JP2019063694A - Liquid supply pipe and chemical reaction device - Google Patents

Abstract

To provide a liquid supply pipe capable of equally draining a fluid out of a plurality of outlets when a plurality of outlets are provided along a fluid flow.SOLUTION: A liquid supply pipe that supplies a liquid used for particle crystallization into an agitation vessel is a liquid supply pipe which has one inlet part provided with an inflow port of the liquid, has n outlets (n is a natural number of 2 or more) provided with outflow ports of the liquid flowing in from the inflow port, the area of each of the n outflow ports being 90% or more and 110% or less of an average area of the n outflow ports, and is provided with at least one of other outlet parts halfway in a flow of the liquid from the inlet part to one of the outlet parts, the total of areas of the n outlet parts being less than the area of the inlet part.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a liquid supply pipe and a chemical reactor.

  2. Description of the Related Art In recent years, with the spread of portable electronic devices such as mobile phones and notebook personal computers, development of small and lightweight secondary batteries having high energy density has been required. In addition, development of a high output secondary battery is also required as a battery for electric vehicles including hybrid vehicles. There is a lithium ion secondary battery as a non-aqueous electrolyte secondary battery satisfying such a demand. The lithium ion secondary battery is composed of a negative electrode, a positive electrode, an electrolytic solution and the like, and a material capable of desorbing and inserting lithium is used as the active material of the negative electrode and the positive electrode.

Especially as lithium complex oxide, lithium cobalt complex oxide (LiCoO ₂ ) relatively easy to synthesize, lithium manganese complex oxide using manganese cheaper than cobalt (LiMn ₂ O ₄ ) and lithium using nickel Nickel composite oxide (LiNiO ₂ ) is used. The lithium nickel composite oxide exhibits a lower electrochemical potential than the lithium cobalt composite oxide, so decomposition by the oxidation of the electrolytic solution is less likely to be a problem, higher capacity can be expected, and battery voltage as high as cobalt type. Development is actively conducted. However, when a lithium ion secondary battery is manufactured using a lithium-nickel composite oxide synthesized purely with only nickel as a positive electrode material, the relative cycle characteristics are inferior to cobalt-based batteries, and the battery is relatively used by using or storing under high temperature environment. Generally, lithium nickel composite oxides in which a part of nickel is replaced with cobalt or aluminum are known because they have the disadvantage of easily degrading the performance.

  The general production method of the positive electrode active material is as follows: (1) First, a nickel composite hydroxide which is a precursor of a lithium nickel composite oxide is produced by a neutralization crystallization method, and (2) the precursor is a lithium compound There is known a method of mixing with and baking. Among them, as a method of producing particles by the neutralization crystallization method of (1), a typical embodiment is a process using a stirring tank.

  In Patent Document 1, particles of a nickel-cobalt composite hydroxide are supplied by allowing a mixed aqueous solution containing a nickel salt and a cobalt salt, an aqueous solution containing an ammonium ion supplier, and an aqueous caustic aqueous solution to the inside of a stirring tank to react. Precipitate out.

  In patent document 1, the tip of the liquid supply pipe which supplies mixed aqueous solution in a stirring tank is branched to three or more, and mixed aqueous solution is supplied from three or more places. It is described that this makes it possible to increase the diffusion rate of the mixed aqueous solution to obtain particles having a sufficient particle size.

  When the liquid supply pipe has a plurality of outlet parts as in Patent Document 1, the power source (for example, the liquid supply pipe for transmitting the liquid to the number of liquid supply pipes and the liquid supply pipe) compared to the case where the liquid supply pipe has one outlet It is also possible to reduce the number of pumps). This can reduce piping space and cost.

JP, 2011-201764, A

  At least one other outlet may be provided midway through the flow of liquid from the inlet to the one outlet. That is, a plurality of outlets may be provided along the flow of fluid. In this case, there is a problem that the flow rate (volume flowing out per unit time) and the flow rate vary between the outlet on the upstream side and the outlet on the downstream side, and the diffusion rate of the liquid varies.

  This invention is made in view of the said subject, Comprising: When several outlet part is provided along the flow of a fluid, provision of the liquid supply pipe which can flow out a fluid equally from several outlet part is provided. As the main purpose.

According to one aspect of the present invention, in order to solve the above problems,
A liquid supply pipe for supplying a liquid used for crystallization of particles into the inside of a stirring tank,
It has one inlet where the liquid inlet is provided,
N (where n is a natural number of 2 or more) outlet parts provided with outlets for the liquid flowing in from the inlet;
The area of each of the n outlets is 90% to 110% of the average area of the n outlets,
At least one other outlet is provided in the middle of the flow of the liquid from the inlet to one outlet.
A liquid supply pipe is provided, wherein the sum of the area of the n outlets is equal to or less than the area of the inlet.

  According to one aspect of the present invention, there is provided a liquid supply pipe capable of evenly discharging fluid from a plurality of outlets when a plurality of outlets are provided along the flow of fluid.

FIG. 1 is a perspective view of a chemical reactor including a liquid supply tube according to one embodiment. It is a front view which shows the liquid supply pipe of FIG. It is a side view which shows the liquid supply pipe of FIG. It is a top view which shows the liquid supply pipe of FIG. It is a bottom view which shows the liquid supply pipe of FIG. It is a bottom view which shows the liquid supply pipe by a 1st modification. It is a top view which shows the liquid supply pipe by a 2nd modification.

  Hereinafter, although the form for carrying out the present invention is explained with reference to drawings, the same or corresponding numerals are attached about the same or corresponding composition in each drawing, and explanation is omitted.

  FIG. 1 is a perspective view showing a chemical reaction device including a liquid supply pipe according to one embodiment. The chemical reaction device 10 includes, for example, a stirring tank 20, a stirring blade 30, a stirring shaft 40, a baffle 50, and a liquid supply pipe 100.

  The stirring tank 20 accommodates the solution in a cylindrical internal space. Particles are deposited in the solution contained inside the stirring tank 20. The precipitation of particles includes both nucleation and growth from nuclei. The stirring tank 20 may be either a batch system or a continuous system.

  The stirring blade 30 stirs the solution contained inside the stirring tank 20. The stirring blade 30 is a disk turbine blade in FIG. 1, but is not particularly limited, and may be, for example, an inclined paddle blade or the like.

  The stirring shaft 40 is vertically provided, and the stirring blade 30 is attached to the lower end. The stirring blade 30 is rotated by rotating the stirring shaft 40 by a motor or the like. In vertical view, the center of the stirring tank 20, the center of the stirring blade 30, and the center of the stirring shaft 40 may coincide with each other.

  The baffles 50 are also called baffles. The baffles 50 protrude from the inner circumferential surface of the stirring tank 20, and generate an upward flow or a downward flow by interrupting the rotational flow to improve the stirring efficiency of the solution.

  The liquid supply pipe 100 supplies the liquid used for crystallizing particles to the inside of the stirring tank 20. The liquid supplied to the inside of the stirring tank 20 by the liquid supply pipe 100 contains, for example, a metal salt such as a nickel salt. As the metal salt, nitrate, sulfate, hydrochloride and the like are used.

  The liquid supplied to the inside of the stirring tank 20 by the liquid supply pipe 100 is not limited to the raw material liquid containing a metal salt such as a nickel salt, and is preferably an alkaline aqueous solution (for example, caustic soda water) or ammonium ion for complexing metal. And the like (eg, ammonia water).

  A plurality of types of liquids are supplied to the inside of the stirring tank 20 by a liquid supply pipe 100 or the like, and the particles are precipitated by neutralization crystallization. If the metal salt comprises a nickel salt, the particles are nickel containing hydroxides. In addition, the kind of particle | grains is not limited to nickel containing hydroxide.

Assuming that the flow rate of the liquid supplied to the inside of the stirring tank 20 by one liquid supply pipe 100 is Q (L / min) and the volume of the stirring tank 20 is V (L), Q / V is, for example, 0.0004 min. ^-1 or more and 0.0075 min- ¹ or less.

If Q / V is less than 0.0004 min ^−1, it is necessary to reduce the diameter of each outlet portion 120 in order to make the pressure of the fluid equal in the flow path immediately before each outlet portion 120. If the amount of liquid can not be supplied or if the diameter of each outlet 120 is increased, pressure variations are likely to occur in the flow path immediately before each outlet 120, which is not preferable.

Further, when Q / V is larger than 0.0075 min ^−1, the variation in the discharge amount from each outlet portion 120 decreases, but a large amount of liquid is discharged, which is not preferable because it affects the crystallization reaction.

  Q / V can be suitably set by the volume of the stirring tank 20.

  FIG. 2 is a front view showing the liquid supply pipe of FIG. FIG. 3 is a side view showing the liquid supply pipe of FIG. FIG. 4 is a plan view showing the liquid supply pipe of FIG. FIG. 5 is a bottom view showing the liquid supply pipe of FIG. 4 and 5 show the positional relationship between the liquid supply pipe and the stirring shaft.

  The liquid supply pipe 100 has one inlet 110 provided with a liquid inlet 111 (see FIG. 4), and an outlet 120 provided with a liquid outlet 121 (see FIG. 5) flowing in from the inlet 111. There are n (where n is a natural number of 2 or more, for example, n is 8 in FIG. 5). The inlet 110 and the outlet 120 are formed, for example, in a tubular shape. The shape of the inlet 111 and the shape of the outlet 121 are, for example, circular. The outlet 120 is also called a nozzle.

  The area of each of the n outlets 121 is 90% or more and 110% or less of the average area of the n outlets 121. This means that the area of the n outlets 121 is uniform. Since the flow rate at each outlet 121 is expressed by the product of the area and the flow velocity, if the area of n outlets 121 is uniform, the flow at n outlets 121 is made uniform and n flows It is possible to make the flow rate at the outlet 121 uniform.

  The area of each of the n outlets 121 is preferably 95% or more and 105% or less of the average area of the n outlets 121, and more preferably 98% or more of the average area of the n outlets 121. % Or less.

  At least one (three in FIG. 5) other outlet parts 120-2, 120-3, 120-4 are provided in the middle of the flow of liquid from the inlet part 110 to one outlet part 120-1. . That is, along the flow of liquid, from the upstream side to the downstream side, the plurality of (four in FIG. 5) outlet portions 120-4, 120-3, 120-2, 120-1 are spaced in this order Are provided.

  In addition, at least one (three in FIG. 5) other outlet portions 120-6, 120-7, and 120-8 are provided in the middle of the flow of the liquid from the inlet portion 110 to one outlet portion 120-5. Provided. That is, along the flow of liquid, from the upstream side toward the downstream side, the plurality of (four in FIG. 5) outlet portions 120-8, 120-7, 120-6, 120-5 are spaced in this order Are provided.

  The sum of the areas of the n outlets 121 is equal to or less than the area of the inlet 111. If the sum of the areas of the n outlets 121 is equal to or less than the area of the inlet 111, the fluid pressure in the flow path from the inlet 111 to the position just before each outlet 120 is the same regardless of the position in the flow direction Thus, the pressure in the discharge direction acting on the fluid at each outlet portion 120 is approximately the same. As a result, the flow rates at the n outlets 121 can be equalized, and the flow rates at the n outlets 121 can be equalized.

  Here, that the flow rate at the n outlets 121 is uniform means that each flow rate is 90% or more and 110% or less of the average flow rate. Moreover, that the flow velocity in the n outlets 121 is uniform means that each flow velocity is 90% or more and 110% or less of the average flow velocity.

  According to the present embodiment, since the liquid flowing in from one inlet 111 can be equally divided out from n outlets 121, the diffusion velocity of the liquid in n outlets 121 can be made uniform. it can. Therefore, it is easy to control the diffusion rate of the liquid at the n outlets 121, and the quality of the particles can be improved.

  The sum of the area of the n outlets 121 is preferably 80% or less of the area of the inlet 111, and more preferably 50% or less of the area of the inlet 111. The sum of the areas of the n outlets 121 may be 10% or more of the area of the inlet 111.

  The n outlets 121 may be provided on the same horizontal plane and at equal distances from the center of the stirring shaft 40 in the vertical direction. Since the flow of the solution contained in the stirring tank 20 is formed symmetrically about the stirring shaft 40, provide n outlets 121 at the same position of the solution flow speed and the turbulent diffusion coefficient. Can. Therefore, it is easy to control the diffusion rate of the liquid at the n outlets 121, and the quality of the particles can be improved.

  As shown in FIG. 5, in the vertical direction, the distance A between the center of each outlet 121 and the center of the stirring shaft 40 is the distance B between the center of the stirring shaft 40 and the outer peripheral end of the stirring blade 30 (see FIG. 1) Is less than 1.1 times. When the distance A is equal to or less than 1.1 times the distance B, the liquid flowing out of each outlet 121 can be placed on the downward flow (or upward flow) formed along the stirring shaft 40.

  For example, when the upward flow occurs along the baffle 50 due to the rotation of the agitating blade 30 and the downward flow occurs along the agitating shaft 40, each outlet 121 is provided above the agitating blade 30, and the liquid is directed downward. Discharge. The liquid flowing out of each outlet 121 is easily disturbed because it passes between the plurality of blades 32 constituting the stirring blade 30 and is disturbed.

  When the downward flow occurs along the baffle 50 due to the rotation of the agitating blade 30 and the upward flow occurs along the agitating shaft 40, the respective outlets 121 are provided below the agitating blade 30, and the liquid is directed upward Discharge. The liquid flowing out of each outlet 121 is easily disturbed because it passes between the plurality of blades 32 constituting the stirring blade 30 and is disturbed.

  The liquid supply pipe 100 has a straight main pipe 130 provided with an inlet 110 at its proximal end, and extends vertically to the main pipe 130 from the tip opposite to the proximal end of the main pipe 130, and two branch pipes 141 from the middle And a branch pipe 140 branched into 142. The two branch pipes 141, 142 are provided with n outlet parts 120.

  The main pipe 130 is provided vertically and parallel to the stirring shaft 40. The main pipe 130 has an inlet 110 at its upper end. In addition, although the inlet part 110 is an upper end part of the main pipe 130 in this embodiment, it may be a connection part with a flow meter of piping extended from the upper end part of the main pipe 130. The inner diameter of the upper end portion of the main pipe 130 and the inner diameter of the pipe connecting the main pipe 130 and the flow meter may be the same.

  The branch pipe 140 extends horizontally from the lower end of the main pipe 130 and branches into two branch pipes 141 and 142 along the way. The two branch pipes 141, 142 are provided with n outlet parts 120. Thus, the branch pipes 140 can be provided to surround the stirring shaft 40, and the n outlet portions 120 can be provided at positions equidistant from the stirring shaft 40.

  As shown in FIG. 4, in the vertical direction, the gap C between the cuts formed between the two branch pipes 141 and 142 may be larger than the diameter D of the stirring shaft 40. Since the stirring shaft 40 can pass through the above-mentioned cut, the workability at the time of maintenance is good.

  The end of each branch pipe 141, 142 (the end opposite to the branch point where these branch pipes 141, 142 branch) is closed in this embodiment so as not to leak fluid, but it is open Good. In the latter case, the two branch pipes 141, 142 are connected by a connecting pipe, and the two branch pipes 141, 142 and the connecting pipe form an annular pipe. The connecting pipe may be removably connected to each branch pipe 141, 142 in order to improve maintainability.

  The two branch pipes 141, 142 may have the same size and the same shape as shown in FIG. For example, the two branch pipes 141 and 142 may be provided in line symmetry about a straight line 150 which is centered on the main pipe 130 and the center of the stirring axis 40 when viewed from the axial direction (for example, vertical direction) of the main pipe 130.

  The two branch pipes 141, 142 have the same size and the same shape as described above. More precisely, the branch pipe 141 viewed from above and the branch pipe 142 viewed from below have the same size and the same shape. Since the pressure drop of two branch pipes 141 and 142 becomes the same by this, a liquid can be equally distributed to two branch pipes 141 and 142. As shown in FIG.

  Each branch pipe 141, 142 is provided with an outlet portion 120 of n / 2 (n is an even number of 4 or more, for example, 8 in FIG. 5). Therefore, the number of the outlet parts 120 provided in each branch pipe 141, 142 is the same. Thus, the liquid can be evenly distributed to the two branch pipes 141 and 142.

  Each branch pipe 141, 142 may be formed in an arc shape as shown in FIG. 5 from the viewpoint of reducing pressure loss. The center of the circle in which each branch pipe 141, 142 is disposed may coincide with the center of the stirring shaft 40.

  In addition, the shape of each branch pipe 141, 142 is not specifically limited, For example, a polygonal line shape etc. may be sufficient. When the shape of each branch pipe 141, 142 is a broken line or the like, it is possible to provide n outlet parts 120 at positions equidistant from the stirring shaft 40.

In Example 1, the flow rate at each outlet of the liquid supply pipe shown in FIG. 1 is measured, and the maximum value Δx of the magnitude (| x−x ′ |) of the difference between the flow rate x and the average flow rate x ′ at each outlet Was calculated. Here, Δx is standardized with the average flow rate x ′ as 100%. In Example 1, since the diameter of the inlet is 7.1 mm and the diameter of each outlet is 1.0 mm, the sum (S1) of the areas of the eight outlets is 16 of the area of one inlet (S2). %Met. Here, the eight outlets had exactly the same diameter. In Example 1, Q / V was 0.0017 min ⁻¹ .

  In Examples 2 to 14, the flow rate at each outlet is measured under the same conditions as Example 1 except for the conditions shown in Table 1, and the magnitude of the difference between the flow rate x at each outlet and the average flow rate x ' The maximum value Δx of x ′ |) was calculated.

  Table 1 summarizes the evaluation results of Examples 1 to 14.

表１から明らかなように、例１、例２、例４〜例７、および例９〜例１４では、８個の流出口の面積の総和（Ｓ１）が１個の流入口の面積（Ｓ２）以下であったため、８個の流出口における流量が均一であった。例１、例２、例４〜例７、および例９〜例１４では、８個の流出口が全く同じ面積を有するとしたため、８個の流出口における流量が均一であったことは、８個の流出口における流速が均一であったことを表す。

As is clear from Table 1, in Example 1, Example 2, Example 4 to Example 7, and Example 9 to Example 14, the sum (S1) of the areas of the eight outlets is the area of one inlet (S2). The flow rates at the eight outlets were uniform because the values were below. In Example 1, Example 2, Example 4 to Example 7, and Example 9 to Example 14, it was assumed that the flow rates at the eight outlets were uniform because the eight outlets had the same area. It represents that the flow velocity at the individual outlets was uniform.

  On the other hand, in Examples 3 and 8, since the sum (S1) of the areas of the eight outlets was larger than the area (S2) of one inlet, the flow rates at the eight outlets varied. Since in Example 3 and Example 8 eight outlets had exactly the same area, the variation in flow rate at eight outlets means that the flow rate at eight outlets was varied.

  Although the embodiment and the like of the liquid supply pipe have been described above, the present invention is not limited to the above embodiment and the like, and various modifications may be made within the scope of the subject matter of the present invention described in the claims. An improvement is possible.

  FIG. 6 is a bottom view showing a liquid supply pipe according to a first modification. The liquid supply pipe 100A shown in FIG. 6 has a main pipe 130A and a sub pipe 140A. The main pipe 130A is provided vertically and in parallel with the stirring shaft 40. The main pipe 110A has an inlet at its upper end.

  The secondary pipe 140A extends horizontally from the lower end of the main pipe 130A and is formed to surround the stirring shaft 40. The auxiliary pipe 140A is provided with n (n is a natural number of 2 or more, for example, n is 8 in FIG. 6) outlet portions 120. N outlets 120 can be provided equidistant from the stirring shaft 40.

  As shown in FIG. 6, in the vertical direction, the gap E between the cuts formed between the main pipe 130A and the sub pipe 140A may be larger than the diameter D of the stirring shaft 40. Since the stirring shaft 40 can pass through the above-mentioned cut, the workability at the time of maintenance is good.

  The sub-tube 140A may have an arc-shaped portion from the viewpoint of reducing pressure loss. The arc-shaped portion is formed to surround the stirring shaft 40. In this arc-shaped portion, n outlet portions 120 are provided.

  FIG. 7 is a plan view showing a liquid supply pipe according to a second modification. The liquid supply pipe 100B shown in FIG. 7 has a main pipe 130B and a branch pipe 140B. The main pipe 130B is disposed on the same straight line as the stirring shaft 40, and is provided below the stirring blade 30 (see FIG. 1). The main pipe 110B has an inlet at its lower end.

  The branch pipe 140B branches into four branches from the upper end of the main pipe 130B, and has four branch pipes 141B, 142B, 143B, and 144B linearly extending horizontally. The end of each branch pipe 141B, 142B, 143B, 144B (the end opposite to the branch point where these branch pipes 141B, 142B, 143B, 144B branch) is closed so as not to leak fluid. The number of branch pipes is not limited to four, and may be two or more.

  The four branch pipes 141B, 142B, 143B, 144B have the same size and the same shape. For example, the four branch pipes 141B, 142B, 143B, and 144B may be provided so as to be rotationally symmetrical about the main pipe 130B when viewed from the axial direction (for example, the vertical direction) of the main pipe 130B.

  The four branch pipes 141B, 142B, 143B, 144B have the same size and the same shape as described above. Thereby, since the pressure drop of four branch pipes 141B, 142B, 143B, and 144B becomes the same, a liquid can be equally distributed to four branch pipes 141B, 142B, 143B, and 144B.

  The four branch pipes 141B, 142B, 143B, and 144B may be provided in rotational symmetry about the main pipe 130B as viewed from the axial direction (for example, the vertical direction) of the main pipe 130B.

  In each of the branch pipes 141B, 142B, 143B and 144B, n / k (n is an even number of 4 or more and k is the number of branches of the branch pipe 140B, for example, n is 8 and k is 4 in FIG. 7). An outlet 120 is provided. Therefore, as shown in FIG. 7, the number of the outlet parts 120 provided in each branch pipe 141B, 142B, 143B, 144B is the same. Therefore, the liquid can be evenly distributed to the four branch pipes 141B, 142B, 143B, and 144B.

  Each branch pipe 141B, 142B, 143B, 144B may be formed in a straight line as shown in FIG. 7 from the viewpoint of reducing pressure loss. The number k of branches of the branch pipe 140B is not limited to four, and may be two or more.

  In order to adjust the number of outlet parts 120 shown in FIG.5, FIG.6, FIG.7, you may use the cap which obstruct | occludes the outflow port 121 of the outlet part 120. FIG. The cap is removably attached to the outlet 120. The capped outlet 120 loses its function as the outlet 120.

DESCRIPTION OF SYMBOLS 10 Chemical reaction apparatus 20 stirring tank 30 stirring blade 40 stirring shaft 50 baffle 100 liquid supply pipe 110 inlet part 111 inlet 120 outlet part 121 outlet 130 main pipe 140 branch pipe 141 branch pipe 142 branch pipe

Claims (8)

A liquid supply pipe for supplying a liquid used for crystallization of particles into the inside of a stirring tank,
It has one inlet where the liquid inlet is provided,
N (where n is a natural number of 2 or more) outlet parts provided with outlets for the liquid flowing in from the inlet;
The area of each of the n outlets is 90% to 110% of the average area of the n outlets,
At least one other outlet is provided in the middle of the flow of the liquid from the inlet to one outlet.
The liquid supply pipe, wherein the sum of the area of the n number of outlets is equal to or less than the area of the inlet. A straight main pipe provided with the inlet at its proximal end;
And a branch pipe extending perpendicularly to the main pipe from a tip opposite to the proximal end of the main pipe, and branching into two branch pipes from the middle;
The liquid supply pipe according to claim 1, wherein n of the outlet portions are provided in two of the branch pipes.   The liquid supply pipe according to claim 2, wherein the two branch pipes have the same size and the same shape.   The liquid supply pipe according to claim 2 or 3, wherein each of the branch pipes is provided with n / 2 (n is an even number of 4 or more) of the outlet portions. The liquid supply pipe according to any one of claims 1 to 4;
The stirring tank,
A stirring blade for stirring a solution contained inside the stirring tank;
A chemical reaction device comprising: a stirring shaft vertically disposed and having the stirring blade attached at its lower end.   The chemical reaction device according to claim 5, wherein the n outlets are provided on the same horizontal surface and at equal distances from the center of the stirring shaft in a vertical direction.   The vertical distance between the center of each of the outlets and the center of the stirring shaft is 1.1 times or less of the distance between the center of the stirring shaft and the outer peripheral end of the stirring blade. Chemical reactor as described.   The chemical reaction device according to claim 7, wherein each of the outlets is provided above the stirring blades and discharges the liquid downward.

Images