JPH0764781B2 - Method for producing allyl acetate - Google Patents
Method for producing allyl acetateInfo
- Publication number
- JPH0764781B2 JPH0764781B2 JP60082024A JP8202485A JPH0764781B2 JP H0764781 B2 JPH0764781 B2 JP H0764781B2 JP 60082024 A JP60082024 A JP 60082024A JP 8202485 A JP8202485 A JP 8202485A JP H0764781 B2 JPH0764781 B2 JP H0764781B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- palladium
- reaction
- volume
- allyl acetate
- 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
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 77
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 66
- 239000003054 catalyst Substances 0.000 claims description 56
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 47
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 229910052763 palladium Inorganic materials 0.000 claims description 38
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 27
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 27
- 239000007789 gas Substances 0.000 claims description 24
- 239000000377 silicon dioxide Substances 0.000 claims description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 20
- 239000001301 oxygen Substances 0.000 claims description 20
- 229910052760 oxygen Inorganic materials 0.000 claims description 20
- 239000011148 porous material Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 13
- -1 alkali metal acetate Chemical class 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 22
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 235000011056 potassium acetate Nutrition 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011734 sodium Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- 101150003085 Pdcl gene Proteins 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002940 palladium Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- TXECTBGVEUDNSL-UHFFFAOYSA-N 1-acetyloxyprop-2-enyl acetate Chemical compound CC(=O)OC(C=C)OC(C)=O TXECTBGVEUDNSL-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 235000002498 Azalea indica Nutrition 0.000 description 1
- 244000020190 Azalea indica Species 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 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
- 150000004646 arylidenes Chemical group 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052566 spinel group Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、プロピレン、酸素及び酢酸を気相で反応させ
ることによつて酢酸アリルを製造する方法に関する。TECHNICAL FIELD The present invention relates to a method for producing allyl acetate by reacting propylene, oxygen and acetic acid in a gas phase.
〔従来の技術〕 パラジウム触媒の存在下にプロピレン、酸素及び酢酸を
気相で反応させることによつて酢酸アリルを製造する方
法はすでに知られている（例えば、特公昭44−29046
号、同48−23408号、同50−28934号公報など参照）。こ
れらの特許公報には、アルミナ、シリカ、活性炭、スピ
ネル類、軽石又は酸化チタン等の担体に、パラジウムを
0.1〜10重量％、アルカリ金属またはアルカリ土類金属
の酢酸塩を１〜20重量％ならびに周期表第Ｖ−VIII族の
金属、金及び銅からなる群から選ばれる少なくとも一種
の金属を担持させた触媒の存在下にプロピレン、酸素及
び酢酸を気相で反応させることによつて酢酸アリルを製
造する方法が記載されている。[Prior Art] A method for producing allyl acetate by reacting propylene, oxygen and acetic acid in the gas phase in the presence of a palladium catalyst is already known (for example, JP-B-44-29046).
No. 48-23408, No. 50-28934, etc.). In these patent publications, palladium is added to a carrier such as alumina, silica, activated carbon, spinels, pumice or titanium oxide.
0.1 to 10% by weight, 1 to 20% by weight of an alkali metal or alkaline earth metal acetate salt, and at least one metal selected from the group consisting of metals of Group V-VIII of the periodic table, gold and copper are supported. A process for producing allyl acetate by reacting propylene, oxygen and acetic acid in the gas phase in the presence of a catalyst is described.
しかしながら、本発明者らが前記の公知方法に従つて酢
酸アリルの合成を試みた結果、酢酸アリルの収率及び選
択率が低く、そのうえ触媒活性の経時低下が大きいこと
が判明した。すなわち、かかる方法は工業的規模で実施
するうえで致命的な欠点を有している。However, as a result of the present inventors attempting to synthesize allyl acetate according to the above-mentioned known method, it was found that the yield and selectivity of allyl acetate are low, and that the catalytic activity is largely decreased with time. That is, such a method has a fatal drawback when it is carried out on an industrial scale.
しかして、本発明の目的は、プロピレン、酸素及び酢酸
を気相で反応させることによつて酢酸アリルを工業的に
有利に製造しうる方法を提供することにある。Therefore, an object of the present invention is to provide a method capable of industrially advantageously producing allyl acetate by reacting propylene, oxygen and acetic acid in a gas phase.
本発明者らは上記目的を達成するため鋭意検討を重ね、
プロピレン、酸素及び酢酸から気相反応で酢酸アリルを
有利に製造するためには、該反応に適した触媒を選択す
ること、ならびにプロピレン、酸素及び酢酸を特定の組
成範囲内において反応系に供給することが重要であるこ
とを見出し、本発明に至つた。すなわち本発明は、パラ
ジウム触媒の存在下にプロピレン、酸素及び酢酸を気相
で反応させることによつて酢酸アリルを製造するに際
し、20〜200m2/gの表面積、0.3〜1.5ml/gの細孔容積及
び40〜500Å（オングストローム）の平均細孔半径を有
するシリカからなる担体にパラジウムを内部まで実質的
に均一に担持させ、かつアルカリ金属の酢酸塩を担持さ
せた触媒を存在させた反応系に、５〜20容量％のプロピ
レン、３〜15容量％の酸素及び５〜25容量％の酢酸から
なるガスを供給することを特徴とする酢酸アリルの製造
法である。The present inventors have earnestly studied to achieve the above object,
In order to advantageously produce allyl acetate from propylene, oxygen and acetic acid in a gas phase reaction, a catalyst suitable for the reaction is selected, and propylene, oxygen and acetic acid are supplied to the reaction system within a specific composition range. It has been found that what is important is the present invention. That is, the present invention is propylene in the presence of a palladium catalyst, when producing by connexion allyl acetate to the reaction of oxygen and acetic acid in the gas phase, surface area of 20 to 200 m 2 / g, the 0.3~1.5ml / g fine A reaction system in which a catalyst made of silica having a pore volume and an average pore radius of 40 to 500 Å (angstroms) is substantially uniformly loaded with palladium to the inside and a catalyst carrying an alkali metal acetate is present. In addition, 5 to 20% by volume of propylene, 3 to 15% by volume of oxygen and 5 to 25% by volume of acetic acid are supplied as a gas.
本発明において、プロピレン、酸素及び酢酸から気相反
応で酢酸アリルを有利に製造するためには、先ず該反応
に適した触媒を選択して使用する必要がある。In the present invention, in order to advantageously produce allyl acetate from propylene, oxygen and acetic acid by a gas phase reaction, it is first necessary to select and use a catalyst suitable for the reaction.
本発明の方法において用いられる触媒の担体は、20〜20
0m2/gの表面積、0.3〜1.5ml/gの細孔容積及び40〜500Å
の平均細孔半径を有するシリカからなる。20m2/gより小
さい表面積、1.5ml/gより大きい細孔容積又は500Åより
大きい平均細孔半径を有するシリカを担体とする触媒は
活性が低く、逆に200m2/gより大きい表面積、0.3ml/gよ
り小さい細孔容積又は40Åより小さい平均細孔半径を有
するシリカを担体とする触媒は反応中における活性の経
時低下が著しい。なお、担体であるシリカの表面積の測
定は通常のBET法により、又シリカの細孔容積及び平均
細孔半径の測定は高圧水銀ポロシメーターを用いること
によつて常法に従い容易に行うことができる。The carrier of the catalyst used in the method of the present invention is 20 to 20.
Surface area of 0 m 2 / g, pore volume of 0.3-1.5 ml / g and 40-500 Å
Consisting of silica having an average pore radius of A silica-supported catalyst with a surface area of less than 20 m 2 / g, a pore volume of more than 1.5 ml / g or an average pore radius of more than 500Å has low activity, conversely a surface area of more than 200 m 2 / g, 0.3 ml. The catalyst with silica as a carrier having a pore volume smaller than / g or an average pore radius smaller than 40 Å has a remarkable decrease in activity during the reaction. The surface area of silica as a carrier can be easily measured by an ordinary BET method, and the pore volume and average pore radius of silica can be easily measured by a conventional method using a high pressure mercury porosimeter.
本発明の方法において使用される触媒は、上述のシリカ
にパラジウム及びアルカリ金属の酢酸塩を担持すること
によつて得られるが、パラジウムはシリカ担体に内部ま
で実質的に均一に担持する必要がある。パラジウムが内
部まで実質的に均一に担持されているかどうかは、触媒
断面のパラジウム濃度分布を例えばＸ線マイクロアナラ
イザーで測定することによつて確認することができる。
すなわち、本発明においては、Ｘ線マイクロアナライザ
ーで測定された触媒断面のパラジウム濃度の最大値を表
わすカウント数と最小値を表わすカウント数の比が2.0
以下、好ましくは1.5以下になるようにパラジウムを担
持させた触媒を用いるのが望ましい。パラジウム濃度の
最大値と最小値のカウント数における比が2.0を越える
ような触媒を用いて反応を行うと、ジアセトキシプロパ
ン、アリリデンジアセテートなどのジアセテート類の生
成が過大となり、目的とする酢酸アリルへの選択率が大
巾に低下する。なお、シリカに担持させるパラジウムの
量は、触媒としての機能及び酢酸アリルへの選択率の点
から、シリカ担体に対して0.1〜5.0重量％の範囲内が好
ましく、さらに好ましくは0.3〜1.0重量％の範囲内であ
る。パラジウムのシリカへの担持は、例えば、Na2PdCl4
などのパラジウム塩の水溶液をシリカに含浸させ、得ら
れる混合物をそのまま又は乾燥したのちに、ヒドラジン
のアルカリ水溶液を用いて還元処理に付し、充分に水洗
したのち乾燥することによつて行われる。また、パラジ
ウムとともにシリカに担持させるアルカリ金属の酢酸塩
としては、具体的には酢酸ナトリウム、酢酸カリウムな
どが例示され、特に好ましいのは酢酸カリウムである。
かかるアルカリ金属の酢酸塩は、パラジウムの触媒活性
をさらに向上させる作用を有するが、触媒中でのその含
有割合が低すぎると活性向上効果がほとんどなく、逆に
高すぎるとむしろ活性向上効果が低減するので、通常は
シリカ担体に対して１〜15重量％の範囲内、好ましくは
５〜10重量％の範囲内の量で担持される。The catalyst used in the method of the present invention is obtained by supporting the above-mentioned silica with palladium and an alkali metal acetate, but the palladium needs to be supported on the silica carrier substantially uniformly up to the inside. . Whether or not palladium is supported substantially uniformly inside can be confirmed by measuring the palladium concentration distribution in the catalyst cross section, for example, by an X-ray microanalyzer.
That is, in the present invention, the ratio of the count number representing the maximum value and the count value representing the minimum value of the palladium concentration in the catalyst cross section measured by an X-ray microanalyzer is 2.0.
Hereafter, it is desirable to use a catalyst on which palladium is supported so as to be preferably 1.5 or less. When the reaction is carried out using a catalyst in which the ratio of the maximum value to the minimum value of the palladium concentration and the count value of the palladium value exceeds 2.0, the production of diacetates such as diacetoxypropane and arylidene diacetate becomes excessive, and the target acetic acid The selectivity to allyl is greatly reduced. The amount of palladium supported on silica is preferably 0.1 to 5.0% by weight, more preferably 0.3 to 1.0% by weight, based on the silica carrier, from the viewpoint of the function as a catalyst and the selectivity to allyl acetate. Within the range of. For example, loading of palladium on silica is carried out by using Na 2 PdCl 4
Silica is impregnated with an aqueous solution of a palladium salt such as the above, and the resulting mixture is directly or dried and then subjected to a reduction treatment using an alkaline aqueous solution of hydrazine, thoroughly washed with water, and then dried. Specific examples of the alkali metal acetate to be supported on silica along with palladium include sodium acetate and potassium acetate, with potassium acetate being particularly preferred.
Such an alkali metal acetate has the effect of further improving the catalytic activity of palladium, but if its content in the catalyst is too low, there is almost no activity improving effect, and conversely if it is too high, the activity improving effect is rather reduced. Therefore, it is usually supported in an amount of 1 to 15% by weight, preferably 5 to 10% by weight, based on the silica carrier.
本発明の方法において用いられる触媒の形状はとくに規
定されず、球状、タブレツト状あるいはペレツト状など
の任意の形状のものが使用できる。The shape of the catalyst used in the method of the present invention is not particularly limited, and any shape such as a spherical shape, a tablet shape or a pellet shape can be used.
本発明の方法においては、上述の触媒を存在させた反応
系にプロピレン、酸素及び酢酸を特定の割合で供給する
ことによつて反応を行う必要がある。In the method of the present invention, it is necessary to carry out the reaction by supplying propylene, oxygen and acetic acid at a specific ratio to the reaction system in which the above catalyst is present.
本発明の方法において反応系に供給するガスは、実質的
にはプロピレン、酸素、酢酸及び希釈ガスである。かか
る供給ガス全量に対してプロピレンは５〜20容量％、好
ましくは10〜15容量％の割合となる量で；酸素は３〜15
容量％、好ましくは５〜10容量％の割合となる量で；酢
酸は５〜25容量％、好ましくは６〜10容量％の割合とな
る量で、各々反応系に供給される。プロピレンの供給割
合が全供給ガスに対して５容量％より低いと反応生成物
における酢酸アリルへの選択率が低くなり、逆に全供給
ガスに対して20容量％より高いと反応系中の触媒におけ
る活性の経時低下が著しくなる。酸素の供給割合が全供
給ガスに対して３容量％より低いと反応速度が低くな
り、逆に全供給ガスに対して15容量％より高いと形成さ
れるガス状混合物が爆発範囲内に入る危険性がある。ま
た酢酸の供給割合が全供給ガスに対して５容量％より低
いと生成物における二酸化炭素への選択率が高くなつて
酢酸アリルへの選択率が低くなる。逆に酢酸の供給割合
が全供給ガスに対して25容量％より高いと反応系中の触
媒における活性の経時低下が大きくなる。なお、ブテ
ン、ブタジエンなどのプロピレンよりも高い沸点を有す
るオレフインが原料として使用するプロピレン中に不純
物として混入している場合があるが、これらのプロピレ
ンよりも高い沸点を有するオレフインは反応系中におい
て触媒活性の経時低下を大きくする傾向がある。このた
め、原料として用いるプロピレンはできるだけ高純度で
あることが望ましく、とくに好ましくは99.0％以上の純
度を有するもの（例えば、一般に「重合グレード」と称
される市販のプロピレン）である。反応系に供給する酸
素としては、空気を用いることが実用上有利である。ま
た反応系に供給するプロピレン、酸素及び酢酸以外のガ
ス成分である希釈ガスとしては、窒素、二酸化炭素、水
蒸気、及びプロパンなどの飽和炭化水素などの本反応に
対して不活性なガスを単独で又はこれらの混合物として
使用することができる。なお、反応中、触媒に担持させ
たアルカリ金属の酢酸塩が少しずつ脱離して反応系外に
流出する場合がある。そこで、触媒中におけるアルカリ
金属の酢酸塩の担持量を希望する範囲内に維持するため
に、アルカリ金属の酢酸塩を例えば水溶液又は酢酸の溶
液として供給ガスに添加することなどの方法によつて反
応系中に加えてもよい。The gas supplied to the reaction system in the method of the present invention is substantially propylene, oxygen, acetic acid and a diluent gas. Propylene is in an amount of 5 to 20% by volume, preferably 10 to 15% by volume, based on the total amount of the feed gas; oxygen is 3 to 15% by volume.
%, Preferably 5 to 10% by volume; acetic acid is supplied to the reaction system in an amount of 5 to 25% by volume, preferably 6 to 10% by volume. When the propylene feed ratio is lower than 5% by volume with respect to the total feed gas, the selectivity to allyl acetate in the reaction product is low, and conversely, when it is higher than 20% by volume with respect to the total feed gas, the catalyst in the reaction system. The decrease in activity with time becomes remarkable. If the oxygen supply rate is lower than 3% by volume with respect to the total supply gas, the reaction rate will be slow, and conversely, if the oxygen supply rate is higher than 15% by volume with respect to the total supply gas, the gaseous mixture formed will be in the explosion range. There is a nature. When the supply ratio of acetic acid is lower than 5% by volume with respect to the total supply gas, the selectivity to carbon dioxide in the product is high and the selectivity to allyl acetate is low. On the other hand, when the supply rate of acetic acid is higher than 25% by volume with respect to the total supply gas, the activity of the catalyst in the reaction system decreases with time. Incidentally, butene, olefin such as butadiene having a boiling point higher than that of propylene may be mixed as an impurity in propylene used as a raw material, but these olefins having a boiling point higher than that of propylene are used as a catalyst in the reaction system. It tends to increase the decrease in activity over time. Therefore, it is desirable that propylene used as a raw material has a purity as high as possible, and particularly preferably propylene having a purity of 99.0% or more (for example, commercially available propylene generally referred to as "polymerization grade"). It is practically advantageous to use air as oxygen to be supplied to the reaction system. Further, as the diluent gas which is a gas component other than propylene, oxygen and acetic acid supplied to the reaction system, nitrogen, carbon dioxide, water vapor, and a gas inert to the present reaction such as saturated hydrocarbon such as propane are used alone. Alternatively, they can be used as a mixture thereof. During the reaction, the alkali metal acetate supported on the catalyst may be gradually released and flow out of the reaction system. Therefore, in order to maintain the amount of the alkali metal acetate supported in the catalyst within a desired range, the reaction is carried out by a method such as adding the alkali metal acetate to the feed gas as an aqueous solution or a solution of acetic acid. It may be added to the system.
反応は120〜200℃で実施されるが、140〜170℃で実施す
るのが実用上、有利である。また反応圧力は設備の点か
ら常圧〜30気圧であることが実用上有利であり、さらに
好ましくは常圧〜10気圧である。The reaction is carried out at 120 to 200 ° C, but it is practically advantageous to carry out at 140 to 170 ° C. In terms of equipment, the reaction pressure is practically advantageous from atmospheric pressure to 30 atm, more preferably from atmospheric pressure to 10 atm.
反応形式としては、固定床、流動床などの形式をとり得
るが、耐蝕性を有する反応管に前述の触媒を充填した固
定床を採用することが実用上有利である。The reaction system may be a fixed bed, a fluidized bed or the like, but it is practically advantageous to employ a fixed bed in which a reaction tube having corrosion resistance is filled with the above catalyst.
生成した酢酸アリルは、例えば反応系から取得された反
応生成ガスを凝縮したのちに凝縮成分を蒸留に付すな
ど、任意の公知の方法によつて分離することができる。The produced allyl acetate can be separated by any known method, for example, by condensing the reaction product gas obtained from the reaction system and then subjecting the condensed component to distillation.
以下、本発明を実施例によつて具体的に説明するが、本
発明はこれらの実施例によつて限定されるものではな
い。Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
実施例１ 担体の製造:350m2/gの表面積、1.04ml/gの細孔容積及び
54Åの平均細孔容積を有するシリカゲル（富士デビソン
化学株式会社製IDゲル）をボールミルで粉砕し、得られ
た粉末5.0kgに対し、シリカゾル（シリカを10重量％含
有する水溶液：日産化学工業株式会社製スノーテツクス
−Ｎ）９を加え、転動式造粒機により、直径約5mmの
球状成形物に造粒した。これを100℃で５時間乾燥さ
せ、900℃で４時間焼成した。得られたシリカ成形物の
表面積は200m2/g、細孔容積は0.72ml/g、平均細孔半径
は60Å、嵩密度は0.45ml/gであつた。Example 1 Preparation of support: 350 m 2 / g surface area, 1.04 ml / g pore volume and
Silica gel having an average pore volume of 54 Å (ID gel manufactured by Fuji Devison Chemical Co., Ltd.) was pulverized with a ball mill, and 5.0 kg of the obtained powder was silica sol (aqueous solution containing 10% by weight of silica: Nissan Chemical Industries, Ltd.). Snowtex-N) 9 was added and granulated into a spherical molded product having a diameter of about 5 mm by a rolling granulator. This was dried at 100 ° C. for 5 hours and calcined at 900 ° C. for 4 hours. The surface area of the obtained silica molded product was 200 m 2 / g, the pore volume was 0.72 ml / g, the average pore radius was 60 Å, and the bulk density was 0.45 ml / g.
触媒の調製：上記シリカ成形物１（290g）を、Na2PdC
l46.24gを水400mlに溶解した溶液に浸漬し（シリカ成形
物の吸水量は380g/であつた）、得られた混合物をロ
ータリーエバポレーター中に移し、ロータリーエバポレ
ーターを回転させながら減圧下に水分を蒸発させた。得
られたNa2PdCl4が含有されたシリカ成形物を、ヒドラジ
ン20gおよび水酸化ナトリウム8gを含む１の水溶液に
投入し、０℃で３時間放置することによつてNa2PdCl4の
還元を行つた。得られた混合物を、蒸留水を用いて流出
水から塩素イオンが検出されなくなるまで洗浄したの
ち、静置式乾燥器中、100℃で３時間乾燥させた。得ら
れた乾燥物を、酢酸カリウム28.7gを水400mlに溶解した
溶液に浸漬したのちロータリーエバポレーター中に移
し、ロータリーエバポレーターを回転させながら水を減
圧下に蒸発させることによつて酢酸カリウムを含浸させ
た。最後に、残留物を静置式乾燥器中、100℃で３時間
乾燥させることによつて、パラジウムを0.77重量％及び
酢酸カリウムを9.0重量％の含量で担持する触媒を得
た。得られた球状触媒粒子をその芯を通る面で切断した
場合における該触媒断面の直径方向のパラジウム濃度分
布をＸ線マイクロアナライザー（株式会社島津製作所製
ARLエレクトロンマイクロプローブＸ線アナライザーEMX
−2A型）で測定したところ、第１図に示すようにパラジ
ウム濃度の最大値を示すカウント数（130cps）と最小値
を表わすカウント数（110cps）の比は1.2であり、パラ
ジウムは担体上に内部まで均一に担持されていることが
判明した。Preparation of catalyst: The above silica molded product 1 (290 g) was mixed with Na 2 PdC.
Immerse a solution of 6.24 g of l 4 in 400 ml of water (the water absorption of the silica molded product was 380 g /), transfer the resulting mixture into a rotary evaporator, and rotate the rotary evaporator to remove water under reduced pressure. Was evaporated. The obtained silica molded product containing Na 2 PdCl 4 was added to an aqueous solution of 1 containing 20 g of hydrazine and 8 g of sodium hydroxide, and left at 0 ° C. for 3 hours to reduce Na 2 PdCl 4 I went. The obtained mixture was washed with distilled water until chlorine ions were not detected in the outflow water, and then dried in a static dryer at 100 ° C. for 3 hours. The obtained dried product was immersed in a solution of 28.7 g of potassium acetate dissolved in 400 ml of water, then transferred to a rotary evaporator, and impregnated with potassium acetate by evaporating water under reduced pressure while rotating the rotary evaporator. It was Finally, the residue was dried in a static dryer at 100 ° C. for 3 hours to obtain a catalyst supporting 0.77% by weight of palladium and 9.0% by weight of potassium acetate. An X-ray microanalyzer (manufactured by Shimadzu Corporation) was used to determine the palladium concentration distribution in the diameter direction of the catalyst cross section when the obtained spherical catalyst particles were cut along the plane passing through the core.
ARL Electron Microprobe X-Ray Analyzer EMX
As shown in Fig. 1, the ratio of the maximum count (130 cps) of the palladium concentration to the minimum count (110 cps) of the palladium concentration was 1.2, as shown in Fig. 1, and palladium was deposited on the carrier. It was found that the particles were evenly supported inside.
反応：上記球状触媒250mlを加熱ジヤケツト付のステン
レス鋼（SUS−316）製反応管（内径23mm）に充填し、そ
れに純度99.5％のプロピレン12容量％、酸素７容量％、
酢酸９容量％及び窒素72容量％からなるガスを空間速度
（０℃、１気圧基準）1800hr-1、ジヤケツト中の熱媒温
度140℃及び圧力５気圧の条件下で通過させた。なおこ
の際、反応器に供給する酢酸中に酢酸カリウムを20ppm
の濃度で含有させた。得られた生成物を分析した結果、
酢酸アリルの空間時間収率（以下、空間時間収率をSTY
と称する）は3.8t/m3・日であり、消費されたプロピレ
ン基準において酢酸アリルへの選択率は95.9モル％、ジ
アセテート類への選択率は1.9モル％及び二酸化炭素へ
の選択率は2.2モル％であることが判明した。この反応
を長期にわたつて継続したところ、反応開始から４箇月
後において、酢酸アリルのSTYは3.6t/m3・日であり、酢
酸アリルなど各生成物への選択率はいずれも上記の値が
維持されていることが判明した。Reaction: 250 ml of the above spherical catalyst was filled in a stainless steel (SUS-316) reaction tube (inner diameter 23 mm) with a heating jacket, and 12% by volume of propylene having a purity of 99.5% and 7% by volume of oxygen,
A gas consisting of 9% by volume of acetic acid and 72% by volume of nitrogen was passed under the conditions of a space velocity (0 ° C., 1 atm standard) of 1800 hr −1 , a heating medium temperature in a jacket of 140 ° C. and a pressure of 5 atm. At this time, 20 ppm of potassium acetate was added to the acetic acid supplied to the reactor.
It was contained at a concentration of. As a result of analyzing the obtained product,
Space-time yield of allyl acetate (hereinafter space-time yield
Is 3.8 t / m 3 · day, and the selectivity to allyl acetate is 95.9 mol%, the selectivity to diacetates is 1.9 mol% and the selectivity to carbon dioxide is 3.8 t / m 3 · day. It was found to be 2.2 mol%. When this reaction was continued for a long time, the STY of allyl acetate was 3.6 t / m 3 · day 4 months after the start of the reaction, and the selectivity for each product such as allyl acetate was the above value. Was found to be maintained.
実施例２ 直径5mm及び高さ5mmのタブレツト状の120m2/gの表面
積、0.85ml/gの細孔容積、120Åの平均細孔半径及び0.5
0の嵩比重を有するシリカ（日揮化学株式会社製シリカE
8G1）を担体として用いた以外は実施例１と同様にし
て、パラジウム0.9重量％及び酢酸カリウム9.0重量％を
担持する触媒を調製した。実施例１と同様にしてＸ線マ
イクロアナライザーによる触媒断面の直径方向における
パラジウム濃度の最大値を表わすカウント数と最小値を
表わすカウント数の比を求めたところ、かかる比は1.3
であり、パラジウムが担体に内部まで均一に担持されて
いることが判明した。Example 2 A surface area of 120 m 2 / g in the form of a tablet having a diameter of 5 mm and a height of 5 mm, a pore volume of 0.85 ml / g, an average pore radius of 120Å and 0.5
Silica having a bulk density of 0 (Silica E manufactured by JGC Chemicals Co., Ltd.
A catalyst carrying 0.9% by weight of palladium and 9.0% by weight of potassium acetate was prepared in the same manner as in Example 1 except that 8G1) was used as the carrier. When the ratio of the count number representing the maximum value and the count value representing the minimum value of the palladium concentration in the diameter direction of the catalyst cross section was determined by an X-ray microanalyzer in the same manner as in Example 1, the ratio was 1.3.
Therefore, it was found that palladium was uniformly supported on the inside of the carrier.
上記触媒を用いた以外は実施例１と同様にして反応を行
つたところ、酢酸アリルのSTYは3.8t/m3・日であり、消
費されたプロピレン基準における酢酸アリル、ジアセテ
ート類及び二酸化炭素への選択率は各々94.5モル％、2.
5モル％及び3.0モル％であつた。また、反応を20日間維
持した時点における酢酸アリルのSTYは3.3t/m3・日であ
つた。When the reaction was carried out in the same manner as in Example 1 except that the above catalyst was used, the STY of allyl acetate was 3.8 t / m 3 · day, and allyl acetate, diacetates and carbon dioxide based on the consumed propylene were used. Selectivity to 94.5 mol%, 2.
It was 5 mol% and 3.0 mol%. The STY of allyl acetate when the reaction was maintained for 20 days was 3.3 t / m 3 · day.
実施例３ 担体に含浸させるNa2PdCl4水溶液を、Na2PdCl46.24gを
水350mlに溶解させることによつて調製した以外は実施
例１と同様にして触媒を調製し、パラジウム担持率0.7
重量％、酢酸カリウム担持率9.0重量％の触媒を得た。
実施例１と同様にして該触媒断面の直径方向のパラジウ
ム濃度をＸ線マイクロアナライザーで調べたところ第２
図に示す結果が得られ、パラジウム濃度の最大値を表わ
すカウント数（140cps）と最小値を表わすカウント数
（100cps）の比は1.4であることが判明した。Example 3 A catalyst was prepared in the same manner as in Example 1 except that the Na 2 PdCl 4 aqueous solution with which the carrier was impregnated was prepared by dissolving 6.24 g of Na 2 PdCl 4 in 350 ml of water.
A catalyst having a weight percentage and a potassium acetate loading of 9.0 wt% was obtained.
When the palladium concentration in the diameter direction of the catalyst cross section was examined by an X-ray microanalyzer in the same manner as in Example 1, it was found to be 2
The results shown in the figure were obtained, and it was found that the ratio of the number of counts (140 cps) showing the maximum value of palladium concentration to the number of counts (100 cps) showing the minimum value was 1.4.
上記触媒250mlを用いた以外は実施例１と同様にして反
応を行つたところ、酢酸アリルのSTYは3.4t/m3・日であ
り、消費されたプロピレン基準における酢酸アリル、ジ
アセテート類及び二酸化炭素への選択率は各々、95モル
％、2.1モル％及び2.9モル％であつた。また、反応を20
日間継続した時点における酢酸アリルのSTYは3.2t/m3・
日であつた。When the reaction was carried out in the same manner as in Example 1 except that 250 ml of the above catalyst was used, the STY of allyl acetate was 3.4 t / m 3 · day, and allyl acetate, diacetates and dioxide based on the consumed propylene were used. The carbon selectivities were 95 mol%, 2.1 mol% and 2.9 mol%, respectively. Also, the reaction is 20
The STY of allyl acetate at the time of continuing the day was 3.2 t / m 3
It was the day.
実施例４ プロピレン、酸素、酢酸及び窒素が各々10容量％、９容
量％、25容量％及び56容量％含有されてなるガスを空間
速度（０℃、１気圧基準）1500hr-1、圧力１気圧及び反
応器のジヤケツト中の熱媒温度170℃の条件下で反応さ
せた以外は実施例１と同様にして反応を行つた。得られ
た結果を第１表（後述）に示す。Example 4 Gas containing propylene, oxygen, acetic acid and nitrogen in an amount of 10% by volume, 9% by volume, 25% by volume and 56% by volume in space velocity (0 ° C, 1 atm standard) 1500 hr -1 , pressure 1 atm. And the reaction was carried out in the same manner as in Example 1 except that the reaction was carried out under the condition that the heating medium temperature in the jacket of the reactor was 170 ° C. The obtained results are shown in Table 1 (described later).
比較例１ 実施例１と同じシリカ担体を用い、同様の方法でパラジ
ウム塩を含浸させたのち、100℃で３時間空気中で乾燥
した。得られた乾燥物を0.05規定の水酸化ナトリウム水
溶液に浸漬して密栓し、24時間室温で静置した。水切り
後、残留物を５容量％ヒドラジン水溶液に浸漬して０℃
で３時間静置したのち、実施例１と同様にして水洗し乾
燥させた。得られた触媒中のパラジウムは0.7重量％、
酢酸カリウムは9.0重量％であつた。実施例１と同様に
して該触媒断面の直径方向のパラジウム濃度をＸ線マイ
クロアナライザーによつて調べたところ第３図に示す結
果が得られ、パラジウム濃度の最大値を表わすカウント
数（600cps）と最小値を表わすカウント数（80cps）の
比は7.5であることが判明した。Comparative Example 1 Using the same silica carrier as in Example 1, a palladium salt was impregnated in the same manner and then dried in air at 100 ° C. for 3 hours. The obtained dried product was immersed in a 0.05 N sodium hydroxide aqueous solution, sealed, and allowed to stand at room temperature for 24 hours. After draining, the residue is immersed in a 5% by volume hydrazine aqueous solution and the temperature is 0 ° C.
After leaving it to stand for 3 hours, it was washed with water and dried in the same manner as in Example 1. Palladium in the obtained catalyst is 0.7% by weight,
The potassium acetate was 9.0% by weight. When the palladium concentration in the diametrical direction of the catalyst cross section was examined by an X-ray microanalyzer in the same manner as in Example 1, the results shown in FIG. 3 were obtained, and it was found that the count value (600 cps) representing the maximum value of the palladium concentration was obtained. The ratio of the number of counts (80 cps) representing the minimum value was found to be 7.5.
上記触媒を用いた以外は実施例４と同様にして反応を行
つた。得られた結果を第１表（後述）に示す。The reaction was carried out in the same manner as in Example 4 except that the above catalyst was used. The obtained results are shown in Table 1 (described later).
比較例２ 比較例１において、0.05規定水酸化ナトリウム水溶液の
代りに0.45規定水酸化ナトリウム水溶液を用いた以外
は、比較例１と同様にして触媒を調製した。実施例１と
同様にして該触媒断面の直径方向のパラジウム濃度をＸ
線マイクロアナライザーによつて調べたところ第４図に
示す結果が得られ、パラジウム濃度の最大値を表わすカ
ウント数（1200cps）と最小値を表わすカウント数（55c
ps）の比は22であることが判明した。Comparative Example 2 A catalyst was prepared in the same manner as in Comparative Example 1 except that 0.45N sodium hydroxide aqueous solution was used in place of 0.05N sodium hydroxide aqueous solution. In the same manner as in Example 1, the palladium concentration in the diameter direction of the catalyst cross section was X.
A line micro-analyzer was used to obtain the results shown in Fig. 4. The count number indicating the maximum palladium concentration (1200 cps) and the count number indicating the minimum palladium concentration (55 c
The ps) ratio was found to be 22.
上記触媒を用いた以外は実施例４と同様にして反応を行
つた。得られた結果を第１表に示す。The reaction was carried out in the same manner as in Example 4 except that the above catalyst was used. The results obtained are shown in Table 1.
比較例３〜７ シリカの代りに第２表を示す担体を用いた以外は実施例
１と同様にしてパラジウム0.66重量％及び酢酸カリウム
６重量％を担持した触媒を調製し、この触媒を用いた以
外は実施例４と同様にして反応を行つた（比較例３〜
７）。得られた結果を前記実施例４における結果ととも
に第２表に示す。 Comparative Examples 3 to 7 A catalyst carrying 0.66% by weight of palladium and 6% by weight of potassium acetate was prepared in the same manner as in Example 1 except that the carrier shown in Table 2 was used instead of silica, and this catalyst was used. The reaction was carried out in the same manner as in Example 4 except for the above (Comparative Examples 3 to 3).
7). The obtained results are shown in Table 2 together with the results in Example 4 above.
比較例８〜９ 担体として第３表に示すシリカを用いた以外は実施例１
と同様にして触媒を調製し、得られた触媒を用いた以外
は実施例４と同様にして反応を行つた。得られた結果を
前記実施例４における結果とともに第３表に示す。 Comparative Examples 8 to 9 Example 1 except that silica shown in Table 3 was used as the carrier.
A catalyst was prepared in the same manner as in, and the reaction was carried out in the same manner as in Example 4 except that the obtained catalyst was used. The obtained results are shown in Table 3 together with the results in Example 4.
比較例10 触媒調製時にNa2PdCl46.24gとともにHAuCl41.50gを溶解
した水溶液を使用した以外は実施例１と同様にして、パ
ラジウム0.78重量％、金0.3重量％及び酢酸カリウム9.0
重量％を担持した触媒を得た。 Comparative Example 10 Palladium 0.78% by weight, gold 0.3% by weight and potassium acetate 9.0 were prepared in the same manner as in Example 1 except that an aqueous solution of HAuCl 4 1.50 g was used together with Na 2 PdCl 4 6.24 g in preparing the catalyst.
A catalyst supporting wt% was obtained.
該触媒を用いた以外は実施例４と同様にして反応を行つ
た結果、酢酸アリルのSTYは2.46t/m3・日、酢酸アリル
への選択率は78.7モル％、ジアセテート類への選択率は
13.3モル％及び二酸化炭素への選択率は８モル％（選択
率はいずれも消費されたプロピレン基準）であつた。The reaction was carried out in the same manner as in Example 4 except that the catalyst was used. As a result, the STY of allyl acetate was 2.46 t / m 3 · day, the selectivity to allyl acetate was 78.7 mol%, and the selection to diacetates was performed. Rate is
The selectivity to 13.3 mol% and carbon dioxide was 8 mol% (selectivity is based on consumed propylene).
本発明の方法によれば、ジアセトキシプロパン、アリリ
デンジアセテート等のジアセテート類及び二酸化炭素の
副生が少なく、極めて高い選択率及び極めて高い収率で
酢酸アリルを製造することができる。しかも、触媒活性
の経時低下が小さく、酢酸アリルを長期にわたつて安定
に製造することができるので産業上の有用性が極めて大
きい。According to the process of the present invention, diacetates such as diacetoxypropane and allylidene diacetate, and by-products of carbon dioxide are small, and allyl acetate can be produced with extremely high selectivity and extremely high yield. In addition, the catalytic activity is less likely to decrease with time, and allyl acetate can be stably produced over a long period of time, which is extremely useful in industry.
第１図は、Ｘ線マイクロアナライザーにより測定され
た、実施例１で使用した触媒を芯を通る面で切断した場
合における断面の直径方向のパラジウム濃度分布を示す
図であり、第２図は同じく実施例３で使用した触媒を芯
を通る面で切断した場合における断面の直径方向のパラ
ジウム濃度分布を示す図である。 第３図は比較例１、第４図は比較例２で使用した触媒の
各々を芯を通る面で切断した場合における断面の直径方
向のパラジウム濃度分布を示す図である。FIG. 1 is a diagram showing a palladium concentration distribution in a diameter direction of a cross section when the catalyst used in Example 1 was cut by a plane passing through a core, which was measured by an X-ray microanalyzer, and FIG. 5 is a diagram showing a palladium concentration distribution in a diametrical direction of a cross section when the catalyst used in Example 3 is cut along a plane passing through a core. FIG. FIG. 3 is a diagram showing the palladium concentration distribution in the diameter direction of the cross section when each of the catalysts used in Comparative Example 1 was cut along the plane passing through the core.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 松本 光郎 岡山県倉敷市酒津青江山2045番地の１ 株 式会社クラレ内 (72)発明者 守屋 四郎 岡山県倉敷市酒津1621番地 株式会社クラ レ内 (56)参考文献 特開 昭51−36413（ＪＰ，Ａ) 特開 昭50−84516（ＪＰ，Ａ) 特公 昭49−30809（ＪＰ，Ｂ２) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Mitsuro Matsumoto One share company in Kuraray, 2045 Saezu Aoeyama, Kurashiki City, Okayama Prefecture (72) Inventor Shiro Moriya 1621, Satsuki, Kurashiki City, Okayama Prefecture Kuraray Co., Ltd. ( 56) References JP-A-51-36413 (JP, A) JP-A-50-84516 (JP, A) JP-B-49-30809 (JP, B2)
Claims (1)
素及び酢酸を気相で反応させることによって酢酸アリル
を製造するに際し、20〜200m2/gの表面積、0.3〜1.5ml/
gの細孔容積及び40〜500Åの平均細孔半径を有するシリ
カからなる担体にパラジウムを内部まで実質的に均一に
担持させ、かつアルカリ金属の酢酸塩を担持させた触媒
を存在させた反応系に、５〜20容量％のプロピレン、３
〜15容量％の酸素及び５〜25容量％の酢酸からなるガス
を供給することを特徴とする酢酸アリルの製造法。1. When producing allyl acetate by reacting propylene, oxygen and acetic acid in the gas phase in the presence of a palladium catalyst, a surface area of 20 to 200 m 2 / g, 0.3 to 1.5 ml /
Reaction system in which a catalyst made of silica having a pore volume of g and an average pore radius of 40 to 500 Å is loaded with palladium substantially uniformly inside and a catalyst loaded with an alkali metal acetate is present. 5-20% by volume of propylene, 3
A process for producing allyl acetate, which comprises supplying a gas consisting of -15 vol% oxygen and 5-25 vol% acetic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60082024A JPH0764781B2 (en) | 1985-04-16 | 1985-04-16 | Method for producing allyl acetate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60082024A JPH0764781B2 (en) | 1985-04-16 | 1985-04-16 | Method for producing allyl acetate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61238759A JPS61238759A (en) | 1986-10-24 |
| JPH0764781B2 true JPH0764781B2 (en) | 1995-07-12 |
Family
ID=13762957
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60082024A Expired - Lifetime JPH0764781B2 (en) | 1985-04-16 | 1985-04-16 | Method for producing allyl acetate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0764781B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2552161B2 (en) * | 1988-02-03 | 1996-11-06 | ダイセル化学工業株式会社 | Method for producing allyl acetate |
| JP2940917B2 (en) * | 1988-05-27 | 1999-08-25 | ダイセル化学工業株式会社 | Method for producing allyl acetate |
| JP2003026632A (en) * | 2001-07-16 | 2003-01-29 | Mitsubishi Gas Chem Co Inc | Method for producing hydroxycarboxylic acid ester |
| JP5608403B2 (en) | 2010-03-31 | 2014-10-15 | 昭和電工株式会社 | Method for producing n-propyl acetate |
| JP5662747B2 (en) | 2010-09-21 | 2015-02-04 | 昭和電工株式会社 | Allyl acetate production process |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4930809A (en) * | 1972-07-21 | 1974-03-19 | ||
| JPS5084516A (en) * | 1973-11-30 | 1975-07-08 | ||
| JPS5136413A (en) * | 1974-09-10 | 1976-03-27 | Kuraray Co | Fuhowaesuteru no seizoho |
-
1985
- 1985-04-16 JP JP60082024A patent/JPH0764781B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61238759A (en) | 1986-10-24 |
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