CN111534821B - Regeneration method of polishing waste acid - Google Patents

Regeneration method of polishing waste acid Download PDF

Info

Publication number
CN111534821B
CN111534821B CN202010244508.1A CN202010244508A CN111534821B CN 111534821 B CN111534821 B CN 111534821B CN 202010244508 A CN202010244508 A CN 202010244508A CN 111534821 B CN111534821 B CN 111534821B
Authority
CN
China
Prior art keywords
acid
resin
glass column
column
sleeve
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202010244508.1A
Other languages
Chinese (zh)
Other versions
CN111534821A (en
Inventor
陈亚刚
周国权
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ningbo Sanda Chemical Co ltd
Original Assignee
Ningbo Sanda Chemical Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ningbo Sanda Chemical Co ltd filed Critical Ningbo Sanda Chemical Co ltd
Priority to CN202010244508.1A priority Critical patent/CN111534821B/en
Publication of CN111534821A publication Critical patent/CN111534821A/en
Application granted granted Critical
Publication of CN111534821B publication Critical patent/CN111534821B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F3/00Brightening metals by chemical means
    • C23F3/02Light metals
    • C23F3/03Light metals with acidic solutions
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J47/00Ion-exchange processes in general; Apparatus therefor
    • B01J47/02Column or bed processes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J49/00Regeneration or reactivation of ion-exchangers; Apparatus therefor
    • B01J49/60Cleaning or rinsing ion-exchange beds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/42Treatment of water, waste water, or sewage by ion-exchange
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/42Treatment of water, waste water, or sewage by ion-exchange
    • C02F2001/425Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00Specific treatment goals
    • C02F2303/16Regeneration of sorbents, filters

Abstract

The invention relates to a regeneration method of polishing waste acid, which comprises the following steps: (1) a resin column is filled, YK-20 color-changing resin, D001-CC type cation exchange resin and 001 x 4 gel type strong-acid styrene cation exchange resin are sequentially filled in a glass column from bottom to top, the upper end of the glass column is a liquid inlet end, and the lower end of the glass column is a liquid outlet end; (2) passing the waste acid through a resin column; (3) compounding polishing acid; (4) and (5) eluting the resin column. The YK-20 color-changing resin has higher adsorption limit and lower adsorption capacity, the 001 multiplied by 4 gel type strong-acid styrene cation exchange resin has lower adsorption limit and higher adsorption capacity, the adsorption capacity and the adsorption limit of the D001-CC type cation exchange resin are both positioned between the two, and the removal rate of aluminum ions can be effectively improved through gradient adsorption from top to bottom, so that the removal rate of the aluminum ions reaches over 95 percent, and the resin can be recycled through simple elution, thereby being convenient for operation and high in economic benefit.

Description

Regeneration method of polishing waste acid
Technical Field
The invention relates to the technical field of waste acid regeneration, in particular to a regeneration method of polishing waste acid.
Background
Currently, polishing of aluminum and aluminum alloy articles relies primarily on a tri-acid polishing acid for treatment. The triacid polishing acid is based on phosphoric acid, and sulfuric acid and nitric acid are added according to a certain proportion. After the polishing acid is used for many times, the content of aluminum ions in the acid is higher and higher, and the polishing effect is seriously influenced. If the waste acid is treated as three wastes, it will bring great pressure to environmental protection treatment, so the removal and recycling of aluminum ions in the waste acid is a new research topic.
At present, a document (Hydrometallurgy of China, Vol.29No.3(Sum.115) 2009) reports that sodium hydroxide and hydrofluoric acid in a certain proportion are added into an ineffective phosphate-based polishing solution to react with aluminum in the polishing solution to generate insoluble cone cryolite (Na5Al3F14) to precipitate, and the treated phosphate-based polishing solution is concentrated to a certain concentration and then added with a certain amount of nitric acid and sulfuric acid to be recycled. However, the cryolite produced in this way is gelatinous and very troublesome in post-treatment.
Therefore, it is particularly necessary to provide a method for efficiently and conveniently treating polishing waste acid.
Disclosure of Invention
The first technical problem to be solved by the invention is to provide a regeneration method of polishing waste acid, which can reasonably arrange different resins according to different adsorption capacities and adsorption limits of the resins so as to improve the aluminum ion removal effect, aiming at the current situation of the prior art.
The second technical problem to be solved by the present invention is to provide a regeneration method of polishing waste acid, which can effectively improve the flow stability of waste acid, and prolong the retention time of waste acid in a specific adsorption layer, thereby improving the removal effect of aluminum ions.
The technical scheme adopted by the invention for solving the technical problems is as follows: a regeneration method of polishing waste acid is characterized by comprising the following steps:
(1) packed resin column
Sequentially filling YK-20 color-changing resin, D001-CC type cation exchange resin and 001 x 4 gel type strong-acid styrene cation exchange resin in a glass column from bottom to top, wherein the upper end of the glass column is a liquid inlet end, and the lower end of the glass column is a liquid outlet end;
(2) waste acid passing through resin column
Inputting waste acid from a liquid inlet end and outputting waste acid from a liquid outlet end of the glass column, wherein the ratio of the mass of the waste acid treated in a single process to the total amount of resin filled in the glass column is 1 (5-50);
(3) polishing acid compounding
Adding nitric acid and sulfuric acid into the acid solution treated by the resin column to obtain regenerated polishing acid;
(4) resin column elution
And (3) eluting the used resin by using 1-10% of dilute sulfuric acid or dilute hydrochloric acid, and reusing the eluted resin.
Preferably, the glass column is hollow to form an inner cavity for filling resin, a sleeve capable of slowing down the flow rate of waste acid is arranged in the middle of the inner cavity, and the D001-CC type cation exchange resin is filled in the sleeve. By adopting the structure, the flow velocity of waste acid passing through the D001-CC type cation exchange resin can be effectively reduced, so that the ion exchange effect is improved, and the removal rate of aluminum ions is improved.
Preferably, the top edge of the sleeve is provided with a supporting edge which extends outwards and is connected with the inner wall of the glass column, an end cover is arranged on an upper port of the sleeve in a covering mode, a flow channel for waste acid to flow into the sleeve is arranged on the end cover, the cross section of the flow channel is arc-shaped, so that the waste acid forms an eccentric flowing state in the sleeve, the bottom of the sleeve is provided with a closed bottom plate, and a plurality of first output ports for the waste acid to flow to the downstream are formed in the side wall of the sleeve. By adopting the structure, waste acid entering the sleeve is filled in the sleeve after being eccentrically flowed, and is fully subjected to ion exchange with D001-CC type cation exchange resin, and then enters downstream YK-20 color-changing resin from a first output port on the side wall of the sleeve for ion exchange, and the eccentric flow of the waste acid in the sleeve can improve the stability of liquid flowing in the sleeve; the YK-20 color-changing resin has higher adsorption limit and lower adsorption capacity, the 001 multiplied by 4 gel type strong-acid styrene cation exchange resin has lower adsorption limit and higher adsorption capacity, and the adsorption capacity and the adsorption limit of the D001-CC type cation exchange resin are both positioned between the adsorption limit and the adsorption limit, so that the retention time of waste acid in the D001-CC type cation exchange resin is prolonged, and the flow stability of the waste acid is improved, thereby balancing the adsorption effect of upstream and downstream resins on aluminum ions at the position, and being beneficial to improving the removal rate of aluminum ions.
Preferably, the top wall of the glass column is provided with a liquid inlet, the upper port of the flow channel is positioned at the central part of the end cover, and the liquid inlet is close to the edge of the glass column so as to be staggered with the upper port of the flow channel. The structure is favorable for improving the flow uniformity of waste acid in 001 x 4 gel type strong-acid styrene cation exchange resin and improving the adsorption effect.
Preferably, a gap is formed between the outer wall of the sleeve and the inner wall of the glass column, and the width of the gap in the radial direction gradually increases from top to bottom. After the adsorption of the D001-CC type cation exchange resin, the residual aluminum ion amount in the waste acid is less, and the structure is favorable for guiding the liquid entering the YK-20 color-changing resin, improving the flow velocity and further improving the treatment efficiency.
Preferably, the bottom wall of the glass column is provided with a liquid outlet, the liquid outlet is positioned at the central part of the bottom wall of the glass column, the bottom plate of the sleeve is also provided with a second outlet, and the second outlet is close to the edge of the sleeve and is arranged with the liquid outlet in a staggered manner. The structure is beneficial to improving the flow uniformity of waste acid in YK-20 color-changing resin and improving the adsorption effect.
In the invention, the filling mass ratio of the YK-20 color-changing resin, the D001-CC type cation exchange resin and the 001 x 4 gel type strong-acid styrene cation exchange resin is 1 (1.2-2) to 0.5-0.8. By adopting the proportion, the aluminum ion removing effect is favorably improved.
The total amount of the nitric acid and the sulfuric acid which are added in the step (3) is 2-15% of the polishing waste acid, and the mass ratio of the nitric acid to the sulfuric acid is 2: 1. In the step (4), the usage amount of 1% sulfuric acid is 2-4 times of the mass of the polishing waste acid, the usage amount of 2% -3% sulfuric acid is 1-2 times of the mass of the polishing waste acid, the usage amount of 4% -10% sulfuric acid is 0.5-1 time of the mass of the polishing waste acid, and the usage amount of the same mass fraction hydrochloric acid is 2 times of the mass of the sulfuric acid.
Compared with the prior art, the invention has the advantages that: the YK-20 color-changing resin, the D001-CC type cation exchange resin and the 001 x 4 gel type strong-acid styrene cation exchange resin are filled in the glass column from the bottom to the top, the YK-20 color-changing resin has higher adsorption limit and lower adsorption capacity, the 001 x 4 gel type strong-acid styrene cation exchange resin has lower adsorption limit and higher adsorption capacity, the adsorption capacity and the adsorption limit of the D001-CC type cation exchange resin are positioned between the two, and the aluminum ion removal rate can be effectively improved by gradient adsorption from top to bottom, so that the aluminum ion removal rate reaches over 95 percent, and the resin can be recycled by simple elution, thereby being convenient to operate and high in economic benefit.
Drawings
FIG. 1 is a schematic structural view of a resin column in an embodiment of the present invention;
FIG. 2 is a schematic structural diagram of an elution apparatus in an embodiment of the present invention.
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
Example 1:
the method for regenerating polishing waste acid comprises the following steps:
(1) packed resin column
Sequentially filling 800gYK-20 color-changing resin a, 1200gD001-CC type cation exchange resin b and 1000g001 x 4 gel type strongly acidic styrene cation exchange resin c in the glass column 1 from bottom to top; the upper end of the glass column 1 is a liquid inlet end, and the lower end is a liquid outlet end;
(2) waste acid passing through resin column
100g of waste acid with the mass fraction of aluminum ions of 1.5 percent is input from the liquid inlet end and output from the liquid outlet end of the glass column 1, the mass fraction of the aluminum ions in the acid liquid flowing out of the resin column is 0.06 percent, and the removal rate of the aluminum ions is 96 percent;
(3) polishing acid compounding
Supplementing nitric acid and sulfuric acid into the acid solution treated by the resin column, wherein the total addition amount of the nitric acid and the sulfuric acid is 5g (sulfuric acid: nitric acid is 2:1), so as to obtain regenerated polishing acid;
(4) resin column elution
The used resin was eluted with 1% dilute sulfuric acid in an amount of 200g, and the eluted resin was reused.
As shown in FIG. 1, the glass column 1 of this embodiment is hollow inside to form an inner cavity for filling resin, a sleeve 2 capable of slowing down the flow rate of waste acid is arranged in the middle of the inner cavity, and D001-CC type cation exchange resin b is filled in the sleeve 2. The top edge of the sleeve 2 is provided with a support edge 21 which extends outwards and is connected with the inner wall of the glass column 1, an end cover 22 is covered on the upper port of the sleeve 2, a flow passage 221 for waste acid to flow into the sleeve 2 is arranged on the end cover 22, the cross section of the flow passage 221 is arc-shaped so that the waste acid forms an eccentric flow state in the sleeve 2, the bottom of the sleeve 2 is provided with a closed bottom plate 222, and a plurality of first output ports 223 for waste acid to flow downstream are formed in the side wall of the sleeve 2. The top wall of the glass column 1 is provided with a liquid inlet 11, the upper end opening of the flow channel 221 is positioned at the central part of the end cover 22, the upper side is covered with a filter screen, the liquid inlet 11 is close to the edge of the glass column 1 so as to be staggered with the upper end opening of the flow channel 221, so that the flowing uniformity of waste acid in 001 x 4 gel type strong acid styrene cation exchange resin c is improved. The bottom wall of the glass column 1 is provided with a liquid outlet 12, the liquid outlet 12 is located at the central position of the bottom wall of the glass column 1, the bottom plate 222 of the sleeve 2 is further provided with a second output port 224, and the second output port 224 is close to the edge of the sleeve 2 and is arranged in a staggered manner with the liquid outlet 12.
Waste acid entering the sleeve 2 is filled in the sleeve 2 after being eccentrically flowed, and is fully subjected to ion exchange with D001-CC type cation exchange resin b, and then enters downstream YK-20 color-changing resin a from a first output port 223 and a second output port 224 on the side wall of the sleeve 2 for ion exchange, and the eccentric flowing of the waste acid in the sleeve 2 can improve the flowing stability of liquid in the sleeve 2; since the YK-20 color-changing resin a of the embodiment has higher adsorption limit and lower adsorption capacity, the 001 × 4 gel type strong-acid styrene cation exchange resin c has lower adsorption limit and higher adsorption capacity, and the adsorption capacity and the adsorption limit of the D001-CC type cation exchange resin b are both positioned between the two, the retention time of waste acid in the D001-CC type cation exchange resin b is prolonged, and the flow stability of the waste acid is improved, so that the adsorption effect of upstream and downstream resins on aluminum ions is balanced at the position, and the removal rate of the aluminum ions is improved.
Most of the spent acid of this example descends through the first output 223 and a small amount of spent acid descends through the second output 224. A gap 13 is formed between the outer wall of the sleeve 2 and the inner wall of the glass column 1, and the width of the gap 13 in the radial direction is gradually enlarged from top to bottom. After the adsorption of the D001-CC type cation exchange resin b, the residual aluminum ion amount in the waste acid is less, and the structure is favorable for guiding the liquid entering the YK-20 color-changing resin a, improving the flow velocity and further improving the treatment efficiency.
When the resin column of this embodiment is used for a long time and the removal rate of aluminum ions is detected to be lower than 95%, the resin can be taken out from the glass column 1 and put into the elution device 3 for elution. As shown in fig. 2, the elution device 3 comprises a box 31 for containing the resin to be eluted, an input port 311 is opened on the top wall of the box 31, an output port 312 is opened on the bottom, and the top of the box 31 is provided with a strengthening device capable of inputting the eluent with micro-bubbles into the box 31 so as to strengthen the elution effect. The strengthening device comprises a hollow shell 321, wherein the top of the shell 321 is provided with a liquid inlet port 323, the lower part of the shell 321 is provided with a transverse partition plate 324, the partition plate 324 is provided with a tapered hole 325 with a small upper end and a large lower end, the axial length of the tapered hole 325 is 22mm, the aperture of the upper port is 0.8mm, and the aperture of the lower port is 4.5 mm. The housing 321 communicates with the output port 312. After eluent enters the shell 321 from the input port 311, the upper end of the tapered hole 325 is covered by the liquid seal, along with the increase of the input amount of waste acid, the pressure in the shell 321 is increased rapidly, air is dissolved in liquid rapidly, when the pressure in the shell 321 reaches a critical value capable of being borne by the upper end port of the tapered hole 325, the liquid with a large amount of air dissolved therein is released rapidly downwards from the tapered hole 325, negative pressure is generated in the process of passing through the tapered hole 325, and therefore a large amount of micro-bubbles are generated in the liquid, and the washing effect of the eluent on resin is improved.
Example 2:
the method for regenerating polishing waste acid comprises the following steps:
(1) packed resin column
700gYK-20 color-changing resin a, 2000g D001-CC type cation exchange resin b and 1000g001 x 4 gel type strongly acidic styrene type cation exchange resin c are sequentially filled in the glass column 1 from bottom to top; the upper end of the glass column 1 is a liquid inlet end, and the lower end is a liquid outlet end;
(2) waste acid passing through resin column
Inputting 80g of waste acid with the aluminum ion mass fraction of 3% from the liquid inlet end and outputting from the liquid outlet end of the glass column 1; the mass fraction of aluminum ions in the acid liquid flowing out of the resin column is 0.03 percent, and the removal rate of the aluminum ions is 98 percent;
(3) polishing acid compounding
Adding nitric acid and sulfuric acid into the acid solution treated by the resin column, wherein the total addition amount of the nitric acid and the sulfuric acid is 7g (sulfuric acid: nitric acid is 2:1), so as to obtain regenerated polishing acid;
(4) resin column elution
The used resin was eluted with 5% diluted hydrochloric acid in an amount of 160g, and the eluted resin was reused.
Example 3:
the method for regenerating polishing waste acid comprises the following steps:
(1) packed resin column
The glass column 1 is sequentially filled with 500gYK-20 color-changing resin a, 1300g D001-CC type cation exchange resin b and 1000g001 x 4 gel type strongly acidic styrene cation exchange resin c from bottom to top; the upper end of the glass column 1 is a liquid inlet end, and the lower end is a liquid outlet end;
(2) waste acid passing through resin column
Inputting 80g of waste acid with the aluminum ion mass fraction of 0.5% from a liquid inlet end and outputting from a liquid outlet end of the glass column 1, wherein the aluminum ion mass fraction of the acid liquid flowing out of the resin column is 0.02%, and the aluminum ion removal rate is 98%;
(3) polishing acid compounding
Supplementing nitric acid and sulfuric acid into the acid solution treated by the resin column, wherein the total addition amount of the nitric acid and the sulfuric acid is 2g (sulfuric acid: nitric acid is 2:1), so as to obtain regenerated polishing acid;
(4) resin column elution
The used resin was eluted with 10% diluted hydrochloric acid in an amount of 80g, and the eluted resin was reused.
Comparative example 1:
the regeneration method of waste polishing acid of the comparative example does not adopt the resin column structure in the example 1, but only fills different resins in a glass column with a constant upper and lower inner diameters according to a proportion, and specifically comprises the following steps:
(1) packed resin column
Sequentially filling 800gYK-20 color-changing resin a, 1200gD001-CC type cation exchange resin b and 1000g001 x 4 gel type strongly acidic styrene cation exchange resin c in the glass column 1 from bottom to top; the upper end of the glass column 1 is a liquid inlet end, and the lower end is a liquid outlet end;
(2) waste acid passing through resin column
100g of waste acid with the mass fraction of 1.5 percent of aluminum ions is input from the liquid inlet end and output from the liquid outlet end of the glass column 1, the mass fraction of the aluminum ions in the acid liquid flowing out of the resin column is 0.14 percent, and the removal rate of the aluminum ions is 91 percent.
Comparative example 2:
the regeneration method of waste polishing acid of the comparative example adopts the resin column structure in the example 1, and only a single resin is selected for filling, and the method specifically comprises the following steps:
(1) packed resin column
3000gYK-20 color-changing resin a is sequentially filled in the glass column 1 from bottom to top, the upper end of the glass column 1 is a liquid inlet end, and the lower end of the glass column 1 is a liquid outlet end;
(2) waste acid passing through resin column
100g of waste acid with the mass fraction of aluminum ions of 1.5 percent is input from the liquid inlet end and output from the liquid outlet end of the glass column 1, the mass fraction of the aluminum ions in the acid liquid flowing out of the resin column is 0.51 percent, and the removal rate of the aluminum ions is 66 percent.
Comparative example 3:
the regeneration method of waste polishing acid of the comparative example adopts the resin column structure in the example 1, and only a single resin is selected for filling, and the method specifically comprises the following steps:
(1) packed resin column
2000g of 001X 4 type strong acid cation resin c is sequentially filled in the glass column 1 from bottom to top, the upper end of the glass column 1 is a liquid inlet end, and the lower end of the glass column 1 is a liquid outlet end;
(2) waste acid passing through resin column
100g of waste acid with the mass fraction of aluminum ions of 1.5 percent is input from the liquid inlet end and output from the liquid outlet end of the glass column 1, the mass fraction of the aluminum ions in the acid liquid flowing out of the resin column is 0.53 percent, and the removal rate of the aluminum ions is 65 percent.
Comparative example 4:
the regeneration method of waste polishing acid of the comparative example adopts the resin column structure in the example 1, and only a single resin is selected for filling, and the method specifically comprises the following steps:
(1) packed resin column
Sequentially filling 1000g of D001-CC type cation exchange resin b in the glass column 1 from bottom to top, wherein the upper end of the glass column 1 is a liquid inlet end, and the lower end of the glass column 1 is a liquid outlet end;
(2) waste acid passing through resin column
100g of waste acid with the mass fraction of 1.5 percent is input from the liquid inlet end and output from the liquid outlet end of the glass column 1, the mass fraction of aluminum ions in the acid liquid flowing out of the resin column is 0.15 percent, and the removal rate of the aluminum ions is 90 percent.
Comparative example 5:
the regeneration method of the polishing waste acid of the comparative example does not adopt the resin column structure in the example 1, and only selects a single resin for filling, and specifically comprises the following steps:
(1) packed resin column
Sequentially filling 1000gYK-20 color-changing resins a into the glass column 1 from bottom to top, wherein the upper end of the glass column 1 is a liquid inlet end, and the lower end of the glass column 1 is a liquid outlet end;
(2) waste acid passing through resin column
100g of waste acid with the mass fraction of aluminum ions of 1.5 percent is input from the liquid inlet end and output from the liquid outlet end of the glass column 1, the mass fraction of the aluminum ions in the acid liquid flowing out of the resin column is 1.2 percent, and the removal rate of the aluminum ions is 23 percent.
According to the embodiment and the comparative example data, different resins are reasonably arranged according to different adsorption capacities and adsorption limits of the resins, and the aluminum ion removal effect can be effectively improved after the slow flow structure of the middle layer is combined.
The YK-20 color-changing resin in the embodiment is purchased from Tianjin Kaishi resin science and technology Limited; D001-CC type cation exchange resin was purchased from Shanghai biological net; the 001X 4 gel type strongly acidic styrene cation exchange resin was purchased from Weibo technologies, Guangzhou.

Claims (4)

1. A regeneration method of polishing waste acid is characterized by comprising the following steps:
(1) packed resin column
Sequentially filling YK-20 color-changing resin, D001-CC type cation exchange resin and 001 x 4 gel type strong-acid styrene cation exchange resin in a glass column from bottom to top, wherein the upper end of the glass column is a liquid inlet end, and the lower end of the glass column is a liquid outlet end; the filling mass ratio of the YK-20 color-changing resin, the D001-CC type cation exchange resin and the 001 multiplied by 4 gel type strong-acid styrene cation exchange resin is 1 (1.2-2) to 0.5-0.8;
(2) waste acid passing through resin column
Inputting waste acid from a liquid inlet end and outputting waste acid from a liquid outlet end of the glass column, wherein the ratio of the mass of the waste acid treated in a single process to the total amount of resin filled in the glass column is 1 (5-50);
(3) polishing acid compounding
Adding nitric acid and sulfuric acid into the acid solution treated by the resin column to obtain regenerated polishing acid;
(4) resin column elution
And eluting the used resin by using 1-10% of dilute sulfuric acid or dilute hydrochloric acid, and reusing the eluted resin.
2. A method of regenerating spent polishing acid as claimed in claim 1, wherein: the glass column is internally hollow to form an inner cavity for filling resin, a sleeve capable of slowing down the flow velocity of waste acid is arranged in the middle of the inner cavity, and the D001-CC type cation exchange resin is filled in the sleeve;
the top edge of the sleeve is provided with a supporting edge which extends outwards and is connected with the inner wall of the glass column, an end cover is covered on an upper port of the sleeve, a flow passage for waste acid to flow into the sleeve is arranged on the end cover, the cross section of the flow passage is arc-shaped, so that the waste acid forms an eccentric flowing state in the sleeve, the bottom of the sleeve is provided with a closed bottom plate, and the side wall of the sleeve is provided with a plurality of first output ports for the waste acid to flow to the downstream;
the top wall of the glass column is provided with a liquid inlet, the upper port of the flow channel is positioned at the central part of the end cover, and the liquid inlet is close to the edge of the glass column so as to be arranged in a staggered way with the upper port of the flow channel;
a gap is formed between the outer wall of the sleeve and the inner wall of the glass column, and the width of the gap in the radial direction is gradually enlarged from top to bottom;
the bottom wall of the glass column is provided with a liquid outlet, the liquid outlet is positioned at the central part of the bottom wall of the glass column, the bottom plate of the sleeve is also provided with a second outlet, and the second outlet is close to the edge of the sleeve and is staggered with the liquid outlet.
3. A process for regenerating spent polishing acid according to claim 1 or 2, characterized in that: and (3) adding 2-15% of the total amount of the nitric acid and the sulfuric acid in the step (3), wherein the mass ratio of the nitric acid to the sulfuric acid is 2: 1.
4. A process for regenerating spent polishing acid according to claim 1 or 2, characterized in that: in the step (4), the usage amount of 1% sulfuric acid is 2-4 times of the mass of the polishing waste acid, the usage amount of 2% -3% sulfuric acid is 1-2 times of the mass of the polishing waste acid, the usage amount of 4% -10% sulfuric acid is 0.5-1 time of the mass of the polishing waste acid, and the usage amount of the same mass fraction hydrochloric acid is 2 times of the mass of the sulfuric acid.
CN202010244508.1A 2020-03-31 2020-03-31 Regeneration method of polishing waste acid Active CN111534821B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010244508.1A CN111534821B (en) 2020-03-31 2020-03-31 Regeneration method of polishing waste acid

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010244508.1A CN111534821B (en) 2020-03-31 2020-03-31 Regeneration method of polishing waste acid

Publications (2)

Publication Number Publication Date
CN111534821A CN111534821A (en) 2020-08-14
CN111534821B true CN111534821B (en) 2022-02-22

Family

ID=71973167

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010244508.1A Active CN111534821B (en) 2020-03-31 2020-03-31 Regeneration method of polishing waste acid

Country Status (1)

Country Link
CN (1) CN111534821B (en)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5580445A (en) * 1993-12-27 1996-12-03 Organo Corporation Continuous ion exchange apparatus
CN102659568A (en) * 2012-05-03 2012-09-12 中粮生物化学(安徽)股份有限公司 Method for continuously removing cations out of solution containing citric acid
CN205868289U (en) * 2016-07-11 2017-01-11 常州瑞福电力成套设备有限公司 Resin normal position regenerating unit in hydrogen ion exchange column
CN206434953U (en) * 2017-01-03 2017-08-25 煤科集团杭州环保研究院有限公司 The vertical resin catcher in recovery system is purified for waste hydrochloric acid containing iron
CN107417007A (en) * 2017-07-20 2017-12-01 上海立科化学科技有限公司 A kind of resin method recovery process for electroplating spent acid and diluted acid waste water
CN109399591A (en) * 2018-12-26 2019-03-01 江苏新宏大集团有限公司 A kind of preparation method of purification of wet process phosphoric acid
WO2020013070A1 (en) * 2018-07-11 2020-01-16 伸栄化学産業株式会社 Acidic liquid regeneration device and regeneration method
CN110902922A (en) * 2019-12-02 2020-03-24 长沙华时捷环保科技发展股份有限公司 Process for separating acid from salt in salt-containing waste acid

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5580445A (en) * 1993-12-27 1996-12-03 Organo Corporation Continuous ion exchange apparatus
CN102659568A (en) * 2012-05-03 2012-09-12 中粮生物化学(安徽)股份有限公司 Method for continuously removing cations out of solution containing citric acid
CN205868289U (en) * 2016-07-11 2017-01-11 常州瑞福电力成套设备有限公司 Resin normal position regenerating unit in hydrogen ion exchange column
CN206434953U (en) * 2017-01-03 2017-08-25 煤科集团杭州环保研究院有限公司 The vertical resin catcher in recovery system is purified for waste hydrochloric acid containing iron
CN107417007A (en) * 2017-07-20 2017-12-01 上海立科化学科技有限公司 A kind of resin method recovery process for electroplating spent acid and diluted acid waste water
WO2020013070A1 (en) * 2018-07-11 2020-01-16 伸栄化学産業株式会社 Acidic liquid regeneration device and regeneration method
CN109399591A (en) * 2018-12-26 2019-03-01 江苏新宏大集团有限公司 A kind of preparation method of purification of wet process phosphoric acid
CN110902922A (en) * 2019-12-02 2020-03-24 长沙华时捷环保科技发展股份有限公司 Process for separating acid from salt in salt-containing waste acid

Also Published As

Publication number Publication date
CN111534821A (en) 2020-08-14

Similar Documents

Publication Publication Date Title
CN111534821B (en) Regeneration method of polishing waste acid
CN103288172A (en) Recycling method of board washing wastewater produced in PCB (Printed Circuit Board) etching section
CN109868157B (en) Double-field coupling dehydration device and parameter optimization method
CN106702184A (en) Clear water desorption process of alkalescence anion resin
CN208667178U (en) Regeneration of ion-exchange resin device
CN105080624B (en) A kind of ion exchange resin regeneration method
CN105754673A (en) Integrated device for natural gas desulphurization and desulfurizing liquid regeneration
CN105621733A (en) Fluoride-containing wastewater processing method
WO2021169482A1 (en) Device and method for multistage selective removal of heavy metal ions in photovoltaic waste liquid
CN205303415U (en) Be applied to MC -ICPMS's semi -automatic cold atom mercury vapor gas -liquid separation sampling device of binary channels
CN102381749B (en) Method for treating low-concentration mercury-containing wastewater
CN203508044U (en) Exchange-resin regenerative treatment device
CN102285704B (en) Ion exchange resin arsenic removal method for acidic etching liquid, resin regeneration method and treatment system thereof
JP6097104B2 (en) Method for treating heavy metal-containing solution
CN103223355A (en) Top-pressure-free countercurrent regeneration cation exchanger
CN1923711A (en) Method of eliminating lead from nickel chloride solution
CN207581424U (en) Ion exchange water processor
CN105256367B (en) A kind of nickel ion recovery method carried out using low concentration nickel ion recycling machine
CN208151247U (en) A kind of elution system for colistin sulfate
CN203577407U (en) Resin trapper
CN203922802U (en) The Electrolytic Manganese Wastewater ion exchange treatment system of aeration type ion exchange unit is controlled, adopted to a kind of whole process automatically
CN103991926B (en) Electrolytic manganese waste water ion exchange treatment system under automatic control in whole process and adopting aeration type ion exchange device
CN203525729U (en) Water-saving device for cleaning ion exchange resin
CN207031149U (en) A kind of underground water softening plant
CN216368017U (en) Xylose mother liquor ion exchange system

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant