JPH0538433A - Preparation of catalyst for producing acrylic acid - Google Patents
Preparation of catalyst for producing acrylic acidInfo
- Publication number
- JPH0538433A JPH0538433A JP3198015A JP19801591A JPH0538433A JP H0538433 A JPH0538433 A JP H0538433A JP 3198015 A JP3198015 A JP 3198015A JP 19801591 A JP19801591 A JP 19801591A JP H0538433 A JPH0538433 A JP H0538433A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- oxygen
- acrylic acid
- acrolein
- gas
- 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
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)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、アクロレインの気相接
触酸化によりアクリル酸を製造する際に使用する触媒に
関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst used for producing acrylic acid by vapor phase catalytic oxidation of acrolein.
【０００２】[0002]
【従来の技術】従来、アクロレインを気相接触酸化して
アクリル酸を製造する方法に関して特開昭４９−４７２
７６号、同５０−８４５２１号、同５２−１５３８８９
号、同５３−７６１４号及び同５８−１６６９３９号公
報等、極めて数多くの特許が提案されているが、工業用
触媒としては、更に性能を向上させることが望まれてい
る。2. Description of the Related Art Conventionally, a method for producing acrylic acid by vapor-phase catalytic oxidation of acrolein has been disclosed in JP-A-49-472.
No. 76, No. 50-84521, No. 52-153889.
Although a great number of patents have been proposed, such as JP-A Nos. 53-7614 and 58-166939, it is desired to further improve the performance as an industrial catalyst.
【０００３】[0003]
【発明が解決しようとする課題】本発明はアクロレイン
からアクリル酸を有利に製造する方法の提供を目的と
し、特に活性、選択性、寿命ともに実用性の高い触媒を
用いたアクリル酸の製造法を提供しようとするものであ
る。DISCLOSURE OF THE INVENTION The present invention aims to provide a method for producing acrylic acid from acrolein in an advantageous manner, and particularly to a method for producing acrylic acid using a catalyst having high activity, selectivity and long life. It is the one we are trying to provide.
【０００４】[0004]
【問題を解決するための手段】本発明はアクロレインを
気相接触酸化しアクリル酸を製造するにあたり、一般式
ＭｏaＶbＳｉcＡdＸeＹfＯg（ここで式中Ｍｏ，Ｖ，Ｓ
ｉ及びＯはそれぞれモリブデン、バナジウム、ケイ素及
び酸素を示し、Ａは鉄、コバルト、クロム及びストロン
チウムからなる群より選ばれた少なくとも１種の元素を
示し、Ｘはゲルマニウム、ホウ素、ヒ素、セレン、銀、
ナトリウム、スズ、テルル、セリウム及びサマリウムか
らなる群より選ばれた少なくとも１種の元素を示し、Ｙ
はマグネシウム、アルミニウム、チタン、マンガン、
銅、亜鉛、ジルコニウム、二オブ、タングステン、タン
タル及びビスマスからなる群より選ばれた少なくとも１
種の元素を示す。ａ，ｂ，ｃ，ｄ，ｅ，ｆ及びｇは各元
素の原子比率を表し、ａ＝１２のときｂ＝１〜６，ｃ＝
０．１〜１５，ｄ＝０．１〜３，ｅ＝０．０１〜３，ｆ
＝０〜３であり、ｇは前記各成分の原子価を満足するの
に必要な酸素原子数である。）で表される組成を有する
触媒を使用することを特徴とし、かつ、触媒を使用前に
酸素濃度０．１〜１０容量％の濃度範囲の含酸素ガス雰
囲気下、３００〜６００℃の温度範囲で熱処理を行うこ
とを特徴とするアクリル酸製造用触媒の製造法及び該触
媒を用いてのアクリル酸の製造法である。According to the present invention, when acrolein is subjected to vapor-phase catalytic oxidation to produce acrylic acid, the general formula Mo a V b Si c A d X e Y f O g (wherein Mo, V , S
i and O represent molybdenum, vanadium, silicon and oxygen, A represents at least one element selected from the group consisting of iron, cobalt, chromium and strontium, and X represents germanium, boron, arsenic, selenium and silver. ,
Represents at least one element selected from the group consisting of sodium, tin, tellurium, cerium and samarium, and Y
Is magnesium, aluminum, titanium, manganese,
At least one selected from the group consisting of copper, zinc, zirconium, niobium, tungsten, tantalum and bismuth.
Indicates the element of the seed. a, b, c, d, e, f and g represent the atomic ratio of each element, and when a = 12, b = 1 to 6, c =
0.1-15, d = 0.1-3, e = 0.01-3, f
= 0 to 3, and g is the number of oxygen atoms required to satisfy the valence of each component. ) Is used, and a temperature range of 300 to 600 ° C. is used in an oxygen-containing gas atmosphere having an oxygen concentration of 0.1 to 10% by volume before using the catalyst. And a method for producing acrylic acid using the catalyst, wherein the method comprises:
【０００５】本発明によれば、アクロレインからアクリ
ル酸を高収率で得ることが可能であり、特に長期にわた
って高い触媒活性並びに選択率が維持されるので工業的
価値は極めて大きい。According to the present invention, it is possible to obtain acrylic acid from acrolein in a high yield, and particularly high catalytic activity and selectivity are maintained over a long period of time, so that the industrial value is extremely large.
【０００６】触媒の調製に用いる原料としては、各元素
の酸化物あるいは強熱することにより酸化物になり得る
塩化物、硝酸塩、炭酸塩、アンモニウム塩、硫酸塩、水
酸化物等を組み合わせて使用することができる。As raw materials used for preparing the catalyst, a combination of oxides of each element or chlorides, nitrates, carbonates, ammonium salts, sulfates, hydroxides, etc. which can be converted into oxides by igniting is used. can do.
【０００７】本発明に用いられる触媒を製造する方法と
しては、特殊な方法に限定する必要はなく、成分の著し
い偏在を伴わない限り、従来からよく知られている蒸発
乾固法、沈殿法、酸化物混合法等の種々の方法を用いる
ことができる。蒸発乾固法としては、例えばパラモリブ
デン酸アンモニウム及びメタバナジン酸アンモニウムを
純水等に溶解して、そこに硝酸金属塩及び金属酸化物等
を純水等に溶解または懸濁したものを加え、混合液を加
熱撹拌しながら蒸発乾固する。これを乾燥後成型し、熱
処理することによって本発明の触媒が得られる。ここで
の熱処理とは、酸素濃度０．１〜１０容量％の濃度範囲
の含酸素ガス雰囲気下、３００〜６００℃の温度範囲で
の熱処理を意味する。特に好ましいのは、酸素濃度０．
３〜７容量％、温度範囲３５０〜５５０℃である。この
様なガスとして、アクロレインを酸化してアクリル酸を
得る際に生成するガスから回収した非凝縮性廃ガス又は
この燃焼ガスが用いられる。単に酸素濃度０．１〜１０
容量％の雰囲気下での密閉系でも熱処理は可能である
が、特に好ましいのはガスの流通下での熱処理である。
熱処理の時間は１〜１０時間、好ましくは３〜７時間で
ある。The method for producing the catalyst used in the present invention does not have to be limited to a special method, and as long as there is no significant uneven distribution of the components, the well-known evaporation drying method, precipitation method, Various methods such as an oxide mixing method can be used. As the evaporation-drying method, for example, ammonium paramolybdate and ammonium metavanadate are dissolved in pure water or the like, and then metal nitrate and metal oxide are dissolved or suspended in pure water or the like, and the mixture is mixed. The liquid is evaporated to dryness with heating and stirring. The catalyst of the present invention can be obtained by drying, molding, and heat-treating this. The heat treatment here means a heat treatment in a temperature range of 300 to 600 ° C. under an oxygen-containing gas atmosphere having a concentration range of oxygen concentration of 0.1 to 10% by volume. Particularly preferred is an oxygen concentration of 0.
It is 3 to 7% by volume and the temperature range is 350 to 550 ° C. As such a gas, a non-condensable waste gas recovered from a gas generated when acrolein is oxidized to obtain acrylic acid or a combustion gas thereof is used. Simply oxygen concentration 0.1-10
Although the heat treatment is possible even in a closed system in a volume% atmosphere, the heat treatment under a gas flow is particularly preferable.
The heat treatment time is 1 to 10 hours, preferably 3 to 7 hours.
【０００８】本発明方法により得られた触媒は、無担体
でも有効であるが、シリカ、アルミナ、シリカ−アルミ
ナ、シリコンカーバイト、マグネシア、チタニア等の不
活性担体に担持させるか、あるいはこれで希釈して用い
ることが好ましい。The catalyst obtained by the method of the present invention is effective even without a carrier, but it is supported on an inert carrier such as silica, alumina, silica-alumina, silicon carbide, magnesia, titania or diluted with it. It is preferable to use.
【０００９】本発明方法により得られた触媒を用いてア
クリル酸を製造する場合は、原料ガス中のアクロレイン
の濃度は広い範囲で変えることができるが、容量で１〜
２０％特に３〜１０％が好ましい。When acrylic acid is produced using the catalyst obtained by the method of the present invention, the concentration of acrolein in the raw material gas can be varied within a wide range, but the volume of the acrolein is from 1 to 1.
20%, especially 3 to 10% is preferable.
【００１０】原料のアクロレインは水、低級飽和アルデ
ヒド等の不純物を少量含んでいてもよく、これらの不純
物は反応に実質的な影響を与えない。酸素源としては空
気を用いるのが経済的であるが、必要に応じ純酸素で富
化した空気を用いることもできる。原料ガス中の酸素濃
度はアクロレインに対するモル比で規定され、この値は
０．３〜４特に０．４〜２．５が好ましい。原料ガスは
窒素、水蒸気、炭酸ガス等の不活性ガスを加えて希釈し
てもよい。反応圧力は常圧ないし数気圧が好ましい。反
応温度は２００〜４２０℃、特に２２０〜４００℃が好
ましい。反応は固定床でも流動床でも行うことができ
る。The raw material acrolein may contain a small amount of impurities such as water and lower saturated aldehydes, and these impurities do not substantially affect the reaction. It is economical to use air as the oxygen source, but air enriched with pure oxygen can also be used if necessary. The oxygen concentration in the raw material gas is defined by the molar ratio to acrolein, and this value is preferably 0.3 to 4 and particularly 0.4 to 2.5. The raw material gas may be diluted by adding an inert gas such as nitrogen, steam or carbon dioxide gas. The reaction pressure is preferably normal pressure to several atmospheres. The reaction temperature is preferably 200 to 420 ° C, particularly preferably 220 to 400 ° C. The reaction can be carried out in a fixed bed or a fluidized bed.
【００１１】[0011]
【実施例】下記実施例及び比較例中のアクロレインの反
応率及び生成するアクリル酸の選択率は下記のように定
義される。 アクロレインの反応率（％）＝反応したアクロレインの
モル数／供給したアクロレインのモル数×１００ アクリル酸の選択率（％）＝生成したアクリル酸のモル
数／反応したアクロレインのモル数×１００ 下記実施例及び比較例中の部は重量部を意味し、分析は
ガスクロマトグラフィーによった。EXAMPLES The reaction rate of acrolein and the selectivity of acrylic acid produced in the following Examples and Comparative Examples are defined as follows. Acrolein reaction rate (%) = mol number of reacted acrolein / mol number of acrolein supplied × 100 Acrylic acid selectivity (%) = mol number of generated acrylic acid / mol number of reacted acrolein × 100 Parts in the examples and comparative examples mean parts by weight, and analysis was by gas chromatography.
【００１２】実施例１ パラモリブデン酸アンモニウム１００部及びメタバナジ
ン酸アンモニウム１６．６部を純水１０００部に溶解し
た。これに硝酸第二鉄２１．０部を純水２００部に溶解
したものを加え、更に酸化ゲルマニウム１．０部を加え
た。次に２０％シリカゾル６１．０部を加え、混合液を
加熱撹拌しながら蒸発乾固した。得られた固形物を１３
０℃で１６時間乾燥後、加圧成型し、酸素１容量％及び
窒素９９容量％からなるガス流通下に３８０℃で５時間
熱処理したものを触媒として用いた。得られた触媒の酸
素以外の元素の組成（以下同じ）は、Ｍｏ12Ｖ3Ｓｉ4.3
Ｆｅ1.1Ｇｅ0.2であった。本触媒を反応器に充填し、ア
クロレイン５％、酸素１０％、水蒸気３０％、窒素５５
％（容量％）の混合ガスを反応温度２７０℃、接触時間
３．６秒で通じた。生成物を捕集し、ガスクロマトグラ
フィーで分析したところ、アクロレイン反応率９９．１
％、アクリル酸選択率９６．２％であった。Example 1 100 parts of ammonium paramolybdate and 16.6 parts of ammonium metavanadate were dissolved in 1000 parts of pure water. To this, a solution prepared by dissolving 21.0 parts of ferric nitrate in 200 parts of pure water was added, and further 1.0 part of germanium oxide was added. Next, 61.0 parts of 20% silica sol was added, and the mixture was evaporated to dryness while heating and stirring. 13 solids obtained
After drying at 0 ° C. for 16 hours, pressure molding and heat treatment at 380 ° C. for 5 hours under a gas flow consisting of 1% by volume of oxygen and 99% by volume of nitrogen were used as a catalyst. The composition of elements other than oxygen of the obtained catalyst (hereinafter the same) was Mo 12 V 3 Si 4.3.
It was Fe 1.1 Ge 0.2 . This catalyst was charged into a reactor and acrolein 5%, oxygen 10%, water vapor 30%, nitrogen 55
% (Volume%) of the mixed gas was passed through at a reaction temperature of 270 ° C. and a contact time of 3.6 seconds. The product was collected and analyzed by gas chromatography to find that the acrolein conversion rate was 99.1.
%, And the acrylic acid selectivity was 96.2%.
【００１３】比較例１ 実施例１において加圧成型後、酸素３０容量％及び窒素
７０容量％からなるガス流通下で３８０℃で５時間処理
したものを触媒として用いた以外は、実施例１と同じ方
法で反応させたところ、アクロレイン反応率９９．０
％、アクリル酸選択率９５．０％であった。Comparative Example 1 The same as Example 1 except that after pressure molding in Example 1, the catalyst was treated at 380 ° C. for 5 hours under a gas flow consisting of 30% by volume of oxygen and 70% by volume of nitrogen. When reacted in the same manner, the acrolein conversion rate is 99.0.
%, And the acrylic acid selectivity was 95.0%.
【００１４】実施例２ パラモリブデン酸アンモニウム１００部及びメタバナジ
ン酸アンモニウム１６．６部を純水１０００部に溶解し
た。これに硝酸第二鉄１３．３部を純水２００部に溶解
したものを加え、次に硝酸ストロンチウム３．０部を純
水２００部に溶解したものを加えた。更に亜セレン酸
１．２部及び２０％シリカゾル４９．６部を順次加え、
混合液を加熱撹拌しながら蒸発乾固した。得られた固形
物を１３０℃で１６時間乾燥後加圧成型し、酸素３容量
％、窒素９７容量％からなるガス流通下に３８０℃で５
時間熱処理したものを触媒として用いた。得られた触媒
の組成は、Ｍｏ12Ｖ3Ｓｉ3.5Ｆｅ0.7Ｓｒ0.3Ｓｅ0.2で
あった。実施例１と同じ条件で反応させたところアクロ
レイン反応率９９．３％、アクリル酸選択率９６．１％
であった。Example 2 100 parts of ammonium paramolybdate and 16.6 parts of ammonium metavanadate were dissolved in 1000 parts of pure water. To this, 13.3 parts of ferric nitrate dissolved in 200 parts of pure water was added, and then 3.0 parts of strontium nitrate dissolved in 200 parts of pure water was added. Further, 1.2 parts of selenious acid and 49.6 parts of 20% silica sol are sequentially added,
The mixture was evaporated to dryness with heating and stirring. The solid obtained is dried at 130 ° C. for 16 hours and then pressure-molded, and the mixture is allowed to stand at 380 ° C. under a gas flow of 3% by volume oxygen and 97% by volume nitrogen.
What was heat-treated for a while was used as a catalyst. The composition of the obtained catalyst was Mo 12 V 3 Si 3.5 Fe 0.7 Sr 0.3 Se 0.2 . When the reaction was performed under the same conditions as in Example 1, the acrolein conversion rate was 99.3% and the acrylic acid selectivity was 96.1%.
Met.
【００１５】比較例２ 実施例２において加圧成型後、酸素１５容量％及び窒素
８５容量％からなるガス流通下で３８０℃で５時間熱処
理したものを触媒として用いた以外は、実施例１と同じ
方法で反応させたところ、アクロレイン反応率９９．４
％、アクリル酸選択率９５．０％であった。Comparative Example 2 As in Example 1, except that the catalyst obtained was heat-treated at 380 ° C. for 5 hours in a gas flow consisting of 15% by volume of oxygen and 85% by volume of nitrogen after pressure molding. When reacted in the same manner, the acrolein conversion rate is 99.4.
%, And the acrylic acid selectivity was 95.0%.
【００１６】実施例３〜９ 熱処理のガス組成を変えた以外は、実施例１に準じて表
−１の各触媒を調製し、実施例１と同一条件で反応し表
−１の結果を得た。Examples 3 to 9 Each catalyst shown in Table 1 was prepared according to Example 1 except that the gas composition for heat treatment was changed, and the catalysts were reacted under the same conditions as in Example 1 to obtain the results shown in Table 1. It was
【００１７】実施例１０〜１５ 熱処理のガス組成を変えた以外は実施例１に準じて表−
２の各触媒を調整し、実施例１と同一条件で反応し表−
２の結果を得た。Examples 10 to 15 Tables according to Example 1 except that the gas composition for heat treatment was changed.
Each catalyst of No. 2 was prepared and reacted under the same conditions as in Example 1.
Two results were obtained.
【００１８】比較例３〜８ 熱処理のガス組成を変えた以外は、比較例１に準じて表
−１の各触媒を調製し、実施例１と同一条件で反応し表
−１の結果を得た。Comparative Examples 3 to 8 Each catalyst of Table-1 was prepared according to Comparative Example 1 except that the gas composition of the heat treatment was changed, and the reaction was conducted under the same conditions as in Example 1 to obtain the results of Table-1. It was
【００１９】比較例９〜１５ 熱処理のガス組成を変えた以外は比較例１に準じて表−
２の各触媒を調整し、実施例１と同一条件で反応し表−
２の結果を得た。Comparative Examples 9 to 15 Tables according to Comparative Example 1 except that the gas composition for heat treatment was changed.
Each catalyst of No. 2 was prepared and reacted under the same conditions as in Example 1.
Two results were obtained.
【表１】 [Table 1]
【表２】 [Table 2]
【発明の効果】本発明の方法で調整した触媒はアクロレ
インからアクリル酸を製造する方法に適したもので、従
来法に比べてアクリル酸の選択率が向上する。The catalyst prepared by the method of the present invention is suitable for the method for producing acrylic acid from acrolein, and the selectivity of acrylic acid is improved as compared with the conventional method.
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Claims (8)
こで式中Ｍｏ，Ｖ，Ｓｉ及びＯはそれぞれモリブデン、
バナジウム、ケイ素及び酸素を示し、Ａは鉄、コバル
ト、クロム及びストロンチウムからなる群より選ばれた
少なくとも１種の元素を示し、Ｘはゲルマニウム、ホウ
素、ヒ素、セレン、銀、ナトリウム、スズ、テルル、セ
リウム及びサマリウムからなる群より選ばれた少なくと
も１種の元素を示し、Ｙはマグネシウム、アルミニウ
ム、チタン、マンガン、銅、亜鉛、ジルコニウム、二オ
ブ、タングステン、タンタル及びビスマスからなる群よ
り選ばれた少なくとも１種の元素を示す。ａ，ｂ，ｃ，
ｄ，ｅ，ｆ及びｇは各元素の原子比率を表し、ａ＝１２
のときｂ＝１〜６，ｃ＝０．１〜１５，ｄ＝０．１〜
３，ｅ＝０．０１〜３，ｆ＝０〜３であり、ｇは前記各
成分の原子価を満足するのに必要な酸素原子数であ
る。）で表される組成を有する触媒を使用することを特
徴とし、かつ、触媒を使用前に酸素濃度０．１〜１０容
量％の濃度範囲の含酸素ガス雰囲気下、３００〜６００
℃の温度範囲で熱処理を行うことを特徴とするアクリル
酸製造用触媒の製造法。1. A general formula Mo a V b Si c A d X e Y f O g ( wherein wherein Mo, V, Si and O represent molybdenum,
Represents vanadium, silicon and oxygen, A represents at least one element selected from the group consisting of iron, cobalt, chromium and strontium, X represents germanium, boron, arsenic, selenium, silver, sodium, tin, tellurium, At least one element selected from the group consisting of cerium and samarium is shown, and Y is at least selected from the group consisting of magnesium, aluminum, titanium, manganese, copper, zinc, zirconium, niobium, tungsten, tantalum and bismuth. Indicates one element. a, b, c,
d, e, f and g represent the atomic ratio of each element, and a = 12
Then b = 1-6, c = 0.1-15, d = 0.1
3, e = 0.01-3, f = 0-3, and g is the number of oxygen atoms required to satisfy the valence of each component. ) Is used, and the catalyst is used in an oxygen-containing gas atmosphere having an oxygen concentration of 0.1 to 10% by volume before being used for 300 to 600.
A method for producing a catalyst for producing acrylic acid, which comprises performing a heat treatment in a temperature range of ° C.
特徴とする請求項１の製造法。2. The method according to claim 1, wherein the oxygen-containing gas atmosphere is a closed system.
ることを特徴とする請求項１の製造法。3. The method according to claim 1, wherein the oxygen-containing gas atmosphere is under the flow of the gas.
求項１，２又は３の製造法。4. The method according to claim 1, wherein the catalyst is carrier-free.
は希釈されていることを特徴とする請求項１，２又は３
の製造法。5. The catalyst as claimed in claim 1, wherein the catalyst is supported on an inert carrier or diluted.
Manufacturing method.
レインを分子状酸素で気相接触酸化することを特徴とす
るアクリル酸の製造法。6. A method for producing acrylic acid, which comprises subjecting acrolein to gas phase catalytic oxidation with molecular oxygen using the catalyst obtained in claim 1.
蒸気及び／又は炭酸ガス等の不活性ガスで希釈されてい
ることを特徴とする請求項６の製造法。7. The method according to claim 6, wherein the raw material gas containing acrolein is diluted with an inert gas such as nitrogen, steam and / or carbon dioxide.
水蒸気を含まないものであることを特徴とする請求項６
の製造法。8. The material gas containing acrolein is substantially free of water vapor.
Manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3198015A JPH0538433A (en) | 1991-08-07 | 1991-08-07 | Preparation of catalyst for producing acrylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3198015A JPH0538433A (en) | 1991-08-07 | 1991-08-07 | Preparation of catalyst for producing acrylic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0538433A true JPH0538433A (en) | 1993-02-19 |
Family
ID=16384097
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3198015A Pending JPH0538433A (en) | 1991-08-07 | 1991-08-07 | Preparation of catalyst for producing acrylic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0538433A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010214217A (en) * | 2009-03-13 | 2010-09-30 | Nippon Shokubai Co Ltd | Catalyst for producing acrolein and method of producing acrolein and/or acrylic acid using the catalyst |
| JP2010214218A (en) * | 2009-03-13 | 2010-09-30 | Nippon Shokubai Co Ltd | Catalyst for producing acrylic acid and method of producing acrylic acid using the catalyst |
| CN103285888A (en) * | 2013-04-18 | 2013-09-11 | 沈阳化工大学 | Catalyst used in preparation of acrylic acid through one-step oxidation of propylene and preparation method thereof |
| JP2013242031A (en) * | 2012-05-23 | 2013-12-05 | Showa Corp | Hydraulic shock absorber |
| JP2016515938A (en) * | 2013-04-08 | 2016-06-02 | サウディ ベーシック インダストリーズ コーポレイション | Catalyst for the conversion of propylene to products containing carboxylic acid groups |
-
1991
- 1991-08-07 JP JP3198015A patent/JPH0538433A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010214217A (en) * | 2009-03-13 | 2010-09-30 | Nippon Shokubai Co Ltd | Catalyst for producing acrolein and method of producing acrolein and/or acrylic acid using the catalyst |
| JP2010214218A (en) * | 2009-03-13 | 2010-09-30 | Nippon Shokubai Co Ltd | Catalyst for producing acrylic acid and method of producing acrylic acid using the catalyst |
| JP2013242031A (en) * | 2012-05-23 | 2013-12-05 | Showa Corp | Hydraulic shock absorber |
| JP2016515938A (en) * | 2013-04-08 | 2016-06-02 | サウディ ベーシック インダストリーズ コーポレイション | Catalyst for the conversion of propylene to products containing carboxylic acid groups |
| CN103285888A (en) * | 2013-04-18 | 2013-09-11 | 沈阳化工大学 | Catalyst used in preparation of acrylic acid through one-step oxidation of propylene and preparation method thereof |
| CN103285888B (en) * | 2013-04-18 | 2016-03-16 | 沈阳化工大学 | A kind of Catalysts and its preparation method preparing acrylic acid reaction for propylene oxidation step |
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