JPS5953686A - Treatment of pickling solution - Google Patents

Abstract

PURPOSE:To enable the execution of stable pickling, by withdrawing the pickling soln. in a pickling tank, bringing the same into contact with metallic iron to deposit the impurities in the soln. on the iron and to remove the same and reusing the soln. CONSTITUTION:At least a part of the pickling soln. in a pickling tank 1 is withdrawn through a pipe 11 and is brought into contact with metallic iron in a contact device 2. Irons such as iron scrap and reduced iron are used for the metallic iron and are brought into contact with the pickling soln. for about 10min whereby the impurities, particularly copper-component, are deposited on the iron and can be thereby removed. The treated soln. is further processed with a separator 3 for solid suspensions and is returned through pipes 12, 13, 14 to the tank 1. More preferably, the treated liquid is returned through the pipes 12, 15 to a diffusion dialysis device 4 where the liquid is treated with an anion exchange membrane. The treated liquid is returned to a pickling soln. tank 5 and is reused.

Description

[Detailed description of the invention] The present invention is a method for treating pickling liquid for all seats.

Conventionally, when applying plating, painting, or other surface treatments to metals such as plates made of t'A or iron alloy, these treatments were used.
It is well known that prior to (1), pickling is carried out for purposes such as rust removal.

Acid in general? The solution that can be used first is 1! acid, lI
l! The waste liquid generated from the pickling of metals still contains 5 acids.

If this BP is discarded, it will not only cause a loss of resources but also cause pollution problems (1) It will be necessary to carry out C1IllII+, which will increase the cost. Is there any attempt to collect and reuse it?4'1.'1.I
117 using negative A exchange 11j for I; fB! A metal pickling system combined with dialysis has been proposed. In such a system, a part of the solution in the pickling tank is taken out of the tank and expanded (for dialysis, f=J L, acid is recovered and reused, and the liquid to be treated is the same). Next, J3 goes through another process to recover iron compounds, etc., and then is disposed of.

In addition to this system, there are other methods for effectively utilizing acids.
．． L ir"fl decreases considerably compared to people from the past. For this reason, the efficiency of acid usage has increased (3, but on the other hand, there is another problem: metals due to pickling). It has been found that impurities unavoidably introduced from the agents used accumulate in the pickling solution.The accumulation of copper components causes various problems. , El +, and if copper ∆ accumulates on a certain surface, it will precipitate on the surface of metal such as iron, which will adversely affect the surface treatment in the next process.
(, [J's C is.

The present invention proposes a method for treating a metal pickling solution that prevents these negative effects 9Xi+. That is, Kikomei extracts the pickling liquid from the pickling tank and supplies 7Jj to the external circulation 1τ1.
There is a treatment method-C for a total pickling solution, which is characterized by avoiding contact of the solution with a single metal. Particularly preferred embodiments of this light (3L
After the pickling solution taken out from the pickling tank is brought into contact with metal iron, a portion is preferably filtered or other means to remove the precipitate, and then the pickling solution is brought into contact with metal iron. The purpose is to collect the (ζJ L ''C acid in a diffusion column (11) using a Δn exchange membrane and supply it to the pickling tank.

Therefore, in the water statement, the expression 113 (resupply of pickling solution) indicates that the pickling solution handled from the pickling tank should be treated in some way, or that it should be returned to the pickling tank after 4f. 1. Returned and treated like diffusion dialysis treatment. :The liquid is almost discarded! 1. This includes an embodiment in which only certain components are supplied solely (in addition to the water supplied to the pickling tank).

The present invention will be specifically explained below with reference to FIG. 1 in the diagram
There is a pickling tank, which is generally a 1 to 10N aqueous solution, preferably a 4 to 8N aqueous solution of a mineral acid such as Jn acid or 431 sulfuric acid,
Pickling (11 is partially reacted with metal etc. to give <1-. For example (J
j: Pickling 8 &
exists and the metal to be processed is added to this)? The metal is then subjected to a known cleaning process, such as by immersion in the metal or by exposing the metal to a shower of the above-mentioned pickling solution. In the main defense
) Then, reduce the pickling temperature (k) in the pickling tank, take out a part through the vibrator 11, adjust the temperature as necessary, and remove part of the pickling tank (,, I, depending on the situation). By J2+, re-bypass and transfer the remainder to (Pickling tank/\Return 1).

The shape of the device (11) and the metal iron are particularly limited.
1. inside (kot'), scraps and dents, etc.
J, 1iiN zz 8 Kumuto's 1 IA, 1 Osugi)
, seasonal h! j4 charge J Shinshita charge j Shin' iris, and the liquid is light i] k: i Ll state or (yo) IL liquid state pickling)
1 day and let them touch 1). Generally, the distance between 11) and 11) is about 10 minutes]'- is sufficient for -C. In addition, it is effective to use reduction 1') preparation □ □) a) 1 etc. in a state of turbidity. Using the contact tank of this 1-stroke punching machine,
-1, "The method of removing il', i is also a preferred embodiment. Impurities in the liquid are brought into contact with acid pickling. ! 1, copper or iron;
1 product (1 person) bIiXi 1 metal component such as iron oxide, paper thickness 1 - The cleaning tank is heated to 13C and constantly comes into contact with the metal to be cleaned, such as an iron plate.However, by avoiding further contact with metal 1) outside of 1?+1, the oxidation in the pickling solution is reduced. 14 Monoga, for example copper ii A 1
Although it is not necessarily obvious that C is the contact surface of the middle intercostal area (
(The +1 is large, the metal iron used as a +t4 filtrate is ζ 11 compared to the gold to be washed.)
Since the surface is in contact with the intermediate acid, the surface is activated by J and T.
Jj-3, b) The contact 'JAii& is compared to the pickling tank, and JV) is for forming a reducing atmosphere. 1g! It is preferable that the crystal J is 4 (the contact of the invention [I'7 satisfies the above conditions (Ar1 and tM)?i and R]). Therefore, copper etc. are included J, / J, 1] A small metal U with a surface area, for example + Jl reduction reduced powder 1 Masaru Konazawa)'19. /1lIi degree of J: Use a glico etc. to involve air.
C Closed type filling J? 1 includes J, submerged contact type, etc. 11
Recommended. In some cases, it has been found that adding a reducing agent of +3 to the contacting device has yielded good results.
be.

Then, the circulating liquid after the contact is transferred to a solid 1 slurry pulverizer 3, if necessary. This (, 1, generally filtration, centrifugation H1, j') is
Il 1 dingdan or usage 1 shiru. In this case, it is best to take precautions to prevent exposure to oxidation such as air oxidation.

The portion 11' is passed through two pieces or covered (, 1 line Ill b
<r Lz circulation? In the evening, vibrator 12. The pickling liquid is supplied to the pickling tank through paths +3 and 14 for circulation.

A preferred embodiment of the present invention (J, all vibrators 12) (1
branch out at least a part of the
The dialysis device α4 is J, processed 1, the device is a generally known dialysis device 6, and the dialysis membrane is C1; is used-
There is C.

One of the special features of the present invention is that the pickling solution in the diffusion column (J1) is brought into contact with the metal iron in advance and is in a reducing atmosphere. For this reason, the molten metal does not change its low valence state to the saturated F1i11i state to form the negative charge complex ions that often occur in the saturated F1i11i state, so the acid separation efficiency is particularly high. Mukai 1 is in Ruru-sada.

In the diffusion dialysis device "?1, on the one hand, water is supplied, and the acid is recovered and transferred from the bar 1G to the tank 5i.
1. Remove the ten thousand acid and pour out 17J of liquid out of the system and filter 4'1. As a result, the metal components were recovered and processed, and the waste was removed. , tank 5 smell-
(Depending on the condition of the pickling tank, add additional acid 1) 11. Replenish water or add the chemical described in (■). 1! Pickling in Suu (re-supplied to Te 11).

In the present invention, the fQ of the circulating pickling solution varies depending on the pressure, but generally the agitation condition in the pickling tank is maintained at a good condition.
r tJ [1 purpose, or the purpose of bringing the acidity level in the tank within a predetermined range, and furthermore, unavoidably bringing it into the tank, ■
Purpose 4: Keeping the temperature of impurities within a certain limit
All you need to do is select a skewer that fits your purpose.

In general, the copper component as an impurity should be kept at GOO1+1+ml, preferably below 5001111m.
j, yes.

In addition, when at least a portion of the circulating fluid is expanded to 1) dialysis treatment Jjp, the supply amount of diffusion dialysis
The metal salts such as salts are kept constant within the
Keep it below 1 degree! In other words, 'the by-product per unit intercostal space of the metal salt of the nuclide and 't' of the present invention! in
'l'r When in contact with a metal lead, J: corresponds to the sum of the amount of by-products per unit + 7. ．．
XM: Enough to remove u filter. Attach one suspension to the diffusion dialysis device.
I, salary, 98I] 1! Cover (,1,J,i.

The following example was carried out, and the test device was installed on 10 culms as shown in Figure 1 of the example.
First, conduct a temporary pickling experiment. In this example, ((,1, pickling 1
The composition of 1 is hydrochloric acid 5N, dissolved iron 40 g, 'Q,
Impurity '1 force and 1114γ bending (copper content c) 0.5
g/2 What are they going to do? 1. Rir. Immediately I'), the pickling tank liquid was taken out of the tank at 80 Q y' l+ r, and J4t
1.2. - J-knee 1 static tank 711! After removing solid suspended matter by a wet storage tank, 72 Q,” l+
zl, 11II′I ring as it is to r + J acid washing l, and the remaining 8 Q ′Ill”l i!; (original 471 +; t
, 'a charge L7t was 1J in the light tower, and it came into contact with the iron 1
±ru. [8 touches 11''i (, 12, go back for about 1 minute. il+'i that left the contact device] ζ゛; 1k (ma, l!l
l'l acid I 1.77 N, 4*min 43 g,'Q,
! Ai content 0.4 g, 'Q'g content i8i++7-
climb,, After passing this through a 4A filter made of Bolibu (-) cotton, 64Q, I+r1.
Return to J pickling tank and leave remaining 1. Branch G Q /" hl and extend this 4 to 11 (f" for dialysis).

iF; 41? The tank was made using a diaphragm-bound (J-L pig Δ [-N (commercial) 1 1 ipp 111 j
, using a device with + 7 n2].

Transmission 4ir strip A'1 is 1.8 (! / l+1'-C
Supply water and recover acid.

The recovered liquid is 4.2N salt ft! i Cυ, min 5.4s/Q
, copper content 0.29υ 'Qa, 1.7 Q ,, -'l
+r and 7. ; ・J/j o Kone's new 430Q,・
'Add 12N hydrochloric acid in the old 1) pickling tank l\yama (
11. Supply.

With the above circulation system, the system was balanced and stable pickling could be carried out.

[Brief explanation of the drawing]

FIG. 1 is a process diagram showing the defense processing system 11. . In the figure, 1 is the pickling tank, 2 is the metal iron contact rate: l'vI, 3 (,
J filtration (number, 4 is enlarged 111! dialysis machine, 5 shows each tank, 1471 J'l applicant 11 wa 111st! 7)

Claims (2)

[Claims] (1) A method for treating a metal pickling solution that involves discharging the pickling solution from a pickling tank and bringing the re-supplied external circulating fluid into contact with metal iron for 1Qr. (2) After contacting the metal υ, a small portion of the circulating il& is irradiated in the diffusion permeation 41j, the acid is recovered, and the nucleic acid is recycled to the acid δ°C (11-). The lj method described in Range 1.