CN111977863A - Method for classified collection and recycling of acid-base waste liquid generated by regeneration of fine-processed resin - Google Patents
Method for classified collection and recycling of acid-base waste liquid generated by regeneration of fine-processed resin Download PDFInfo
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- CN111977863A CN111977863A CN202010830580.2A CN202010830580A CN111977863A CN 111977863 A CN111977863 A CN 111977863A CN 202010830580 A CN202010830580 A CN 202010830580A CN 111977863 A CN111977863 A CN 111977863A
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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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/4618—Devices therefor; Their operating or servicing for producing "ionised" acidic or basic water
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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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/001—Upstream control, i.e. monitoring for predictive control
Abstract
The invention relates to a method for classifying, collecting and recycling acid-base waste liquid generated by regenerating resin in a fine processing way, which comprises the following steps: step 1, after acid feeding is started, detecting the concentration of sodium ions and collecting wastewater; and 2, after the alkali feeding is started, detecting the concentration of silicate ions and collecting the wastewater. The invention has the beneficial effects that: according to the invention, by accurately measuring indexes such as acid-base concentration, ammonia-nitrogen concentration, conductivity and silicate ions in the fine treatment regeneration process, the part of wastewater with the highest salt content and ammonia-nitrogen concentration in the acid inlet process or the alkali inlet process or the acid replacement process or the alkali replacement process is separated out, the acid-base solution with high purity is recycled, the high-salt wastewater is concentrated by electrodialysis, and the acid-base solution generated by the bipolar membrane is recycled in the next fine treatment regeneration process. The invention can recycle the fine treatment wastewater by 85-90%, save the acid and alkali dosage by 50-70%, reduce the introduction of ions in the acid and alkali process, and save the cost for zero discharge of the rear-end wastewater.
Description
Technical Field
The invention belongs to the field of water treatment of thermal power plants, and particularly discloses a method for classifying, collecting and recycling acid-base waste liquid generated by regenerating resin.
Background
At present, most of coal-fired units of 300MW and above in service in China are provided with a condensate fine treatment system. The condensate water fine treatment aims to remove condensate water containing a small amount of ions and ammonia nitrogen, such as condensate water after steam in a steam turbine works, various kinds of hydrophobic and boiler make-up water and the like, through resin adsorption, so that the condensate water can be recycled.
After the condensate polishing resin is saturated in adsorption, ions adsorbed by the condensate polishing resin need to be removed through regeneration, so that the adsorption capacity of the resin is recovered. In general, 3-5% of sodium hydroxide and hydrochloric acid are used for flushing the resin during regeneration, and ions adsorbed on the resin are replaced, so that the exchange capacity of the resin is recovered. The fine treatment regeneration comprises positive resin regeneration and negative resin regeneration, wherein the positive resin regeneration comprises four steps of scrubbing, acid feeding, acid replacement and flushing, and the negative resin regeneration comprises four steps of scrubbing, alkali feeding, alkali replacement and flushing.
At present, the classification collection method for recovering scrubbing and washing water in the processes of cation resin regeneration and anion resin regeneration is common, but the defects of the classification collection method are that 70% of low-salt wastewater in the regeneration process can be recycled, 10% of high-salt wastewater still needs to be treated, the water quantity is large, and the concentration and the purity of acid-base solution discharged in the later stage of acid replacement and the later stage of alkali replacement are high; if the waste water is directly mixed with the rest acid-base regeneration waste water with impurities, acid-base resource waste can be caused, the waste water amount needing to be treated in the later period is increased, and the subsequent treatment difficulty and cost are increased.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a method for classifying, collecting and recycling the acid-base waste liquid generated by resin fine treatment.
The method for classifying, collecting and recycling the acid-base waste liquid generated by the regeneration of the finely processed resin comprises the following steps:
step 1, after acid feeding is started, detecting the concentration of sodium ions and collecting wastewater, and recording the wastewater collected in a time period from the start of acid feeding to the time when the concentration of ammonia ions is lower than a set value A as wastewater a; after acid is fed in and before acid replacement is finished, recording the wastewater collected in the time period of reducing the concentration of ammonia ions from a set value A to a set value B as wastewater B; recording the wastewater collected from the time when the ammonia ion concentration is lower than a set value B to the end of acid replacement as wastewater c; after the acid is placed, recording cation resin regeneration washing water as waste water d;
step 2, after the alkali feeding is started, detecting the concentration of silicate ions and collecting wastewater, and recording the wastewater collected from the alkali feeding to a time period when the concentration of the silicate ions is lower than a set value C as wastewater e; after alkali is added and before alkali replacement is finished, the wastewater collected in the time period of reducing the concentration of silicate ions from a set value C to a set value D is recorded as wastewater f; recording the waste water collected from the time when the concentration of silicate ions is lower than a set value D to the end of alkali replacement as waste water g; marking the anion resin regeneration washing water as waste water h;
step 3, mixing the wastewater b and the wastewater f, and filtering the mixture through a disc type filter with the precision of 3-5 microns; performing electrodialysis concentration on the effluent of the disc type filter, wherein the ratio of concentrated water to fresh water obtained after the electrodialysis concentration is 1:4 to 1: 6; simultaneously, most silicate ions are transferred to fresh water, and concentrated water contains ammonia, sodium chloride and a small amount of silicate ions;
step 4, treating the concentrated water obtained after filtering in the step 3 by an electrically-driven bipolar membrane;
step 4.1, taking the wastewater c and the wastewater d as anode membrane side circulating water of the electrically-driven bipolar membrane, generating a 7-10% hydrochloric acid solution on the anode membrane side of the electrically-driven bipolar membrane by the wastewater c and the wastewater d, and recycling the hydrochloric acid solution;
step 4.2, taking the wastewater g and the wastewater h as cathode side circulating water of the electrically-driven bipolar membrane, and treating the wastewater g and the wastewater h by the electrically-driven bipolar membrane to obtain the wastewater g and the wastewater h containing 7-10% of sodium hydroxide and 100-200 mg/L of ammonia; extracting the wastewater g and the wastewater h under negative pressure to obtain pure ammonia gas, and using the pure ammonia gas in a denitration ammonia injection system of a power plant; recycling the alkali liquor of the sodium hydroxide solution;
step 5, taking the wastewater a and the wastewater e as final wastewater to be used in a back-end process; the fresh water in step 3 is also used as final wastewater for the back-end process.
Preferably, the wastewater a in the step 1 contains hydrochloric acid, and the wastewater a also contains ammonia ions, iron ions and copper ions exchanged from the functional groups of the cation resin; the waste water b contains hydrochloric acid and sodium ions; the wastewater c contains hydrochloric acid and sodium ions; the waste water d contains hydrochloric acid.
Preferably, the wastewater e in the step 2 contains sodium hydroxide, ammonia ions and silicate ions; the waste water f contains sodium hydroxide and silicate ions; the waste water g contains sodium hydroxide and silicate ions; the waste water h contains sodium hydroxide.
Preferably, the hydrochloric acid solution and the sodium hydroxide solution recycled in the step 4.1 and the step 4.2 are used for next fine treatment resin regeneration.
Preferably, the set value A in the step 1 is not less than 2000mg/L, and the set value B is not less than 400 mg/L; in the step 2, the set value C is not less than 1000mg/L, and the set value D is not less than 200 mg/L.
The invention has the beneficial effects that: according to the invention, by accurately measuring indexes such as acid-base concentration, ammonia-nitrogen concentration, conductivity and silicate ions in the fine treatment regeneration process, the part of wastewater with the highest salt content and ammonia-nitrogen concentration in the acid inlet process or the alkali inlet process or the acid replacement process or the alkali replacement process is separated out, the acid-base solution with high purity is recycled, the high-salt wastewater is concentrated by electrodialysis, and the acid-base solution generated by the bipolar membrane is recycled in the next fine treatment regeneration process. The invention can recycle the fine treatment wastewater by 85-90%, save the acid and alkali dosage by 50-70%, reduce the introduction of ions in the acid and alkali process, and save the cost for zero discharge of the rear-end wastewater.
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FIG. 1 is a flow chart of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples. The following examples are set forth merely to aid in the understanding of the invention. It should be noted that, for a person skilled in the art, several modifications can be made to the invention without departing from the principle of the invention, and these modifications and modifications also fall within the protection scope of the claims of the present invention.
Aiming at the problems of high treatment difficulty, high cost and the like of the prior condensate polishing regeneration wastewater, the invention classifies and collects polishing regeneration wastewater through the accurate control of the regeneration process, and acid-base waste liquid is regenerated into acid-base with higher purity and then is recycled for resin regeneration.
As an embodiment, taking a 300WM generator set fine processing system as an example, as shown in fig. 1, the method specifically includes:
acid feeding time is 60min, acid replacement time is 60min, and the wastewater generated by single regeneration of cation resin acid: generating 3t of wastewater in 0-10 min, wherein the ammonia nitrogen concentration is more than or equal to 5000mg/L, and the sodium ion concentration is more than or equal to 300mg/L (wastewater a); generating 30t of wastewater in 10-110 minutes, wherein the ammonia nitrogen is less than 10mg/L, and the sodium ion concentration is less than 10mg/L (wastewater b); generating 3t of wastewater, 100t of scrubbing water and 100t of washing water in 110-120 minutes;
alkali regeneration alkali entering time of the fine treatment anion resin is 60min, alkali replacement time is 60min, and wastewater generated in a single time is as follows: generating high-salinity wastewater in 0-60 minutes and 9t in 0-30 minutes, wherein silicate ions are more than or equal to 1000mg/L, and the wastewater amount is 2-3 t (wastewater c); generating low-salt wastewater within 30-120 minutes, wherein the wastewater amount is 27t, and silicate ions are less than 10mg/L (wastewater d). Generating 3t of wastewater, 100t of scrubbing water and 100t of washing water in 110-120 minutes.
And mixing the wastewater b and the wastewater d to obtain wastewater e, wherein the wastewater e contains 20000-25000 mg/L of sodium chloride, and the water amount of the wastewater e is 57 t.
And carrying out selective electrodialysis treatment on the wastewater e to generate 12t (solution f) of 80-100 g/L sodium chloride solution and 45t (solution g) of 4000-5000 mg/L sodium chloride solution.
The flushing water and the waste water of 110 min-120 min are mixed to be used as circulating water on the acid-base side of the electrically-driven bipolar membrane, the solution f is used as a feed liquid, and 6t (solution h) of hydrochloric acid and sodium hydroxide solution of about 2mol/L and 12t (solution i) of sodium chloride solution of 50g/L are obtained through treatment of the electrically-driven bipolar membrane.
400t of scrubbing water and washing water are removed, the total amount of single acid-base regeneration wastewater is 72t, the final wastewater after the treatment by the process is 16t, the amount of terminal wastewater is greatly reduced, and the acid-base amount can be reduced by about 50% in the next acid-base regeneration.
According to the embodiment, the invention can recycle the fine treatment wastewater by 85-90%, save the acid and alkali dosage by 50-70%, reduce the introduction of ions in the acid and alkali process, and save the cost for zero discharge of the rear-end wastewater.
Claims (5)
1. A method for classifying, collecting and recycling acid-base waste liquid generated by resin fine treatment is characterized by comprising the following steps:
step 1, after acid feeding is started, detecting the concentration of sodium ions and collecting wastewater, and recording the wastewater collected in a time period from the start of acid feeding to the time when the concentration of ammonia ions is lower than a set value A as wastewater a; after acid is fed in and before acid replacement is finished, recording the wastewater collected in the time period of reducing the concentration of ammonia ions from a set value A to a set value B as wastewater B; recording the wastewater collected from the time when the ammonia ion concentration is lower than a set value B to the end of acid replacement as wastewater c; after the acid is placed, recording cation resin regeneration washing water as waste water d;
step 2, after the alkali feeding is started, detecting the concentration of silicate ions and collecting wastewater, and recording the wastewater collected from the alkali feeding to a time period when the concentration of the silicate ions is lower than a set value C as wastewater e; after alkali is added and before alkali replacement is finished, the wastewater collected in the time period of reducing the concentration of silicate ions from a set value C to a set value D is recorded as wastewater f; recording the waste water collected from the time when the concentration of silicate ions is lower than a set value D to the end of alkali replacement as waste water g; marking the anion resin regeneration washing water as waste water h;
step 3, mixing the wastewater b and the wastewater f, and filtering the mixture through a disc type filter with the precision of 3-5 microns; performing electrodialysis concentration on the effluent of the disc type filter, wherein the ratio of concentrated water to fresh water obtained after the electrodialysis concentration is 1:4 to 1: 6; simultaneously, most silicate ions are transferred to fresh water, and concentrated water contains ammonia, sodium chloride and a small amount of silicate ions;
step 4, treating the concentrated water obtained after filtering in the step 3 by an electrically-driven bipolar membrane;
step 4.1, taking the wastewater c and the wastewater d as anode membrane side circulating water of the electrically-driven bipolar membrane, generating a 7-10% hydrochloric acid solution on the anode membrane side of the electrically-driven bipolar membrane by the wastewater c and the wastewater d, and recycling the hydrochloric acid solution;
step 4.2, taking the wastewater g and the wastewater h as cathode side circulating water of the electrically-driven bipolar membrane, and treating the wastewater g and the wastewater h by the electrically-driven bipolar membrane to obtain the wastewater g and the wastewater h containing 7-10% of sodium hydroxide and 100-200 mg/L of ammonia; extracting the wastewater g and the wastewater h under negative pressure to obtain pure ammonia gas, and using the pure ammonia gas in a denitration ammonia injection system of a power plant; recycling the alkali liquor of the sodium hydroxide solution;
step 5, taking the wastewater a and the wastewater e as final wastewater to be used in a back-end process; the fresh water in step 3 is also used as final wastewater for the back-end process.
2. The method for classified collection and recycling of the acid-base waste liquid generated by regeneration of the finely processed resin according to claim 1, which is characterized in that: in the step 1, the wastewater a contains hydrochloric acid, and also contains ammonia ions, iron ions and copper ions exchanged from the cation resin functional groups; the waste water b contains hydrochloric acid and sodium ions; the wastewater c contains hydrochloric acid and sodium ions; the waste water d contains hydrochloric acid.
3. The method for classified collection and recycling of the acid-base waste liquid generated by regeneration of the finely processed resin according to claim 1, which is characterized in that: the wastewater e in the step 2 contains sodium hydroxide, ammonia ions and silicate ions; the waste water f contains sodium hydroxide and silicate ions; the waste water g contains sodium hydroxide and silicate ions; the waste water h contains sodium hydroxide.
4. The method for classified collection and recycling of the acid-base waste liquid generated by regeneration of the finely processed resin according to claim 1, which is characterized in that: and the hydrochloric acid solution and the sodium hydroxide solution recycled in the step 4.1 and the step 4.2 are used for next fine treatment resin regeneration.
5. The method for classified collection and recycling of the acid-base waste liquid generated by regeneration of the finely processed resin according to claim 1, which is characterized in that: in the step 1, the set value A is not less than 2000mg/L, and the set value B is not less than 400 mg/L; in the step 2, the set value C is not less than 1000mg/L, and the set value D is not less than 200 mg/L.
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| CN202010830580.2A CN111977863A (en) | 2020-08-18 | 2020-08-18 | Method for classified collection and recycling of acid-base waste liquid generated by regeneration of fine-processed resin |
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| CN202010830580.2A CN111977863A (en) | 2020-08-18 | 2020-08-18 | Method for classified collection and recycling of acid-base waste liquid generated by regeneration of fine-processed resin |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN206467016U (en) * | 2017-01-18 | 2017-09-05 | 绍兴蓝极膜技术有限公司 | A kind of integrated apparatus that ion exchange resin regeneration brine waste is handled with bipolar film electrodialysis method |
| CN108117140A (en) * | 2017-12-14 | 2018-06-05 | 杭州水处理技术研究开发中心有限公司 | A kind of Bipolar Membrane reclamation set of resin regeneration waste water |
| CN208667178U (en) * | 2018-05-24 | 2019-03-29 | 上海轻工业研究所有限公司 | Regeneration of ion-exchange resin device |
| CN111003779A (en) * | 2019-11-18 | 2020-04-14 | 浙江浙能技术研究院有限公司 | Fine treatment regeneration system and wastewater classified collection method |
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- 2020-08-18 CN CN202010830580.2A patent/CN111977863A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN206467016U (en) * | 2017-01-18 | 2017-09-05 | 绍兴蓝极膜技术有限公司 | A kind of integrated apparatus that ion exchange resin regeneration brine waste is handled with bipolar film electrodialysis method |
| CN108117140A (en) * | 2017-12-14 | 2018-06-05 | 杭州水处理技术研究开发中心有限公司 | A kind of Bipolar Membrane reclamation set of resin regeneration waste water |
| CN208667178U (en) * | 2018-05-24 | 2019-03-29 | 上海轻工业研究所有限公司 | Regeneration of ion-exchange resin device |
| CN111003779A (en) * | 2019-11-18 | 2020-04-14 | 浙江浙能技术研究院有限公司 | Fine treatment regeneration system and wastewater classified collection method |
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