Binder-free high strength, low steam-to-oil ratio ethylbenzene dehydrogenation catalyst

Abstract

The invention discloses a binder-free high strength and low steam-to-oil ratio ethylbenzene dehydrogenation catalyst, which is characterized by comprising the following components in percentage by weight: (a) 60-85% Fe.sub.2O.sub.3; (b) 3-25% K.sub.2O; (c) 0.1-5% MoO.sub.3; (d) 3-20% CeO.sub.2; (e) 0.1-5% CaO; (f) 0.1-5% Na.sub.2O; (g) 0.1-5% MnO.sub.2, wherein the weight ratio of sodium oxide to manganese dioxide is 0.1-10, and no binder is added during the preparation of the catalyst. The low steam-to-oil ratio ethylbenzene dehydrogenation catalyst provided by the present invention contains no binder and maintains high strength, and has high activity and stability at low steam-to-oil ratio.

Claims

1. A binder-free high strength and low steam-to-oil ratio ethylbenzene dehydrogenation catalyst, comprising the following components by weight percentage: (a) 60-85% Fe.sub.2O.sub.3; (b) 3-25% K.sub.2O; (c) 0.1-5% MoO.sub.3; (d) 3-20% CeO.sub.2; (e) 0.1-5% CaO; (f) 0.1-5% Na.sub.2O; (g) 0.1-5% MnO.sub.2, wherein the weight ratio of Na.sub.2O and MnO.sub.2 is 0.1-10; and no binder is added during the preparation of the catalyst.

2. The binder-free high strength, low steam-to-oil ratio ethylbenzene dehydrogenation catalyst according to claim 1, wherein the weight ratio of Na.sub.2O and MnO.sub.2 is 0.2-8.

3. The binder-free high strength and low steam-to-oil ratio ethylbenzene dehydrogenation catalyst according to claim 2, wherein the weight ratio of Na.sub.2O and MnO.sub.2 is 0.5-5.

4. The binder-free high strength and low steam-to-oil ratio ethylbenzene dehydrogenation catalyst according to claim 1, further comprising 0.05 to 2% CuO.

5. The binder-free high strength and low steam-to-oil ratio ethylbenzene dehydrogenation catalyst according to claim 1, further comprising 0.05 to 2% ZnO.

6. The binder-free high strength and low steam-to-oil ratio ethylbenzene dehydrogenation catalyst according to claim 1, further comprising 0.05 to 2% MgO.

7. The binder-free high strength and low steam-to-oil ratio ethylbenzene dehydrogenation catalyst according to claim 1, further comprising 0.1-100 ppm of Pb or oxide thereof.

8. The binder-free high strength and low steam-to-oil ratio ethylbenzene dehydrogenation catalyst according to claim 1, further comprising 0.1-100 ppm of Pt or oxide thereof.

9. The binder-free high strength and low steam-to-oil ratio ethylbenzene dehydrogenation catalyst according to claim 1, further comprising 0.1-100 ppm of Pd or oxide thereof.

10. The binder-free high strength and low steam-to-oil ratio ethylbenzene dehydrogenation catalyst according to claim 1, further comprising 0.1-100 ppm of Ag or oxide thereof.

11. The binder-free high strength and low steam-to-oil ratio ethylbenzene dehydrogenation catalyst according to claim 1, further comprising 0.1-100 ppm of Au or oxide thereof.

12. The binder-free high strength and low steam-to-oil ratio ethylbenzene dehydrogenation catalyst according to claim 1, further comprising 0.1-100 ppm of Sn or oxide thereof.

13. The binder-free high strength and low steam-to-oil ratio ethylbenzene dehydrogenation catalyst according to claim 1, having a crush strength of at least 45 N/mm as measured according to HG/T 2782-1996.

14. The binder-free high strength and low steam-to-oil ratio ethylbenzene dehydrogenation catalyst according to claim 1, having a crush strength of at least 51 N/mm as measured according to HG/T 2782-1996.

15. The binder-free high strength and low steam-to-oil ratio ethylbenzene dehydrogenation catalyst according to claim 1, having a crush strength of at least 60 N/mm as measured according to HG/T 2782-1996.

Description

EXAMPLES

(1) The above solution is further described with specific examples. It should be understood that these examples are for the purpose of illustrating the invention and are not intended to limit the scope of the invention. The implementation conditions employed in the examples can be further adjusted according to the specific manufacturer's conditions, and the unspecified implementation conditions are usually the conventional experiment conditions.

(2) The raw materials for preparing the catalyst are iron oxide red, ferric oxide yellow, potassium carbonate, manganese oxide, ammonium heptamolybdate, calcium hydroxide, sodium carbonate, cerium sources (cerium carbonate, cerium oxalate, cerium carbonate, cerium oxide), Gold nitrate, palladium nitrate, platinum nitrate, silver nitrate, lead oxide, tin oxide, zinc oxide, copper oxide and magnesium oxide.

Comparative Example 1

(3) The raw materials as iron oxide red, iron oxide yellow, potassium carbonate, cerium carbonate, ammonium heptamolybdate and calcium hydroxide were mixed in a kneader for 1 hour, added with deionized water and stirred for 1 hour. Then the paste was extruded into particles 3 mm in diameter and 8 to 10 mm in length. The particles were dried for 2 hours at 80 C. and another 2 hours at 120 C., and then placed in a muffle furnace and calcined at 900 C. for 4 hours. It is catalyst A

(4) Catalyst A comprises 76.6% Fe.sub.2O.sub.3, 11.2% K.sub.2O, 7.5% CeO.sub.2, 2.2% CaO and 2.5% MoO.sub.3 by weight percentage. See Table 1

(5) The activity of the catalyst prepared was evaluated in an isothermal fixed bed. The specific process is: the deionized water and ethylbenzene were fed into the preheat mixer respectively by a metering pump, where they were preheated and mixed into gas and fed into the reactor; the reactor was a 1 inch stainless steel tube which can load 100 ml catalyst of 3 mm particle size and was heated by electric heating wires to the required temperature for reaction; the reaction product coming out of the reactor was condensed with water and the composition thereof was analyzed by gas chromatography; and the ethyl benzene (EB) conversion and styrene selectivity were calculated according to the following formulas:
EB conversion %=(EB concentration before reaction wt %EB concentration after reaction wt %)/EB concentration before reaction wt %
Styrene selectivity %=concentration of styrene wt %/(EB concentration before reaction wt %EB concentration after reaction wt %)

(6) The reactor was loaded with 100 ml catalyst, and the catalyst activity was evaluated at atmospheric pressure, liquid hour space velocity 1.0 h.sup.1, 620 C. and steam-to-oil ratio (by weight) of 1.0 and 0.75. The test results are shown in Table 2-3.

Comparative Example 2

(7) It was mostly the same as in Comparative Example 1 except that sodium carbonate was added into the raw materials for preparing the catalyst (Catalyst B) in Comparative Example 2. The catalyst B component comprises, by weight percent, 75.1% Fe.sub.2O.sub.3, 11.2% K.sub.2O, 7.5% CeO.sub.2, 2.2% CaO, 2.5% MoO.sub.3 and 1.5% Na.sub.2O, as shown in Table 1. After the catalyst is prepared, the activity of the catalyst was evaluated according to the evaluation method of Comparative Example 1, and the test results are shown in Table 2-3.

Comparative Example 3

(8) It was mostly the same as in Comparative Example 1 except that manganese oxide was added into the raw materials for preparing the catalyst (catalyst C) in Comparative Example 3. The catalyst C component comprises 75.4% Fe.sub.2O.sub.3, 11.2% K.sub.2O, 7.5% CeO.sub.2, 2.2% CaO, 2.5% MoO.sub.3 and 1.2% MnO.sub.2 in weight percentage.

(9) The catalyst components are shown in Table 1. Catalyst activity was evaluated according to the evaluation method of Comparative Example 1. The test results are shown in Table 2-3.

Working Examples 1-5

(10) A series of catalysts, DEFGH, were prepared by adding different amounts of MnO.sub.2, wherein the cerium source was cerium carbonate in catalyst D, cerium oxalate in catalyst E, basic cerium carbonate in catalyst F, cerium nitrate in catalyst G, and cerium oxide in the rest of the catalysts. Pt, Pd, Ag and Au were added in the form of nitrates, and Pb and Sn were added in the form of oxides. The content of sodium oxide in each catalyst was set to 2.5%, and the amounts of other raw materials used were in accordance with the compositions of the actual oxides shown in Table 1. After the catalyst was prepared, the catalyst activity was evaluated according to the evaluation method of Example 1, and the test results are shown in Table 2-3.

Working Examples 6-14

(11) A series of catalysts I-R were prepared by adding different amounts of MnO.sub.2 and Na.sub.2O. The amounts of other raw materials were according to the compositions of the actual oxides as shown in Table 1.

(12) TABLE-US-00001 TABLE 1 Catalyst Composition and strength Catalyst A B C D E F G H I J K L M N O P Q R Fe.sub.2O.sub.3/% 76.6 75.1 75.4 72.35 71.4 70 70.45 67 70.2 71.55 74.1 73.55 69.6 68.7 74.9 69.6 72 71.6 K.sub.2O/% 11.2 11.2 11.2 11.2 11.2 11.2 11.2 11.2 11.2 11.2 11.2 11.2 11.2 11.2 11.2 11.2 11.2 11.2 CeO.sub.2/% 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 CaO/% 2.2 2.2 2.2 2.2 2.2 2.2 2.2 2.2 2.2 2.2 2.2 2.2 2.2 2.2 2.2 2.2 2.2 2.2 MoO.sub.3/% 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Na.sub.2O/% 1.5 2.5 2.5 2.5 2.5 2.5 0.5 0.7 1.6 0.9 3.0 5 0.1 4.2 2.8 2.5 MnO.sub.2/% 1.2 0.25 0.5 2.5 3.6 5.0 5 3.5 0.2 0.1 0.5 1.0 0.7 1.3 0.6 2.5 Na.sub.2O/MnO.sub.2 10 5 1.0 0.69 0.5 0.1 0.20 8.0 9.0 6.0 5.0 0.14 4.0 4.7 1.0 CuO 0.2 1.0 1.1 0.8 0.05 2 0.7 1.5 ZnO 2 0.3 0.05 0.1 0.7 1.5 1.2 MgO 1.5 0.3 1.0 0.8 0.05 2.0 0.9 1.2 Pt/ppm 5 80 5 Pd/ppm 30 3 Ag/ppm 50 66 55 60 10 PbO.sub.2/ppm 80 100 SnO.sub.2/ppm 60 75 30 30 Au/ppm 2 3 Strength 25.2 28.1 20.2 45.2 60 70.3 66.5 65 42.2 48 49 46 51 60 45 66 61 68.2 (N/mm)

(13) As can be seen from Table 1, addition of Na.sub.2O and MnO.sub.2 increases the catalyst crush strength.

(14) Table 2 shows the performance of the catalyst at a steam-to-oil ratio of 0.75.

(15) TABLE-US-00002 TABLE 2 Catalyst performance at a steam-to-oil oil ratio of 0.75. Na.sub.2O MnO.sub.2 conversion selectivity Styrene yield Catalyst wt % wt % wt % wt % wt % A 67.8 96.1 65.2 B 1.5 67.2 95.9 64.4 C 1.2 66.5 95.8 63.7 D 2.5 0.25 72.4 95.9 69.4 E 2.5 0.5 74.3 96.0 71.3 F 2.5 2.5 76.6 96.5 73.9 G 2.5 3.6 76.3 95.8 73.1 H 2.5 5 70.4 95.7 67.4 I 0.5 5 72.7 95.3 69.3 J 0.7 3.5 72.5 95.6 69.3 K 1.6 0.2 70.4 95.5 67.2 L 0.9 0.1 72.5 96.0 69.6 M 3 0.5 72.5 95.2 69.0 N 5 1 71.8 95.7 68.7 O 0.1 0.7 74.3 95.8 71.2 P 4.2 1.3 70.7 95.6 67.6 Q 2.8 0.6 71.1 95.3 67.8 R 2.5 2.5 72.6 95.1 69

(16) Table 3 shows Catalyst performance at steam-to-oil ratio of 0.75 and Table 3 shows the decrease in styrene yield Y when the steam-to-oil ratio is decreased from 1.0 to 0.75.

(17) TABLE-US-00003 TABLE 3 Catalyst performance at steam-to-oil ratio 1.0 Conver- Selec- Styrene cata- Na.sub.2O MnO.sub.2 sion tivity yield Y lyst wt % wt % wt % wt % wt % 1.0.fwdarw.0.75 A 74.6 96.2 71.8 6.6 B 1.5 75.4 95.8 72.2 7.8 C 1.2 74.5 95.9 71.4 7.7 D 2.5 0.25 76.3 96.0 73.2 3.8 E 2.5 0.5 77.5 96.1 74.5 3.2 F 2.5 2.5 78.1 96.6 75.4 1.5 G 2.5 3.6 79.5 95.9 76.2 3.1 H 2.5 5 75.4 95.8 72.2 4.8 I 0.5 5 76.2 95.5 72.8 3.5 J 0.7 3.5 74.4 95.8 71.3 2.0 K 1.6 0.2 73.1 95.7 70 2.8 L 0.9 0.1 75.5 96.1 72.6 3.0 M 3 0.5 75.7 95.2 72.1 3.1 N 5 1 75.4 95.8 72.2 3.5 O 0.1 0.7 77.4 95.7 74.1 2.9 P 4.2 1.3 73.2 95.7 70.1 2.5 Q 2.8 0.6 75.7 95.1 72 4.2 R 2.5 2.5 75.6 95.5 72.2 3.2

(18) As can be seen from comparison of the test results of the working examples and comparative examples, the catalyst has high strength and good activity at steam-to-oil ratio of 1.0. When the steam-to-oil ratio is decreased from 1.0 to 0.75, the loss of catalyst activity is small and the catalyst is stable.

(19) The above examples are only for illustrating the technical idea and features of the present invention, which could enable those who are skilled in the art to understand and implement the contents of the present invention. However, they could not limit the protection scope of the present invention. Any equivalent transformation or modification made according to the spirit of the present invention shall fall within the protection scope of the present invention.