DEVICE FOR PROCESSING AND CONDITIONING OF MATERIAL TRANSPORTED THROUGH THE DEVICE

Abstract

The present invention relates to a device for treatment of material transported through the device having a specific design.

Claims

1. Reactor tube having an inlet end and an outlet end for treating a fluid flowing through the reactor tube, with a plurality of grid structures arranged in series in the flow direction in the reactor tube for mixing the fluid, wherein each grid structure consists of three sets of parallel partitions which bound flow channels with a flow cross section in the form of a (regular) polygon, and wherein the sets of partitions of adjacent grid structures are offset and/or rotated with respect to one another.

2. Reactor tube according to claim 1, wherein, in each set of parallel partitions, the adjacent partitions are equally spaced.

3. Reactor tube according to claim 1, wherein the three sets of parallel partitions intersect in each case at an angle of 120 degrees, and in that the partitions bound flow channels with a flow cross section in the form of an equilateral triangle.

4. Reactor tube according to claim 3, wherein the length of the grid structures in the flow direction approximately corresponds to the side length of the equilateral triangles.

5. Reactor tube according to claim 1, wherein the sets of partitions of adjacent grid structures are offset with respect to one another in a direction perpendicular to the plane of one of the partitions.

6. Reactor tube according to claim 1, wherein the sets of partitions of adjacent grid structures are rotated with respect to one another by an angle of 60 degrees.

7. Reactor tube according to claim 1, wherein the orientation of the grid structures repeats periodically.

8. Reactor tube according to claim 1, wherein the orientation of the grid structures repeats, in each case after three grid structures.

9. Reactor tube according to claim 1, wherein the triangle height of the reactor tube is from 1-10 mm, (preferably 1-5 mm, more preferred 2-3 mm).

10. Reactor tube according to claim 1, wherein the periodic unit length of the reactor tube is 3-30 mm (preferably 6-20 mm, more preferred 6-9 mm). The preferred periodic unit length is 3 times the triangle height.

11. Reactor tube according to claim 1, wherein, in two out of three grid structures arranged in series, a central axis of the reactor tube runs through the intersection line of two partitions, and in the third grid structure it runs through the middle of one of the polygons.

12. Reactor tube according to claim 1, wherein the grid structures are coated with an oxide primer layer and a catalyst layer.

13. Reactor tube according to claim 12, wherein the primer layer is a mixed oxide, containing cerium oxide and zinc oxide.

14. Reactor tube according to claim 12, wherein the catalyst layer contains palladium nanoparticles.

15. Hydrogenation reactor, characterized by a plurality of reactor tubes according to claim 1.

Description

FIGURES

[0121] FIG. 1: Left) View of triangular structure and pipe. [0122] Right) Hexagonal unit cell of the triangular structure.

[0123] FIG. 2: View of structured reactor of the prior art (for comparison)

[0124] FIG. 3: Simplified scheme of the experimental setup. (1) pump, (2) electrical heater, (3) hydrogen tank, (4) static mixer, (5) view cell, (6) structured reactor (7) gas-liquid separator, (8) off-gas cooler, (9) nitrogen tank.

[0125] The following examples serve to illustrate the invention. All percentages are related to weight and the temperatures are given in degree Celsius, if not otherwise stated.

EXAMPLES

Example 1 Manufacturing of a Reactor Tube

[0126] The described reactor (the exact dimensions are listed below) was prepared by Laser Sintering Technique. The reactor tune was produced out of EOS Maraging Steel MS1 (from EOS GmbH). With this technology, a three-dimensional structure of nearly every shape can be designed in a Computer Assisted Design (CAD) software and then manufactured as one single part. This is done by depositing a layer of metal powder, directing energy on a selected position corresponding to the CAD model to sinter it before depositing a new layer and begin the procedure again as it is for example described in U.S. Pat. Nos. 5,639,070, 5,732,323 and 6,676,892.

[0127] Dimensions of the reactor tube (with the triangular structure): [0128] Inner pipe diameter: 14 mm [0129] Total structure length: 202.86 mm (28 periodic units) [0130] Inner triangle side length: 2.415 mm [0131] Triangle height: 2.415 mm [0132] Periodic unit length: 7.245 mm (3 triangle height) [0133] Porosity: 76.6%

Preparation of Catalyst and Base-Layer Coated Structures

[0134] The triangular structure was subjected to a thermal pre-treatment at 450 C. for 3 h. For preparation of the primer solution, Ce(NO.sub.3).sub.3.6H.sub.2O (508 mmol) and 700 mL water were added to a beaker. The mixture was stirred with a stirring bar until the salt was dissolved completely. The solution was heated up to 90 C. and the ZnO (508 mmol) was slowly added to the solution. The stirring was maintained at 90 C. and 65% nitric acid was added dropwise until all ZnO was completely dissolved (final C.sub.HNO3=1 M). Afterwards the solution was cooled to room temperature and filtrated through a 0.45 m membrane filter. The deposition of ZnO/CeO.sub.2 was performed by rinsing the inside of the thermally pre-treated triangular structure with 50 mL of the primer solution. The structure was then dried at 60 C. at 125 mbar for 2 h followed by calcination at 450 C. for 1 h. This process was repeated 3 times. Sodium tetrachloropalladate(II) (0.32 mmol) was dissolved in 96 mL of Millipore water and PEG-MS40 (2 mmol) were added. The solution was heated up to 60 C. and sonication was started at this temperature. Afterwards a freshly prepared solution of sodium formate (16 mM, 48 mL) was added. The solution was sonicated for further 60 minutes at this temperature and then cooled to room temperature. The resulting solution was rinsed through the triangular structure in vertical position four times, until the solution was almost colorless. The structured reactor was then dried at 40 C. under reduced pressure for 2 h. The structure was subjected to a temperature treatment at 300 C. for 4 h (temperature ramp10/min) under H2-Ar flow (1:9; total flow rate450 ml/min).

Selective Hydrogenation Reactions Using the Reactor Tube

[0135] The reactor tube, which was produced as describe above (Example 1) was used and the arrangement for the hydrogenation process can be seen in FIG. 3.

[0136] In the typical hydrogenation experiment the liquid phase (10 wt % 2-methyl-3-butyne-2-ol (MBY), 90 wt % 2-methyl-3-butene-2-ol (MBE)) is recirculated through the system at high velocity and heated up in order to reach the desired reaction temperature. The electrical heater consists in a block of brass equipped with two heating cartridges (400 W each). The temperature is controlled directed at the outlet of the heater by means of a PID temperature controller. A back-pressure regulator controls the pressure at the reactor inlet. After stabilization of pressure and temperature, the flowrate is regulated to the desired value and pure hydrogen is supplied from an external tank (flowrate=1 nL/min). As soon as hydrogen bubbles are visible in the view cell, valve V5 is closed and valve V6 is simultaneously opened (Scheme 3). Before entering the reactor, the gas and the liquid phase are pre-mixed in a static mixer (length=200 mm, diameter=14 mm, porosity=87%). The off-gas is separated from the liquid and cooled down with cooling water to condense eventual organic vapours. The triangular structure is thermally insulated to minimize heat losses. After each experiment the setup is emptied and flushed by nitrogen. Liquid samples are withdrawn at defined intervals of time through a manual valve and analysed using a GC-450 gas-chromatograph.

[0137] To show the improved properties of the new reactor tube, comparison test with a reactor tube from the prior art (WO2010/142806) were carried out. The reactor tube for the comparison test was produced in the same way and it was also coated the same way as the new reactor tube

TABLE-US-00001 TABLE 1 Reactions run in continuous mode (to evaluate activity); pressure was varied Reaction conditions: gas flow rate: 1 nL/min, liquid flow rate: 10 kg/h, reaction temperature: 90 C. Reactor Pressure Activity Exp. Tube type (bar) (mol/s mol Pd) 1 Structured (Comparison) 3 0.6159 2 Triangular (Invention) 3 1.0812 3 Structured (Comparison) 5 0.8715 4 Triangular (Invention) 5 1.5164 5 Structured (Comparison) 7 1.0923 6 Triangular (Invention) 7 1.7406

[0138] It can be seen that the activity of the new reactor tube is improved significantly.

TABLE-US-00002 TABLE 2 Reactions run in continuous mode (to evaluate activity); reaction temperature was varied Reaction conditions: gas flow rate: 1 nL/min, liquid flow rate: 10 kg/h, pressure 7 bar Reactor Temp Activity Exp. Tube type ( C.) (mol/s mol Pd) 7 Structured (Comparison) 90 1.0923 8 Triangular (Invention) 90 1.7406 9 Structured (Comparison) 80 0.9378 10 Triangular (Invention) 80 1.5314 11 Structured (Comparison) 70 0.7994 12 Triangular (Invention) 70 1.2648 13 Structured (Comparison) 60 0.6901 14 Triangular (Invention) 60 0.9687

[0139] It can be seen that the activity of the new reactor tube is improved significantly.

TABLE-US-00003 TABLE 3 Reactions run in semi-batch mode (to evaluate selectivity) Reaction conditions: 80 C., 4 bar H.sub.2, gas flow rate: 0.7 nL/min, liquid flow rate: 70 kg/h Reactor Selectivity Time Exp. Tube type Conversion (MBE) (min) 15 Structured 99.8% 89.3% 421 (Comparison) 16 Triangular 99.9% 90.7% 390 (Invention)

[0140] It can be seen that the conversion and the selectivity are improved (at shorter reaction time).