JPS58188823A - Preparation of 1,3-butadiene - Google Patents

Abstract

PURPOSE:To obtain 1,3-butadiene, by oxidizing n-butene with O2 in the presence of a catalyst prepared by adding Ni to a system of Mo, Bi, Fe, Co and Sb, and further adding a metal selected from K, Rb, and Cs and a metal selected from Li, Na and Tl thereto. CONSTITUTION:n-Butene is catalytically oxidized with molecular oxygen in the vapor phase in the presence of a catalyst of the formula (X is at least one element selected from K, Rb and Cs; Y is at least one element selected from Li, Na and Tl ; a-i are the respectively atomic composition ratio, and when a is 12, b is 0.1-8; c is 0.1-15; d is 0.1-15; e is 0.01-5; f is 0.1-8; g is 0-0.7; h is 0-10; i depends on the valences of the respective elements) to give the aimed 1,3-butadiene. EFFECT:The amount of deposited carbon on the catalyst can be reduced, and the catalyst life is long. The regeneration temperature of the catalyst is low, and the apparatus cost is low. Therefore, the cost of regeneration energy is reduced.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing 1,3-butadiene, and more particularly, to a method for producing 1,3-butadiene by catalytically oxidizing lubutene in the presence of a specific catalyst.

Conventionally, rubene was catalytically oxidized in the gas phase in the presence of a catalyst.
．． It is known to produce 3-butadiene, and various catalysts have been proposed for use in this process.For example, a catalyst containing Ma, Bi and F as essential components (Japanese Patent Publication No.
9-3498, Special Publication No. 49-5321), kBi,
Catalyst containing Cr and N as essential components (4I Kaisho 56-
140931, JP-A-56-150023), etc. are known. Furthermore, a method for simultaneously producing methacrolein and 1,3-butadiene using a mixture of isobutylene and lubutene as raw materials is also known, and various catalysts for use in this process have been proposed (for example, Japanese Patent Publication No. 47-42
No., Special Publication No. 50-4643, etc.). In particular, blo, Bi, Fg%Co, S, which the present inventors discovered earlier
The catalyst containing b as an essential component is extremely excellent as a catalyst for the production of methacrolein and for the simultaneous production of methacrolein with 1,3-butadiene (Japanese Patent Application Laid-Open No. 50-401
No. 0, JP-A-50-130709, JP-A-51-70
No. 709) 6 However, these catalysts have low activity when producing 1,3-butadiene as a raw material of the lubutene fraction, and there is a problem in industrial practice.

Furthermore, when producing 1,3-butadiene using these catalysts, if the reaction is continued for a long time, carbon will deposit on the catalyst and the looptene conversion rate and 1,3-butadiene selectivity will gradually decrease. Therefore, it was necessary to appropriately regenerate the catalyst.

Regeneration of the catalyst can be carried out relatively easily by passing oxygen diluted with a suitable inert gas over the catalyst maintained at a high temperature. However, unless the catalyst bed temperature at this time is set much higher than the reaction temperature, a sufficient regeneration effect cannot be obtained, and as a result, there is a drawback that thermal deterioration of the catalyst is likely to occur and the catalyst life is shortened.

As a result of intensive research to eliminate these drawbacks of the conventional methods, the present inventors found that MoR1Ft-('o Sb-based catalyst Vt
, -Nt has been found to significantly improve the activity and, unexpectedly, to significantly lower the regeneration temperature of the catalyst. Furthermore, the activity and selectivity are increased by adding at least one metal selected from the group consisting of K, Rh, and Cz to these metal components;
The present inventors have discovered that carbon adhesion to the catalyst can be reduced by adding at least one metal selected from the group consisting of Na and Tl, and have completed the present invention.

The present invention combines looptene and molecular oxygen with the general formula %.
(1) (wherein X &i K%Rh and C, at least one element selected from the group consisting of; α, b, c, d, e, f, fi, A and L
are Mo, Bi, Fg, Co, Sb, Ni, and X, respectively.
, indicates the atomic composition ratio of Y and 0, and when α-12, b = 0.1 ~ 8, C ~ 0.1 ~ 15, d ~ 0
．． 1-15, g=0.01-5, f=0.1-81
．． 9 = 0-0.7.4-: O ~ to, i is a value determined by the valence of each element) The gas phase catalytic reaction is carried out in the presence of a catalyst. 1.3
- A method for producing butanene.

The catalyst used in the present invention is represented by the general formula (1).
RuyoK contains locus as an essential component. Traditionally, N7 has often been used as a component of oxidation reaction catalysts (
In the catalyst system of the present invention, the addition of NZ has the effect of improving the activity and significantly lowering the regeneration temperature of the catalyst.

Further, the catalyst of the present invention contains K and R/ as optional components.

and at least one w selected from the group consisting of Cz
, IE with Li, Na and TI as optional components.
Contains at least one element selected from the group consisting of: When the latter Lt, Na or TI is added in a relatively large amount, it is effective in reducing carbon deposition on the catalyst that occurs during the reaction.

Furthermore, the former K 2 , RA or CJF is used in a relatively small amount, which is effective in improving reaction activity and selectivity.

Ll, NeL and K, RA, Ct belong to the same group IA in the periodic table as alkali metals and are said to have similar general chemical properties, but the effect of catalyst H of the present invention on both is completely different. different. In other words, even if a relatively large amount of LP or Ni7 is added, it has almost no effect on the performance or the adhesion of carbon to the catalyst. , Na, or Tl in a relatively large amount, the reaction activity is greatly reduced, and even if the amount of carbon attached to the catalyst is small, it cannot be considered a practical catalyst.

It is generally said that the salt properties of Tl are similar to those of alkali metal salts (Chemistry Encyclopedia, 5, p. 681).
(Kyoritsu Shuppan)), the effect of the catalyst of the present invention is the above-mentioned L
i is similar to translation a.

In this way, in the present invention, Mo Bi Fa-C□
-8b state, the effect on the reaction activity and selectivity of the system catalyst is that of Li, Na or TI, K, Rh or C,?
Taking advantage of the difference between the two, the former aims to reduce the amount of carbon deposited on the catalyst, while the latter aims to improve reaction activity and selectivity.

In the present invention, high activity and low catalyst regeneration temperature are obtained by using NZ as an essential component of the catalyst, but excessive addition of Nt is undesirable and undesirable because it lowers the selectivity, and the suitable amount of Nt to be used is Atomic ratio: 0.1 to -12 of Mo
-8, preferably 0.3-3.

Furthermore, the addition of K, RA or C5 is effective in improving reaction activity and selectivity as mentioned above, especially when adding RA or C5.
It is preferable to add J. However, adding a large amount of J is also undesirable because it will actually lower the conversion rate, and the preferable amount used is a small amount of 0.7 or less in terms of atomic ratio to 12 of Mo.

The addition of LL% Na or Tl has the effect of reducing carbon deposits deposited on the catalyst during the reaction as described above. However, if these are used in larger amounts than necessary, the catalytic activity will decrease, and the rate of production of carbon oxide and carbon dioxide will increase, which is undesirable. 10 or less, preferably 0
．． 2 to 8.

Although Sh has the effect of improving reaction activity, selectivity, and life span, a trivalent antimony compound and a pentavalent antimony compound can also be used together.

The composition ratio of the catalyst used in the present invention is Mo:Bz:Fe:Co:SA as shown in formula (1).
:Nt:X:Y:0 has an atomic composition ratio of 12:(0,1~
8):(0,1~15):(o,i~15):(0,
01~5):(0,1~g):(0~0.7):(0~
10): (value determined by the valence of each element),
Particularly preferably 12:(0,2-3):(1-12)
: (1~12):(0,1~3) :(0,3~3)
:(0~o,s) :(0~8):(value determined by the valence of each element).

As the raw material for each element used in the preparation of the catalyst, its oxide or a substance that decomposes into an oxide upon calcination is used. Examples of the latter include ammonium salts of each element, nitrates, carbonates, organic acid groups, salts such as halides, hydroxides, free beaks, acid anhydrides, condensed acids or heteropolyacids or their ammonium salts, metals. Examples include salt.

As a method for preparing the catalyst, known methods such as evaporation to dryness method and oxide mixing method can be used, and a carrier can also be used to reduce the actual amount of catalyst used.

When using a carrier, examples of carrier inserts include silica,
Alumina, silicon carbide, etc. can be used. The catalyst is prepared by molding the catalyst components or supporting them on a carrier, and then heating the catalyst to, for example, 400 to 750°C, preferably 45°C.
After firing at 0 to 650°C, it is subjected to reaction.

In the method of the present invention, Kn-butene and molecular oxygen are subjected to a gas phase catalytic reaction in the presence of a catalyst represented by the general formula (1).

Looptenes used as reaction raw materials include 1-butene,
Cis-2-butene and trans-2-butene alone or in combination. Industrially, 1,3-butadiene, imbutylene, and most paraffins are separated from the C4 fraction produced as a by-product in naphtha cracking.
Distillates whose main components are butene and 2-butene, isobutylene and most paraffins removed from C4 fractions produced as by-products from fluid catalytic crackers (FCC) in petroleum refining processes, or dehydrogenation or oxidation of loubutane. The butene fraction produced by dehydrogenation can be used. Butanes do not significantly affect the reaction and may be included in the raw material hydrocarbon, but their presence in large amounts is undesirable as it increases the cost of the recovery system. Some of the above reactions result in co and CCh
However, since its reactivity is low, it may be included in the raw material. Furthermore, 1,2-butadiene and C4 acetylenes react on the catalyst of the present invention, but if the butadiene production reaction is not inhibited due to the small amount, they may be contained in the raw materials. 600~4000 r (Q
℃, 1 atm), but preferably 800 to 300
The molar ratio of loopenes to molecular oxygen in the feedstock introduced into the reaction system is 1t 1 : 0.
．． It is in the range of 6-5. In this reaction, the reaction gas can also be diluted with an inert gas (for example, nitrogen, water vapor, carbon dioxide, waste gas after removing hydrocarbons from the reaction product, etc.) that does not adversely affect the reaction. It is preferable to use air as the oxygen-containing gas. In addition, the presence of water vapor is preferred in this reaction.The reaction temperature in the present invention (in the present invention) is 250 to 600°C, preferably 3ooL4s.

The 0 reaction pressure, which is in degrees Celsius, is the pressure around atmospheric pressure, i.e. 0.
A fixed bed, moving bed or fluidized bed can be used for the reactor which gives sufficiently good results at 9/1rI (absolute pressure) for 5 to 4.0. The reaction product can be recovered and separated by conventional methods such as condensation, absorption, extraction, and distillation.

Next, in the catalyst regeneration process in the present invention, the catalyst bed is
The temperature is maintained at ~750°C, preferably 250-600°C, particularly preferably 300-SOO°C, and oxygen diluted with an inert gas is passed through. However, from the viewpoint of catalyst life, it is preferable to use a low regeneration temperature. . Inert gases used in this case include, for example, nitrogen, water vapor, carbon dioxide, and waste gas after removing hydrocarbons from reaction products, but it is preferable that at least a part of the inert gas is water vapor. It is particularly preferable that the water vapor concentration therein be 5 or more. The ratio (molar ratio) of oxygen and inert gas supplied onto the catalyst during regeneration varies depending on the regeneration temperature and the amount of carbon deposited, but is usually 0. OO may be 1 to 0.1, preferably 0.00
It is 2 to 0.05.

According to the method of the present invention, since the catalyst represented by the general formula (1) is used, even if the gas phase catalytic reaction is continued for a long time using a high concentration of lubutene as a raw material, the amount of carbon deposited on the catalyst is reduced. In addition, since Ni is an essential component, it exhibits high activity, and the regeneration temperature of the catalyst is much lower than that of a catalyst that does not contain Ni, so the temperature of the catalyst during regeneration is much lower than that of conventional catalysts. It can prevent thermal deterioration and extend the life of the catalyst. In addition, since the catalyst regeneration temperature is low in the method of the present invention, there is no need for the reactor and the supply gas equipment for catalyst regeneration to be made of special high heat-resistant materials, which is advantageous in terms of equipment cost. The energy cost required for regeneration is also low, which is a huge industrial advantage.

Hereinafter, the present invention will be explained with reference to examples. In the examples, the looptene conversion rate, 1,3-butadiene selectivity and yield, and the selectivity to carbon oxide or carbon dioxide are calculated by the following formula. In addition, the display of oxygen in the catalyst components is omitted.

Supply Roof-Ten (Morph 1.3-Butadiene occupancy rate (Molch) = Rubch A Bihi (Molch) XI, 3-Butadiene selectivity (Molch) x
100 Example 1 Into an aqueous solution of ammonium molybdate 13.25F, an aqueous solution of cobalt nitrate 9.09# and nickel nitrate i,
Add 2 g of an aqueous solution of antimony trichloride and add an acidic aqueous solution of hydrochloric acid of 1.28 F with good stirring. antimony oxide 0
．． 303 F was added one after another with stirring, and then evaporated to dryness. This was pyrolyzed at 300°C for 4 hours and then ground in a mortar. To the obtained powder 151 was added granular silicon carbide (particle size 3 wax) 22,5 F and distilled water 10
0- was added and evaporated to dryness while stirring to adhere the catalyst component to the carrier.

This was calcined at 550° C. for 4 hours to obtain a catalyst. The atomic ratio of each metal in the catalyst components is Mo:B t:F g:Co:
S A:Ni=12:1:8:5:
It was 1.2:1.

The obtained catalyst LO*l was packed into a quartz reaction chamber with an inner diameter of 20 m, and 13.8 molar width of 1-butene and 6 mol width of cis-2-butene were added.
A raw material gas consisting of 15 moles of a C4 mixture containing 2.2 moles, 17.5 moles of trans-2-butene and 6.5 moles of butanes, 655 moles of air and 200 moles of water vapor was heated at a space velocity (0 ℃, 1 atm standard) 1600
The zero reaction temperature (maximum temperature in the catalyst bed) contacted at hr was 370°C. Reaction start 6.150 and 20
The reaction results after 0 hours are shown in Table 1. After 200 hours, a small amount of carbon was observed on the bottom of the catalyst bed.

After the reaction for 200 hours, the reaction was stopped when carbon adhesion occurred on the catalyst bed, and the catalyst was regenerated. This regeneration process switches the feed gas to the catalyst bed to a regeneration gas consisting of 3.8 moles of air, 56.5 moles of nitrogen, and 397 moles of water vapor, which has a space velocity of s o o hr.
was passed through the catalyst bed.

The temperature of the catalyst bed was initially maintained at 300°C for 5 hours, and then at 35°C.
It was kept at 0°C for 10 hours and then at 400°C for 2 hours. Through this regeneration treatment 4, all of the carbon on the catalyst disappeared.

Example 2 The catalyst subjected to the regeneration treatment in Example 1 was subjected to a reaction under pressure in the same manner as in Example 1. The reaction results 6.150 and 200 hours after restarting the reaction are shown in Table 1. After 200 hours, a small amount of carbon had adhered to the bottom of the catalyst bed. From the reaction results shown in Table 1, it can be seen that the catalyst was completely regenerated by the regeneration operation performed in Example 1.

It can also be seen that even with the catalyst subjected to the regeneration treatment of Example 1, the carbon deposition rate was comparable to that of a new catalyst.

Example 3 In Example 2, the reaction was carried out for 200 hours and the reaction was stopped when carbon adhesion occurred, and the catalyst was regenerated in the same manner as in Example 1. Thereafter, the same pressure as in Example 1 was applied to 200
Table 1 shows the reaction results for 1,950 and 3,950 hours of cumulative reaction time (not including regeneration time), in which the reaction was carried out for a time, and then the catalyst was regenerated in the same manner as in Example 1.

Comparative Example 1 A catalyst was prepared in the same manner as in Example 1, except that nickel nitrate was not used, and the reaction was carried out in the same manner as in Example 1. The reaction results at 6.150 and 120 hours after the start of the reaction are shown in @1 display. 200 hours after the start of the reaction, a small amount of carbon was observed at the bottom of the catalyst bed.

The reaction was interrupted 200 hours after the start of the reaction, and the catalyst was regenerated by applying pressure in the same manner as in Example 1.

Carbon in the catalyst bed could not be completely removed, and some carbon remained.

Comparative Example 2 The catalyst regenerated in Comparative Example 1 was reacted in the same manner as in Example 1. Table 1 shows the reaction results 6 and 50 hours after restarting the reaction. It can be seen that the treatment does not have a sufficient regeneration effect. Furthermore, 50 hours after the reaction was restarted, a considerable amount of carbon was observed at the bottom of the catalyst bed.

Next, the reaction was stopped 50 hours after the start of the reaction, and the temperature during regeneration was first maintained at 400°C for 5 hours, then at 450'C for 15 hours, and then at 500°C for 5 hours. Performed playback processing. Through this regeneration treatment, carbon on the catalyst completely disappeared.

Comparative Example 3 Regarding the catalyst pressure that was regenerated in Comparative Example 2, actual example 1
0 reaction restarted in the same manner as 6,150 and 2
The reaction results after 00 hours are shown in Table 1. From the reaction results in Table 1, it can be seen that sufficient regeneration was achieved in the regeneration treatment of Comparative Example 2. Further, 200 hours after restarting the reaction, a small amount of carbon adhesion was observed at the bottom of the catalyst bed.

The reaction was stopped 200 hours after the start of the reaction, and the catalyst was regenerated in the same manner as in Comparative Example 2. Thereafter, the reaction was carried out for 200 hours in the same manner as in Comparative Example 3, and the catalyst was further regenerated in the same manner as in Comparative Example 2, and this process was repeated.

Cumulative reaction time (not including playback time) 2000 and 3
The reaction results after 000 hours are shown in Table 1. It can be seen from the table that the activity decreases faster than in Example 3.

Example 4 In an aqueous solution of ammonium molybdate 13.25II,
Cobal nitrate) 9.09 jl aqueous solution, nickel nitrate 1.
821i1 aqueous solution and cesium nitrate 0.2431 aqueous solution were added, and while stirring well, antimony trichloride 1.
A 28# hydrochloric acid aqueous solution was added. Then ferric nitrate 2
0.19 g of an aqueous solution and an acidic nitric acid aqueous solution of 3.03 # of bismuth nitrate were sequentially added with stirring, and then evaporated to dryness. This was pyrolyzed at 500°C for 4 hours and then ground in a mortar. 22.5 g of granular α-alumina (particle size 3 ypa) and 100 d of distilled water were added to the obtained powder 14M, and the mixture was evaporated to dryness while stirring, thereby adhering the catalyst component to the carrier. This was calcined at 550° C. for 4 hours to obtain a catalyst.

The atomic ratio of each metal in the catalyst components is Mo:Bi:Fg:
Ca:SA:Nt:C,? = 12:1:8:5:0.
The ratio was 9:1:0.2.

The obtained catalyst 10- was filled in a quartz reaction tube having an inner diameter of 20 g, and the reaction was carried out in the same manner as in Example 1.

The reaction results 6,150 and 200 hours after the start of the reaction are shown in Table 2.

Next, the same pressure as in Example 1 was applied to regenerate the catalyst. Through this regeneration treatment, the carbon deposited on the catalyst completely disappeared. Furthermore, the reaction was carried out in the same manner as in Example 1, and the reaction results after restarting the reaction at 6.150 and 200 hours are shown in Table 2.

Example 5 The amount of ferric nitrate was changed to 7.57 g, the amount of cobalt nitrate was changed to 10.911 g, the amount of nickel nitrate was changed to 3.64 g, and 0.1 rubidium nitrate was added instead of cesium nitrate.
A catalyst was prepared in the same manner as in Example 4 except that 84 g was used. The atomic ratio of each metal in the catalyst components is MO:Bi
:Fg:Co:Sb:Ni:RIPl 22l:3:6
:0.9:2:0.2.

Using the obtained catalyst, the reaction was carried out for -C20 hours in the same manner as in Example 4, followed by catalyst regeneration treatment and further reaction for 200 hours. The reaction results obtained are shown in Table 2. This catalyst was also treated in the same manner as in Example 2 and could be completely regenerated.

X Example 6 The amount of bismuth nitrate is 6.0fi1! A catalyst gI4 was prepared in the same manner as in Example 4 except that 0.126 g of potassium nitrate was used in place of cesium nitrate.

The atomic ratio of each metal in the catalyst components is MO:Bt:Fm:C
o:SA:Ni:ni=12:2:8:5
: 0.9 : 1 : 0.2.

Using the obtained catalyst, reaction was carried out under the same pressure as in Example 4 for 200 hours, followed by catalyst regeneration treatment 1, and further 20 hours.
The reaction was carried out for 0 hours. The reaction results obtained are shown in Table 2. This catalyst was also treated in the same manner as in Example 2 and could be completely regenerated.

Example 7 Next to cesium nitrate, 0.64751 l of lithium nitrate was added, and the rest was the same as in Example 4 (a shite catalyst was prepared. The atomic ratio of each metal in the catalyst components was MO:Bt:Fg:Cc+:
SA:Nt:C#:I,i=12:1:8
: 5 : 0.9 : l : 0.2 : 1.5.

Using the obtained catalyst, a reaction was carried out for 500 hours in the same manner as in Example 1. After 400 hours, there was no carbon adhesion on the catalyst bed, but after 500 hours, there was a small amount of carbon adhesion.Next, the temperature of the catalyst bed was initially maintained at 300°C for 3 hours, and then at 350°C for an additional 15 hours. The catalyst was then regenerated.

Through this regeneration treatment, the carbon attached to the catalyst completely disappeared. Further, the reaction was carried out for 500 hours in the same manner as in Example 1, and then the catalyst was regenerated, and this process was repeated for a total reaction time of 3900 hours. The reaction results are shown in Table 2.

Example 8 A catalyst was prepared in the same manner as in Example 4 except that 0.184 I of rubidium nitrate and 0.531 F of sodium nitrate were used in place of cesium nitrate. The atomic ratio of each metal in the catalyst components is MO:Bt:Fg:CO:Sh:Ni
:Rh:Nα=12:1:8:5:0.9:1:0.2
:1.

Using the obtained catalyst, a reaction was carried out for 500 hours in the same manner as in Example 8, followed by catalyst regeneration treatment, and a further 500 hours of reaction. The reaction results obtained are shown in Table 2. This catalyst was also regenerated in the same manner as in Example 7, and the attached carbon could be completely removed.

Example 9 Potassium nitrate 0.1261 and thallium nitrate 1.66 JF were used instead of cesium nitrate, and the rest was Example 4.
A catalyst was prepared in the same manner as above. The atomic ratio of each metal in the catalyst components is Mo:Bi:Fg:C (1:S, 6
:NL:ni:T/=12:1:8:5:0.9:1:0
．． The ratio was 2:1.

Using the obtained catalyst, a reaction was carried out for 500 hours in the same manner as in Example 7, followed by catalyst regeneration treatment, and a further 500 hours of reaction. The reaction results obtained are shown in Table 2. This catalyst was also regenerated in the same manner as in Example 7, and the attached carbon could be completely removed.

Comparative Example 5 A catalyst was prepared in the same manner as in Example 4 except that nickel nitrate was not used. The atomic ratio of each gold ellipse in the catalyst component is MO:
Bi:Fg:Co:SA:Cr=12:1:
The ratio was 8:5:0.9:0.2.

Using the obtained catalyst, a reaction was carried out in the same manner as in Example 1. The reaction results at 6.150 and 200 hours after the start of the reaction are shown in Table 2.

Next, the catalyst was regenerated in the same manner as in Example 1. The carbon in the catalyst bed could not be completely removed and some carbon remained. Further, the reaction was carried out in the same manner as in Example 1, and the reaction results 6 and 50 hours after restarting the reaction are shown in Table 2. This result shows that sufficient regeneration processing cannot be performed. Furthermore, 50 hours after the start of the reaction, a considerable amount of carbon had adhered to the lower part of the catalyst bed.

Comparative Example 6 A catalyst was prepared in the same manner as in Example 9 except that nickel nitrate was not used. The atomic ratio of each metal in the catalyst component is Mo:
Bz:Fg:Co:Sb:ni:TV = 12:1
: 8 : 5 : 0.9 : 0.2 : 1.0
It was made.

A reaction was carried out in the same manner as in Example 1 using the obtained catalyst. The reaction results 6.400 and 500 hours after the start of the reaction are shown in Table 2.

Next, the catalyst was regenerated in the same manner as in Example 7.
child. However, the carbon in the catalyst bed could not be completely removed, and some carbon remained. Further, the reaction was carried out in the same manner as in Example 1, and the reaction results 6 and 50 hours after restarting the reaction are shown in Table 2.

This result shows that sufficient regeneration treatment was not performed and the activity and selectivity of the catalyst were not recovered.

Furthermore, 50 hours after the start of the reaction, a considerable amount of carbon had adhered to the lower part of the catalyst bed.

Comparative Example 7 A catalyst was prepared in the same manner as in Example 4 except that the amount of cesium nitrate was changed to 1.221. The atomic ratio of each metal in the catalyst components is Mo:Bi:Fe:Co:Sb:Ni:Cs
-12:1:8:5:0.9:1:1.0.

Using the obtained catalyst, a reaction was carried out in the same manner as in Utility Model Application No. 1.

The reaction results at 6.150 and 200 hours after the start of the reaction are shown in Table 3. Although there was no carbon deposit on the catalyst after 200 hours, the catalyst activity was found to be very low.

Comparative Example 8.9 Catalysts having different metal ratios of RA or K were prepared in the same manner as in Example 5 or 6 except that the amounts of rubidium nitrate or potassium nitrate were varied.

Using the obtained catalysts, a reaction was carried out in the same manner as in Example 5 or 6, respectively. The reaction results at 6.150 and 200 hours after the start of the reaction are shown in Table 3.

Even after 200 hours with both catalysts, there was very little carbon adhesion on the catalyst, but the catalytic activity was very low, and it is clear that it is not practical for industrial use.

Examples 10 to 12 Catalysts having different metal ratios of Li, Nα, or Tl were prepared in the same manner as in Example 7.8 or 9, except that the amounts of lithium nitrate, sodium nitrate, or thallium nitrate were changed.

Using the obtained catalysts, a reaction was carried out in the same manner as in Example 7.8 or 9, respectively. Reaction start 6.150 or 20
The reaction results after 0 hours are shown in Table 3.

No carbon adhesion was observed in any of the catalysts after 150 hours, but a small amount was observed at the bottom of the catalyst bed after 200 hours.

Below are the margins Procedures Amendment Written on July 25, 1981 Mr. Kazuo Wakasugi, Commissioner of the Japan Patent Office 1 Indication of the case Patent Application No. 69546 of 1982 2 Title of the invention 1.3 - Process for producing butadiene 3, Amendment Patent Applicant 4, Daisan Hito 103 Address 11-8-6 Nihonbashi Kayaba-cho, Chuo-ku, Tokyo
, increase in number of inventions (due to amendment) 07. Subject of amendment
Column for detailed explanation of the invention in the specification, Jl, l+
, +ゝ・ 8. Contents of the amendment (1) In the 12th line, 14th line of the specification, "I will explain," has been changed to "
As I will explain, the reaction products were qualitatively determined by GC-Mis (gas chromatography) analysis using GC-Mis (gas chromatography) analysis.
11 and the presence of furan. ”.

a) Change "selection rate" in line 17 of line 12 of the specification to "rl!4 selection rate, etc."

(3) [l,3-butadiene selectivity (Mo>%) = s-butene conversion rate] in line 13 of the specification, 1.3-
butadiene yield (mol 1 g) - % - butene conversion rate.

(4) Add the following statement to Tsumugi in line 7 (Example 1) of Section 13 of the specification.

The amount of 1,3-butadiene produced was determined by analyzing the reaction product gas by gas chromatography.
Calculate the amount of O, Cot, and furan using the equation t1.

1.3-Butadiene (mol) produced - Loubutene (mol) consumed (5) Page 18 (Table 1) of the specification has been amended as shown in the attached sheet.

(6) Specification Nos. 26 to 28 (Table 2 and Table 2 (Continued 1) are amended as shown in the attached sheet.

(7) Attached statement No. 31 (Table 3): II! I'll change it.

(See next page for attached sheet)

Claims (1)

[Claims] (1) N-butene and molecular oxygen are combined with the general formula % formula % (1
) (wherein X means at least one element selected from the group consisting of K, R, 5 and C, Y means at least one element selected from the group consisting of Lt, Na and Tl, a, b, c, d, g, f, l, h oyo7j i are respectively Mo, Bi, Fe, Co,
Sh, Ni%X%Y indicates the atomic composition ratio of 0, when α=12, b=O, t~8, e=0.1
~15, d = 0.1 ~ 15, e = o, o t ~ 5, f
= o, 1 to 8, Ii = O to 0.7, n = o to t
o. A method for producing 1,3-butadiene, characterized by carrying out a gas phase catalytic reaction in the presence of a catalyst represented by (t is a value determined by the valence pressure of each element).