JP2920503B2 - Catalyst for oxidative condensation reaction of lower hydrocarbon and method for oxidative condensation of lower hydrocarbon - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a catalyst for oxidative condensation of lower hydrocarbons and a method for oxidative condensation of lower hydrocarbons.

[0002]

2. Description of the Related Art If a hydrocarbon having a higher number of carbon atoms can be synthesized from a lower hydrocarbon, the utilization rate of the lower hydrocarbon can be increased, and a new technology for synthesizing a hydrocarbon as a basic chemical can be industrially used. It is clear that it has significance. In particular, if a technology for synthesizing ethylene using methane as a raw material can be established, natural gas, which has more reserves than crude oil, can be used as a raw material for chemicals instead of crude oil used as a raw material for chemicals. Can be done, and its industrial significance is great.

[0003] In view of the above, much research has been devoted to the development of methods for synthesizing lower hydrocarbons, especially methane, having higher carbon numbers from methane. As one of such methods, a method of oxidatively condensing a lower hydrocarbon in the presence of a catalyst and oxygen is known. In this method, the catalyst plays an important role,
The selectivity and the yield of the obtained condensed hydrocarbon largely depend on the catalyst.

The following catalysts (a) to (e) have been proposed as catalysts for the oxidative condensation reaction of lower hydrocarbons. (A) A supported catalyst containing a metal oxide of group IVB, VB, VIIA such as Pb, Sn, Sb, Bi, Mn as an active component (eg, J. Catal., 73 , 9 (1
982)), (b) Alkaline earth metal oxides such as MgO, CaO, BeO, and SrO to which alkali metal compounds such as Li, Na, and Rb are added (eg, T. Ito and JH Lunsford, Nature, 314 , twenty five
(1985)), (c) Transition metal oxides to which alkali metal chlorides such as LiCl and NaCl are added (eg, Chem. Lett., 1986 , 90
3), (d) Halogen-modified alkaline earth metal oxide
(E.g., Chem. Lett., 1987 , 2157), (e) Rare earth metal oxides and composite metal oxides containing the same (e.g., Chem. Lett., 19)
85 , 499; J. Chem. Soc., Chem. Commun., 1987 , 163.
9). However, these catalysts are not yet satisfactory in terms of selectivity and yield of the obtained condensed hydrocarbon.

[0005]

SUMMARY OF THE INVENTION The present invention provides a catalyst for an oxidative condensation reaction of a lower hydrocarbon which gives a condensed hydrocarbon with an increased selectivity and yield, and a process for oxidatively condensing a lower hydrocarbon using the same. To provide that challenge.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, according to the present invention, there is provided a catalyst for an oxidative condensation reaction of a lower hydrocarbon, wherein lithium is supported on an oxide superacid. A method for oxidatively condensing a lower hydrocarbon, comprising subjecting a lower hydrocarbon to an oxidative condensation reaction in the presence of the catalyst and in the presence of oxygen.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The catalyst of the present invention is obtained by supporting lithium on an oxide superacid. In this case, the oxide superacid is a conventionally known one, and is composed of group 3A or 4A of the periodic table.
Oxides of at least one element selected from the group consisting of Group 4B and Group 8 elements are used as a carrier, and an oxide is supported on the carrier oxide or boron oxide or an oxide of a Group 6B element of the periodic table (Second oxide) can be obtained. For such oxide superacid, for example, “Surface” by Makoto Hino and Kazushi Arata, 34 (2),
119-129 (1996).

Said group 3A, group 4A to provide a carrier oxide;
Group 4B and Group 8 elements include aluminum, silicon, tin, lead, titanium, zirconium, hafnium,
Examples include iron, nickel, and cobalt. Examples of the carrier oxide include aluminum oxide (alumina), silicon oxide (silica), tin oxide (SnO ₂ , SnO), zirconium oxide (zirconia), titanium oxide (titania), hafnium oxide (HfO ₂ ), and iron oxide. (Fe
₂ O ₃ and Fe ₃ O ₄ ) can be preferably used.

An oxide superacid in which an acid radical is supported on a carrier oxide is prepared by adding an inorganic acid or a salt thereof to the carrier oxide,
It can be obtained by firing at 0 to 800 ° C. As inorganic acids or salts thereof, sulfuric acid, hydrochloric acid, phosphoric acid,
Carbonic acid, nitric acid, boric acid and salts thereof, for example, ammonium salt, sodium salt, potassium salt and the like can be mentioned. In the present invention, particularly, sulfuric acid, ammonium sulfate, sodium sulfate and the like are preferably used. Further, the oxide supporting a sulfate group can also be formed by adding thionyl chloride to the carrier oxide.

As a method for incorporating an inorganic acid or an inorganic acid salt into a carrier oxide, a method of incorporating an inorganic acid or an inorganic acid salt solution into the oxide by a method such as an impregnation method or a kneading method is employed. . The carrier oxide used in the present invention generally has an amorphous structure except aluminum oxide. An oxide having an amorphous structure can be obtained by calcining a hydroxide of an element corresponding to the oxide while avoiding crystallization or by hydrolyzing a soluble salt or alkoxide of the element corresponding to the oxide. The hydroxide precursor that produces a precipitate of the substance is hydrolyzed in the presence of an acid or a base to form a precipitate of the hydroxide, and the precipitate is separated and dried, and the obtained dried product is avoided from crystallization. While 20
It can be easily obtained by baking at 0 to 350 ° C, preferably 250 to 300 ° C. When the carrier oxide is aluminum oxide, it is preferable to use crystalline aluminum oxide. The crystalline aluminum oxide contains an inorganic acid or an inorganic acid salt, and is calcined to obtain an aluminum oxide carrying an acid radical. be able to. In the method for producing an oxide containing an acid radical by allowing a carrier oxide to contain sulfuric acid as an aqueous solution and then firing, the type of the oxide, a preferable sulfuric acid concentration and a preferable firing temperature are shown in the following table.

[0011]

Table 1 Oxide Sulfuric acid concentration Firing temperature (N) (° C) Aluminum oxide 4-6 550-650 Tin oxide 5-8 550-650 Zirconium oxide 0.5-2 650-750 Titanium oxide 0.5-2500 -600 Hafnium oxide 1-3 650-750 Iron oxide 0.2-1 450-550

The supporting of the sulfate group on the silicon oxide is preferably carried out using thionyl chloride. An oxide supporting an acid group such as a sulfate group can be obtained by calcining an inorganic acid salt of an element corresponding to the oxide. In this case, the sintering temperature is set at 50 times higher than the sintering temperature shown in Table 1.
It is preferable to raise the temperature by about 100 ° C.

The amount of the acid radical to be carried on the carrier oxide is 0.01 to 0.8 gram equivalent, preferably 0.03 to 0.5 gram equivalent, per 100 g of the carrier oxide.

In the case where an oxide superacid is produced by supporting a second oxide on a carrier oxide, the second oxide contains at least one element selected from boron and group 6B elements. An oxide is used. In this case, the group 6B element includes chromium, molybdenum, and tungsten. As a method of supporting the second oxide on the carrier oxide, a method of impregnating or mixing a solution of a soluble compound of an element corresponding to the second oxide with the carrier oxide and then firing the mixture can be used.

Specific examples of the soluble compound of the element corresponding to the second oxide include ammonium molybdate [(NH ₄ ) ₆ M
o ₇ O ₂₄ ] .4H ₂ O, ammonium phosphomolybdate [(NH ₄ ) ₃ PM
o ₁₂ O ₄₀ ] .xH ₂ O, ammonium metatungstate [(NH ₄ )
₆ (H ₂ W ₁₂ O ₄₀ )]. XH ₂ O, 12 ammonium tungstate
[(NH ₄ ) ₁₀ W ₁₂ O ₄₂ H ₂ ] .10H ₂ O, ammonium dodecane gastrophosphate [(NH ₄ ) ₃ PW ₁₂ O ₄₀ ] .14H ₂ O, trimethyl borate, orthoboric acid, etc. . The amount of the second oxide supported on the carrier oxide and the firing temperature are shown. In the case of molybdenum oxide (MoO, Mo ₂ O ₃ ), the supported amount is 1
１５15 wt%, preferably 3-8 wt%, and the firing temperature is 700-900 ° C. Tungsten oxide (W ₂
O ₃ , WO ₂ , and WO ₃ ), the supported amount is 5 to 30.
wt%, and the firing temperature is 700-900 ° C. In the case of boron oxide (B ₂ O ₃ ), the supported amount is 1 to 10 w
t%, preferably 3 to 6 wt%, and the calcination temperature is 55%.
0-750 ° C.

In order to carry lithium on the oxide superacid, a lithium compound is added to the oxide superacid and the mixture is fired in the air. Thereby, the catalyst of the present invention can be obtained. As a method for incorporating the lithium compound into the carrier oxide, a conventionally known method such as a physical mixing method, an impregnation method, and a kneading method can be adopted. Examples of the lithium compound include, in addition to lithium hydroxide, lithium salts of various inorganic or organic acids, for example, lithium hydroxide, lithium carbonate, lithium acetate, lithium nitrate, lithium phosphate, lithium chloride, lithium sulfate and the like. These lithium compounds are usually contained in the carrier oxide as an aqueous solution. The firing temperature of the carrier oxide containing the lithium compound is 400 to 900 ° C., preferably 500 to 700 ° C.
It is about ° C. The supported amount of the lithium compound is 0.2 to 10 g per 100 g of the carrier oxide as lithium metal,
Preferably, it is 0.5 to 2 g.

The method for oxidatively condensing lower hydrocarbons according to the present invention is carried out by oxidatively condensing lower hydrocarbons in the presence of the catalyst of the present invention and in the presence of oxygen. As lower hydrocarbons, the number of carbon atoms is 1 to 6,
Preferably, 1 to 4 hydrocarbons, for example, methane, ethane, propane, butane, etc. are used, but preferably methane is used. The oxidative condensation reaction includes an oxidative dimerization reaction and an oxidative dehydrogenation reaction of a lower hydrocarbon. For example, when methane is used as a reaction raw material,
2 moles of methane oxidatively condensed C ₂ hydrocarbons (ethane, ethylene, acetylene) as a main component, as a by-product, small amounts of C ₃ hydrocarbons, C ₄ hydrocarbons, C ₅ hydrocarbons and benzene Is obtained. In the oxidative condensation reaction of the lower hydrocarbon, the reaction temperature is usually 600 to
900 ° C., and the reaction pressure is normal pressure or reduced pressure.
Oxygen is used in an amount of 0.1 to 1 mole per lower hydrocarbon.
The ratio is 10 mol, preferably 0.25 to 1 mol.
The raw material lower hydrocarbon can be used after being diluted with an inert gas such as nitrogen gas or helium gas.

[0018]

Next, the present invention will be described in more detail with reference to examples.

EXAMPLE 1 10 g of zirconyl nitrate is dissolved in 250 ml of distilled water and heated to 80.degree. 25 ml of ammonia is slowly added dropwise to form a precipitate of zirconium hydroxide. After filtration and washing, it was dried at 100 ° C. overnight (5.72 g) and calcined at 300 ° C. for 3 hours (5.04 g, B
ET surface area = 252.8m ² / g). 1.2 g of the obtained zirconium hydroxide is taken, mixed with 0.0991 g of ammonium sulfate (6% by weight in terms of sulfate) and 250 ml of distilled water, and stirred at 80 ° C. for 3 hours. Evaporate the distilled water to dryness and leave it at 100 ° C overnight, then 700
Calcination for 3 hours at ℃ to obtain 1.11g of sulfated zirconia
(BET surface area = 72.8 m ² / g). This is distilled water 2
0.293 g of lithium carbonate dissolved in 50 ml (5 wt% in terms of lithium)
%) And stirred at 80 ° C for 3 hours. After evaporation to dryness, 100 ℃
For 3 hours, and calcined in air at 600 ° C. for 3 hours to finally obtain 1.249 g of a zirconia catalyst supported on lithium / sulfate.
(BET surface area = 7.3m ² / g).

Examples 2 to 5 Catalysts were prepared in the same manner as in Example 1 except that the sintering temperature after supporting ammonium sulfate was 600 ° C. and the amount of the supported catalyst was as shown in Table 1.

Comparative Example 1 A catalyst was prepared in the same manner as in Example 1 except that neither ammonium sulfate nor lithium carbonate was used. Comparative Example 2 A catalyst was prepared in the same manner as in Example 1 except that only ammonium sulfate was not used. Comparative Example 3 A catalyst was prepared in the same manner as in Example 1 except that only lithium carbonate was not used.

Examples 6 to 8 The sintering temperature after supporting ammonium sulfate was 500 and 80, respectively.
A catalyst was prepared in the same manner as in Example 1 except that the temperature was changed to 0 and 1000 ° C.

Examples 9 to 12 Catalysts were prepared in the same manner as in Example 1, except that ammonium nitrate, ammonium chloride, ammonium phosphate and trimethyl borate were used instead of ammonium sulfate.

Example 13 Sodium carbonate was used instead of ammonium sulfate.
A catalyst was prepared in the same manner as in Example 1, except that the catalyst was calcined at 00 ° C.

Example 14 1N sulfuric acid was used in place of ammonium sulfate.
A catalyst was prepared in the same manner as in Example 1 except that zirconia calcined at 300 ° C. was soaked for 15 minutes, filtered, washed, and dried at 100 ° C. overnight.

Examples 15 to 16 Catalysts were prepared in the same manner as in Example 1 except that ammonium molybdate and ammonium metatungstate were used instead of ammonium sulfate, and the calcination temperatures were 800 and 830 ° C., respectively.

Example 17 A catalyst was prepared in the same manner as in Example 1 except that lithium carbonate was used in an amount of 10 wt% based on zirconia supporting sulfate.

Examples 18 to 20 Instead of zirconyl nitrate, titanium tetraisopropoxide, tin sulfate, and tetraethoxysilane were used, and the firing temperatures after supporting the sulfate groups were 570, 600, and 450 ° C., respectively. A catalyst was prepared in the same manner as in Example 1.

Example 21 A catalyst was prepared in the same manner as in Example 1 except that zirconium sulfate was used instead of zirconyl nitrate.

Tables 2 and 3 show the carrier oxide raw materials, additives, and the amount of the additives used in the above Examples and Comparative Examples, the firing temperature after the addition of the additives, the lithium compound, the amount of the lithium compound supported, The firing temperatures after supporting the lithium compound are shown.

[0031]

TABLE 2 oxide material additive amount of supported calcination temperature lithium loading amount firing temperature (wt%) (℃) Compound (wt%) of (℃) real _{1. ZrO (NO 3) 2 .2H} 2 O (NH 4 _{) 2 SO 4 6 700 Li 2} CO 3 5 600 real _{2. ZrO (NO 3) 2 .2H} 2 O (NH 4) 2 SO 4 6 600 Li 2 CO 3 5 600 real 3. ZrO (NO _{3) 2. 2H 2 O (NH 4) 2} SO 4 3 600 Li 2 CO 3 5 600 real _{4. ZrO (NO 3) 2 .2H} 2 O (NH 4) 2 SO 4 10 600 Li 2 CO 3 5 600 actual 5. ZrO _{(NO 3) 2 .2H 2 O} (NH 4) 2 SO 4 20 600 Li 2 CO 3 5 600 ratio _{1. ZrO (NO 3) 2 .2H} 2 O (NH 4) 2 SO 4 0 - Li 2 CO 3 0 - The ratio _{2. ZrO (NO 3) 2 .2H} 2 O (NH 4) 2 SO 4 0 - Li 2 CO 3 5 600 ratio _{3. ZrO (NO 3) 2 .2H} 2 O (NH 4) 2 SO 4 6 - Li ₂ CO ₃ 0 - real _{6. ZrO (NO 3) 2 .2H} 2 O (NH 4) 2 SO 4 6 500 Li 2 CO 3 5 600 real _{7. ZrO (NO 3) 2 .2H} 2 O ( _{NH 4) 2 SO 4 6 800} Li 2 CO 3 5 600 real _{8. ZrO (NO 3) 2 .2H} 2 O (NH 4) 2 SO 4 6 1000 Li 2 CO 3 5 600 real 9. ZrO (NO _{3) 2 .2H 2 O (NH 4)} NO 3 6 600 Li 2 CO 3 5 600 real _{10. ZrO (NO 3) 2 .2H} 2 O (NH 4) Cl 6 600 Li 2 CO 3 5 600 real 11. ZrO ( _{NO 3) 2 .2H 2 O (} NH 4) 3 _{PO 4 3H 2 O 6 600 Li} 2 CO 3 5 600 Real _{12. ZrO (NO 3) 2 .2H} 2 O (NH 4) BO 2 6 600 Li 2 CO 3 5 600 Real 13. ZrO (NO _{3) 2. 2H 2 O Na 2 CO 3 6} 1000 Li 2 CO 3 5 600 real _{14. ZrO (NO 3) 2 .2H} 2 O 1N H 2 SO 4 6 600 Li 2 CO 3 5 600

[0032]

TABLE 3 oxide material additive amount of supported calcination temperature lithium loading amount firing temperature (wt%) (℃) Compound (wt%) of (℃) Real _{15. ZrO (NO 3) 2 .2H} 2 O (NH 4 _{) 6 Mo 7 O 24 - 5} 800 Li 2 CO 3 5 600 4H 2 O real _{16. ZrO (NO 3) 2 .2H} 2 O [(NH 4) 6 - 13 830 Li 2 CO 3 5 600 (H 2 W ₁₂ O _40)] actual _{17. ZrO (NO 3) 2 .2H} 2 O (NH 4) 2 SO 4 6 600 Li 2 CO 3 10 600 real _{18. Ti (i-Pr) 4} (NH 4) 2 SO 4 6 570 Li ₂ CO ₃ 5 600 real 19. SnSO ₄ (NH ₄ ) ₂ SO ₄ 6 600 Li ₂ CO ₃ 5 600 real 20.Si (OEt) ₄ (NH ₄ ) ₂ SO ₄ 6 450 Li ₂ CO ₃ 5 600 Real 21. ZrSO ₄ (NH ₄ ) ₂ SO ₄ 6 600 Li ₂ CO ₃ 5 600

Example 22 0.2 g of the catalyst obtained in Example 1 was put into a quartz reaction tube together with 2 g of quartz sand as a diluent, and nitrogen gas was fed at 50 ml / m 2.
Pretreatment was performed by heating at 600 ° C. for 1 hour while flowing at a flow rate of “in”. In this case, the heating rate was 8 ° C./min. After that, change the gas to a mixed gas of nitrogen, methane, and oxygen (volume ratio (methane / oxygen / nitrogen = 7/3/40), introduce the gas into the reaction tube at a flow rate of 50 ml / min, and raise the temperature by 4 ° C / min. The reaction was carried out at the same temperature up to 800 ° C. The product after the reaction at the same temperature for 1 hour was analyzed by gas chromatography to find that the methane conversion was 32.1% and the methane standard C ₂ (ethane + ethylene + acetylene) selectivity of 80.2% absolute yield of C ₂ with respect to the raw material methane was 25.8%. produced as a by-product, COx (the sum of carbon monoxide and carbon dioxide) selectivity of 15.4%, an absolute 4.9% yield In addition, small amounts of C ₃ , C ₄ , C ₅ and benzene were detected.

The methane conversion rate, C ₂ and COx selectivity, their absolute yield was calculated as follows for convenience. Methane conversion [C (M)] = A / (A + B) × 100
(%) A: product weight B: unreacted methane weight In this case, the product weight A is [2 × C ₂ + 3 × C ₃ , 4 ×
C ₄ , 5 × C ₅ , 6 × C ₅ + 6 × Bz + COx]. However, in this formula, C ₂ , C ₃ , C ₄ ,
C ₅ , Bz and COx are the number of moles of a hydrocarbon having 2 carbon atoms, the number of moles of a hydrocarbon having 3 carbon atoms, the number of moles of a hydrocarbon having 4 carbon atoms, the number of moles of a hydrocarbon having 5 carbon atoms, and benzene, respectively. And the total number of moles of carbon monoxide and carbon dioxide. The unreacted methane weight B was the number of moles of unreacted methane × 1. C ₂ selectivity [S (C ₂ )] = [2 × C ₂ ] / A × 100
(%) However, C ₂ and A have the same meaning as described above. C ₂ absolute yield [Y (C ₂ )] = C (M) × S (C ₂ ) × 1
/ 100 (%) COx selectivity [S (COx)] = [COx] / A × 1 /
100 (%) COx absolute yield [Y (COx)] = C (M) × S (CO
x) x 1/100 (%)

Examples 23 to 38 and Comparative Examples 4 to 6 The reaction was carried out at 800 ° C. in the same manner as in Example 22 except that the catalysts of Examples 2 to 17 and Comparative Examples 1 to 3 were respectively used.
The results are shown in Table 4 together with the results of Example 22.

Examples 39 to 40 Using the catalyst of Example 2, a reaction was carried out in the same manner as in Example 22 except that oxygen was changed to 8 kPa and 11 kPa, respectively. Table 5 shows the results.

Examples 41 to 45 Using the catalyst of Example 1, a linear velocity of 99.5 cm / min, 117 cm / mi
Example 2 except that n and methane partial pressure were 6 kPa, 9 kPa and 11 kPa
The reaction was carried out in the same manner as in Example 2, and the results are shown in Table 5.

Examples 46 to 49 The reaction was carried out in the same manner as in Example 22 except that the catalyst prepared using the oxide raw materials of Examples 18 to 21 was used instead of zirconyl nitrate. 48 is 850
° C). Table 5 shows the results. A value of 79.6% C ₂ selectivity and 34.5% absolute yield (Example 45) was obtained, which is the highest level in the world as a result of using a simple gas phase flow reactor.

[0039]

[Table 4] Catalyst Reaction conditions Methane S (C ₂ ) / S (COx) / CH ₄ / O ₂ Linear velocity Conversion Y (C ₂ ) Y (COx) (kPa / kPa) (cm / min) (%) Example 22. Actual 1.16 / 5.0 44.2 32.1 80.2 / 25.8 15.4 / 4.90 Example 23. Actual 2.16 / 5.0 44.2 37.3 77.6 / 28.9 18.7 / 6.97 Example 24. Actual 3.16 / 5.0 44.2 30.1 77.4 / 23.3 16.4 / 4.90 Example 25. Actual 4.16 / 5.0 44.2 29.2 73.5 / 21.5 21.8 / 6.36 Example 26. Actual 5.16 / 5.0 44.2 27.6 68.1 / 18.8 27.6 / 7.62 Comparative example 4. Ratio 1. 16 / 5.0 44.2 16.0 18.2 / 2.92 81.5 / 13.1 Comparative Example 5.Comparative 2.16 / 5.0 44.2 17.2 50.7 / 8.74 48.3 / 8.33 Comparative Example 6.Comparative 3.16 / 5.0 44.2 16.8 18.2 / 3.06 81.5 / 13.7 Example 27. 16 / 5.0 44.2 30.6 74.6 / 22.8 21.3 / 6.54 Example 28. Actual 7. 16 / 5.0 44.2 26.3 72.5 / 19.1 24.4 / 6.43 Example 29. Actual 8. 16 / 5.0 44.2 22.4 73.5 / 16.4 22.6 / 5.05 Example 30. Actual 9. 16 / 5.0 44.2 23.2 71.0 / 16.5 25.4 / 5.90 Example 31. Actual 10. 16 / 5.0 44.2 29.6 77.2 / 22.9 17.9 / 5.30 Example 32. Actual 11. 16 / 5.0 44.2 31.2 62.0 / 19.3 35.6 /11.1 Example 33. Actual 12.16 / 5.0 44.2 26.1 86.0 / 22.5 12.5 / 3.26 Example 34. Actual 13.16 / 5.0 44. 2 25.4 68.7 / 17.4 28.0 / 7.11 Example 35. Actual 14.16 / 5.0 44.2 35.5 70.7 / 25.1 26.0 / 9.25 Example 36. Actual 15.16 / 5.0 44.2 21.8 73.7 / 16.1 21.4 / 4.67 Example 37. Actual 16 16 / 5.0 44.2 39.0 64.5 / 25.2 33.7 / 13.1 Example 38. Real 17.16 / 5.0 44.2 26.4 72.2 / 19.0 25.7 / 6.77

[0040]

[Table 5] Catalyst Reaction conditions Methane S (C ₂ ) / S (COx) / CH ₄ / O ₂ Linear velocity Conversion Y (C ₂ ) Y (COx) (kPa / kPa) (cm / min) (%) Example 39. Actual 2.16 / 8.0 44.2 43.5 58.0 / 25.2 39.8 / 17.3 Example 40. Actual 2.16 / 11.0 44.2 54.8 44.3 / 24.3 53.6 / 29.3 Example 41. Actual 1.16 / 5.0 99.5 26.2 80.4 / 21.1 16.5 / 4.33 Example 42. Actual 1.16 / 5.0 177 27.0 86.1 / 23.3 11.5 / 3.10 Example 43. Actual 1.6 / 5.0 177 50.0 73.3 / 36.7 25.2 / 12.6 Example 44. Actual 1. 9 / 5.0 177 43.9 78.4 / 34.4 19.5 / 8.56 Example 45. Actual 1.11 / 5.0 177 43.3 79.6 / 34.5 17.8 / 7.71 Example 46. Actual 18.11 / 5.0 177 (850 ° C) 11.5 83.4 / 9.58 14.9 / 1.71 Example 47. Actual 19.11 / 5.0 177 39.7 82.4 / 32.7 15.7 / 6.22 Example 48. Actual 20.11 / 5.0 177 (850 ° C) 17.4 75.4 / 13.1 23.3 / 4.06 Example 49. Actual 21. 11 / 5.0 177 51.7 60.6 / 31.3 38.0 / 19.6

[0041]

By using the catalyst of the present invention, a lower hydrocarbon can be efficiently oxidatively condensed and a condensed hydrocarbon can be obtained with an increased selectivity and yield.

Claims (3)

(57) [Claims] 1. A catalyst for an oxidative condensation reaction of a lower hydrocarbon, wherein lithium is supported on an oxide superacid. 2. A method for oxidatively condensing a lower hydrocarbon, wherein the lower hydrocarbon is subjected to an oxidative condensation reaction in the presence of the catalyst and oxygen. 3. The method of claim 2, wherein said lower hydrocarbon is methane.
The described method.