CN113248047A - Comprehensive treatment process for waste acid of electric polishing and waste hydrochloric acid of high-speed rail - Google Patents
Comprehensive treatment process for waste acid of electric polishing and waste hydrochloric acid of high-speed rail Download PDFInfo
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- CN113248047A CN113248047A CN202110538952.9A CN202110538952A CN113248047A CN 113248047 A CN113248047 A CN 113248047A CN 202110538952 A CN202110538952 A CN 202110538952A CN 113248047 A CN113248047 A CN 113248047A
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
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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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/203—Iron or iron compound
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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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Abstract
The invention relates to the technical field of hazardous waste treatment, in particular to a comprehensive treatment process for waste acid generated by electro-polishing and waste hydrochloric acid generated by high-speed rail, which comprises the following steps: a. waste liquid proportioning: adding water into a reaction kettle, and respectively pumping the waste acid and the waste hydrochloric acid into the reaction kettle according to the mass ratio of 0.5-1.5: 1; b. adding alkali for reaction: b, stirring the solution in the step a, adding 30% of liquid caustic soda by mass into a reaction kettle, adjusting the pH value of the solution in the reaction kettle to be 6.0-9.0, and reacting for 10-20 minutes; c. primary filter pressing: leading out the solution in the reaction kettle, performing filter pressing by using a filter press, conveying the sludge to a landfill, and returning the filtrate to the reaction kettle; d. adding calcium hypochlorite for reaction: calcium hypochlorite is added into the reaction kettle in a gathering way to react for 0.5 to 2 hours; e. secondary filter pressing: leading out the solution in the reaction kettle, performing secondary filter pressing by using a filter press, conveying sludge to a landfill, and performing biochemical system after the filtrate is qualified through analysis; the sludge yield is small, the disposal efficiency is improved, the operation cost is reduced, and the waste of land resources is reduced.
Description
Technical Field
The invention relates to the technical field of hazardous waste treatment, in particular to a comprehensive treatment process for waste acid generated by electro-polishing and waste hydrochloric acid generated by high-speed rail.
Background
As a common hazardous waste, waste acid can contaminate surface water, drinking water, soil; causing the withering of the vegetation and even crops, and the death of fish and aquatic organisms; causing corrosion of pipelines and the like, and causing great harm to the environment. The waste acid has the characteristics of large total amount, wide distribution, strong toxicity and difficult management, and seriously threatens the safety of ecological environment if the waste acid is not collected, stored or disposed properly.
Acid pickling galvanization is a steel treatment process, and aims to delay environmental corrosion of steel materials, hydrochloric acid is commonly used as a cleaning agent in the process, a large amount of high-iron waste hydrochloric acid can be generated every year, a small amount of zinc ions are contained in the waste hydrochloric acid, and the waste hydrochloric acid has the characteristic of high ammonia nitrogen. The waste acid for electro-polishing comes from the metal surface treatment industry, consists of phosphoric acid and sulfuric acid, and is characterized by high acidity and high viscosity, a large amount of lime milk needs to be added for treatment, the water content of the generated calcium sulfate precipitate is high, and the sludge yield is very high. No matter which waste acid all has strong corrosivity, need consume a large amount of alkaline medicaments during the processing and neutralize, the process produces a large amount of deposits, and the processing efficiency is lower, and the running cost is higher, and follow-up direct entering landfill or entering landfill through solidification back can cause the waste of land resource.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides the comprehensive treatment process of the waste acid from the electro-polishing and the waste hydrochloric acid from the high-speed rail, which has the advantages of small sludge production, improved treatment efficiency, reduced operation cost and reduced waste of land resources.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a comprehensive treatment process for waste acid of electric polishing and waste hydrochloric acid of high-speed rail comprises the following steps:
a. waste liquid proportioning: adding water into a reaction kettle, and respectively pumping the waste acid and the waste hydrochloric acid into the reaction kettle according to the mass ratio of 0.5-1.5: 1;
b. adding alkali for reaction: b, stirring the solution in the step a, adding 30% of liquid caustic soda by mass into a reaction kettle, adjusting the pH value of the solution in the reaction kettle to be 6.0-9.0, and reacting for 10-20 minutes;
c. primary filter pressing: leading out the solution in the reaction kettle, performing filter pressing by using a filter press, conveying the sludge to a landfill, and returning the filtrate to the reaction kettle;
d. adding calcium hypochlorite for reaction: calcium hypochlorite is added into the reaction kettle in a gathering way, the adding amount of the calcium hypochlorite is 1-2% of the comprehensive mass of the waste acid and the waste hydrochloric acid after the electric polishing, and the reaction lasts for 0.5-2 h;
e. secondary filter pressing: and (3) leading out the solution in the reaction kettle, performing secondary filter pressing by using a filter press, conveying the sludge to a landfill, and performing biochemical system after the filtrate is qualified by analysis.
Preferably, the mass ratio of the waste liquid from the electric polishing in the step a to the waste hydrochloric acid is 0.5-0.7: 1.
Preferably, the pH value of the solution in the reaction kettle is adjusted to 7.0-8.5 in the step b.
Preferably, the adding amount of the calcium hypochlorite in the step d is 1-1.3% of the total mass of the waste liquid of the electric polishing and the waste hydrochloric acid.
Preferably, the reaction time after the calcium hypochlorite is added in the step d is 0.5-1 h.
(III) advantageous effects
Compared with the prior art, the invention provides a comprehensive treatment process for waste acid from electro-polishing and waste hydrochloric acid from high-speed rail, which has the following beneficial effects:
1. according to the comprehensive treatment process of the waste acid from the electro-polishing and the high-iron waste hydrochloric acid, when the high-iron waste acid (mainly the high-iron waste hydrochloric acid) is treated independently, Fe (OH) is mainly generated2Mainly generating Ca by independently treating waste acid generated by precipitation and electric polishing3(PO4)2Precipitation and CaSO4Precipitation, assuming 3mol/L Fe in hydrochloric acid2+2mol/L of SO in the waste acid from the electric polishing4 2-And 2mol/L PO4 3-When 1L of hydrochloric acid and 1L of waste acid from electro-polishing are treated, the theoretical sludge yield is 3M(Fe(OH)2)+M(Ca3(PO4)2)+2*M (CaSO4)3 + 90+310+2 + 136-852 g, and the theoretical sludge yield at the time of integrated treatment was M(Fe3(PO4)2)358g, namely the theoretical mud yield can be reduced by about 58 percent, and Fe is mainly generated during comprehensive treatment3(PO4)2Precipitation and Fe (OH)3The liquid caustic soda and the lime cream are saved during comprehensive disposal, the mud yield is greatly reduced, the operation cost is reduced, and the waste of land resources is reduced;
2. according to the comprehensive treatment process of the waste acid from the electro-polishing and the waste hydrochloric acid from the high-iron industry, the waste acid from the electro-polishing contains sulfate ions, and is easy to combine with calcium ions to generate calcium sulfate hydrate, namely gypsum, so that the waste of the agent is caused, a large amount of sludge is generated, the treatment cost is increased, the sulfate ions can be neutralized in the early stage through comprehensive treatment, and the waste of the agent is reduced;
3. according to the comprehensive treatment process of the electro-polishing waste acid and the high-iron waste hydrochloric acid, aiming at the characteristic of high ammonia nitrogen content of the waste hydrochloric acid, the mixed waste acid is neutralized, then is subjected to filter pressing and then is pumped back to the reaction kettle, and calcium hypochlorite is added, ammonia nitrogen in reaction mother liquor is removed by using the break point chlorine adding method principle, the adding amount of the calcium hypochlorite can be reduced, and the ammonia nitrogen removal efficiency is improved.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention;
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example (b):
taking waste hydrochloric acid generated by a certain steel processing enterprise and waste acid generated by electro-polishing of a certain automobile part manufacturer as examples, wherein the iron content in the waste hydrochloric acid is 80000mg/mL, the zinc content is 10000mg/mL, the phosphoric acid content in the waste acid generated by electro-polishing accounts for about 5%, and the sulfuric acid accounts for about 5%;
the single treatment process of the waste hydrochloric acid comprises the following steps: adding 5 tons of waste hydrochloric acid into a reaction kettle, adding 50 kilograms of calcium hypochlorite, adding 3.0 tons of lime milk with the concentration of 10% and 2.5 tons of liquid caustic soda with the concentration of 30%, wherein the pH value is 9.0, reacting for 60 minutes, performing filter pressing, and obtaining 2.5 tons of sludge (the water content is 51%) after filter pressing, wherein the filtrate is colorless and transparent, and the heavy metal is qualified;
the independent treatment process of the waste acid after electric polishing comprises the following steps: adding 2 tons of water into a reaction kettle, adding 0.8 ton of electro-polishing waste acid, adding 4.5 tons of lime milk with the concentration of 10% for neutralization, wherein the pH value is 10.0, performing pressure filtration after reacting for 60 minutes, wherein the filtrate is colorless and transparent, contains 0.02mg/L of phosphorus, is qualified for heavy metals and 246mg/L of total nitrogen, and generating 3.8 tons of sludge (the water content is 58%) after pressure filtration;
the comprehensive treatment process of the mixed waste acid comprises the following steps: referring to the attached figure 1, 2 tons of water are added into a reaction kettle, then 2.2 tons of waste hydrochloric acid and 1.4 tons of waste acid are respectively added, 4.2 tons of 30% liquid caustic soda are added, the pH value is adjusted to 8.0, and the reaction is carried out for 20 minutes; returning the filtrate after filter pressing to a reaction kettle, adding 40 kg of calcium hypochlorite, reacting for 0.5h, sampling and testing the filtrate, adding a proper amount of calcium hypochlorite for reaction if the filtrate is unqualified, discharging the filtrate after filter pressing into a biochemical system if the filtrate is qualified in testing, finally generating 5.2 tons of filtrate, producing 4.6 tons of sludge (with water content of 52%), generating sludge for testing, directly burying the sludge if the sludge is qualified in testing, and solidifying the sludge if the sludge is unqualified in testing and then burying the sludge;
when the method is separately treated, each ton of waste hydrochloric acid produces 0.5 ton of mud, and each ton of waste electro-polishing acid produces 4.8 tons of mud. When the method is comprehensively treated, 1.3 tons of mud is produced per ton of mixed waste acid, and compared with the method for treating wet mud alone, the method is reduced by about 41 percent.
Sample analysis data is as follows:
and (4) cost accounting: the liquid caustic soda with the concentration of 30 percent is calculated according to 1050 yuan/ton, the lime is calculated according to 800 yuan/ton, the calcium hypochlorite is calculated according to 7900 yuan/ton, the sludge disposal cost is calculated according to 3000 yuan/ton, and the cost of comprehensive disposal through accounting is reduced by 27 percent compared with that of single disposal.
According to the comprehensive treatment process of the waste acid from the electro-polishing and the high-iron waste hydrochloric acid, when the high-iron waste acid (mainly the high-iron waste hydrochloric acid) is treated independently, Fe (OH) is mainly generated2Mainly generating Ca by independently treating waste acid generated by precipitation and electric polishing3(PO4)2Precipitation and CaSO4Precipitation, assuming 3mol/L Fe in hydrochloric acid2+2mol/L of SO in the waste acid from the electric polishing4 2-And 2mol/L PO4 3-When 1L of hydrochloric acid and 1L of waste acid from electro-polishing are treated, the theoretical sludge yield is 3M(Fe(OH)2)+M(Ca3(PO4)2)+2*M (CaSO4)3 + 90+310+2 + 136-852 g, and the theoretical sludge yield at the time of integrated treatment was M(Fe3(PO4)2)358g, namely the theoretical mud yield can be reduced by about 58 percent, and Fe is mainly generated during comprehensive treatment3(PO4)2Precipitation and Fe (OH)3The liquid caustic soda and the lime cream are saved during comprehensive disposal, the mud yield is greatly reduced, the operation cost is reduced, and the waste of land resources is reduced; the waste acid from the electro-polishing contains sulfate ions, and is easy to combine with calcium ions to generate calcium sulfate hydrate, namely gypsum, which causes waste of the medicament and generates a large amount of sludge, thus increasing the disposal cost, and the waste of the medicament can be reduced by comprehensively disposing the sulfate ions in the early stage; aiming at the characteristic of high ammonia nitrogen content of waste hydrochloric acid, the mixed waste acid is neutralized, then is subjected to filter pressing and then is pumped back to a reaction kettle, and then is addedCalcium chlorate removes ammonia nitrogen in the reaction mother liquor by using the break point chlorination method principle, can reduce the dosage of calcium hypochlorite and improve the ammonia nitrogen removal efficiency.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (5)
1. The comprehensive treatment process of the electro-polishing waste acid and the high-iron waste hydrochloric acid is characterized by comprising the following steps of:
a. waste liquid proportioning: adding water into a reaction kettle, and respectively pumping the waste acid and the waste hydrochloric acid into the reaction kettle according to the mass ratio of 0.5-1.5: 1;
b. adding alkali for reaction: b, stirring the solution in the step a, adding 30% of liquid caustic soda by mass into a reaction kettle, adjusting the pH value of the solution in the reaction kettle to be 6.0-9.0, and reacting for 10-20 minutes;
c. primary filter pressing: leading out the solution in the reaction kettle, performing filter pressing by using a filter press, conveying the sludge to a landfill, and returning the filtrate to the reaction kettle;
d. adding calcium hypochlorite for reaction: calcium hypochlorite is added into the reaction kettle in a gathering way, the adding amount of the calcium hypochlorite is 1-2% of the comprehensive mass of the waste acid and the waste hydrochloric acid after the electric polishing, and the reaction lasts for 0.5-2 h;
e. secondary filter pressing: and (3) leading out the solution in the reaction kettle, performing secondary filter pressing by using a filter press, conveying the sludge to a landfill, and performing biochemical system after the filtrate is qualified by analysis.
2. The comprehensive treatment process of the waste acid from the electro-polishing and the waste hydrochloric acid from the high-iron production according to claim 1, wherein the mass ratio of the waste liquid from the electro-polishing to the waste hydrochloric acid in the step a is 0.5-0.7: 1.
3. The comprehensive treatment process of the waste acid from the electro-polishing and the waste hydrochloric acid from the high-iron production as claimed in claim 1, wherein the pH value of the solution in the reaction kettle in the step b is adjusted to 7.0-8.5.
4. The comprehensive treatment process of the waste acid from the electro-polishing and the waste hydrochloric acid from the high iron according to claim 1, wherein the addition amount of the calcium hypochlorite in the step d is 1-1.3% of the total mass of the waste liquid from the electro-polishing and the waste hydrochloric acid.
5. The comprehensive treatment process of the waste acid from the electro-polishing and the waste hydrochloric acid from the high-iron production according to claim 1, wherein the reaction time after the calcium hypochlorite is added in the step d is 0.5-1 h.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120103914A1 (en) * | 2010-06-24 | 2012-05-03 | Gang Yuan | Centralized Sump Oil and Acid Oil treatment process and System |
| CN103145196A (en) * | 2013-03-28 | 2013-06-12 | 青岛新世纪环境工程有限公司 | Method for producing polymerization ferric chloride by utilizing waste hydrochloric acid and waste ferrous mud |
| CN107572718A (en) * | 2017-08-31 | 2018-01-12 | 新奥环保技术有限公司 | A kind of hazardous waste materializing strategy system and method |
| CN110436721A (en) * | 2019-08-12 | 2019-11-12 | 江苏荣信环保科技有限公司 | A kind of metal surface pickling sludge and spent acid comprehensive processing technique |
| CN112010493A (en) * | 2019-06-01 | 2020-12-01 | 祝来宏 | Novel process for treating electroplating wastewater |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120103914A1 (en) * | 2010-06-24 | 2012-05-03 | Gang Yuan | Centralized Sump Oil and Acid Oil treatment process and System |
| CN103145196A (en) * | 2013-03-28 | 2013-06-12 | 青岛新世纪环境工程有限公司 | Method for producing polymerization ferric chloride by utilizing waste hydrochloric acid and waste ferrous mud |
| CN107572718A (en) * | 2017-08-31 | 2018-01-12 | 新奥环保技术有限公司 | A kind of hazardous waste materializing strategy system and method |
| CN112010493A (en) * | 2019-06-01 | 2020-12-01 | 祝来宏 | Novel process for treating electroplating wastewater |
| CN110436721A (en) * | 2019-08-12 | 2019-11-12 | 江苏荣信环保科技有限公司 | A kind of metal surface pickling sludge and spent acid comprehensive processing technique |
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