JP3020489B2 - Method for producing lower fatty acid ester - Google Patents
Method for producing lower fatty acid esterInfo
- Publication number
- JP3020489B2 JP3020489B2 JP11030705A JP3070599A JP3020489B2 JP 3020489 B2 JP3020489 B2 JP 3020489B2 JP 11030705 A JP11030705 A JP 11030705A JP 3070599 A JP3070599 A JP 3070599A JP 3020489 B2 JP3020489 B2 JP 3020489B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- acid
- fatty acid
- lower fatty
- 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.)
- Expired - Lifetime
Links
- 235000014113 dietary fatty acids Nutrition 0.000 title claims description 14
- 239000000194 fatty acid Substances 0.000 title claims description 14
- 229930195729 fatty acid Natural products 0.000 title claims description 14
- -1 fatty acid ester Chemical class 0.000 title claims description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000003054 catalyst Substances 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 12
- 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 11
- 238000010574 gas phase reaction Methods 0.000 claims description 8
- 150000001336 alkenes Chemical class 0.000 claims description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 6
- 150000004665 fatty acids Chemical class 0.000 claims description 5
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910001868 water Inorganic materials 0.000 description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 235000011054 acetic acid Nutrition 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 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
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- ZDHURYWHEBEGHO-UHFFFAOYSA-N potassiopotassium Chemical compound [K].[K] ZDHURYWHEBEGHO-UHFFFAOYSA-N 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 229940005605 valeric acid Drugs 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)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、低級脂肪酸と低級
オレフィンとを反応させ、効率よく低級脂肪酸エステル
を製造する方法に関する。The present invention relates to a method for producing a lower fatty acid ester efficiently by reacting a lower fatty acid with a lower olefin.
【０００２】[0002]
【従来の技術】従来、低級脂肪酸と低級オレフィンとを
反応させて低級脂肪酸エステルを製造する方法として
は、強酸性陽イオン交換樹脂を触媒として用いる方法、
リン酸等の鉱酸、リンタングステン酸等のヘテロポリ酸
を触媒として用いる方法（特公昭５３−６１３１号公
報）、芳香族ジスルホン酸および／またはそのエステル
を触媒として用いる方法（特開昭５７−１８３７４３号
公報）等が知られている。2. Description of the Related Art Conventionally, as a method of producing a lower fatty acid ester by reacting a lower fatty acid and a lower olefin, a method using a strongly acidic cation exchange resin as a catalyst,
A method using a mineral acid such as phosphoric acid or a heteropoly acid such as phosphotungstic acid as a catalyst (Japanese Patent Publication No. 53-6131), a method using an aromatic disulfonic acid and / or an ester thereof as a catalyst (Japanese Unexamined Patent Publication No. 57-183743). Is known.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、上記従
来の方法は、いずれも触媒１リットルによる１時間あた
りの目的生成物の生産量（以下、空時収率、ｇ／ｈｒ・
触媒リットルという）も少ないばかりでなく、触媒寿命
も短く、工業的に使用できる方法ではない。本発明者ら
は、空時収率が高く、触媒寿命の長い方法を得るべく鋭
意研究を行った結果、気相反応における触媒としてリン
タングステン酸のカリウム塩が有効なことを発見した。
本発明は上記の発見に基づいてなされたもので、空時収
率が高く、触媒寿命の長い、工業生産に適した低級脂肪
酸エステルの製造方法を提供することを目的とする。However, in each of the above-mentioned conventional methods, the production amount of the desired product per hour by one liter of catalyst (hereinafter referred to as space-time yield, g / hr ·
This is not a method that can be used industrially, as well as the catalyst life is short. The present inventors have conducted intensive studies to obtain a method having a high space-time yield and a long catalyst life, and as a result, have found that potassium phosphotungstic acid is effective as a catalyst in a gas phase reaction.
The present invention has been made based on the above findings, and has as its object to provide a method for producing a lower fatty acid ester having a high space-time yield, a long catalyst life, and suitable for industrial production.
【０００４】[0004]
【課題を解決するための手段】上記の目的を達成するた
め、本発明の低級脂肪酸エステルの製造方法において
は、気相反応においてリンタングステン酸のカリウム塩
を触媒として用いることを問題解決の手段とした。Means for Solving the Problems In order to achieve the above object, the method for producing a lower fatty acid ester of the present invention comprises using a potassium salt of phosphotungstic acid as a catalyst in a gas phase reaction as a means for solving the problem. did.
【０００５】[0005]
【発明の実施の形態】本発明の方法に用いられる低級脂
肪酸としては、炭素数４以下の飽和或は不飽和脂肪酸、
例えば、ぎ酸、酢酸、プロピオン酸、吉草酸、アクリル
酸、クロトン酸があげられ、低級オレフィンとしは、炭
素数４以下のオレフィン、例えばエチレン、プロピレ
ン、ブテン−１、ブテン−２があげられる。炭素数が５
以上のオレフィンを用いると、脂肪酸エステルの生成反
応が遅くなり、これを早くするために反応圧力、或いは
反応温度を高くすると、重合物等の副生物が増大するば
かりでなく、触媒寿命が著しく短くなる。BEST MODE FOR CARRYING OUT THE INVENTION The lower fatty acids used in the method of the present invention include saturated or unsaturated fatty acids having 4 or less carbon atoms,
For example, formic acid, acetic acid, propionic acid, valeric acid, acrylic acid and crotonic acid are mentioned, and as the lower olefin, olefins having 4 or less carbon atoms, for example, ethylene, propylene, butene-1 and butene-2 are mentioned. 5 carbon atoms
When the above olefin is used, the reaction for producing the fatty acid ester is slowed down. When the reaction pressure or the reaction temperature is increased to speed up the reaction, not only the by-products such as polymers increase, but also the catalyst life is significantly shortened. Become.
【０００６】本発明の方法における反応形式は、気相反
応とされる。気相反応においては低級脂肪酸に対して低
級オレフィンを大過剰とする必要がある。反応圧力は０
〜１０ｋｇ／ｃｍ2Ｇの範囲で、液相反応の場合の圧力
１０〜１５０ｋｇ／ｃｍ2Ｇより大幅に低い。反応温度
は、５０〜３００℃、特に１００〜２５０℃の範囲が好
ましい。反応温度が５０℃未満では、反応速度が遅くな
り、空時収率が著しく低下する。また、３００℃を越え
ると、副生物が増大するとともに触媒寿命が短くなる。
また、気相反応において水が存在するとアルコールが生
成するが、理由は定かではないが原料ガスに容積比で１
％程度の水蒸気を添加すると触媒寿命が長くなる。気相
反応においては、混合ガスを標準状態において、空間速
度（ＳＶ）１００〜５０００ｈ-1、特に３００〜２００
０ｈｒ-1で触媒に通すのが好ましい。[0006] The type of reaction in the method of the present invention is a gas phase reaction. In a gas phase reaction, it is necessary to make a large excess of a lower olefin relative to a lower fatty acid. Reaction pressure is 0
In the range of 10 to 10 kg / cm 2 G, the pressure is much lower than the pressure of 10 to 150 kg / cm 2 G in the liquid phase reaction. The reaction temperature is preferably in the range of 50 to 300C, particularly preferably 100 to 250C. If the reaction temperature is lower than 50 ° C., the reaction rate becomes slow, and the space-time yield remarkably decreases. On the other hand, when the temperature exceeds 300 ° C., by-products increase and the catalyst life is shortened.
Alcohol is generated in the presence of water in the gas phase reaction, although the reason is not clear.
%, The catalyst life is prolonged. In the gas phase reaction, the mixed gas is used under a standard condition at a space velocity (SV) of 100 to 5000 h -1 , particularly 300 to 200 h -1 .
It is preferred to pass through the catalyst at 0 hr -1 .
【０００７】本発明に用いられるリンタングステン酸の
カリウム塩は、表面積が大きく、酸強度が強く、かつ酸
量が多いもの程よく、それ自体でも、或いは担体に担持
させて用いてもよい。使用される担体は、一般に担体と
して用いられる多孔質、或いは多孔質に造粒できる物質
であればよく、例えば、シリカ、ケイ藻土、チタニア、
活性炭等があげられる。上記タングステン酸カリウム塩
触媒の調整は、例えば市販のリンタングステン酸を水に
溶解し、これにカリウムの硝酸塩、炭酸塩を粉末のま
ま、或は水溶液として添加混合する。次いで温浴によっ
て大部分の水分を蒸発除去し、得られた固形物を、空気
または窒素等の不活性ガス雰囲気下で、５０〜３５０
℃、好ましくは１００〜３００℃で加熱処理することに
よって得られる。温度が５０℃未満では、水分の除去が
不十分となり、３５０℃を越えると、触媒が劣化する。The potassium phosphotungstic acid salt used in the present invention preferably has a large surface area, a high acid strength, and a large amount of acid, and may be used by itself or supported on a carrier. The carrier used is generally a porous material used as a carrier, or any substance that can be granulated into a porous material, such as silica, diatomaceous earth, titania, and the like.
Activated carbon and the like. For the preparation of the potassium tungstate catalyst, for example, commercially available phosphotungstic acid is dissolved in water, and potassium nitrate and carbonate are added as powder or as an aqueous solution. Then, most of the water is removed by evaporation in a warm bath, and the obtained solid is dried under an inert gas atmosphere such as air or nitrogen in the range of 50-350.
C., preferably by heating at 100 to 300.degree. If the temperature is lower than 50 ° C., the removal of water becomes insufficient, and if it exceeds 350 ° C., the catalyst deteriorates.
【０００８】上記触媒は選択率が高くアクリル酸等の不
飽和カルボン酸においては、９０％以上を示し、酢酸な
どの飽和カルボン酸においては９５％以上を示す。The above catalyst has a high selectivity and shows 90% or more of unsaturated carboxylic acids such as acrylic acid and 95% or more of saturated carboxylic acids such as acetic acid.
【０００９】（実施例１）市販のリンタングステン酸
（和光純薬製）１５０ｇ（約０．０４３８モル）と純水
６０ｃｃとを３００ｃｃのフラスコに入れ、溶解した。
別に硝酸カリウム（ＫＮＯ3）１１．１ｇ（０．１１０
モル）を水に溶解し、これを滴下ロートを用いて、攪拌
しながら、上記リンタングステン酸水溶液中に滴下し
た。この際、滴下すると同時にリンタングステン酸カリ
ウム塩の白色微粒結晶が析出する。この白色微粒子が析
出したフラスコを温浴によってフラスコ中の水を蒸発さ
せた。水が除去された塊状物をシャーレ上に取出して乾
燥機に入れ、空気中、１５０℃で６時間乾燥した。この
乾燥物を粉砕し、篩を用いて径１〜２ｍｍのものを分取
し、３５ｃｃを反応管に充填して反応に供した。反応
は、温度１８０℃、反応圧力５ｋｇ／ｃｍ2Ｇに保持し
ながら、アクリル酸：エチレン：水蒸気を容積比１：１
８：１の割分に混合したガスを、標準状態で３５リット
ル／ｈｒの流速で流した。混合気体を流し始めてから４
ｈｒ後における流出液とガスをサンプリングし、ガスク
ロマトマトグラフィーで測定したところ、アクリル酸の
転化率は５８．７％、アクリル酸エチルのアクリル酸に
対する収率は５４．０％であった。また得られたアクリ
ル酸エチルの空時収率は１３０ｇ／ｈｒ・触媒リットル
であった。(Example 1) 150 g (about 0.0438 mol) of commercially available phosphotungstic acid (manufactured by Wako Pure Chemical Industries) and 60 cc of pure water were put into a 300 cc flask and dissolved.
Separately, 11.1 g (0.110 g) of potassium nitrate (KNO 3 )
Mol) was dissolved in water, and this was added dropwise to the above phosphotungstic acid aqueous solution with stirring using a dropping funnel. At this time, white fine crystals of potassium phosphotungstate are precipitated simultaneously with the dropwise addition. The water in the flask in which the white fine particles were deposited was evaporated by a warm bath. The lump from which water had been removed was taken out on a petri dish, placed in a dryer, and dried in air at 150 ° C. for 6 hours. The dried product was pulverized, fractionated in a size of 1 to 2 mm using a sieve, and filled with 35 cc into a reaction tube for a reaction. The reaction was carried out at a temperature of 180 ° C. and a reaction pressure of 5 kg / cm 2 G, while maintaining a volume ratio of acrylic acid: ethylene: steam of 1: 1.
The gas mixed in a ratio of 8: 1 was flowed at a flow rate of 35 L / hr under standard conditions. 4 after starting to flow the mixed gas
After sampling the effluent and gas after hr and measuring them by gas chromatography, the conversion of acrylic acid was 58.7% and the yield of ethyl acrylate with respect to acrylic acid was 54.0%. The space-time yield of the obtained ethyl acrylate was 130 g / hr · liter of catalyst.
【００１０】（比較例１）市販のリンタングステン酸
（和光純薬製）を１５０℃で６時間乾燥した後、錠剤に
成型し、これを粉砕して篩分けし、１〜２ｍｍの径のも
のを分取し、その３５ｃｃを触媒として使用した他は実
施例１と同じにした。Comparative Example 1 A commercially available phosphotungstic acid (manufactured by Wako Pure Chemical Industries) was dried at 150 ° C. for 6 hours, then formed into tablets, which were crushed and sieved to obtain tablets having a diameter of 1 to 2 mm. And the same procedure as in Example 1 was carried out except that 35 cc of the fraction was used as a catalyst.
【００１１】（実施例２）実施例１において触媒とした
リンタングステン酸のカリウム塩１０．７ｃｃを触媒と
し、反応温度１５０℃、反応圧力を常圧に保持しながら
酢酸：エチレン：水蒸気の容積比６：８：９２．２：１
の混合気体を、標準状態で１０．７リットル／ｈｒの流
速で流した。混合気体を流し始めてから４時間後、流出
液とガスをサンプリングしてガスクロマトグラフィによ
って分析したところ、酢酸の転化率は６５．０％、酢酸
に対する酢酸エチルの収率は６４．０％であった。この
結果より求めた酢酸エチルの空時収率は、１７２ｇ／ｈ
ｒ・触媒リットルであった。(Example 2) A volume ratio of acetic acid: ethylene: steam with 10.7 cc of potassium phosphotungstic acid as a catalyst in Example 1 and a reaction temperature of 150 ° C. and a reaction pressure of normal pressure was used. 6: 8: 92.2: 1
Was flowed at a flow rate of 10.7 liter / hr under standard conditions. Four hours after the start of flowing the mixed gas, the effluent and the gas were sampled and analyzed by gas chromatography. As a result, the conversion of acetic acid was 65.0%, and the yield of ethyl acetate based on acetic acid was 64.0%. . The space-time yield of ethyl acetate determined from this result was 172 g / h.
r · liter of catalyst.
【００１２】（実施例３）触媒としてリンタングステン
酸のカリウム塩を用い、エチレンの代わりにプロピレン
を用いた以外は実施例２と同じにした。Example 3 Example 2 was the same as Example 2 except that potassium potassium phosphotungstic acid was used as the catalyst and propylene was used instead of ethylene.
【００１３】（比較例２）比較例１と同じ触媒を用いた
以外は実施例２と同じにした。上記実施例および比較例
の結果を一括して第１表に示す。なお、実施例１等の結
果はすでに示されているが、比較のため再度記載してあ
る。上記実施例１〜３においては、９６時間運転を続け
たが、アクリル酸、或は酢酸に対する目的成分の収率、
空時収率は殆んど低下せず、比較例１および２において
は、２０時間で収率が２〜５％低下した。Comparative Example 2 The procedure of Example 2 was repeated except that the same catalyst as in Comparative Example 1 was used. Table 1 summarizes the results of the above Examples and Comparative Examples. Although the results of Example 1 and the like have already been shown, they are described again for comparison. In the above Examples 1 to 3, the operation was continued for 96 hours, but the yield of the target component with respect to acrylic acid or acetic acid,
The space-time yield hardly decreased, and in Comparative Examples 1 and 2, the yield decreased by 2 to 5% in 20 hours.
【００１４】[0014]
【表１】 [Table 1]
【００１５】[0015]
【発明の効果】以上説明したように、本発明の方法にお
いては、気相反応において、リンタングステン酸のカリ
ウム塩を触媒として用いるので、アクリル酸エステルや
酢酸エステル等の低級脂肪酸エステルを効率よく生産出
来る利点がある。As described above, in the method of the present invention, the potassium salt of phosphotungstic acid is used as a catalyst in the gas phase reaction, so that lower fatty acid esters such as acrylates and acetates can be efficiently produced. There are advantages that can be done.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 若林 正一郎 大分県大分市大字中の洲２ 昭和電工株 式会社 大分研究所内 (56)参考文献 特開 昭48−39425（ＪＰ，Ａ) 特許2947602（ＪＰ，Ｂ２) 特公 昭56−30334（ＪＰ，Ｂ２) 特公 昭53−6131（ＪＰ，Ｂ１) 特公 昭47−42808（ＪＰ，Ｂ１) (58)調査した分野(Int.Cl.7，ＤＢ名) C07C 69/14 C07C 67/04 C07C 69/54 ＣＡＰＬＵＳ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ) ＷＰＩＤＳ（ＳＴＮ)──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Shoichiro Wakabayashi 2 Oita, Oita City, Oita Prefecture Showa Denko Co., Ltd. Oita Research Laboratory (56) References JP, B2) JP-B-56-30334 (JP, B2) JP-B, 53-6131 (JP, B1) JP-B, 47-42808 (JP, B1) (58) Fields investigated (Int. Cl. 7 , DB name) C07C 69/14 C07C 67/04 C07C 69/54 CAPLUS (STN) REGISTRY (STN) WPIDS (STN)
Claims (2)
ンでエステル化する低級脂肪酸エステルの製造方法にお
いて、リンタングステン酸のカリウム塩を触媒として用
いて反応せしめることを特徴とする低級脂肪酸エステル
の製造方法。1. A method for producing a lower fatty acid ester in which a lower fatty acid is esterified with a lower olefin by a gas phase reaction, wherein the reaction is carried out by using a potassium salt of phosphotungstic acid as a catalyst. Method.
を特徴とする請求項１記載の低級脂肪酸エステルの製造
方法。2. The method for producing a lower fatty acid ester according to claim 1, wherein the catalyst is a catalyst supported on a carrier.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11030705A JP3020489B2 (en) | 1999-02-08 | 1999-02-08 | Method for producing lower fatty acid ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11030705A JP3020489B2 (en) | 1999-02-08 | 1999-02-08 | Method for producing lower fatty acid ester |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2258233A Division JP2947602B2 (en) | 1990-09-27 | 1990-09-27 | Method for producing lower fatty acid ester |
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| Publication Number | Publication Date |
|---|---|
| JPH11286468A JPH11286468A (en) | 1999-10-19 |
| JP3020489B2 true JP3020489B2 (en) | 2000-03-15 |
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