CN114988520B - Process for efficiently recycling acid and salt by utilizing modified special resin - Google Patents
Process for efficiently recycling acid and salt by utilizing modified special resin Download PDFInfo
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- CN114988520B CN114988520B CN202210416985.0A CN202210416985A CN114988520B CN 114988520 B CN114988520 B CN 114988520B CN 202210416985 A CN202210416985 A CN 202210416985A CN 114988520 B CN114988520 B CN 114988520B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J47/00—Ion-exchange processes in general; Apparatus therefor
- B01J47/02—Column or bed processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
- B01J49/60—Cleaning or rinsing ion-exchange beds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
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Abstract
The invention discloses a process for efficiently recycling acid and salt by utilizing modified special resin, which comprises the following steps: s1: loading the salt-containing waste acid into a low-bed adsorption column from bottom to top, and collecting effluent liquid at the upper end of the low-bed adsorption column; s2: when the effluent in the step S1 contains acid, introducing water into a low-bed adsorption column from top to bottom for eluting, and collecting the effluent at the lower end; wherein the low-bed adsorption column is a low-bed adsorption column containing modified special resin; wherein the modified special resin is an amphoteric polymer resin taking styrene-divinylbenzene or acrylic acid as a main structure. Wherein, the pH value of the salt-containing liquid obtained by separation and recovery is more than 4, the recovery rate of the obtained acid is more than 99.5 percent, and the concentration c/c0 is more than 0.8, and the salt-containing liquid can be directly returned to a pickling tank for use. The invention realizes the high-efficiency recovery of the acid in the waste liquid, has good separation effect and long service life of the resin, can meet the requirement of industrial stable production, and can be popularized and applied on a large scale.
Description
Technical Field
The invention belongs to the field of wastewater treatment and chemical industry, and relates to a process for efficiently recycling acid and salt by utilizing modified special resin.
Background
With the rapid development of the economy in China, the market demand for steel, aluminum alloy and other sectional materials is increasing. Enterprises such as steel, metallurgy, electroplating and the like often use a large amount of inorganic strong acid to clean or polish raw materials or equipment. The current treatment of high-concentration acid waste liquid containing heavy metals generated and discharged in the metal surface treatment, electroplating and chemical industries is one of the difficulties in the environment protection field. Typically, an alkali neutralization or stone-charcoal neutralization treatment is employed. The former can recycle heavy metals, but the treatment cost exceeds the recycling value; the latter is low cost, heavy metals are difficult to recycle, and a large amount of sludge is brought. If the waste acid is effectively recycled and a useful chemical product is produced, not only can the environmental pollution be reduced, but also the waste of resources can be reduced, so that the waste acid is necessary to be subjected to recycling research.
Waste acid of enterprises in China is mainly divided into three types according to sources: regenerated waste liquid of ion exchange resin, waste acid washing liquid of iron and steel industry and waste acid of metallurgical electroplating industry. Common waste acid treatment methods include a neutralization method, a diffusion dialysis method, a spray roasting method, an acid retarding method and the like. The neutralization method generates a large amount of sludge, pollutes the environment and wastes acid and metal resources in the wastewater; the diffusion dialysis method has high requirements on the membrane quality, the acid recovery rate is slow, the yield can only reach 80-90%, and 10-20% of acid is mixed into salt, so that additional treatment is needed, and the problem of waste acid can not be fundamentally solved; the spray roasting method has high energy consumption, large equipment investment, complex process and high operation management cost; the acid retardation method is the most economical and effective method for treating waste acid at present, but still has the problems of medium, equipment, process and the like. The technology reported in China for separating acid and salt by using the acid retardation dwarf bed technology adopts strong alkaline anion resin, and the resin has the serious problem of too strong acid retention. After the equipment runs for a period of time, acid accumulates layer by layer on the resin, the concentration of the acid in the collected salt solution is increased, so that the separation effect of the acid and the salt is poor, the salt solution also contains the acid, and the acid needs to be treated again, so that the problem of waste acid cannot be fundamentally solved, and the requirement of stable industrial production cannot be met, and the equipment cannot be popularized and applied on a large scale. The waste liquid produced in the industries of steel, aluminum and the like is treated, and the aim is to recycle the waste acid, reduce environmental pollution, reduce resource waste and realize circular economy.
Disclosure of Invention
The invention aims to: the invention aims to solve the technical problem of providing a process for efficiently recycling acid and salt by utilizing modified special resin aiming at the defects of the prior art.
In order to solve the technical problems, the invention discloses a process for efficiently recycling acid and salt by utilizing modified special resin, which comprises the following steps:
s1: loading the salt-containing waste acid into a low-bed adsorption column from bottom to top, and collecting effluent at the upper end of the low-bed adsorption column; firstly, residual washing and dehydrating are collected, and when the salt content in effluent liquid is 0-1 g/L, deacidification and salt-containing liquid is collected;
s2: when the effluent in the step S1 contains acid, introducing water into a low-bed adsorption column from top to bottom for eluting, and collecting the effluent at the lower end; the residual salty spent acid is collected first, and when the salt content in the effluent begins to decrease, the desalted acid-containing liquid begins to be collected.
In some embodiments, the salt content in the salt-containing waste acid is 2-30 g/L; in some embodiments, the salt content in the salt-containing waste acid is 7-25 g/L; in some embodiments, the salt content of the salt-containing waste acid is 12-20 g/L.
In some embodiments, the acidity of the salty spent acid is 190-260 g/L; in some embodiments, the acidity of the salty spent acid is 200-250 g/L; in some embodiments, the acidity of the salty spent acid is 210-240 g/L; in some embodiments, the acidity of the salty spent acid is 220-230 g/L; the acidity is H + And (5) counting.
In some embodiments, the low bed adsorption column is a modified specialty resin containing low bed adsorption column.
In some embodiments, the modified specialty resin is an ampholytic polymeric resin with styrene-divinylbenzene or acrylic acid as the host structure; in some embodiments, the modified specialty resin is an amphoteric snake cage resin having a styrene-divinylbenzene host structure.
In some embodiments, the amphoteric polymeric resin comprises a strong base strong acid type polymeric resin, a strong base weak base type polymeric resin, a weak base type polymeric resin; in some embodiments, the amphoteric polymeric resin is a strong base strong acid type polymeric resin and/or a strong base weak acid type polymeric resin.
In some embodiments, the weak base group comprises: methylamine, dimethylamine, ethylamine, diethylamine, etc.; in some embodiments, the strong base group comprises: type I quaternary ammonium salt, type II quaternary ammonium salt; in some embodiments, the weak acid group comprises: maleic acid, acetic acid, phosphoric acid, etc.; in some embodiments, the strong acid group comprises: benzenesulfonic acid, alkylbenzenesulfonic acid, and the like.
In some embodiments, the degree of crosslinking is 2-10%.
The matrix of the modified special resin is hydrophobic styrene-divinylbenzene, and the resin is changed into hydrophilic through the combination of the groups, and meanwhile, the acid-base property of the resin is also adjusted.
In some embodiments, the amphoteric polymeric resin has a particle size of 0.05 to 0.3mm, a moisture content of 40% to 80%, and a wet true density of 1.05 to 1.10g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the In some embodiments, the particle size of the amphoteric polymeric resin is from 0.01 to 0.3mm.
Influence of the particle size of the resin particles on separation: the particle size of the resin particles is relatively smaller, the specific surface area is larger, the exchange dynamics is greatly improved, the contact adsorption is more sufficient when the acid is blocked, and the acid and salt separation effect is better.
In some embodiments, the low bed adsorption column has a height of 0.1 to 3.0m and a diameter of 0.1 to 3.0m.
In some embodiments, before first use, the low bed adsorption column is filled with modified special resin, 10% NaCl is injected in countercurrent for soaking for 3 hours, new resin is added for soaking after the resin is contracted until the resin is fully filled, then the separator is closed, pure water is injected in parallel to wash the resin column, the purpose is to wash salt on the resin, the resin is expanded to be in a compacted state, any air in the resin bed cannot be paid attention to in the pure water washing process, and the moisture in the resin bed is emptied.
The process of the invention can break through the limit of the height of the resin column, and the filling height of the resin can generally reach 1-2 m, even higher to 3m, so the process can be suitable for the maximum single-set equipment throughput, and the exchange dynamics of substances is improved.
In some embodiments, in step S1, the loading amount of the salt-containing waste acid is 1-5 BV.
In some embodiments, in step S1, the loading rate is 1-10 BV/h.
In some embodiments, in step S2, the water is used in an amount of 1 to 5BV.
In some embodiments, in step S2, the elution rate is 1-10 BV/h.
According to different feed liquid and process requirements, in some embodiments, the collection amount of the residual washing and dewatering is 0.1-2.5 BV, and the collection amount of the deacidification salt-containing liquid is 0.2-1.5 BV; in some embodiments, the residual spent acid containing salt is collected in an amount of 0.1-2.5 BV and the desalted acid containing solution is collected in an amount of 0.2-1.5 BV during elution. The volume of each solution section is regulated, so that the treatment capacity and the separation effect can be regulated, and the optimization is realized.
In some embodiments, in step S1, the spent acid comprising salt is a spent acid stock solution comprising salt and/or a spent acid comprising residual salt.
In some embodiments, in step S2, the water is freshly injected water and/or residual wash water.
In some embodiments, the process for efficient recovery of acids and salts using modified specialty resins is a multicycle adsorption-elution process comprising the steps of:
s1, first period adsorption: cleaning an acid adsorption resin column, loading salt-containing waste acid into a low-bed adsorption column from bottom to top, and collecting effluent liquid at the upper end of the low-bed adsorption column; firstly, residual washing and dewatering are collected, when the salt content in effluent liquid is 0-1 g/L, deacidification and salt-containing liquid is collected, and after the upper end liquid reaches the volume requirement, liquid feeding (1-5 BV) is stopped;
s2, first period elution: when the effluent in the step S1 contains acid, introducing water into a low-bed adsorption column from top to bottom for eluting, and collecting the effluent at the lower end; firstly, collecting residual salt-containing waste acid, when the salt content in effluent begins to decrease, starting to collect desalted acid-containing liquid, and stopping water inflow (1-5 BV) after the lower-end effluent reaches the volume requirement;
s3, second period adsorption: loading the residual salty waste acid and/or salty waste acid stock solution obtained in the previous period into a low-bed adsorption column from bottom to top, and collecting effluent liquid at the upper end of the low-bed adsorption column; firstly, residual washing and dewatering are collected, when the salt content in effluent liquid is 0-1 g/L, deacidification and salt-containing liquid is collected, and after the upper end liquid reaches the volume requirement, liquid inlet (1-5 BV) is stopped;
s4, eluting in a second period: when the effluent in the step S3 contains acid, introducing eluting water and/or residual eluting water into a low-bed adsorption column from top to bottom for eluting, and collecting the effluent at the lower end; firstly, collecting residual salt-containing waste acid, when the salt content in effluent liquid starts to decrease, starting to collect desalted acid-containing liquid, and stopping water inlet (1-5 BV) after the lower-end effluent liquid reaches the volume requirement;
s5: repeating the adsorption-elution for a plurality of times according to the adsorption-elution process of the second period until the treatment of the salt-containing waste acid is completed.
The process mainly comprises the steps of enabling the salt-containing waste acid to pass through a modified special resin column to enable the acid to be adsorbed, obtaining deacidified salt-containing liquid, eluting the resin column by using eluting water, and obtaining desalted acid-containing liquid. The desalted acid-containing liquid can be returned to the system for recycling, so that the effective utilization rate of market resources is improved.
In the process, two processes of adsorption and elution are carried out through the modified special resin column, and the two processes are alternately and circularly carried out.
In the adsorption process, the feed liquor is fed from the lower port of the column, residual salty waste acid in the upper period is fed from the lower port of the column, and after the feed liquor is fed completely, the feed liquor is fed through salty waste acid stock solution until the volume of the feed liquor reaches the requirement, and then the feed liquor is stopped (1-5 BV); the first period is to fully feed the salt-containing waste acid stock solution.
In the adsorption process, liquid is fed, and quantitative residual washing, dehydrating and deacidifying salt-containing liquid is sequentially collected from an upper port; wherein, the residual washing and dehydrating is returned to the next period of eluting process for use, and the deacidified salt-containing liquid is used as a product to enter the subsequent process.
In the elution process, the inlet liquid is fed from the upper port of the column, residual water is fed from the upper port of the column for washing and dewatering, and after the residual water is fed completely, the raw liquid of the eluting water is fed until the volume of the outlet liquid reaches the requirement, and then water feeding is stopped (1-5 BV); the first cycle is to wash and dewater all.
In the elution process, feeding liquid and sequentially collecting quantitative residual salt-containing waste acid liquid and desalted acid liquid from a lower port; wherein, the residual hydrochloric acid pickle returns to the next period of adsorption process for use, and the desalted hydrochloric acid pickle is the product and enters the subsequent process.
Through the process, the pH value of the deacidified salt-containing liquid obtained by separation and recovery is more than 4; the recovery rate of the acid in the desalted acid-containing liquid is more than 99.5%, and the concentration c/c0 of the acid is more than 0.9, and the desalted acid-containing liquid can be directly returned to a pickling tank for use.
The process of the invention is not only applicable to the separation of inorganic strong acid and corresponding metal ions in the electrode foil aluminum waste acid, metallurgical waste water, ion exchange waste water, steel pickling waste liquid and electroplating waste water, but also applicable to a separation system of sugar acid.
The separator and the low-bed adsorption column are all low-bed devices.
The invention has the advantages of good separation effect, long service life of resin and wide applicability, can meet the requirement of industrial stable production, and can be popularized and applied on a large scale. Meanwhile, the invention truly realizes the resource recycling of the industrial waste acid, ensures the long-term stable production of enterprises, protects the ecological balance of the environment, and effectively solves the problems of poor acid and salt separation effect, low concentration of the recovered acid, unstable equipment operation and incapability of long-time stable production.
The beneficial effects are that: compared with the prior art, the invention has the main innovation points that:
(1) The acid only enters into the resin holes but is not retained by the modified special resin, so the acid is easy to be eluted by water, the recovery rate of the acid in the desalted acid-containing liquid obtained by the method can reach more than 99.5 percent, the removal rate of the metal ions in the desalted acid-containing liquid can also reach more than 99.5 percent, and the concentration c/c of the obtained acid is recovered 0 >0.9, can be directly returned to the production line for use; and collecting the pH of the deacidified salt-containing liquid>4, the separation effect is obviously better than that of the traditional strong-alkaline anion exchange resin, and meanwhile, the separation effect can be further optimized and adjusted by controlling the technological parameters.
(2) Based on the low bed device, the height of the inactive area of the traditional resin bed is reduced, the resin in the column is fully utilized, the exchange kinetics is greatly improved, the batch waste liquid treatment capacity is increased, and the acid concentration is improved.
(3) The treatment capacity per cycle is increased, and the resin in a single cycle basically reaches a saturated state in the adsorption process, so that the separation efficiency is improved.
(4) The resin has stable performance, is easy to regenerate, can be repeatedly used, has low running cost, and can meet the requirement of long-time stable production of enterprises.
Drawings
The foregoing and/or other advantages of the invention will become more apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings and detailed description.
FIG. 1 is a schematic diagram of a low bed apparatus (left: conventional ion exchange column; right: low bed column).
FIG. 2 is a graph showing the adsorption section of a stock solution of salt-containing waste acid passing through an adsorption column.
FIG. 3 is an elution profile when eluting an adsorption column with elution water.
Detailed Description
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials, unless otherwise specified, are commercially available.
The respective acid-containing waste liquids described in the following examples are shown in Table 1.
TABLE 1 basic chemical Properties of the feedstock
| Raw materials | Metal salt content/(g/L) | Acidity (in H) + Meter)/(g/L) |
| Iron and steel smelting plant waste liquid | 20 | 229 |
| Electrode foil aluminate waste liquor | 12 | 230 |
| Waste liquid from electroplating plant | 15 | 220 |
In the following examples, the modified amphoteric resin having a particle size of 0.15 to 0.3mm, a crosslinking degree of 2%, a water content of 80% and a wet true density of 1.10g/cm 3 。
In the following examples, the modified special strong base strong acid (quaternary amine alkyl benzene sulfonic acid) snake cage resin has a particle size of 0.05-0.1 mm, a crosslinking degree of 4%, a water content of 60%, and a wet true density of 1.08g/cm 3 。
In the following examples, the modified amphoteric resin with a specific strong base and weak acid (Ji Anshun butene maleic acid) has a particle size of 0.05 to 0.15mm, a crosslinking degree of 2%, a water content of 70%, and a wet true density of 1.09g/cm 3 。
In the following examples, the strongly basic (quaternary amine type) anion exchange resin had a particle size of 0.15 to 0.3mm, a degree of crosslinking of 8%, a water content of 40%, and a wet true density of 1.05g/cm 3 。
In the following examples, the low bed adsorption column had a height of 80cm and a diameter of 50cm.
In the following examples, the loading amount and loading rate of the salt-containing waste acid in each cycle, and the elution amount and elution rate of water are the same as those of the first cycle unless otherwise specified.
In the following examples, the fine filtration is to filter the salt-containing waste acid through a microfiltration membrane (the filtration precision is 300-800), and the obtained filtrate is the salt-containing waste acid stock solution after fine filtration.
In the following examples, the filling height of the characteristic resin was 80cm.
Example 1: the process for efficiently recycling waste acid by utilizing modified special resin adopts the salt-containing waste liquid of a certain steel smelting plant, and comprises the following steps of:
(1) Before first use, filling a low-bed adsorption column with modified special strong alkali and strong acid (Ji Anben sulfonic acid) amphoteric resin, injecting 10% NaCl in a countercurrent mode, soaking for 3 hours, adding new resin after resin shrinkage until the resin is fully filled, filling the modified special resin with the inner diameter of 10.5cm multiplied by the height of 15cm in a low-bed device, sealing a separator, injecting pure water in a downstream mode to wash the resin column, and aiming at cleaning salt on the resin, so that the resin expands the whole bed body to be in a compacted state, paying attention to the fact that any air cannot exist in the resin bed in the pure water washing process, and evacuating water in the resin bed;
(2) The first period adsorption is to pump the salt-containing waste acid stock solution (1L, flow 6 BV/h) after precise filtration into a modified special strong alkali strong acid resin column from the lower countercurrent, and respectively collect 0.4L of residual washing and dewatering and 0.5L of deacidification salt-containing liquid from the upper end in sequence. Then performing first period elution, eluting with pure water (0.8L, flow rate 6 BV/h), pumping pure water into the elution blocking acid liquor from the upper side, and collecting residual salt-containing acid liquor of 0.4L and desalted acid liquor of 0.5L from the lower end in sequence respectively;
(3) In the second period, adsorption is carried out first, and the residual salty waste acid liquid with the period of 0.4L is fed into the column from the lower end in sequence, and then the salty waste acid stock solution with the period of 0.8L is fed into the column. Similarly, 0.4L of residual washing and dehydrating liquid and 0.5L of deacidified salt-containing liquid are sequentially collected from the upper end. Then eluting, sequentially carrying out residual washing and dewatering with the period of 0.4L, and then carrying out downstream eluting with 0.8L of pure water. Similarly, 0.4L of residual acid pickle and 0.5L of desalted acid pickle are respectively and sequentially collected from the lower end;
(4) Repeating the process according to the second period for 3 times. The average results obtained are shown in Table 2.
Example 2: the process for efficiently recycling the waste acid by utilizing the modified special resin adopts a salt-containing waste liquid of the aluminum waste acid of a certain electrode foil, and the process comprises the following steps:
(1) Before first use, filling a low-bed adsorption column with modified special strong alkali strong acid (quaternary amine alkyl benzene sulfonic acid) snake cage resin, countercurrent injecting 10% NaCl, soaking for 3 hours, adding new resin after resin shrinkage until the resin is fully filled, filling special resin with an inner diameter of 10.5cm multiplied by a height of 15cm in a low-bed device, sealing a separator, and downstream injecting pure water to wash the resin column, so as to clean salt on the resin, make the resin expand the whole bed body in a compacted state, and taking care that no air exists in the resin bed in the pure water washing process, and draining water in the resin bed;
(2) The first period adsorption is to pump the salt-containing waste acid stock solution (2L, flow 6 BV/h) after precise filtration into a modified special strong alkali strong acid type snake cage resin column from the lower countercurrent, and respectively collect 0.8L of residual washing and dewatering and 1.2L of deacidification salt-containing liquid from the upper end in sequence. Then performing first period elution, eluting with pure water (1.8L, flow rate 6 BV/h), pumping pure water into the elution blocking acid liquor from the upper side, and collecting 0.8L of residual salt-containing acid pickle and 1.2L of desalination acid pickle from the lower end in sequence;
(3) In the second period, adsorption is carried out first, and residual salty waste acid liquid with the period of 0.8L is fed from the lower end of the column in sequence, and then 1L salty waste acid stock solution is fed. Similarly, 0.8L of residual washing and dehydrating solution and 1.2L of deacidified salt-containing solution were collected from the upper end in this order. Then eluting, sequentially carrying out residual washing and dewatering with the period of 0.8L, and then carrying out pure water forward elution with the period of 2.0L. Similarly, 0.8L of residual acid pickle and 1.2L of desalted acid-containing liquor are respectively and sequentially collected from the lower end;
(4) Repeating the process according to the second period for 3 times. The average results obtained are shown in Table 2.
Example 3: the process for efficiently recycling waste acid by utilizing modified special resin adopts salt-containing waste liquid of a certain electroplating plant, and comprises the following steps of:
(1) Before first use, filling a low-bed adsorption column with modified special strong base weak acid (Ji Anshun butene maleic acid) amphoteric resin, injecting 10% NaCl in a countercurrent mode for soaking for 3 hours, adding new resin after the resin is contracted until the resin is fully filled, filling special amphoteric resin with an inner diameter of 10.5cm and a height of 15cm in a low-bed device, then sealing a separator, injecting pure water in a downstream mode to wash the resin column, and aiming at cleaning salt on the resin, enabling the resin to expand the whole bed body to be in a compacted state, paying attention to the fact that any air cannot exist in the resin bed in the pure water washing process, and evacuating water in the resin bed;
(2) The first period adsorption is to pump the salt-containing waste acid stock solution (3L, flow 8 BV/h) after precise filtration into a modified special strong alkali strong acid resin column from the lower countercurrent, and sequentially collect 1.2L of residual washing and dewatering and 1.75L of deacidified salt-containing liquid from the upper end. Then performing first period elution, eluting with pure water, pumping pure water (3L, flow rate of 8 BV/h) into the eluting retarding acid solution from the upper side, and sequentially collecting 1L of residual salt-containing waste acid solution and 1.75L of desalted acid solution from the lower end respectively;
(3) In the second period, adsorption is carried out first, and 1L of residual salty waste acid liquid in the upper period is fed from the lower end of the column in sequence, and then 1.5L of salty waste acid stock solution is fed. Similarly, 0.8L of residual washing and dehydrating liquid and 1.75L of deacidified salt-containing liquid were collected from the upper end in this order. Then eluting, sequentially carrying out residual washing and dewatering with the period of 0.8L, and then carrying out pure water forward elution with the period of 2.75L. Similarly, 1L of residual waste acid liquid and 1.75L of desalted acid-containing liquid are respectively and sequentially collected from the lower end;
(4) Repeating the process according to the second period for 3 times. The average results obtained are shown in Table 2.
Comparative example 1: the process of the invention uses strong alkaline anion exchange resin to efficiently recycle waste acid and adopts the salt-containing waste liquid of a certain steel smelting plant, and comprises the following steps:
(1) Before first use, filling a low-bed adsorption column with strong-alkaline (quaternary amine) anion exchange resin, countercurrent-injecting 10% NaCl, soaking for 3 hours, adding new resin after resin shrinkage until the resin is fully filled, filling the low-bed device with strong-alkaline anion exchange resin with the inner diameter of 10.5cm multiplied by the height of 15cm, sealing a separator, and downstream-injecting pure water to wash the resin column, so as to clean salt on the resin, ensure that the whole resin expands to be in a compacted state, and taking care that no air exists in the resin bed in the pure water washing process, and evacuating water in the resin bed;
(2) The first period adsorption is to pump the salt-containing waste acid stock solution (1L, 3 BV/h) after the precise filtration into a strong base anion exchange resin column from the lower countercurrent, and respectively collect 0.4L of residual washing and dewatering and 0.5L of deacidification salt-containing liquid from the upper end in sequence. Then performing first period elution, eluting with pure water, pumping pure water (1L, 3 BV/h) into the eluting stagnation acid liquor from the top downstream, and collecting 0.4L of residual salt-containing waste acid liquor and 0.5L of desalted acid liquor from the lower end in sequence respectively;
(3) In the second period, adsorption is carried out first, and the residual salty waste acid liquid with the period of 0.4L is fed into the column from the lower end in sequence, and then the salty waste acid stock solution with the period of 0.8L is fed into the column. Similarly, 0.4L of residual washing and dehydrating liquid and 0.5L of deacidified salt-containing liquid are sequentially collected from the upper end. Then, elution (1L, 3 BV/h) was performed, and the residual water was sequentially washed and dehydrated for 0.4L of the upper period, followed by 0.8L of pure water downstream elution. Similarly, 0.4L of residual acid pickle and 0.5L of desalted acid pickle are respectively and sequentially collected from the lower end;
(4) Repeating the process according to the second period for 3 times. The average results obtained are shown in Table 2.
The effluent containing ferrous salt (i.e., deacidified salt-containing liquid) and the effluent containing sulfuric acid (i.e., desalted acid-containing liquid) obtained in the above examples and comparative examples (wherein the same effluent of each step was combined) were examined by the following method, and the specific examination results are shown in Table 2. In addition, the first-stage adsorption elution curves in the above-described example 1 and example 2 are shown in fig. 2 and 3, respectively.
The method for detecting the metal salt content comprises the following steps: an atomic absorption spectrometer;
the method for detecting the acid content comprises the following steps: acid-base indicator titration;
the salt yield was calculated as:
the acid yield was calculated as:
acid concentration C/C 0 The calculation formula of (2) is as follows:
TABLE 2 main performance indexes of high-efficient separation and recovery of metal salt and acid solution from waste acid stock solution
| Sequence number | Acid yield/% | Salt yield/% | C/C 0 |
| Example 1 | 99.8 | 93.10 | 0.92 |
| Example 2 | 99.9 | 95.55 | 0.90 |
| Example 3 | 99.9 | 92.30 | 0.91 |
| Comparative example 1 | 70.1 | 78.31 | 0.64 |
As can be seen from the data in Table 2, the recovery rate of the acid in the recovery method of the invention can reach more than 99.8%, the modified special resin can realize high-efficiency separation in the steel waste liquid, the electroplating waste liquid and the aluminate waste liquid, and the concentration C/C of the dilute acid solution obtained by treatment 0 Can reach more than 0.9, and has good acid recovery effect. And the recovery concentration of the acid and the recovery amount of the metal are increased, so that the treatment time of the waste acid can be obviously shortened, the treatment period is shortened, and the energy consumption is reduced.
In conclusion, the invention adopts the non-ion exchange adsorption technology, and utilizes the modified special resin and the low bed device (figure 1) to fundamentally realize the high-efficiency separation of acid and salt. The resin is different from the commonly used strong alkaline ion exchange resin in the acid retardation technology, the separation mechanism belongs to adsorption and distribution functions rather than acid retardation functions, and meanwhile, the low bed equipment matched with the resin can well meet the requirement of high-efficiency separation of acid and salt. The resin used in the invention can adsorb acid, but not corresponding metal salt, and can obviously improve the problem of acid accumulation existing in the waste acid treated by the strong alkaline ion exchange resin at present, thereby truly realizing the high-efficiency separation of the salt and the acid, greatly improving the yield and the concentration of the acid, and having stable structural performance and long service life, meeting the requirements of industrial production and being capable of being popularized and applied on a large scale. The resin bed with strong acid adsorbed therein can be used for eluting acid and regenerating resin by washing with water, and the resin can be used for the next cycle operation without regeneration, thus having low operation cost and short production period.
The invention provides a process idea and a method for efficiently recycling waste acid by utilizing modified special resin, and the technical scheme and the method are particularly realized, the above description is only a preferred embodiment of the invention, and it should be noted that a plurality of improvements and modifications can be made by those skilled in the art without departing from the principle of the invention, and the improvements and modifications are also considered as the protection scope of the invention. The components not explicitly described in this embodiment can be implemented by using the prior art.
Claims (12)
1. A process for efficiently recycling acid and salt by utilizing modified special resin is characterized by comprising the following steps of:
s1: loading the salt-containing waste acid into a low-bed adsorption column from bottom to top, and collecting effluent liquid at the upper end of the low-bed adsorption column; firstly, residual washing and dehydrating are collected, and when the salt content in effluent liquid is 0-1 g/L, deacidification and salt-containing liquid is collected;
s2: when the effluent in the step S1 contains acid, introducing water into a low-bed adsorption column from top to bottom for eluting, and collecting the effluent at the lower end; the method comprises the steps that firstly, residual salty waste acid is collected, and when the salt content in effluent liquid starts to decrease, desalted acid-containing liquid starts to be collected;
wherein the low-bed adsorption column is a low-bed adsorption column containing modified special resin;
wherein the modified special resin is quaternary amine benzenesulfonic acid type strong base strong acid type amphoteric polymeric resin or Ji Anshun butene maleic acid type strong base weak acid type amphoteric polymeric resin which takes styrene-divinylbenzene as a main structure; the degree of crosslinking is 2-10%.
2. The process according to claim 1, wherein the amphoteric polymeric resin has a particle size of 0.05 to 0.3mm, a water content of 40 to 80%, and a wet true density of 1.05 to 1.10g/cm 3 。
3. The process of claim 1, wherein the low bed adsorption column has a height of 0.1 to 3.0m and a diameter of 0.1 to 3.0m.
4. The process according to claim 1, wherein in step S1, the loading amount of the salt-containing waste acid is 1-5 bv.
5. The process according to claim 1, wherein in step S1, the loading rate is 1-10 BV/h.
6. The process according to claim 1, wherein in step S2, the water is used in an amount of 1 to 5bv.
7. The process according to claim 1, wherein in step S2, the elution rate is 1-10 BV/h.
8. The process of claim 1, wherein the residual wash water is collected in an amount of 0.1-2.5 BV.
9. The process of claim 1, wherein the collection amount of the deacidified salt-containing liquid is 0.2-1.5 BV.
10. The process of claim 1, wherein the residual salty spent acid is collected in an amount of 0.1-2.5 BV.
11. The process of claim 1, wherein the collection of desalinated acid-containing liquid is 0.2-1.5 BV.
12. The process according to claim 1, wherein in step S1, the spent acid containing salt is a spent acid stock solution containing salt and/or a spent acid containing salt remained; in step S2, the water is freshly injected water and/or residual wash water.
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