JPS5935896B2 - Simultaneous production method of unsaturated carbonyl compound and 1,3-butadiene - Google Patents
Simultaneous production method of unsaturated carbonyl compound and 1,3-butadieneInfo
- Publication number
- JPS5935896B2 JPS5935896B2 JP57038126A JP3812682A JPS5935896B2 JP S5935896 B2 JPS5935896 B2 JP S5935896B2 JP 57038126 A JP57038126 A JP 57038126A JP 3812682 A JP3812682 A JP 3812682A JP S5935896 B2 JPS5935896 B2 JP S5935896B2
- Authority
- JP
- Japan
- Prior art keywords
- butene
- catalyst
- butadiene
- reaction
- carbonyl compound
- 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
Links
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims description 24
- 150000001728 carbonyl compounds Chemical class 0.000 title claims description 4
- 238000004519 manufacturing process Methods 0.000 title description 2
- 239000003054 catalyst Substances 0.000 claims description 29
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 26
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 7
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- 229910001882 dioxygen Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims 1
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 29
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 6
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910002090 carbon oxide Inorganic materials 0.000 description 4
- 238000003306 harvesting Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- -1 olefin hydrocarbons Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 235000013844 butane Nutrition 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical class CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 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
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は、イソブテンとブテンーｌ、シス及びトランス
ブテンー２を含む炭素数４の脂肪族炭化水素を主成分と
する混合炭化水素（以下ブテン混合物と略記する）を新
規な触媒を用いて気相接触酸化して不飽和カルボニル化
合物と１、３−ブタジエンとを同時に製造する方法に関
する。DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel mixed hydrocarbon (hereinafter abbreviated as butene mixture) whose main component is isobutene and aliphatic hydrocarbons having 4 carbon atoms, including butene-1, cis and trans-butene-2. The present invention relates to a method for simultaneously producing an unsaturated carbonyl compound and 1,3-butadiene by gas phase catalytic oxidation using a catalyst.
従来、オレフィン炭化水素の気相接触酸化触媒には数多
くの多元系触媒が提案されている（例えば特公昭４３−
２３２４、同４７−１１７３３、同４７−３２０４３、
同４７−１１９６４、同４８−４７６２、同４６〜３３
９３０参照）。Conventionally, many multi-component catalysts have been proposed as gas-phase catalytic oxidation catalysts for olefin hydrocarbons (for example, Japanese Patent Publication No.
2324, 47-11733, 47-32043,
47-11964, 48-4762, 46-33
930).
しかしながら、いずれも工業的実施面から見た場合転化
率、選択率、単流収季、触媒寿命などの点でまだ不十分
であるまた本発明者らは、イソブテン及びｎ−ブテンを
倫むブタン−ブテン混合物の気相接触酸化触媒としてＭ
ｏ、Ｂｉ、Ｆｅ、Ｓｂおよびｏからなる５元系触媒が好
ましいことさらに上記の５元系に加えてＳｎまたはＮｉ
を組合わせると一層活性が良くなることを見出しすでに
提案した（特公昭５６一１０２８８号）。However, from an industrial perspective, these methods are still insufficient in terms of conversion rate, selectivity, single-stream yield, catalyst life, etc. Furthermore, the present inventors have found that butenes containing isobutene and n-butene -M as a gas phase catalytic oxidation catalyst for butene mixtures
A five-component catalyst consisting of O, Bi, Fe, Sb and O is preferred.In addition to the above-mentioned five-component catalyst, Sn or Ni
We have already proposed that the activity can be further improved by combining them (Special Publication No. 56-10288).
しかし、この触媒系は転化季、選択率、単流収率等の点
で必ずしも満足し得るものではない。そこでＭｏ、Ｂｉ
、Ｆｅ、Ｓｂ、Ｏなる５元系触媒にＺｎまたは／および
Ｚｒを倉ませることによりブテン混合物の触媒として用
いるときは、混入空気比率が低く、空間速度の高い条件
でも触媒が十分活性であり、転化宰、選択率、単流収季
、触媒寿命などの点で優れることを見出し本発明に到達
した。However, this catalyst system is not necessarily satisfactory in terms of conversion period, selectivity, single flow yield, etc. So Mo, Bi
When used as a catalyst for a butene mixture by storing Zn or/and Zr in a five-element catalyst consisting of , Fe, Sb, and O, the catalyst is sufficiently active even under conditions of a low mixed air ratio and a high space velocity, The present invention was achieved by discovering that the method is excellent in terms of conversion efficiency, selectivity, single-stream yield, catalyst life, etc.
また、上記の触媒は原料として特に高純度のイソブテン
および／またはｎ−ブテンを必要とせず、クラツキング
ナフサのＣ４留分（いわゆるＢ−Ｂ留分）又はＣ４留分
からブタジエンを抽出した残りのスペントＧ４留分、即
ちブテンー１、シスーブテンー２、トランスーブテンー
２、イソブテンの混合物を主成分とする留分を用いても
十分有効にメタクロレインと有用な化学中間原料である
１、３−ブタジエンを同時に生産することができる。Furthermore, the above catalyst does not require particularly high-purity isobutene and/or n-butene as a raw material, and it is possible to use the C4 fraction of cracking naphtha (so-called B-B fraction) or the remainder after butadiene has been extracted from the C4 fraction. The spent G4 fraction, that is, the fraction whose main components are a mixture of 1-butene, 2-cis-butene, 2-trans-butene, and isobutene, can be used to effectively convert methacrolein and 1,3-butadiene, which is a useful chemical intermediate raw material. can be produced at the same time.
本発明は、これらの知見に基づいて完成されたものであ
る。The present invention was completed based on these findings.
即ち、本発明はイソブテンおよびｎ−ブテンを食むブテ
ン混合物と分子状酸素とを一般式ＭＯａＢｉｂＦｅｃＳ
ｂｄＸｅＯｆ（ここでＸはＺｎ及びＺｒのうちの少なく
とも一種の元素であり、Ａ，ｂ，ｃ，ｄ，ｅ，ｆはそれ
ぞれＭＯ，Ｂｉ，Ｆｅ，Ｓｂ，Ｘ，Ｏの原子数でａ＝１
０とした場合ｂ ＝ ０．１〜５、ｃ＝２〜２０，．ｄ
＝０．１〜５、ｅ ＝ ０．１〜１０．ｆ＝各元素の原
子価によつて定まる値で３３〜８０の数値）で示される
触媒の存在下に気相接触反応させることを特徴とする不
飽和カルボニル化合物と１，３−ブタジエンの同時製造
法である。That is, the present invention combines isobutene and n-butene-eating butene mixtures with molecular oxygen using the general formula MOaBibFecS.
bdXeOf (where X is at least one element of Zn and Zr, A, b, c, d, e, f are the number of atoms of MO, Bi, Fe, Sb,
When set to 0, b = 0.1 to 5, c = 2 to 20, . d
=0.1~5, e=0.1~10. Simultaneous production of an unsaturated carbonyl compound and 1,3-butadiene, characterized by carrying out a gas-phase catalytic reaction in the presence of a catalyst, where f = a value determined by the valence of each element, from 33 to 80. It is the law.
触媒の調整法としては、蒸発乾固法や酸化物混合法の公
知の方法でよ＜、担体を使用して、実質上の使用触媒量
を減少することも可能である。The catalyst can be prepared by known methods such as the evaporation to dryness method or the oxide mixing method, but it is also possible to use a carrier to reduce the actual amount of catalyst used.
担体を使用する場合の担体種として、シリカ、アルミナ
、炭化ケイ素、軽石等を使用できるが、アル 一ミナま
たは炭化ケイ素が好ましい。触媒成分を成型して、又は
担体に付着させてから４００〜８００℃の高温で焼成し
たのち、反応に供することが望ましい。反応時の空間速
度は、１０００−５０００ｈｒ−１ ι（ＮＴＰ基準）
でよいが、好ましくは１５００一４０００ｈｒ−１であ
る。When a carrier is used, silica, alumina, silicon carbide, pumice, etc. can be used as the carrier type, but alumina or silicon carbide is preferable. It is desirable that the catalyst component be molded or adhered to a carrier and then calcined at a high temperature of 400 to 800°C before being subjected to the reaction. The space velocity during the reaction is 1000-5000 hr-1 ι (NTP standard)
However, preferably 1500-4000 hr-1.
反応系に導入される供給原料ガス中のブテン類（イソブ
テン、ブテン−１、シスーブテン一２、トランス−ブテ
ン−２）と、分子状酸素とのモル比は、１：（１−４）
の範囲で使用出来るが、実際的には、１：（１．３−
１．８）付近の低い酸素比の範囲で用いて十分目的を達
成出来るので、非常に効季的である。The molar ratio of butenes (isobutene, butene-1, cis-butene-2, trans-butene-2) and molecular oxygen in the feed gas introduced into the reaction system is 1:(1-4).
It can be used in the range of 1:(1.3-
It is very effective as it can be used in the low oxygen ratio range around 1.8) to achieve the purpose.
又、ブタン類や、１，３−ブタジエンは、反応に大きな
影響を与えないので、原料事情等が変つても操作条件を
変えることにより所期の目的を達成できる，，更に、こ
の反応においては、反応に悪影響を及ぼさない不活住ガ
ス（例えば窒素、水蒸気、二酸化炭素あるいは飽和炭化
水素）で反応ガスを希釈することも出来、特に水蒸気の
使用は、本反応に有利である。In addition, butanes and 1,3-butadiene do not have a large effect on the reaction, so even if the raw material situation changes, the desired purpose can be achieved by changing the operating conditions.Furthermore, in this reaction, It is also possible to dilute the reaction gas with an inert gas (eg nitrogen, steam, carbon dioxide or saturated hydrocarbons) that does not adversely affect the reaction, and the use of steam is particularly advantageous for this reaction.
実際的にはブテン類と水蒸気のモル比は、１：（０．３
−５）位にとるのが好ましい。反応温度は３５０−６０
０℃、好ましくは３７０−５００℃である。In practice, the molar ratio of butenes to water vapor is 1:(0.3
-5) is preferable. Reaction temperature is 350-60
0°C, preferably 370-500°C.
反応圧力としては、大気圧下で操作することにより十分
良好な成績が得られる。As for the reaction pressure, sufficiently good results can be obtained by operating under atmospheric pressure.
又、触媒の粒径による本質的な差が認められないので、
反応器は固定床式あるいは流動層式のいずれも使用する
ことが出来る。In addition, since there is no essential difference depending on the particle size of the catalyst,
As the reactor, either a fixed bed type or a fluidized bed type can be used.
反応生成物は通常の一般的な方法例えば、凝縮法、抽出
法、蒸留法などによつて回収分離することが出来る。The reaction products can be recovered and separated by conventional methods such as condensation, extraction, and distillation.
以下に実施例により本発明を説明するが、実施例中のｎ
−ブテン、イソブテンの転化率、１，３−ブタジエン、
メタクロレイン及びメタクリル酸の選択率、収宰は次の
式であられされる。The present invention will be explained below with reference to Examples.
-butene, isobutene conversion rate, 1,3-butadiene,
The selectivity and concentration of methacrolein and methacrylic acid are calculated by the following formula.
実施例 １
モリブテン酸アンモニウム１１．０５９（ ８．９３ミ
リモル）の水溶液に硝酸亜鉛４．６５９（１５．６３−
ミリモル）の水溶液を加えてよく撹拌しつつ、Ξ酸化ア
ンチモン１．８２ｆ１（ ６．２５ミリモル）の粉末を
加える。Example 1 4.659 (15.63 mmol) of zinc nitrate was added to an aqueous solution of 11.059 (8.93 mmol) of ammonium molybutate.
While stirring well, add 1.82 f1 (6.25 mmol) of antimony oxide powder.
更に、硝酸第二鉄２０．２９（ ５０ミリモル）の水溶
液及び硝酸ビスマス４．５５ｆ１（９．３８ミリモル）
の硝酸々性水溶液をつづけて撹拌しつつ加え、蒸発乾固
する。これを２５０℃で４時間熱分解した後乳鉢で粉砕
する。得られた粉末７．５ｆ１に粒状シリコンカーバイ
ド（粒径３ｕ）３０θ及び蒸留水５０ＣＣを加えて撹拌
しつつ蒸発乾固し、触媒成分を担体に付着させる。これ
を５００℃にて４時間焼成し、触媒とする。触媒成分中
の各金属の組成比は、ＭＯ：Ｂｉ：Ｆｅ：Ｓｂ：Ｚｎ＝
１０：１．５：８：２：２．５である。得られた触媒８
．３ＣＣを内径２０ｍｍの石英製反応管に充填し、１−
ブテン２７．７モル弊、シス一２−ブテン４．２モル％
、トランス−２−ブテン８．２モル％、イソブテン４７
．５モル％、ブタン類９．９モル％、１，３−ブタジエ
ン１．０モル％、Ｃ３炭化水素１．５モル％よりなる炭
化水素混合物１０．５モル％、空気６７モル％、水蒸気
２２．５モル％の原料ガスを空間速度（ｏ℃１気圧基準
）３０００ｈｒ−１゛Ｏ妾触させた。反応温度（触媒層
中の最高温度）は４５０℃であつた。反応開始６時間後
におけるイソブテンの転化季は９５．８％で、メタクロ
レイン及びメタクリル酸への選択季は７０．１％及び２
．４％、吸率は６７．２％及び２．３％であり、ｎ−ブ
テンの転化宰は６９．５％で、１，３−ブタジエン−の
選択季は８８．５％、収季は６１．５％であつた。Furthermore, an aqueous solution of 20.29 (50 mmol) of ferric nitrate and 4.55 f1 (9.38 mmol) of bismuth nitrate.
An aqueous solution of nitric acid is added with continuous stirring and evaporated to dryness. This was pyrolyzed at 250°C for 4 hours and then ground in a mortar. To 7.5 f1 of the obtained powder, 30 θ of granular silicon carbide (particle size 3 u) and 50 cc of distilled water are added and evaporated to dryness while stirring, thereby adhering the catalyst component to the carrier. This was calcined at 500° C. for 4 hours to obtain a catalyst. The composition ratio of each metal in the catalyst component is MO:Bi:Fe:Sb:Zn=
The ratio is 10:1.5:8:2:2.5. Obtained catalyst 8
．． A quartz reaction tube with an inner diameter of 20 mm was filled with 3CC, and 1-
Butene 27.7 mol%, cis-2-butene 4.2 mol%
, trans-2-butene 8.2 mol%, isobutene 47
．． 5 mol%, 9.9 mol% of butanes, 1.0 mol% of 1,3-butadiene, 10.5 mol% of a hydrocarbon mixture consisting of 1.5 mol% of C3 hydrocarbons, 67 mol% of air, 22. 5 mol % of the raw material gas was brought into contact at a space velocity of 3,000 hr -1 ゛O (on the basis of 0C and 1 atm). The reaction temperature (the highest temperature in the catalyst layer) was 450°C. The conversion period of isobutene 6 hours after the start of the reaction was 95.8%, and the selection period to methacrolein and methacrylic acid was 70.1% and 2.
．． 4%, the absorption rate is 67.2% and 2.3%, the conversion rate of n-butene is 69.5%, the selection season of 1,3-butadiene is 88.5%, and the harvesting season is 61%. It was .5%.
また、全−ブテンから炭素酸化物（ＣＯ及びＣＯ２）へ
の選択季は１６．０％であつた。実施例 ２
硝酸亜鉛の水溶液にかえて、酸化ジルコニウムの粉末を
用いた他は、実施例−１と同様に触媒を調製した。Furthermore, the selection rate from all-butene to carbon oxides (CO and CO2) was 16.0%. Example 2 A catalyst was prepared in the same manner as in Example 1, except that zirconium oxide powder was used instead of the aqueous solution of zinc nitrate.
得られた触媒中における各金属の組成比は、ＭＯ：Ｂｉ
：Ｆｅ：Ｓｂ：Ｚｒ半１０：１．５：８：１：ｆである
。反応は、実施例−１と同様に行つた。反応開始６時間
後におけるイソブテンの転化季は、９７．０％で、メタ
クロレイン及びメタクリル酸への選択季は６３．５％及
び１．９％、収季は６１．６％及び１．８％であり、ｎ
−ブテンの転化季は７１．２％で、１，３−ブタジエン
−の選択季は８６．１％、収季は６１．３％であつた。The composition ratio of each metal in the obtained catalyst was MO:Bi
:Fe:Sb:Zr half 10:1.5:8:1:f. The reaction was carried out in the same manner as in Example-1. The conversion period of isobutene 6 hours after the start of the reaction is 97.0%, the selection period to methacrolein and methacrylic acid is 63.5% and 1.9%, and the harvest period is 61.6% and 1.8%. and n
The conversion season for -butene was 71.2%, the selection season for 1,3-butadiene was 86.1%, and the harvest season was 61.3%.
また、全ブテンから炭素酸化物への選択率は１８．５％
であつた。参考例 １
第５成分であるＺｎ，又はＺｒを含まない触媒を実施例
−１と同様な方法で調製した。In addition, the selectivity from all butenes to carbon oxides was 18.5%.
It was hot. Reference Example 1 A catalyst containing no Zn or Zr as the fifth component was prepared in the same manner as in Example-1.
得られた触媒中における各金属の組成比はＭＯ：Ｂ１：
Ｆｅ：Ｓｂ−１０： １．５：８：２である。反応は実
施例−１と同様に行つた。反応開始６時間後におけるイ
ソブテンの転化季は８１．３％でメタクロレイン及びメ
タクリル酸への選択季は６５．１％及び２．１％、収率
は５２．９％及び１．７％であり、ｎ−ブテンの転化率
は８９．０％で、１，３−ーブタジエンへの選択季は８
１．３％、収季は４８．０％であつた。また全ブテンか
ら炭素酸化物への選択季は１７．０％であつた。参考例
２
参考例−１と同様にして、ＭＯ：Ｂｉ：Ｆｅ：Ｓｂ″−
１０：１．５：８：１の触媒を試験した。The composition ratio of each metal in the obtained catalyst was MO:B1:
Fe:Sb-10: 1.5:8:2. The reaction was carried out in the same manner as in Example-1. Six hours after the start of the reaction, the conversion period of isobutene was 81.3%, the selection period to methacrolein and methacrylic acid was 65.1% and 2.1%, and the yield was 52.9% and 1.7%. , the conversion rate of n-butene was 89.0%, and the selection season to 1,3-butadiene was 8
1.3%, and 48.0% during the harvest season. Moreover, the selection rate from all butenes to carbon oxides was 17.0%. Reference Example 2 In the same manner as Reference Example-1, MO:Bi:Fe:Sb''-
A 10:1.5:8:1 catalyst was tested.
反応開始６時間後におけるイソブテンの転化率は９２．
０％で、メタクロレイン及びメタクリル酸への選択季は
５１．８％及び１．５％、収季は４７．７％及び１．４
％であり、ｎ−ブテン−の転化率は６５．０％で、１，
３−ブタジエン−の選択季は８５．１％、収率は５５．
３％であつた。また全ブテンから炭素酸化物への選択季
は２４．５％であつた。The conversion rate of isobutene 6 hours after the start of the reaction was 92.
At 0%, the selection season for methacrolein and methacrylic acid was 51.8% and 1.5%, and the yield season was 47.7% and 1.4%.
%, the conversion rate of n-butene was 65.0%, and 1,
The selection rate for 3-butadiene was 85.1%, and the yield was 55.
It was 3%. Moreover, the selection rate from all butenes to carbon oxides was 24.5%.
Claims (1)
分子状酸素とを一般式ＭｏａＢｉｂＦｅｃＳｂｄＸｅＯ
ｆ（ここではＸは、Ｚｎ及びＺｒのうとの少くとも一種
の元素であり、ａ、ｂ、ｃ、ｄ、ｅ、ｆはそれぞれ、Ｍ
ｏ、Ｂｉ、Ｆｅ、Ｓｂ、Ｘ、Ｏの原子数で、ａ＝１０と
した場合、ｂ＝０．１〜５、ｃ＝２〜２０、ｄ＝０．１
〜５、ｅ＝０．１〜１０、ｆ＝各元素の原子価によつて
定まる値で、３３〜８０の数値）で示される触媒の存在
下に気相接触反応させることを特徴とする不飽和カルボ
ニル化合物と１，３−ブタジエンの同時製造法。1 A butene mixture containing isobutene and n-butene and molecular oxygen are combined with the general formula MoaBibFecSbdXeO
f (here, X is at least one element of Zn and Zr, a, b, c, d, e, f are each M
o, Bi, Fe, Sb, X, O atoms, when a = 10, b = 0.1 to 5, c = 2 to 20, d = 0.1
-5, e=0.1-10, f=a value determined by the valence of each element, a numerical value of 33-80) characterized by carrying out a gas phase catalytic reaction in the presence of a catalyst. A method for simultaneously producing a saturated carbonyl compound and 1,3-butadiene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57038126A JPS5935896B2 (en) | 1982-03-12 | 1982-03-12 | Simultaneous production method of unsaturated carbonyl compound and 1,3-butadiene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57038126A JPS5935896B2 (en) | 1982-03-12 | 1982-03-12 | Simultaneous production method of unsaturated carbonyl compound and 1,3-butadiene |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP48104565A Division JPS5748535B2 (en) | 1973-09-18 | 1973-09-18 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57209232A JPS57209232A (en) | 1982-12-22 |
| JPS5935896B2 true JPS5935896B2 (en) | 1984-08-31 |
Family
ID=12516757
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57038126A Expired JPS5935896B2 (en) | 1982-03-12 | 1982-03-12 | Simultaneous production method of unsaturated carbonyl compound and 1,3-butadiene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5935896B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100847206B1 (en) | 2007-05-10 | 2008-07-17 | 에스케이에너지 주식회사 | Zinc ferrite catalyst, preparation method thereof and preparation method of 1,3-butadiene using the same |
-
1982
- 1982-03-12 JP JP57038126A patent/JPS5935896B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57209232A (en) | 1982-12-22 |
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