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1. 发明授权

US4380664A Process for producing unsaturated aldehydes, and unsaturated fatty acids 失效
标题翻译：生产不饱和醛和不饱和脂肪酸的方法
公开(公告)号：US4380664A
公开(公告)日：1983-04-19
申请号：US891222
申请日：1978-03-29
申请人： Hiromichi Ishii , Hideo Matsuzawa , Masao Kobayashi , Kantaro Yamada
发明人： Hiromichi Ishii , Hideo Matsuzawa , Masao Kobayashi , Kantaro Yamada
IPC分类号： B01J23/88 , B01J23/887 , C07C5/48 , C07C45/34 , C07C45/37 , C07C51/235 , C07C51/25 , C07C45/35 , C07C47/22 , C07C57/05
CPC分类号： B01J23/8872 , B01J23/8875 , B01J23/8876 , C07C45/34 , C07C45/35 , C07C45/37 , C07C5/48 , C07C51/235 , C07C51/252 , B01J2523/00
摘要： At least one olefinic hydrocarbon of 3 to 4 carbon atoms is oxidized catalytically in the gas phase in the presence of molecular oxygen at 200.degree.-450.degree. C. to produce the corresponding aldehyde and acid over a calcined catalyst of the formula Mo.sub.a Sb.sub.b Bi.sub.c Fe.sub.d Ni.sub.e Sn.sub.f X.sub.g Y.sub.h O.sub.i wherein X is at least one alkali metal selected from the group consisting of potassium, rubidium and cesium; Y is at least one metal selected from the group consisting of cobalt, uranium, germanium, tungsten and titanium; a to h are atomic ratios wherein a=12, b=0.2 to 20, c=0.2 to 12, d=0.2 to 12, e=0.2 to 12, f=0 to 20, g=0.01 to 4 and h=0 to 6; and i is determined according to the oxidation states of the metal atoms in the catalyst.
摘要翻译：在200-450℃的分子氧存在下，至少一种具有3至4个碳原子的烯烃在气相中被氧化催化，以在式MoaSbbBicFedNeSnfXgYhOi的煅烧催化剂上产生相应的醛和酸，其中X为至少一种选自钾，铷和铯的碱金属; Y是选自钴，铀，锗，钨和钛中的至少一种金属; a至h为原子比，其中a = 12，b = 0.2至20，c = 0.2至12，d = 0.2至12，e = 0.2至12，f = 0至20，g = 0.01至4，h = 0 至6; 并且根据催化剂中的金属原子的氧化态确定i。

2. 发明授权

US4111984A Process for producing unsaturated aldehydes, and unsaturated fatty acids 失效
标题翻译：生产不饱和醛和不饱和脂肪酸的方法
公开(公告)号：US4111984A
公开(公告)日：1978-09-05
申请号：US667371
申请日：1976-03-16
申请人： Hiromichi Ishii , Hideo Matsuzawa , Masao Kobayashi , Kantaro Yamada
发明人： Hiromichi Ishii , Hideo Matsuzawa , Masao Kobayashi , Kantaro Yamada
IPC分类号： B01J23/887 , C07C45/34 , C07C45/37 , C07C51/25 , C07C51/24 , C07C51/32
CPC分类号： C07C45/37 , B01J23/8876 , C07C45/35 , C07C51/252 , B01J2523/00
摘要： At least one compound from the group of unsaturated hydrocarbons of three to four carbon atoms and t-butyl alcohol is oxidized catalytically in the gas phase in the presence of molecular oxygen at 200.degree.-450.degree. C to produce the corresponding aldehyde or acid over a calcined catalyst of the formula Mo.sub.a Sb.sub.b Bi.sub.c Fe.sub.d Ni.sub.e Sn.sub.f X.sub.g Y.sub.h O.sub.i wherein X is at least one of potassium, rubidium or cesium, Y is at least one of cobalt, uranium, germanium, tungsten or titanium, a to h are atomic ratios wherein a=12, b=0.2 to 20, c=0.2 to 12, d=0.2 to 12, e=0.2 to 12, f=0 to 20, g=0.01 to 4 and h=0 to 6 and i is a value determined by the oxidation state of the metal atoms in the catalyst.An embodiment of the calcined catalyst of the invention has the formula Mo.sub.a Sb.sub.b Bi.sub.c Fe.sub.d Ni.sub.e Sn.sub.f X.sub.g Y.sub.h Z.sub.j O.sub.i wherein X and y are as defined above and Z is palladium and a to j are atomic ratios wherein a=12, b=0.2 to 20, c=0.2 to 12, d=0.2 to 12, e=0.2 to 12, f=0 to 20, g=0.01 to 4, h=0.01 to 3, j=0.01 to 3 and i assumes a value determined by the oxidation states of the metal atoms in the catalyst.
摘要翻译：在200-450℃的分子氧存在下，气相中氧化至少一种来自三至四个碳原子的不饱和烃基的化合物和叔丁醇，以产生相应的醛或酸其中X为钾，铷或铯中的至少一种，Y为钴，铀，锗，钨或钛中的至少一种，a至h为原子比，其中a = 12，b = 0.2〜 20，c = 0.2〜12，d = 0.2〜12，e = 0.2〜12，f = 0〜20，g = 0.01〜4，h = 0〜6，i为金属的氧化态本发明的煅烧催化剂的一个实施方案具有式MoaSbbBicFedNieSnfXgYhZjOi其中X和y如上所定义，Z是钯，a至j是原子比，其中a = 12，b = 0.2至20，c = 0.2〜12，d = 0.2〜12，e = 0.2〜12，f = 0〜20，g = 0.01〜4，h = 0.01〜3，j = 0.01〜3，由催化剂中的金属原子的氧化态引起。

3. 发明授权

US3954856A Method for vapor-phase catalytic oxidation of tert.-butyl alcohol 失效
标题翻译：叔丁醇气相催化氧化方法
公开(公告)号：US3954856A
公开(公告)日：1976-05-04
申请号：US501681
申请日：1974-08-29
申请人： Masao Kobayashi , Hideo Matsuzawa , Kantaro Yamada , Hiromichi Ishii
发明人： Masao Kobayashi , Hideo Matsuzawa , Kantaro Yamada , Hiromichi Ishii
IPC分类号： B01J23/89 , B01J27/057 , B01J27/19 , C07C45/37 , C07C51/235 , C07C57/05 , C07C51/26 , C07C45/16
CPC分类号： C07C45/37 , B01J23/8993 , B01J27/0576 , B01J27/19 , C07C51/235 , B01J2523/00
摘要： Oxidation of tert.-butyl alcohol is accomplished by contacting said alcohol with a tungsten-molybdenum-tellurium-nickel catalyst in the vapor phase at an elevated temperature in the presence of oxygen, in order to produce methacrolein and methacrylic acid. The catalyst desirably contains phosphorus and/or antimony in addition to the elements mentioned above.
摘要翻译：叔丁醇的氧化是通过在氧气存在下在升高的温度下在气相中使所述醇与钨 - 钼 - 碲 - 镍催化剂接触来实现的，以产生甲基丙烯醛和甲基丙烯酸。催化剂除了上述元素之外，还期望含有磷和/或锑。

4. 发明授权

US3972920A Process for producing unsaturated aldehydes, unsaturated fatty acids or conjugated dienes 失效
标题翻译：生产不饱和醛，不饱和脂肪酸或共轭二烯的方法
公开(公告)号：US3972920A
公开(公告)日：1976-08-03
申请号：US474218
申请日：1974-05-29
申请人： Hiromichi Ishii , Hideo Matsuzawa , Masao Kobayashi , Kantaro Yamada
发明人： Hiromichi Ishii , Hideo Matsuzawa , Masao Kobayashi , Kantaro Yamada
IPC分类号： B01J23/88 , B01J23/887 , C07C5/48 , C07C45/34 , C07C45/35 , C07C45/37 , C07C51/235 , C07C51/25 , C07C57/055 , C07C51/24 , C07C51/32
CPC分类号： B01J23/8872 , B01J23/8871 , B01J23/8875 , B01J23/8876 , C07C45/34 , C07C45/35 , C07C45/37 , C07C5/48 , C07C51/235 , C07C51/252 , B01J2523/00
摘要： Methacrolein is produced by catalytically oxidizing t-butyl alcohol with oxygen by using a catalyst system of MoSbBiFeNi-alkali. Propylene or isobutylene can also be catalytically oxidized with the same catalyst system to produce acrolein or methacrolein. Methacrolein and 1,3-butadiene can simultaneously be produced by catalytically oxidizing a mixture of isobutylene and n-butene with the same catalyst.
摘要翻译：通过使用MoSbBiFeNi-碱的催化剂体系，用氧催化氧化叔丁醇制备了甲基丙烯醛。丙烯或异丁烯也可以用相同的催化剂体系催化氧化以产生丙烯醛或甲基丙烯醛。通过用相同的催化剂催化氧化异丁烯和正丁烯的混合物可同时制备甲基丙烯醛和1,3-丁二烯。

5. 发明授权

US3998876A Catalytic process for preparation of unsaturated carboxylic acids 失效
标题翻译：用于制备不饱和羧酸的催化方法
公开(公告)号：US3998876A
公开(公告)日：1976-12-21
申请号：US545905
申请日：1975-01-31
申请人： Masaaki Kato , Hiroshi Sonobe , Hiromichi Ishii , Masao Kobayashi , Kantaro Yamada
发明人： Masaaki Kato , Hiroshi Sonobe , Hiromichi Ishii , Masao Kobayashi , Kantaro Yamada
IPC分类号： B01J23/28 , B01J23/34 , B01J23/887 , B01J27/186 , B01J27/24 , C07C51/25 , C07C57/055 , C07C51/32
CPC分类号： B01J27/24 , B01J23/28 , B01J23/34 , B01J23/8876 , B01J27/186 , C07C51/252 , B01J2523/00
摘要： The gas phase catalytic oxidation of an unsaturated aldehyde with molecular oxygen at 240.degree. to 390.degree. C to give the corresponding unsaturated carboxylic acid is conducted in the presence of a catalyst represented by the following formula:P.sub.a Mo.sub.b As.sub.c (NH.sub.4).sub.d X.sub.e Y.sub.f O.sub.gwherein a, b, c, e, f and g represent the atomic ratio of each component and a is 0.03 to 0.2, b is 1, c is 0.015 to 0.15, e is 0.003 to 1, f is 0 to 0.17, g is a value determined by the valencies of the elements present in the catalyst, and d designates the number of ammonium groups which are within the range of 0.01 to 0.3, and wherein X is at least one metal selected from the group consisting of vanadium, tungsten, copper, iron, manganese and tin, and Y is at least one alkali metal element selected from the group consisting of lithium, sodium, potassium, rubidium and cesium. This catalyst is especially effective for the preparation of methacrylic acid from methacrolein, and it has a very long life.

6. 发明授权

US4118419A Catalytic process for the preparation of an unsaturated carboxylic acid 失效
标题翻译：用于制备不饱和羧酸的催化方法
公开(公告)号：US4118419A
公开(公告)日：1978-10-03
申请号：US745406
申请日：1976-11-26
申请人： Kazuhiro Ishii , Hideo Matsuzawa , Masao Kobayashi , Hiromichi Ishii
发明人： Kazuhiro Ishii , Hideo Matsuzawa , Masao Kobayashi , Hiromichi Ishii
IPC分类号： B01J23/31 , B01J23/34 , B01J23/58 , B01J23/63 , B01J23/88 , B01J27/057 , B01J27/186 , B01J27/192 , B01J27/195 , C07C51/25 , C07C57/055 , C07C51/32
CPC分类号： B01J23/63 , B01J23/31 , B01J23/34 , B01J23/58 , B01J23/88 , B01J27/0573 , B01J27/186 , B01J27/192 , B01J27/195 , C07C51/252 , B01J2523/00
摘要： The gas phase catalytic oxidation of an unsaturated aldehyde with molecular oxygen at 240.degree. to 450.degree. C to the corresponding unsaturated carboxylic acid is conducted in the presence of a catalyst of the formula:P.sub.a Mo.sub.b Bi.sub.c Sb.sub.d X.sub.e Y.sub.f O.sub.gwherein Mo is molybdenum, P is phosphorus, Bi is bismuth, Sb is antimony, O is oxygen, X is at least one element selected from the group consisting of potassium rubidium, cesium and thallium; and Y is at least one element selected from the group consisting of cobalt, zinc, niobium, chromium, nickel, iron, silicon, tantalum, cadmium, uranium, manganese, copper, thorium, selenium, aluminum, titanium, tungsten and cerium, and wherein the subscripts a-g represent the atomic ratio of each component such that a is 0.5 to 6, b is 12, c is 0.01 to 6, d is 0.01 to 12, e is 0.2 to 6, f is 0.01 to 6, and g is a value which is determined by the valencies of the elements present in the catalyst.
摘要翻译：不饱和醛与240分钟到450℃的分子氧气相催化氧化成相应的不饱和羧酸，在下式催化剂存在下进行：

7. 发明授权

US4165296A Method for regenerating an oxidation catalyst 失效
标题翻译：再生氧化催化剂的方法
公开(公告)号：US4165296A
公开(公告)日：1979-08-21
申请号：US887802
申请日：1978-03-17
申请人： Hiromichi Ishii , Hideo Matsuzawa , Masao Kobayashi , Masaaki Kato
发明人： Hiromichi Ishii , Hideo Matsuzawa , Masao Kobayashi , Masaaki Kato
IPC分类号： B01J23/28 , B01J27/28 , C07C51/25 , B01J23/92 , C07C45/02 , C07C51/24
CPC分类号： B01J27/285 , B01J23/28 , C07C51/252 , Y02P20/584
摘要： A phosphorus-molybdenum-alkali metal-containing catalyst for the gas-phase oxidation of an unsaturated aldehyde to an unsaturated carboxylic acid is regenerated by treating it with an aqueous solution containing ammonia and hydrogen peroxide or ozone.
摘要翻译：通过用含有氨和过氧化氢或臭氧的水溶液处理来将不饱和醛气相氧化成不饱和羧酸的含磷 - 钼 - 碱金属的催化剂再生。

8. 发明授权

US4035418A Process for producing unsaturated aldehydes and unsaturated carboxylic acids 失效
标题翻译：不饱和醛和不饱和羧酸的制备方法
公开(公告)号：US4035418A
公开(公告)日：1977-07-12
申请号：US663365
申请日：1976-03-03
申请人： Kazuya Okada , Hideo Matsuzawa , Hiromichi Ishii , Masao Kobayashi
发明人： Kazuya Okada , Hideo Matsuzawa , Hiromichi Ishii , Masao Kobayashi
IPC分类号： B01J23/88 , B01J23/89 , B01J27/057 , C07C5/48 , C07C45/35 , C07C45/37 , C07C51/235 , C07C51/25 , C07C57/05 , C07C45/16 , C07C51/24
CPC分类号： B01J23/8873 , B01J23/8872 , B01J23/8876 , B01J23/8877 , B01J23/8993 , B01J27/0573 , B01J27/0576 , C07C45/35 , C07C45/37 , C07C5/48 , C07C51/235 , C07C51/252 , B01J2523/00
摘要： An olefin having 4 carbon atoms or t-butyl alcohol is catalytically oxidized in the gas phase with molecular oxygen at 200.degree. to 450.degree. C to give the corresponding unsaturated aldehyde, unsaturated carboxylic acid and/or conjugated diene in the presence of a catalyst having the formula:Mo.sub.a Sb.sub.b Bi.sub.c Fe.sub.d Ni.sub.e Co.sub.f Sn.sub.g X.sub.h Y.sub.i O.sub.jwherein a to j represent the atomic ratio of each component and a is 12, b is 0.2 to 20, c is 0.2 to 12, d is 0.2 to 12, e is 0.2 to 12, f is 0 to 20, g is 0 to 20, h is 0.01 to 4, i is 0.01 to 4 and j is a value determined by the valencies of the elements in the catalyst, and wherein X is at least one metal selected from the group consisting of potassium, rubidium, cesium and thallium, and Y is at least one metal selected from the group consisting of selenium, tellurium, gallium, vanadium, ruthenium, zinc, niobium, magnesium, chromium, manganese, cadmium and tantalum.
摘要翻译：具有4个碳原子的烯烃或叔丁醇在气相中在分子氧在200-450℃下被催化氧化，得到相应的不饱和醛，不饱和羧酸和/或共轭二烯，在催化剂存在下，公式：

9. 发明授权

US4985592A Process for the preparation of unsaturated carboxylic acids 失效
标题翻译：不饱和羧酸的制备方法
公开(公告)号：US4985592A
公开(公告)日：1991-01-15
申请号：US952111
申请日：1978-10-17
申请人： Hiromichi Ishii , Hideo Matsuzawa , Masao Kobayashi , Kazuhiro Ishii
发明人： Hiromichi Ishii , Hideo Matsuzawa , Masao Kobayashi , Kazuhiro Ishii
IPC分类号： B01J23/28 , B01J23/34 , B01J23/88 , B01J23/89 , B01J27/19 , B01J27/199 , C07C51/25 , C07C57/055
CPC分类号： B01J23/8873 , B01J23/002 , B01J23/28 , B01J23/34 , B01J23/8872 , B01J23/8876 , B01J23/8877 , B01J23/8993 , B01J27/19 , B01J27/199 , C07C51/252 , B01J2523/00
摘要： The gas phase catalytic oxidation of an unsaturated aldehyde with molecular oxygen at 200.degree. to 500.degree. C. to give the corresponding unsaturated carboxylic acid is conducted in the presence of a catalyst represented by the following formula:Mo.sub.12 P.sub.a X.sub.b Y.sub.c Z.sub.d O.sub.ewherein the subscripts represent the atomic ratios of each component and a is 0.5 to 6, b is 0.001 to 6, c is 0.2 to 6, d is 0 to 6, and e is a value determined by the valencies of the elements present in the catalyst; and Mo is molybdenum, P is phosphorus, O is oxygen, X is at least one metal selected from the group consisting of rhodium, cerium and zirconium, Y is at least one alkali metal selected from the group consisting of potassium, rubidium and cesium, and Z is at least one metal selected from the group consisting of iron, cobalt, nickel, zinc, antimony, silicon, bismuth, cadmium, uranium, manganese, copper, vanadium, niobium and tantalum. This catalyst is especially effective for the preparation of methacrylic acid from methacrolein and has a very long life time.
摘要翻译：用分子氧在200〜500℃下不饱和醛进行气相催化氧化，得到相应的不饱和羧酸，在下式表示的催化剂存在下进行：Mo12PaXbYcZdOe，其中下标表示每个组分和a为0.5至6，b为0.001至6，c为0.2至6，d为0至6，e为由催化剂中存在的元素的价数确定的值; Mo是钼，P是磷，O是氧，X是选自铑，铈和锆中的至少一种金属，Y是选自钾，铷和铯中的至少一种碱金属， Z是选自铁，钴，镍，锌，锑，硅，铋，镉，铀，锰，铜，钒，铌和钽中的至少一种金属。该催化剂对于从甲基丙烯醛制备甲基丙烯酸并且具有非常长的使用寿命特别有效。

10. 发明授权

US4341900A Catalytic process for the preparation of unsaturated carboxylic acid 失效
标题翻译：用于制备不饱和羧酸的催化方法
公开(公告)号：US4341900A
公开(公告)日：1982-07-27
申请号：US663361
申请日：1976-03-03
申请人： Hiromichi Ishii , Hideo Matsuzawa , Masao Kobayashi , Masato Otani
发明人： Hiromichi Ishii , Hideo Matsuzawa , Masao Kobayashi , Masato Otani
IPC分类号： B01J23/28 , B01J23/88 , B01J27/186 , C07C51/25 , C07C57/055
CPC分类号： B01J23/8872 , B01J23/28 , B01J23/887 , B01J23/8875 , B01J23/8876 , B01J23/8878 , B01J27/186 , C07C51/252 , B01J2523/00
摘要： The gas phase catalytic oxidation of an unsaturated aldehyde with molecular oxygen at 240.degree. to 450.degree. C. to give the corresponding unsaturated carboxylic acid is conducted in the presence of a catalyst of the following formula:Mo.sub.12 P.sub.a Q.sub.b R.sub.c X.sub.d Y.sub.e Z.sub.f O.sub.gwherein Mo is molybdenum, P is phosphorus, O is oxygen, Q is calcium and/or magnesium, R is at least one metal element selected from the group consisting of potassium, rubidium, cesium and thallium, X is at least one element selected from the group consisting of boron, silicon, manganese, iron, cobalt, zinc, germanium, uranium, tin, lead, chromium, titanium, tantalum, antimony, niobium and bismuth, Y is at least one metal element selected from the group consisting of vanadium, copper and nickel, Z is strontium and/or barium, and wherein the subscripts represent the atomic ratio of each component and a is 0.5 to 6, b is 0.2 to 6, c is 0.2 to 6, d is 0.01 to 6, e is 0 to 6, f is 0 to 6, and g is a value determined by the valencies of the elements present in the catalyst.
摘要翻译：不饱和醛在240-450℃下的气相催化氧化，得到相应的不饱和羧酸，在下式催化剂存在下进行：Mo12PaQbRcXdYeZfOg，其中Mo是钼，P是磷， O是氧，Q是钙和/或镁，R是至少一种选自钾，铷，铯和铊的金属元素，X是选自硼，硅，锰中的至少一种元素，铁，钴，锌，锗，铀，锡，铅，铬，钛，钽，锑，铌和铋，Y是选自钒，铜和镍中的至少一种金属元素，Z是锶， /或钡，其中下标表示各成分的原子比，a为0.5〜6，b为0.2〜6，c为0.2〜6，d为0.01〜6，e为0〜6，f为0〜 6，g是由元素的价值确定的值存在于催化剂中。

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