Catalyst for oxidizing and oxidizing ammonolysis of c3-c4 olefines

专利摘要:
The catalyst composition has a composition represented by the formula:… A0.1 B0.02-1 Mo12 Bi0.5-10 Fe0.5-10 Na0-3 P0-2 Og… wherein A is at least one element selected from cerium, lanthanum, neodymium, praseodymium, samarium, europium, and gadolinium, B is at least one element selected from potassium, rubidium and caesium, and g is the number of oxygen atoms required to satisfy the valence requirements of the other elements present, and is supported on silica. The catalyst composition is used in the production of acrolein, methacrolein, 1,3-butadiene, acrylonitrile or methacrylonitrile by the oxidation or ammoxidation of propylene, isobutylene, tert-butanol or 1-butene.
公开号:SU1217244A3
申请号:SU823505000
申请日:1982-10-19
公开日:1986-03-07
发明作者:Аоки Кинитоси；Хонда Макото；Дозоно Тетсуро；Катсумата Тсутому
申请人:Асахи Касеи Когио Кабусики Кайся (Фирма)；
IPC主号:

专利说明:

The invention relates to the field of catalysts for the oxidation and oxidative ammoniaol of olefins.
The aim of the invention is to increase the activity of the catalyst due to the additional content in the active part of the catalyst of a metal selected from the group comprising cerium, lanthanum, neodymium, praseodymium, samarium, europium, gadolinium or their mixture at a certain ratio of components.
The goal is also to increase the stability of the catalysts, due to the additional content in the active part of the catalyst of sodium and / or phosphorus in a certain amount.
Example 1. Get the catalyst containing 50 wt.% The active part having the composition of the following empirical formula
%, bcHot5Mo, gWH ,, ,,, Og,
and 50 wt.% silica.
To 166.7 g of a silica sol containing 30 wt.% W.O.G, 0.59 g of 85% phosphoric acid is added with stirring, then a solution of 36.2 g of ammonium heptamolybdate (NH4), 4 HjO, dissolved in 90 g of water and a mixed solution of 19.84 g of bismuth nitrate Bi (N0,), 46.61 g of iron nitrate (Ø) .FeCNOjX, 70 g of cerium nitrate Ce (NO,),: 6H. b and 0.1 g of potassium nitrate (KNO), previously dissolved in 33 g of 13.3 wt.% nitric acid. The raw material slurry thus obtained is sent to a spray dryer of a continuous type and dried at 200 C. The drying of the slurry is carried out using a spraying device equipped with a disc-shaped rotor installed in the upper, central part of the dryer. The obtained dried powders are sent to a tunnel-type kiln, calcined first at 400 ° C for one hour, and then fired at 690 ° C for 2 hours.
Using the technology described above, the catalysts provided by the invention and the control catalysts are prepared, and their compositions are given in Table. 1 and 2. For the sources of lanthanum, neodymium, praseodymium, samari, europium, gadrini, rubidium, cesium and sodium, the corresponding nitrates are used in the examples. The firing conditions are changed accordingly. as shown in table. 1 and 2.
Example 2. Ammoxidation of propylene.
2 g catalysts of various compositions are loaded into a Bikor glass reaction tube with an internal diameter of 8 mm, and a gas mixture of 6% by volume of propylene (the volume ratio between propylene: ammonia: oxygen: nitrogen is
ten
20
1: 1.25: 1.9: 12.5) is passed through the tube at a flow rate of 2.1 l / h (recalculated to normal temperature and pressure) at 460 C and atmospheric pressure. The result of this reaction is evaluated according to two indices — the yield of acrylonitrile and the productivity of acryloetrile, the values of which are given in tabLb 1. jc Acrylonitrile yield:
, moth prune e nogch5 acrylonite sludge moth introduced propylene
thirty
35
40
X 100.
Acrylo-I nitrile productivity:
rl wSeSJIPJIX JiilPJlP-SEPSG SIP ™ amount of catalyst used (g)
X 100 X reaction time (h).
Example 3. Ammo-oxidation of isobutylene (or tertiary butanol).
Catalysts of various compositions in the amount of 1 g are loaded into a Vicor glass reaction tube with an internal diameter of B mm, and a gas mixture of 6% by volume of isobutylene (the volume ratio between isobutylene, ammonia, oxygen, and nitrogen is 5: 2.5: 11 , 7) is passed through a tube at a flow rate of 2.4 l / h (recalculated at normal temperature and pressure) at atmospheric pressure. The effect of this reaction is assessed by two indicators: the yield of acrylonitrile and the productivity of acrylonitrile, the values of which are given in Table. 2
The output of methacrylonitrile: 55 moles obtained methacryl "lonitrile (g)
i (/ a) -X
moth entered isobutylene
X 100
50
ri, europium, gadrini, rubidi, cesium and sodium in the examples use the corresponding nitrates. The firing conditions are changed accordingly. as shown in table. 1 and 2.
Example 2. Ammoxidation of propylene.
2 g catalysts of various compositions are loaded into a Bikor glass reaction tube with an internal diameter of 8 mm, and a gas mixture of 6% by volume of propylene (the volume ratio between propylene: ammonia: oxygen: nitrogen is
Methacrylonitrile productivity:
weight of methacryne obtained, lonitrile (g)
K (h) X
amount of catalyst used (g) X 100 X reaction time (h).
Example4. Oxidation of propylene.
 Catalyst containing 50 May.%
the active part of the composition
Clo.t3,076 I ° uB447F 6., 30g
And 50 wt.% SiOj, in an amount of 1., 5 g is loaded into a Vicor glass reaction tube with an internal diameter of 8 mm, and a gas mixture of 6 vol.% Propylene (the volume ratio between propylene, oxygen, water vapor, nitrogen is 1 : 1.9: 3: 10.8) is passed through a tube at a flow rate of 2.3 l / h (calculated at normal temperature and pressure) at 380 ° C and atmospheric pressure.
acrolein
 received
acrolein
moles of injected propylene
X 100 85.8%.
Example 5. The oxidation of isobutylene.
The catalyst containing 50 May.% Active part of the composition
Vg ,, Fe. ., P .0 og and
H ,,
Xie, Kg., Mo, g
50 wt.% Sic., In. amount of 1 g is loaded into a Vicor glass reaction tube with an internal diameter of 8 mm, and gaz12172444
This mixture of 3 vol.% isobutylene (volume ratio of isobutylene, oxygen, water vapor, and nitrogen is .1: 2: 3: 27.3) is passed through a 5 tube at a flow rate of 2.4 l / h (calculated with normal temperature and pressure) at 400 ° C and atmospheric
pressure.
Methacrolein yield
moth received
methacrolein
moth injected isobutylene
X 100 82.6%.
Example 6. The oxidation of 1-butylene.
A catalyst having the composition specified in example 4, in an amount of 1 g, is loaded into a Vicor reaction tube with an internal diameter of 8 mm, and a gas mixture of 6% by volume of 1-butylene (volume ratio of 1-butylene, oxygen, water vapor, nitrogen is 1: 1.8: 3: 10.9), passed through a tube at a flow rate of 2.6 l / h (calculated at normal temperature and pressure) at 370 ° C and atmospheric pressure.
Output 1, 3-butadi.ena
moth obtained 1,3-butadiene
moth entered 1-bootklena
X 100 89.0%.
In tab. 3 presents the results showing the stability of the catalyst according to the invention in the process of oxidative ammonolysis of propylene.
C
ON
in
OO
in
OO
in
OO
o
OO
00
CNJ
m
00
v) 00
SL
CO
a
Ltd
ON-oh
X)
about sh
about sh
about sh
oh oh
oh oh
about
g
r cho
g
vO
about 00
go
gp
cm
CS
oh oh
wh
oh oh
cJF o
about
00
about
0)
and
 cm

权利要求:
Claims (2)
[1]
1. CATALYST FOR THE OXIDATION AND OXIDATIVE AMMONOLYSIS OF SC-C ^ OLEFINS, containing the active part, including the alkali metal potassium, rubidium, cesium, molybdenum, bismuth ^ iron and oxygen, and the carrier is silicon dioxide, characterized in that, in order to increase activity catalyst, the active part of it additionally contains a metal selected from the group consisting of cerium, lanthanum, neodymium, praseodymium, samarium, europium, gadolinium or a mixture thereof, and its composition corresponds to the empirical formula ^A a ^B b ^Mo 'where A is a metal selected from group including erya, Lanthanum, neodymium, praseodymium, samarium, europium, Gado * lines or their mixture;
In ~ alkali metal - potassium, rubidium, cesium, a = 0.1-4.0;
B = 0.02-1, 0;
s = 0.5-9.2;
d = 3.0-10.0;
g is the number of oxygen atoms necessary to satisfy the valency of the incoming elements, with the following content of components, May.%:
Active part 30-70
Media Else
[2]
2. The catalyst according to claim 1, characterized in that, in order to increase the stability of the catalyst, its active part additionally contains sodium and / or phosphorus and its composition corresponds to the empirical formula A _tJ B _b Mo _ft Bi ^ FejNa ^ Oj, or A _a B _b Mo _u Bi _c FejP O., or ^A a4 ^Mo < _Z ^Bi c ^Fe d ^E e ° "> where E is sodium and phosphorus;
e - 2.2-3.3;
A, B, a, b, c, d, g have the meanings indicated above.

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同族专利:

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引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

RU2454277C2|2007-06-25|2012-06-27|ЭСЕНД ПЕРФОРМАНС МАТИРИАЛЗ ЭлЭлСи|Method of producing hydrogen cyanide through catalytic oxidation in ammonia medium|

---

RU2615762C2|2012-09-28|2017-04-11|Асахи Касеи Кемикалз Корпорейшн|Oxide catalyst and method of producing thereof, as well as methods of producing unsaturated aldehyde, diolefin and unsaturated nitrile|JPS4843096B1|1970-01-31|1973-12-17|

---

US3712912A|1970-04-24|1973-01-23|Erdoelchemie Gmbh|Process for preparing acrylonitrile|

---

US4000176A|1970-05-18|1976-12-28|Nitto Chemical Industry Co., Ltd.|Process for simultaneously producing methacrylo-nitrile and butadiene by vapor-phase catalytic oxidation of mixed butenes|

---

NL175175C|1970-10-30|1984-10-01|Standard Oil Co Ohio|PROCESS FOR CONVERTING PROPENE AND / OR ISOBUTENE WITH A MOLECULAR OXYGEN-CONTAINING GAS AND AMMONIA IN THE PRESENCE OF A CATALYST.|

---

DE2104223C3|1971-01-29|1974-07-18|Knapsack Ag, 5033 Huerth-Knapsack|Process for the production of acrylonitrile by the oxidation of propylene|

---

CA975382A|1971-02-04|1975-09-30|Arthur F. Miller|Process for the manufacture of acrylonitrile and methacrylonitrile|

---

US4182907A|1971-02-04|1980-01-08|The Standard Oil Company |Process for the oxidation of olefins to aldehydes and acids|

---

BE785663A|1971-07-02|1973-01-02|American Cyanamid Co|OXIDATION OF PROPANE IN THE PRESENCE OF AMMONIA|

---

IT967894B|1971-09-27|1974-03-11|Fmc Corp|ANTI-STAIN COMPOUNDS BASED ON FLUORINATED POLYURETHANS AND PROCESSES FOR THEIR APPLICATION TO TEXTILE PRODUCTS|

---

US3932551A|1973-10-12|1976-01-13|The Standard Oil Company|Process for the preparation of diolefins from olefins|

---

US4192776A|1973-12-19|1980-03-11|The Standard Oil Company|Catalysts and process for the ammoxidation of olefins|

---

US4139552A|1974-01-04|1979-02-13|The Standard Oil Company|Production of unsaturated nitriles|

---

JPS5432766B2|1974-06-04|1979-10-16|

---

AT353766B|1974-07-22|1979-12-10|Standard Oil Co Ohio|PROCESS FOR PRODUCING UNSATATURATED ALDEHYDE AND ACIDS FROM PROPYLENE OR ISOBUTYLENE|

---

US4001317A|1974-07-22|1977-01-04|Standard Oil Company|Process for the oxidation of olefins using catalysts containing various promoter elements|

---

US4118419A|1975-12-03|1978-10-03|Mitsubishi Rayon Company, Ltd.|Catalytic process for the preparation of an unsaturated carboxylic acid|

---

JPS574631B2|1976-05-11|1982-01-27|

---

US4323520A|1976-08-02|1982-04-06|The Standard Oil Co.|Preparation of methacrylic derivatives from tertiary-butyl-containing compounds|

---

JPS5945415B2|1976-12-13|1984-11-06|Nippon Zeon Co|

---

US4148757A|1977-08-10|1979-04-10|The Standard Oil Company|Process for forming multi-component oxide complex catalysts|

---

JPS582232B2|1977-12-31|1983-01-14|Asahi Chemical Ind|

---

JPS6041665B2|1978-07-25|1985-09-18|Asahi Chemical Ind|

---

JPS6041666B2|1978-07-26|1985-09-18|Asahi Chemical Ind|

---

JPS6123174B2|1978-07-28|1986-06-04|Asahi Chemical Ind|

---

JPS6121459B2|1978-08-08|1986-05-27|Asahi Chemical Ind|

---

DE2841712A1|1978-09-25|1980-04-10|Basf Ag|PROCESS FOR THE PREPARATION OF P-SUBSTITUTED BENZALDEHYDE|

---

JPS5916817B2|1979-04-18|1984-04-18|Ube Industries|

---

JP4849719B2|2001-01-15|2012-01-11|和史 金丸|Information distribution system|

---

WO2006106712A1|2005-03-31|2006-10-12|Matsushita Electric Industrial Co., Ltd.|Communication control method, communication node, and mobile node|

---

JP4716419B2|2005-11-29|2011-07-06|株式会社吉田製作所|Digital panoramic X-ray imaging apparatus and super-resolution tomographic image construction method based on super-resolution theory|

---

JP5495513B2|2008-06-02|2014-05-21|株式会社大貴|Animal excrement disposal materials|

---

ES2391755T3|2009-06-13|2012-11-29|Bandai Co., Ltd.|Yo-yo|

---

JP5519227B2|2009-09-28|2014-06-11|株式会社アマダ|Shelf equipment|

---

JP5517334B2|2009-12-04|2014-06-11|株式会社ジャパーナ|snow board|

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JP5517356B2|2010-10-20|2014-06-11|株式会社堀場製作所|X-ray fluorescence analysis method and X-ray fluorescence analyzer|

---

JP5522639B2|2011-12-08|2014-06-18|防衛省技術研究本部長|Photodetector and imaging device|JPS6158462B2|1983-05-06|1986-12-11|Asahi Chemical Ind|

---

JPH0625085B2|1984-07-24|1994-04-06|三菱レイヨン株式会社|Method for producing methacrolein and methacrylic acid|

---

JPS61204038A|1985-03-07|1986-09-10|Mitsubishi Chem Ind Ltd|Catalyst composition|

---

EP0713724B1|1993-08-10|1999-05-19|Asahi Kasei Kogyo Kabushiki Kaisha|Ammoxidation catalyst composition and process for producing acrylonitrile or methacrylonitrile by using the same|

---

US5658842A|1993-08-10|1997-08-19|Asahi Kasei Kogyo Kabushiki Kaisha|Ammoxidation catalyst composition, and process for producing acrylonitrile or methacrylonitrile using the same|

---

US5780664A|1993-08-17|1998-07-14|Asahi Kasei Kogyo Kabushi Kaisha|Ammoxidation catalyst composition|

---

JP3214975B2|1994-04-25|2001-10-02|旭化成株式会社|Ammoxidation catalyst composition and production method|

---

US5728894A|1994-06-22|1998-03-17|Ashahi Kasei Kogyo Kabushiki Kaisha|Method for producing methacrolein|

---

US5834394A|1996-08-06|1998-11-10|China-Petro-Chemical Corporation|Fluidized-bed catalyst for propylene ammoxidation to acrylonitrile|

---

CN1100612C|1999-08-19|2003-02-05|中国石油化工集团公司|Fluidized bed catalyst for oxidation of propene ammonia|

---

CN1094073C|1999-08-19|2002-11-13|中国石油化工集团公司|Fluidized bed catalyst for production of acrylonitrile|

---

JP4242197B2|2003-04-18|2009-03-18|ダイヤニトリックス株式会社|Catalyst for acrylonitrile synthesis|

---

US7649112B2|2005-07-25|2010-01-19|Saudi Basic Industries Corporation|Integrated plant for producing 2-ethyl-hexanol and methacrylic acid and a method based thereon|

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---

US7732367B2|2005-07-25|2010-06-08|Saudi Basic Industries Corporation|Catalyst for methacrolein oxidation and method for making and using same|

---

US7799946B2|2007-02-14|2010-09-21|Saudi Basic Industries Corporation|Process for separating methacrolein from methacrylic acid in a gas phase product from the partial oxidation of isobutene|

---

JP5130113B2|2008-05-14|2013-01-30|株式会社日本触媒|Acrolein production method|

---

US8455388B2|2010-03-23|2013-06-04|Ineos Usa Llc|Attrition resistant mixed metal oxide ammoxidation catalysts|

---

US8921257B2|2011-12-02|2014-12-30|Saudi Basic Industries Corporation|Dual function partial oxidation catalyst for propane to acrylic acid conversion|

---

US8722940B2|2012-03-01|2014-05-13|Saudi Basic Industries Corporation|High molybdenum mixed metal oxide catalysts for the production of unsaturated aldehydes from olefins|

法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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JP56166423A|JPS6126419B2|1981-10-20|1981-10-20|

---