invention.
ｔ−ブチルアルコールを原料として気相下脱水反応によ
りイソブチレンを製造する方法においテ、 １５００℃
以下で分解するアルミニウム化合物をシリカに担持させ
た後、該アルミニウム化合物が分解する温度以上の温度
で加熱焼成したものを触媒として用いることを特徴とす
るイソブチレンの製造法に関するものである。In the method for producing isobutylene by gas phase dehydration reaction using t-butyl alcohol as a raw material, the temperature is 1500°C.
The present invention relates to a method for producing isobutylene, which is characterized in that an aluminum compound to be decomposed below is supported on silica, and then heated and calcined at a temperature higher than the temperature at which the aluminum compound decomposes, and then used as a catalyst.
本発明方法において使用される原料はｔ−ブチルアルコ
ールである。ｔ−ブチルアルコールは純品を用いてもよ
いが、工業的にはｔ−ブチルアルコールの水溶液が有利
に人手でき、このものを原料として用いることも本発明
の望ましい方法である。The raw material used in the method of the invention is t-butyl alcohol. Although pure t-butyl alcohol may be used, industrially it is advantageous to use an aqueous solution of t-butyl alcohol manually, and it is also a desirable method of the present invention to use this solution as a raw material.
本発明方法において使用される触媒は１５００℃以下で
分解するアルミニウム化合物をシリカに担持させた後該
アルミニウム化合物が分解する温度以上の温度で加熱焼
成したものである。The catalyst used in the method of the present invention is prepared by supporting an aluminum compound that decomposes at 1500° C. or lower on silica, and then heating and calcining the aluminum compound at a temperature higher than the temperature at which the aluminum compound decomposes.
本発明で使用されるアルミニウム化合物の担持方法とし
ては、シリカ担体にアルミニウム化合物を含浸させる方
法（平衡吸着法、蒸発乾固法、スプレー法等）の他、シ
リカ粉末とアルミニウム化合物をよ（混合して成型する
方法、シリカとアルミニウム化合物をスラリー状態で混
練して成型する方法等各種の方法が採用可能であり、要
するにシリカとアルミニウム化合物が共存する状態で加
熱焼成することにより本発明の触媒が得られる。The aluminum compound used in the present invention can be supported by impregnating the silica carrier with the aluminum compound (equilibrium adsorption method, evaporation to dryness method, spray method, etc.), or by mixing silica powder and the aluminum compound. Various methods can be adopted, such as a method in which silica and an aluminum compound are kneaded in a slurry state and molded.In short, the catalyst of the present invention can be obtained by heating and firing in a state where silica and an aluminum compound coexist. It will be done.
本発明で用いられるアルミニウム化合物は、１５００℃
以下で分解するアルミニウム化合物である。具体例とし
ては、アルミニウムの硫酸塩、硝酸塩、ハロゲン化物、
有機酸塩、水酸化物等があげられるが、特に好ましいの
は硫酸塩及び硝酸塩である。The aluminum compound used in the present invention is heated to 1500°C.
It is an aluminum compound that will be decomposed below. Specific examples include aluminum sulfates, nitrates, halides,
Examples include organic acid salts and hydroxides, but sulfates and nitrates are particularly preferred.
焼成温度は通常、アルミニウム化合物が分解する温度か
ら１５００℃迄が運ばれる。ここでいうアルミニウム化
合物が分解する温度とは文献記載のいわゆる分解温度で
はなく、該化合物がシＪ力に担持された状態で実際に分
解を始める温度であり、アルミニウム化合物の純度にも
よるが、通常分解温度よりは低い、アルミニウム化合物
の分解は、例えば硫酸アルミニウム、硝酸アルミニウム
等の場合、イ才つ酸化物、窒素酸化物の発生により容易
に確認できる。この加熱焼成は通常空気雰囲気中で行な
われるが、窒素。The firing temperature is usually from the temperature at which the aluminum compound decomposes to 1500°C. The temperature at which the aluminum compound decomposes here is not the so-called decomposition temperature described in the literature, but the temperature at which the compound actually starts to decompose while supported by J-force, and although it depends on the purity of the aluminum compound, The decomposition of aluminum compounds, which is lower than the normal decomposition temperature, can be easily confirmed, for example, in the case of aluminum sulfate, aluminum nitrate, etc., by the generation of explosive oxides and nitrogen oxides. This heating and firing is usually carried out in an air atmosphere, but nitrogen is used.
二酸化炭素、アルゴンの不活性ガス、水蒸気又はこれら
の混合ガス雰囲気でもよい。An atmosphere of an inert gas such as carbon dioxide, argon, water vapor, or a mixture thereof may be used.
焼成時間は焼成温度にもよるが、通常０．１〜２４時間
、好ましくは０．５〜ｌＯ時間程度である。The firing time depends on the firing temperature, but is usually about 0.1 to 24 hours, preferably about 0.5 to 10 hours.
シリカに担持されるアルミニウム化合物の量に関しては
担体１００部（重量部、以下同じ）に対し０．１〜１０
０部、好ましくは１〜５０部が、さらに好ましくは５〜
３０部が採用される（結晶水を有するアルミニウム化合
物については無水物換算）。Regarding the amount of aluminum compound supported on silica, it is 0.1 to 10 parts by weight per 100 parts (by weight, same below)
0 parts, preferably 1 to 50 parts, more preferably 5 to 50 parts
30 parts are employed (in terms of anhydride for aluminum compounds with water of crystallization).
本発明の方法において使用されるシリカはゾル、ゲルを
問わない、又例えばオルソエチルジノケートから調製し
たような高純度のシリカが使用できることはもちろんで
あるが、通常市販されているシリカ（微量の不純物を含
んでいる）でも十分使用できる。The silica used in the method of the present invention does not matter whether it is a sol or a gel, and it is possible to use high-purity silica, such as one prepared from orthoethyl dinocate, as well as commercially available silica (a trace amount of silica). (contains impurities) can be used satisfactorily.
又、担体として使用するシリカの表面積に特に制限はな
いが１ｍ”７ｇ以上が好ましい。The surface area of the silica used as a carrier is not particularly limited, but it is preferably 7 g or more per meter.
本発明の方法で使用する触媒の性能は活性及び退択性の
点でシリカ又はアルミニウム化合物を単に熱分解したも
ののいずれよりも優れており、詳細は不明であるが、ア
ルミニウム化合物が熱分解する際にシリカが必須である
ことを示している。The performance of the catalyst used in the method of the present invention is superior to either silica or aluminum compounds simply thermally decomposed in terms of activity and regressivity, and although the details are unknown, when aluminum compounds thermally decompose, shows that silica is essential.
又、本発明の触媒を使用した場合、工業的に非常に重要
な触媒寿命についても満足な結果が得られる。Furthermore, when the catalyst of the present invention is used, satisfactory results can be obtained regarding catalyst life, which is of great importance industrially.
本発明方法を実施する場合、通常は固定床方式の気相反
応が採用されるが、他の方式例えば流動床方式でも可能
である。When carrying out the method of the present invention, a fixed bed gas phase reaction is usually employed, but other methods such as a fluidized bed method are also possible.
反応温度は通常１２０〜２５０℃、好ましくは１５０〜
２００℃が採用される。このような２５０℃以下の低温
での気相反応によりイソブチレンがほぼ定量的に得られ
ることは本発明の特徴の一つであり、工業的には非常に
有利な点である。The reaction temperature is usually 120-250°C, preferably 150-250°C.
200°C is adopted. One of the characteristics of the present invention is that isobutylene can be obtained almost quantitatively by such a gas phase reaction at a low temperature of 250° C. or lower, and is very advantageous from an industrial perspective.
反応圧力は特に制限されないが９通常常圧〜２０気圧、
好ましくは常圧〜ｌＯ気圧が選ばれる。The reaction pressure is not particularly limited, but is usually normal pressure to 20 atm,
Preferably, normal pressure to lO atmosphere is selected.
原料の供給速度は反応温度、圧力等によって変化するが
、通常ＬＨ５Ｖで１〜２０時間−１好ましくは３〜ｌＯ
時間−１が採用される。The feed rate of raw materials varies depending on the reaction temperature, pressure, etc., but is usually 1 to 20 hours at LH5V, preferably 3 to 1O.
Time-1 is adopted.
〈実施例〉
以下本発明につき実施例でさらに詳しく説明するが、本
発明はこれらの実施例のみに限定されるものではない。<Examples> The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples.
実施例１
市販シリカ担体（日揮化学株式会社商品名シＪ力Ｎ−６
０８）１００部に対し硫酸アルミニウムを無水物として
１０部となるように含浸法にて担持した。Example 1 Commercially available silica carrier (JGC Chemical Co., Ltd. trade name: J-Riki N-6)
08) Anhydrous aluminum sulfate was supported by an impregnation method in an amount of 10 parts per 100 parts.
このものを空気中１３０℃で３時間、３５０℃で３時間
、各々乾燥後、９００ ’Ｃで５時間窒素中で加熱焼成
した。焼成中にイオウ酸化物のガスの発生を認めた。This product was dried in air at 130° C. for 3 hours and at 350° C. for 3 hours, and then heated and calcined at 900° C. in nitrogen for 5 hours. The generation of sulfur oxide gas was observed during firing.
この触媒 １０ｍ １２を石英製反応管に充填し、常圧
にてｔ−ブチルアルコールを２０ｎｌ ／時間（ＬＨ５
Ｖ＝２．０時間−１）で供給した。この間触媒層の中心
温度は電気炉加熱により１８０℃に保たれた。A quartz reaction tube was filled with 10 m of this catalyst, and 20 nl/hour of t-butyl alcohol was added at normal pressure (LH5
V=2.0 h-1). During this time, the center temperature of the catalyst layer was maintained at 180° C. by heating in an electric furnace.
反応ガスをトラップして分析した結果、ｔ−ブチルアル
コールの転化率は９９．８％であった。As a result of trapping and analyzing the reaction gas, the conversion rate of t-butyl alcohol was 99.8%.
またジイソブチレンの副生は認められず、イソブチレン
は定量的に得られた。Further, no diisobutylene by-product was observed, and isobutylene was quantitatively obtained.
実施例２〜５
第１表に示す条件の他は実施例１と同様にして触媒を：
Ｊ！４製し、実施例１と同じ条件でｔ−ブチルアルコー
ルの脱水反応を行なった。結果を第１表に示す、いずれ
もイソブチレンはｔ−ブチルアルコール転化率に対応し
て定量的に得られた。Examples 2 to 5 Catalysts were prepared in the same manner as in Example 1 except for the conditions shown in Table 1:
J! 4 was prepared, and the dehydration reaction of t-butyl alcohol was carried out under the same conditions as in Example 1. The results are shown in Table 1. In all cases, isobutylene was obtained quantitatively in accordance with the conversion rate of t-butyl alcohol.
実施例６〜８
実施例１で調製した触媒１０ｍ２を用いて、第２表に記
載した反応条件でｔ−ブチルアルコールの脱水反応を行
なった。結果を第２表に示す。Examples 6 to 8 Using 10 m2 of the catalyst prepared in Example 1, a dehydration reaction of t-butyl alcohol was carried out under the reaction conditions listed in Table 2. The results are shown in Table 2.
比較例１
シリカ・アルミナ触媒（日揮化学株式会社製） ｌｏ
ｍｇ、を石英製反応管に充填し、ｔ−ブチルアルコール
の脱水反応を行なった。なお触媒が異なること以外は実
施例１と同じ条件で反応を行なった。Comparative Example 1 Silica-alumina catalyst (manufactured by JGC Chemical Co., Ltd.) lo
mg, was filled into a quartz reaction tube, and t-butyl alcohol was subjected to a dehydration reaction. The reaction was carried out under the same conditions as in Example 1 except that the catalyst was different.
反応ガスをトラップして分析した結果、１−ブチルアル
コールの転化率は９９．２％と高かったがジイソブチレ
ン等の副生物の生成が多く、イソブチレンの選択率は６
８．２％であった。As a result of trapping and analyzing the reaction gas, the conversion rate of 1-butyl alcohol was as high as 99.2%, but many by-products such as diisobutylene were produced, and the selectivity of isobutylene was 6.
It was 8.2%.
比較例２
硫酸アルミニウムを担体に担持せずにそのまま３５０℃
で３時間乾燥後、９００℃で５時間焼成した。Comparative Example 2 Aluminum sulfate was not supported on a carrier and heated to 350°C
After drying at 900° C. for 3 hours, it was fired at 900° C. for 5 hours.
このものを触媒として用い実施例１と同じ条件でｔ−ブ
チルアルコールの脱水反応を行なったところ、ｔ−ブチ
ルアルコールの転化率７２．９％イソブチレン選択率８
９．４％であった。When t-butyl alcohol was dehydrated using this product as a catalyst under the same conditions as in Example 1, the conversion rate of t-butyl alcohol was 72.9%, and the isobutylene selectivity was 8.
It was 9.4%.
〈発明の効果〉
以上の如（本発明によりｔ−ブチルアルコールからイソ
ブチレンが高純度でかつ高収率で得ることができるよう
になった。<Effects of the Invention> As described above, according to the present invention, isobutylene can be obtained from t-butyl alcohol with high purity and high yield.
Claims (1)
応によりイソブチレンを製造する方法において、１５０
０℃以下で分解するアルミニウム化合物をシリカに担持
させた後、該アルミニウム化合物が分解する温度以上の
温度で加熱焼成したものを触媒として用いることを特徴
とするイソブチレンの製造法。(1) In a method for producing isobutylene by gas phase dehydration reaction using t-butyl alcohol as a raw material, 150
A method for producing isobutylene, which comprises using as a catalyst an aluminum compound that decomposes at 0° C. or lower, supported on silica, and then heated and calcined at a temperature higher than the temperature at which the aluminum compound decomposes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63157830A JPH026414A (en) | 1988-06-24 | 1988-06-24 | Preparation of isobutylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63157830A JPH026414A (en) | 1988-06-24 | 1988-06-24 | Preparation of isobutylene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH026414A true JPH026414A (en) | 1990-01-10 |
Family
ID=15658258
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63157830A Pending JPH026414A (en) | 1988-06-24 | 1988-06-24 | Preparation of isobutylene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH026414A (en) |
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|---|---|---|---|---|
| WO2014196517A1 (en) * | 2013-06-07 | 2014-12-11 | 三井化学株式会社 | Production method for olefin, and dehydration catalyst employed in same |
| CN105712831A (en) * | 2014-12-03 | 2016-06-29 | 中国石油化工股份有限公司 | Method used for preparing isobutene from mixture of methyl tertiary butyl ether and tert butyl alcohol |
| CN105712829A (en) * | 2014-12-03 | 2016-06-29 | 中国石油化工股份有限公司 | Method used for preparing isobutylene from MTBE-TBA mixture |
| CN105712818A (en) * | 2014-12-03 | 2016-06-29 | 中国石油化工股份有限公司 | Method used for preparing isobutene from MTBE-TBA mixture |
| CN105712830A (en) * | 2014-12-03 | 2016-06-29 | 中国石油化工股份有限公司 | Preparation method of isobutene |
| TWI568493B (en) * | 2012-01-20 | 2017-02-01 | 三井化學股份有限公司 | Olefin production method |
-
1988
- 1988-06-24 JP JP63157830A patent/JPH026414A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI568493B (en) * | 2012-01-20 | 2017-02-01 | 三井化學股份有限公司 | Olefin production method |
| US9567266B2 (en) | 2012-01-20 | 2017-02-14 | Mitsui Chemicals, Inc. | Olefin production method |
| WO2014196517A1 (en) * | 2013-06-07 | 2014-12-11 | 三井化学株式会社 | Production method for olefin, and dehydration catalyst employed in same |
| JP6076477B2 (en) * | 2013-06-07 | 2017-02-08 | 三井化学株式会社 | Olefin production method and dehydration catalyst used therefor |
| US9682896B2 (en) | 2013-06-07 | 2017-06-20 | Mitsui Chemicals, Inc. | Production method for olefin, and dehydration catalyst employed in same |
| CN105712831A (en) * | 2014-12-03 | 2016-06-29 | 中国石油化工股份有限公司 | Method used for preparing isobutene from mixture of methyl tertiary butyl ether and tert butyl alcohol |
| CN105712829A (en) * | 2014-12-03 | 2016-06-29 | 中国石油化工股份有限公司 | Method used for preparing isobutylene from MTBE-TBA mixture |
| CN105712818A (en) * | 2014-12-03 | 2016-06-29 | 中国石油化工股份有限公司 | Method used for preparing isobutene from MTBE-TBA mixture |
| CN105712830A (en) * | 2014-12-03 | 2016-06-29 | 中国石油化工股份有限公司 | Preparation method of isobutene |
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