JPS59177127A - Packing layer type reaction tower packed with soft packing material - Google Patents

Abstract

PURPOSE:The titled reaction material prevented from the compaction of a soft packing material while inhibiting the increase of pressure loss, characterized in that baffles are inserted into a packing layer comprising the soft packing material toward te direction at right angles to the stream of a liquid to be treated. CONSTITUTION:In a packing layer type reaction tower for producing a useful substance by using an immobilized bio-catalyst such as immobilized enzyme or an immobilized microorganism, baffles 4 are inserted into the reaction tower 1 toward the direction at right angles to the flow direction of a liquid to be treated at predetermined pitches. The spaces between the baffles are packed with the soft packing material 5 to form a packing layer. Each of the baffles 4 is formed into a circular, an oval, a triangular or a square shape or formed into a hollow shape and they are arranged in a parallel, zigzag or grid like state. When the liquid to be treated is flowed through this reaction tower 1, a desired void ratio is held and pressure loss is reduced and, therefore, a production amount per unit catalyst can be increased.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a packed bed reaction column using a flexible packing material. More specifically, the present invention relates to a packed bed type reaction tower in which a baffle is inserted in a packed bed filled with a soft filler in a direction perpendicular to the flow direction of the liquid to be treated.

In recent years, various methods of producing useful substances using immobilized biocatalysts such as immobilized enzymes or immobilized microorganisms have been studied and are being implemented on an industrial scale.

Packed bed reaction towers are more widely used as reactors for such industrial production. However, most of the immobilized biocatalyst particles that are packed are soft materials that have inferior mechanical strength compared to ordinary solid catalysts, and these biocatalysts are difficult to use as the reaction tower becomes larger and the flow rate increases. There is a problem that a compaction phenomenon occurs, and as a result, the effective coefficient of the raw catalyst decreases and the reaction rate becomes extremely low, sometimes making it impossible to process.

As one method for solving the problems inherent to immobilized biocatalysts, a vertical multitubular reaction tower has been proposed that utilizes the wall effect of the reaction tower to prevent compaction. However, in the reaction tower, it is necessary to measure the pressure loss of the six pipes in advance and keep it constant, and if the settings are incorrect, a short path of the liquid to be treated will occur, making it impossible to perform a uniform liquid passage operation. Furthermore, due to the consolidation by self-load, there is a limit to the height of the packed bed, and although it varies depending on the particle size of the flow rate filler during operation, it is generally not possible to use a bed that exceeds about 2 to 6 m.

The present inventors believe that when inserting a baffle in a direction perpendicular to the flow direction of the liquid to be treated into a packed bed filled with a soft filler such as an immobilized biocatalyst, the baffle and the soft filler particles The inventors have discovered that the soft filler can be prevented from becoming loose due to friction, and have completed the present invention.

The baffle in the present invention preferably has a rod-like or elongated cross-sectional shape, such as a circular, elliptical, triangular, square, diamond, L-shape, 7-shape, mouth-shape, or engineering shape. A circular shape that prevents dead spaces.
Oval, diamond, etc. are preferred. Alternatively, a hollow baffle may be used.

The baffle is provided so as to completely traverse the packed bed and span the inside of the reaction column. The baffles may be arranged in a parallel arrangement, a staggered arrangement, a lattice arrangement, or the like.

Next, embodiments of the reaction tower of the present invention will be described based on the drawings, but the present invention is not limited to such embodiments.

Fig. 1 is a schematic plan view of an embodiment of the reaction tower of the present invention, Fig. 2 is a partially cutaway schematic elevational view, and Fig. 3 is (X) in Fig. 2.
- (X) line sectional view.

A liquid to be treated is introduced into the reaction tower (1) from the inlet (2),
It flows out from the outlet (8). Inside the reaction tower, baffles (4) having a circular cross section are inserted at a predetermined pitch. The soft filler (5) is attached to the baffle (4) in the reaction column (1).
), forming a packed layer.

As shown in FIG. 6, the baffle (
The arrangement 4) is a parallel arrangement.

In addition, a staggered arrangement or a lattice arrangement may be used, as shown in FIGS. 4 and 5, respectively.

The size of the baffle in the present invention is preferably selected so that the total surface area (Cm) of the baffle/reaction column volume (om3) (hereinafter, this ratio is referred to as a) is about 0.04 to 0.5. . When the value of a is less than about 0.04, the reaction tower is gradually consolidated, similar to a reaction column without baffles, and when the value of a is larger than about 0.5, dead space is likely to be formed under the baffle and the filling is difficult. It becomes difficult.

The lateral pitch of the baffles is L/dp, where the lateral spacing of the baffles is Ll, and the average particle diameter of the soft filler particles is dp.
It is preferable to select a value of about 2 to 15o1, particularly about 5 to 4o. When the value of L/dp is less than about 2, the spatial density increases and the filling efficiency decreases.
When it is larger, the effectiveness of the baffle decreases. The vertical pitch of the baffle is L2 when the vertical spacing of the baffle is L2.
It is preferable to select the value of /dp to be about 2 to 190, particularly about 7 to 7o. When the value of b2/ap is less than about 2, the spatial density increases and the filling efficiency decreases.
When it is greater than about 190, the effectiveness of the baffle is reduced.

Although the shape of the reaction tower is not particularly limited, it is preferable to have a cross-sectional shape of either circular or square for ease of manufacture. The height of the packed bed in the reaction tower varies depending on the mechanical strength, particle size, particle shape, etc. of the soft packing material, but is usually 1.
It can be raised up to about 0m.

The reaction column of the present invention can be used not only as a reaction column for enzyme reactions using biocatalysts such as immobilized enzymes and immobilized microorganisms, but also as columns for liquid chromatography and ion exchange. .

Examples of the soft packing material used in the present invention include immobilized enzymes and biocatalysts of immobilized microorganisms in which various enzymes and microorganisms are immobilized using soft substances, and soft adsorbents for liquid chromatography and ion exchange. Medications can be given.

Examples of soft substances include agarose carriers, dextran carriers, cellulose carriers, polyacrylamide carriers, and other vinyl polymers that are insoluble in the liquid to be treated.
Examples include materials commonly used for immobilizing enzymes and microorganisms, such as nylon, polystyrene, and amino acid copolymers.

Examples of the adsorbent include activated adsorbents obtained by chemically modifying the above substances, adsorbents for ion exchange, hydrophobic adsorbents, and adsorbents for Awainite chromatography.

The reaction column of the present invention can be particularly suitably used for enzymatic reactions using immobilized enzymes or immobilized microorganisms as described above. One of the characteristics of enzymatic reactions is that they can be carried out under mild conditions such as room temperature and normal pressure, but even in enzymatic reactions, there is an exchange of heat during the reaction, although not to the same extent as in normal chemical reactions. . For example, an aspartase reaction using immobilized E. coli is a reaction that generates an exotherm of about 6°C/mop. However, many of the biocatalysts used in enzymatic reactions are sensitive to heat, and therefore, when carrying out reactions over a long period of time, heat exchange is required to keep the temperature inside the reaction tower constant at all times.

However, biocatalysts that use soft substances such as immobilized enzymes and immobilized microorganisms have relatively low thermal conductivity;
When using a conventionally widely used double back type reaction tower, uniform heat exchange is not possible, and temperature distribution occurs in the radial direction of the packed bed.

Therefore, in order to keep the entire packed bed at a uniform temperature, conventional methods have been to reduce the diameter of the reaction column, lower the temperature when supplying the substrate liquid according to the calorific value to make the reaction non-isothermal, or This required the use of complex equipment that combined heat exchangers and heat exchangers in multiple stages in series. However, such reaction towers have limited processing capacity, complicated operation,
Equipment costs are increasing.

In the reaction tower of the present invention, a hollow baffle is used as the baffle inserted in the packed bed, and by passing a cooling medium or a heating medium through the baffle, uniform heat exchange can be performed throughout the packed bed. The reaction system can be maintained at a predetermined reaction temperature at all times even in the radial direction of the reaction tower.

When performing heat exchange, the thickness of the baffles and the pitch of the baffles are determined based on the above a and L/dp as conditions for preventing compaction, as well as the calorific value of the reaction, heat transfer area, thermal conductivity of the immobilized biocatalyst, etc. may be selected appropriately for each reaction.

FIG. 6 shows a partially cutaway schematic elevational view of an embodiment of the reaction column of the present invention using hollow baffles.

The baffle (6) is hollow, and a heating or cooling medium is introduced through the inlet (8) and taken out through the outlet (a). The baffles (6) are separated every two stages by a partition wall (9) at the mantle portion.

Next, a liquid passage experiment and an enzyme reaction experiment conducted using the reaction tower of the present invention will be shown.

Example 1 A square tower with a cross section of 120 mm on a side (height: 1500 mm)
mm) is used as a reaction tower, and inside this is an outer diameter of 21 mm,
Staggered arrangement of round bars with a length of 120 mm (horizontal pitch: 58 mm)
, 48 pieces were inserted with a vertical pitch of 43 mm). This reaction column contains one carrageenan gel particle (average particle size of gel particles:
1.89 mm, gel concentration = 6.4%) was filled to a height of approximately 1 m. At this time a is 0, 2670m/a
m.

L engineering/dp was 9.0, and L2/dp was 11.6.

A 2% KO/solution was passed through this in a downward flow from the top of the column, and the flow rate (superficial velocity) of the liquid to be treated and the pressure loss and the volume of one packed bed - gel volume porosity 1-, -, , but The relationship between packed bed volume - reactor volume - buff/L' volume) was investigated. The results are shown in Table 1.

Comparative Example 1 Carrageenan gel particles were filled in the same manner as in Example 1, except that no baffle was inserted, and a 2% KO1 solution was passed through to examine the flow rate, pressure loss, and void ratio of the liquid to be treated.

The results are shown in Table 1.

Table 1 As is clear from Table 1, in Example 1 in which the baffle was inserted, both the pressure loss and the void ratio show only a very small increase compared to Comparative Example 1.

Examples 2 to 10 One carrageenan gel particle was filled in the same manner as in Example 1, except that baffles of various shapes were inserted in various arrangements, and two
% KO/solution was passed through the tube at a flow rate of 0.7 cm/sec (superficial velocity), and the pressure drop and void ratio were investigated. The results are shown in Table 2.

The shape and arrangement of the baffles in each example are shown below.

Example 2 Shape: Round bar arrangement with an outer diameter of 21 mm: Staggered arrangement with a horizontal pitch of 38 m and a vertical pitch of 43 mm (
48 pieces) a: 0.267 am2/am3L/(11; l: 9.O L2/dp' 11.6 Example 6 Shape: Round bar with outer diameter of 21 mm Arrangement: 68 horizontal pitches, 4 vertical pitches parallel array (42
Book) 1L: 0.250cm27cm3 L work/dp'9.0 L2/ap: 11.6 Example 4 Shape: Round bar arrangement with outer diameter of 21mm: Parallel arrangement with horizontal pitch of 38-1 and vertical pitch of 135mm (16 bars) IIL: 0.105cm”/am3L
Engineering/dp:9. Q L2/ap: 11.6 Example 5 Shape: Circular pipe arrangement with outer diameter of 9 m: Staggered arrangement (48 pipes) with horizontal pitch of 38 m + t and vertical pitch of 49 mm a: [1, 125 cm 27 a
m3L1/dp: 15.3 L2/dp: 21.2 Example 6 Shape: Circular pipe arrangement with outer diameter of 9 mm: Parallel arrangement with horizontal pitch of 68 na and vertical pitch of 98 na
18 pieces) a: D, 049cm27cm3 L work/dp: 15. L2/dp: 47.1 Example 7 Square pipe arrangement with knee side 20mm: Parallel arrangement (16 pipes) with horizontal pitch 68mm and vertical pitch 142Nn a' 0.113 cm2/C+n
3L work/dp: 9.5 L2/ap: 64.5 Example 8 Diamond shape vibrator array with knee side 20 mm: Parallel array with horizontal pitch 68 threshold and vertical pitch 115 threshold (
16 pieces) a: 0.118cm27am3L/
dp:5. I L27'dp: 45.4 Example 9 Shape: Temporary arrangement of 18mm x 3Trn: Each plate is arranged horizontally in parallel with a horizontal pitch of 38mm and a vertical pitch of 125mm (16 pieces) a' 0.065 am27cm3L/dp:
10.5 L,/dp! 64.6 Example 10 Shape: 18 mm x 5 mm plate arrangement: each plate vertically with a horizontal pitch of 38 mm and a vertical pitch of 125
Parallel array in mm (16 pieces) tL: 0.065am”70m3L/ap:
18.5 L2/dp: 56.6 Table 2 As is clear from Table 2, when inserting a baffle, the pressure loss is lower than when no baffle is inserted (comparative example 1).
) can be suppressed to 26-40%.

Example 11 A square tower with a cross section of 260 mm on a side (700 m in height)
m) outside! 96 20mm circular pipes arranged in a staggered arrangement (
Horizontal pitch '40rnm, vertical pitch: 34.6mm)
reaction tower (A), cross section 200mm x 260m
m rectangular reaction tower (height 700 mm) with an outer diameter of 6
A reaction tower (B) in which 10 circular pipes of 4 mm and a length of 200 mm were arranged in a staggered manner (horizontal pitch N 20 mm, vertical pitch: 104 mm), and a reaction tower (B) in which pipes with an outer diameter of 60 mm were used as pipes (0 ) and X-carrageenan particles (
Geneugel WG) km Filled with immobilized E. coli particles (average particle size s, 56 mm) on which 1% bacteria were immobilized, 2
% KO1 solution was passed through the tube at a flow rate (superficial velocity) of 0.060 m/sec for 10 consecutive days.

As a result, almost no compaction occurred in any of the reaction towers, and continuous liquid flow treatment was possible.

The filling heights are as follows: reaction towers (A), , (E) and (
c) respectively 0.56m, 0.56m and 0
．． 56 m, and a, L, /dp and RI, /dp are 0 and 41 am2/am3. in the reaction column (A), respectively.
6.6 and 2.6, respectively 0 and 0 in the reaction column (B)
7 am2/Qm3.15.5 and 12.6, reaction @
(C) respectively 0, 13 am27cm3.10.
8 and 7.9.

Example 12 A rectangular square tower with a cross section of 640 mm x 780 mm (
A circular pipe 96 with an outer diameter of 60 mm and a height of 2000 mm.
Staggered arrangement of books (horizontal pitch: 120mm, vertical pitch: 1)
The same immobilized E. coli as used in Example 11 was packed into a reaction column (Q4 mm) with an apparent filling volume of 6001 (apparent filling volume).
am0, 15 am"/am", L 1/dp = 1
0.8, L2/dp = 7-9) o Add ammonia 7-malate solution (initial concentration 1.22M,
, pH 8.5) at a rate of 3601/hour to perform an aspartase reaction.

34°C hot water is constantly passed through the pipe, and the substrate liquid is kept at 67°C.
After preheating to 0, the solution was passed through.

Table 6 shows the temperature of the effluent, the number of days of operation until breakthrough, and the total amount of L-aspartic acid produced in the effluent.

Comparative Example 2 Aspartase reaction was carried out in the same manner as in Example 12, except that a reaction tower without a baffle was used, and L-aspartic acid was obtained.

The results are shown in Table 6.

Table 6 As shown in Table 6, when a baffle is inserted and heat exchange is performed by it, the temperature of the effluent is almost constant, the number of breakthrough days is doubled, and the amount of L-aspartic acid per unit of biocatalyst is increased. The production amount can be significantly increased.

Example 16 Instead of immobilized E. coli, immobilized Brevibacterium flavum particles (average particle size 5.56 mm) in which Brevibacterium flavum was immobilized on carrageenan particles (Genyugel WG) by the carrageenan gel method were used (am0 ．．
15cm cm3, L, /dl) = 10.8, r, +
2/4p = 7.9), using a sodium fumarate solution (initial concentration IM, pH 7.0) as the substrate liquid, the flow rate (superficial velocity) was 1201! L-malic acid was produced in the same manner as in Example 12, except that the flask was passed through the flask at a rate of 1/2 hour and the fumarase reaction was carried out.

Table 4 shows the temperature of the effluent, the number of days of operation until breakthrough, and the total amount of L-phosphoric acid produced in the effluent.

Although the reaction temperature was raised to 50° C. during the operation, the temperature distribution in the axial direction was uniform even in that case.

Comparative Example 3 A fumarase reaction was carried out in the same manner as in Example 13, except that a reaction tower without a baffle was used, and L-malic acid was obtained.

The results are shown in Table 4.

Table 4 As shown in Table 4, when inserting a baffle and thereby performing heat exchange, the temperature of the effluent remains almost constant, greatly increasing the production of :l,-IJ malic acid. I can do it.

Example 14 The procedure was repeated in the same manner as in Example 16, except that instead of Brevibacterium flavum, immobilized Brevibacterium ammoniagenes, in which Brevibacterium ammoniagenes was immobilized on carrageenan particles, was used (amQ, 15c).
m”/am3, L, /+ITI = 118, L〆1i
p=7.9), L-malic acid was produced using a sodium fumarate solution.

Table 5 shows the temperature of the effluent, the number of operating days until breakthrough and the amount of total produced I, -IJ malic acid in the effluent.

Comparative Example 4 L-malic acid was obtained by passing liquid in the same manner as in Example 14, except that a reaction tower without a baffle was used.

The results are shown in Table 5.

Table 5 Example 15 The same reaction tower as used in Example 1 was filled with aminoacylase to a height of about 1 m (a = 0.
267 am2/am3, L, /dp = 40.0,
L2/dp = 5l-8).

When a 0.38 M acetyl-a2o-phenylalanine solution was passed through this reaction column at a superficial velocity of 0.11 cm/sec and the pressure drop was measured, it was found to be 42.5 cm-a2o/m-b.
It was ea.

On the other hand, when a similar flow test was conducted in a reaction tower without baffles, the pressure drop was 50 am-H.
It's a large 2o/m-bed and it's ivy.

Example 16 DEAE-
Sephadex A-25 (dextran gel manufactured by Pharmacia) was filled to a height of about 1 m (a =
0.267cm2/am3, Lx/dp=141, L
2/dp = 186).

When water was passed through this reaction tower at a superficial velocity of 0.08+cm/sec and the pressure loss was investigated, it was found to be 755cm-H20/m
-bed.

On the other hand, when a similar liquid flow test was conducted using a reaction tower without baffles, the pressure loss was 888c.
It was as large as m-H20/m-bea.

[Brief explanation of drawings]

FIG. 1 is a schematic plan view of an embodiment of the reaction column of the present invention, FIG. 2 is a partially cutaway schematic elevational view of the embodiment of FIG.
The figure is a sectional view taken along the line (X)-(X) of FIG. FIG. 3 is a partially cutaway schematic elevational view of another embodiment of a reaction column. (Main symbols in the drawing) (Single-door reaction tower (4), (6): Full (5): Soft filler (7); Heat exchange medium outlet (8)! Heat exchange medium inlet: A'2 Ward O 6 map

Claims (1)

[Scope of Claims] 1. A packed bed reaction tower in which a baffle is inserted in a packed bed filled with a soft filler in a direction perpendicular to the flow direction of a liquid to be treated. 2. The baffle according to claim 1, wherein the baffle is a bar-shaped or elongated baffle having a circular, elliptical, triangular, quadrangular, diamond-shaped, L-shaped, 7-shaped, L-shaped, or engineered cross-sectional shape. reaction tower. 6. The reaction tower according to claim 1 or 2, wherein the baffle is a hollow body. 4. The reaction tower according to claim 6, wherein the hollow part of the baffle constitutes a passage for a cooling medium or a heating medium. 5. The reaction column according to claim 1, 2, 6 or 4, wherein the flexible packing material is an immobilized enzyme. 6. The reaction column according to claim 1, 2, 6, or 4, wherein the flexible filler is an immobilized microorganism. 7. The reaction column according to claim 1, 2, 6, or 4, wherein the flexible packing material is an adsorbent for liquid chromatography. 8. The reaction column according to claim 6, wherein the immobilized microorganism is an immobilized E. coli for producing L-aspartic acid. 9. Claim 6, wherein the immobilized microorganism is immobilized Brevibacterium flavum or immobilized Brevibacterium ammoniagenes for the production of 1-malic acid.
Reaction tower described in section.