Metal oxide coated ceramic corrugated plate catalyst, preparation and application in preparation of key intermediates of citral

Abstract

The present disclosure belongs to the technical field of catalysis, and particularly relates to a metal oxide coated ceramic corrugated plate catalyst, its preparation method and application thereof in preparation of key intermediates of citral. The catalyst consists of a ceramic corrugated plate carrier and a metal oxide active layer coated on a surface of the carrier, wherein the metal oxide active layer is a metal oxide formed by active ingredient titanium and at least four other metal elements selected from vanadium, chromium, manganese, iron, zirconium, niobium and molybdenum.

Claims

1. A metal oxide coated ceramic corrugated plate catalyst, consisting of a ceramic corrugated plate carrier and a metal oxide active layer coated on a surface of the carrier, wherein the ceramic corrugated plate carrier is made of cordierite, alumina or silicon carbide, wherein the metal oxide active layer is a metal oxide formed of active ingredients consisting of titanium, vanadium, and molybdenum and two other metal elements selected from chromium, manganese, iron, zirconium, and niobium.

2. The metal oxide coated ceramic corrugated plate catalyst according to claim 1, wherein the two other metal elements comprise manganese and iron, zirconium and iron, zirconium and chromium, or niobium and iron.

3. The metal oxide coated ceramic corrugated plate catalyst according to claim 1, wherein the loading amount of the metal oxide active layer is 0.1-10 wt % of the ceramic corrugated plate.

4. The metal oxide coated ceramic corrugated plate catalyst according to claim 1, wherein the metal oxide active layer is a metal oxide formed by Ti and four metal elements of V, Mn, Fe and Mo, wherein a molar ratio of all the metal elements in the metal oxide is 1-1.5:1-1.2:1:1:1.

5. The metal oxide coated ceramic corrugated plate catalyst according to claim 1, wherein the metal oxide active layer is a metal oxide formed by Ti and four metal elements of V, Zr, Cr and Mo, wherein a molar ratio of all the metal elements in the metal oxide is 1-1.5:1-1.2:1:1:1.

6. A method for preparing the metal oxide coated ceramic corrugated plate catalyst according to claim 1, comprising the steps of: (1) dissolving salts comprising vanadium, molybdenum and the two other metal elements in titanium sol to form uniform mixed colloidal liquid; (2) carrying out spray drying on the mixed colloidal liquid on a surface of the ceramic corrugated plate and high-temperature calcination to obtain the metal oxide coated ceramic corrugated plate catalyst.

7. The method for preparing a metal oxide coated ceramic corrugated plate catalyst according to claim 6, wherein the titanium sol is controlled to have a pH value of 1-5.

8. The method for preparing a metal oxide coated ceramic corrugated plate catalyst according to claim 6, wherein the titanium sol has a mass concentration of 10-30% and the solvent of the titanium sol is water.

9. The method for preparing a metal oxide coated ceramic corrugated plate catalyst according to claim 6, wherein the titanium sol further comprises a surfactant in an amount of 1-5 wt % of the titanium sol.

10. A method for preparing the metal oxide coated ceramic corrugated plate catalyst according to claim 2, comprising the steps of: (1) dissolving salts comprising vanadium, molybdenum and the two other metal elements in titanium sol to form uniform mixed colloidal liquid; (2) carrying out spray drying on the mixed colloidal liquid on a surface of the ceramic corrugated plate and high-temperature calcination to obtain the metal oxide coated ceramic corrugated plate catalyst.

11. A method for preparing the metal oxide coated ceramic corrugated plate catalyst according to claim 3, comprising the steps of: (1) dissolving salts comprising vanadium, molybdenum and the two other metal elements in titanium sol to form uniform mixed colloidal liquid; (2) carrying out spray drying on the mixed colloidal liquid on a surface of the ceramic corrugated plate and high-temperature calcination to obtain the metal oxide coated ceramic corrugated plate catalyst.

12. A method for continuous preparation of prenal or prenol, comprising following steps of: filling a reaction zone of a rectifying tower with a metal oxide coated ceramic corrugated plate catalyst, correspondingly continuously introducing methylbutynol or methylbutenol into the rectifying tower for catalytic rearrangement reaction, and continuously extracting prenal or prenol from a lateral line of the tower kettle, wherein the metal oxide coated ceramic corrugated plate catalyst consists of a ceramic corrugated plate carrier and a metal oxide active layer coated on the surface of the carrier, wherein the ceramic corrugated plate carrier is made of cordierite, alumina or silicon carbide, wherein the metal oxide active layer is a metal oxide formed with active ingredients consisting of titanium and four metal elements of V, Mn, Fe and Mo, titanium and four metal elements of V, Zr, Fe and Mo, titanium and four metal elements of V, Zr, Cr and Mo, or titanium and four metal elements of V, Nb, Fe and Mo.

13. The method for continuous preparation of prenal or prenol according to claim 12, wherein the loading amount of the metal oxide active layer is 0.1-10 wt % of the ceramic corrugated plate.

14. A method for continuous preparation of prenal or prenol, comprising following steps of: filling a reaction zone of a rectifying tower with the metal oxide coated ceramic corrugated plate catalyst according to claim 4, correspondingly continuously introducing methylbutynol or methylbutenol into the rectifying tower for catalytic rearrangement reaction, and continuously extracting prenal or prenol from a lateral line of the tower kettle.

15. A method for continuous preparation of prenal or prenol, comprising following steps of: filling a reaction zone of a rectifying tower with the metal oxide coated ceramic corrugated plate catalyst according to claim 5, correspondingly continuously introducing methylbutynol or methylbutenol into the rectifying tower for catalytic rearrangement reaction, and continuously extracting prenal or prenol from a lateral line of the tower kettle.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1: a 100 micrograph of a (Ti.sub.11V.sub.1Mn.sub.1Fe.sub.1Mo.sub.1)O.sub.11.2 metal oxide coated ceramic corrugated plate catalyst;

(2) FIG. 2: an XDR characterization of the (Ti.sub.1.1V.sub.1Mn.sub.1Fe.sub.1Mo.sub.1)O.sub.11.2 metal oxide coated ceramic corrugated plate catalyst; and

(3) FIG. 3: a catalytic rearrangement reaction system.

DESCRIPTION OF THE EMBODIMENTS

Example 1

Preparation of (Ti.SUB.1.1.V.SUB.1.Mn.SUB.1.Fe.SUB.1.Mo.SUB.1.)O.SUB.11.2 .Metal Oxide Coated Ceramic Corrugated Plate Catalyst

(4) (1) 1 mol ammonium vanadate, 1 mol ferric trichloride, 1 mol molybdenum citrate and 1 mol manganese chloride were added into 1.1 mol titanium dioxide sol (concentration 20%, pH 3), dissolved by ultrasonic waves, and completely and uniformly mixed to obtain mixed colloidal liquid.

(5) (2) The mixed colloidal liquid were spray dried on a surface of ceramic corrugated plate with the weight of 5.5 Kg, thickness of 1 mm, corrugation inclination angle of 45 and wave crest height of 30 mm and wave distance of 10 mm under the condition of 110 C., then placed in a muffle furnace and calcined under air atmosphere with temperature increased to 950 C. at 5 C./min for 6 h. (Ti.sub.1.1V.sub.1Mn.sub.1Fe.sub.1Mo.sub.1)O.sub.11.2 metal oxide coated ceramic corrugated plate catalyst was obtained.

(6) According to FIGS. 1 and 2, the results of the 100 micrograph and XRD diffraction test showed that the catalyst containing the above target component was prepared.

(7) As shown in FIGS. 1 and 2, the metal oxide shown in FIG. 1 is uniform and complete in the coating area without pore channels, and does not influence the separation function of the corrugated plate; FIG. 2 is an XRD characterization of metal oxides.

Examples 2-5

(8) According to the method of Example 1, the following catalysts (Table 1) were obtained by varying the added metal elements and the amounts thereof, the pH value of the titanium sol, the calcination temperature, and the calcination time, respectively.

(9) TABLE-US-00001 TABLE 1 Catalyst Preparation Parameters for Examples 1-5 Calcina- tion temper- Calcina- Catalyst pH ature tion Loading value ( C.) time (h) Catalyst (%) Example 1 3 950 6 (Ti.sub.1.1V.sub.1Mn.sub.1Fe.sub.1Mo.sub.1)O.sub.11.2 9.8 Example 2 3 700 6 (Ti.sub.1V.sub.1Mn.sub.1Fe.sub.1Mo.sub.1)O.sub.11 5.0 Example 3 3 1000 3 (Ti.sub.1V.sub.1Zr.sub.1Fe.sub.1Mo.sub.1)O.sub.11 1.0 Example 4 5 900 6 (Ti.sub.1V.sub.1.2Zr.sub.1Cr.sub.1Mo.sub.1)O.sub.13.5 4.9 Example 5 1 1000 3 (Ti.sub.1V.sub.1Nb.sub.0.8Fe.sub.1Mo.sub.1)O.sub.11 5.0

Example 6

Preparation of (Ti.SUB.1.1.V.SUB.1.Mn.SUB.1.Fe.SUB.1.Mo.SUB.1.)O.SUB.11.2 .Metal Oxide Coated Ceramic Corrugated Plate Catalyst

(10) This comparative example differs from Example 1 only in that the spray drying temperature of step (2) was 200 C.

(11) In order to better reflect the influence of the composition of the metal oxide on the catalyst, the following comparative examples were also carried out. The loading of each catalyst was as follows in Table 2.

Comparative Example 1

Preparation of (Ti.SUB.1.V.SUB.1.Mn.SUB.1.)O.SUB.X .Metal Oxide Coated Ceramic Corrugated Plate Catalyst

(12) It differs from Example 1 in that in step (1), 1 mol ammonium vanadate and 1 mol manganese chloride were added to 1.1 mol titanium dioxide sol (concentration 20%, pH 3), dissolved by ultrasonic wave, and thoroughly mixed uniformly to obtain a mixed colloidal liquid.

Comparative Example 2

Preparation of (Ti.SUB.1.Fe.SUB.1.Mo.SUB.1.)O.SUB.Y .Metal Oxide Coated Ceramic Corrugated Plate Catalyst

(13) It differs from Example 1 in that in step (1), 1 mol ferric trichloride and 1 mol molybdenum citrate were added to 1.1 mol of titanium dioxide sol (concentration 20%, pH 3), dissolved by ultrasonic waves, and mixed uniformly to obtain a mixed colloidal liquid.

(14) TABLE-US-00002 TABLE 2 Catalyst Loading (%) Example 6 9.8 Comparative Example 1 9.6 Comparative Example 2 9.8

Example 7

Preparation of Prenal

(15) Methylbutynol was continuously fed into a rectifying tower, the feeding amount was 100 Kg/h. As shown in FIG. 3, the first reaction zone 2 and the second reaction zone 3 were respectively and regularly packed with metal oxide coated ceramic corrugated plate catalyst prepared from examples 1-5 and comparative examples 1-2, of which the theoretical tray number was 5, and the first separation zone 1 was packed with common ceramic corrugated plate packings with the theoretical tray number of 10; the second separation zone 4 was packed with a common ceramic corrugated plate packing with a theoretical tray number of 25, and the third separation zone 5 was packed with a common ceramic corrugated plate packing with a theoretical tray number of 5. In the rectifying tower, controlling reaction temperature at 120-125 C., reaction pressure at 0.06 MPa and condensation temperature at top of the tower at 80 C., prenal production was started after 2 h of recycle reaction, and the results are shown in Table 3 below.

(16) TABLE-US-00003 TABLE 3 Prenal yield Reaction per hour Prenal Catalyst number time (h) (Kg) purity (%) Example 1 5 96 99.3 Example 2 5 96 99.5 Example 3 5 95 99.1 Example 4 5 97 99.4 Example 5 5 95 99.1 Example 1 50 96 98.7 Example 1 100 96 97.1 Example 6 5 96 99.1 Example 6 24 96 58.3 Comparative Example 1 5 96 84.3 Comparative Example 2 5 96 78.1 Comparative Example 1 24 96 1.3 Comparative Example 2 24 96 0.9

Example 8

Preparation of Prenol

(17) Methylbutenol was continuously fed into a rectifying tower, and the feeding amount was 100 Kg/h. The first reaction zone 2 and the second reaction zone 3 were respectively and regularly packed with metal oxide coated ceramic corrugated plate catalyst prepared from examples 1-10 and comparative examples 1-4, of which the theoretical tray number was 3 and 10, the first separation zone 1 was packed with metal oxide coated ceramic corrugated plate packing prepared from examples 1-10 and comparative examples 1-4, of which the theoretical tray number was 8, the second separation zone 4 was packed with Pall ring packing with a theoretical tray number of 28, and the third separation zone 5 was packed with Pall ring packing with a theoretical tray number of 7. Reaction temperature at 128-133 C., reaction pressure at 0.07 MPa and condensation temperature at top of the tower at 90 C., prenal production was started after 2 h of recycle reaction, and the results are shown in Table 4 below.

(18) TABLE-US-00004 TABLE 4 Reaction Prenal Prenal purity Catalyst number time (h) yield (Kg) (%) Example 1 5 95 99.6 Example 2 5 97 99.2 Example 3 5 96 99.3 Example 4 5 97 99.1 Example 5 5 96 98.9 Example 1 50 95 98.9 Example 1 100 95 98.3 Example 6 5 95 99.3 Example 6 24 95 60.9 Comparative Example 1 5 95 81.2 Comparative Example 2 5 95 79.3 Comparative Example 1 24 95 0.73 Comparative Example 2 24 95 1.32

Example 9

(19) Following the method of Example 1, an additional 10 g dodecyl polyethylene glycol ether was added during the preparation of the mixed colloidal liquid to obtain (Ti.sub.1.1V.sub.1Mn.sub.1Fe.sub.1Mo.sub.1)O.sub.11.2 metal oxide coated ceramic corrugated plate catalyst.

Example 10

(20) Prenal was prepared by catalytic rearrangement according to the method of Example 7 with the catalyst prepared in Example 9, and the reaction results are shown in Table 5 below.

(21) TABLE-US-00005 TABLE 5 Reaction time (h) Prenal yield (Kg) Prenal purity (%) 5 96 99.5 10 96 99.2 20 96 98.7 50 96 98.5 100 96 98.4

(22) Finally, it should be noted that the above description was only intended to illustrate the technical solution of the present disclosure and was not intended to limit the scope of the present disclosure, and that those skilled in the art will be able to make simple modifications or equivalent alterations to the technical solution of the present disclosure without departing from the spirit and scope of the technical solution of the present disclosure.