CN118221245A - Method for efficiently removing chloride ions in polluted acid by using cuprous chloride precipitation method under high acid - Google Patents
Method for efficiently removing chloride ions in polluted acid by using cuprous chloride precipitation method under high acid Download PDFInfo
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- 239000002253 acid Substances 0.000 title claims abstract description 97
- 238000000034 method Methods 0.000 title claims abstract description 79
- 229910021591 Copper(I) chloride Inorganic materials 0.000 title claims abstract description 27
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 title claims abstract description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title claims abstract description 25
- 229940045803 cuprous chloride Drugs 0.000 title claims abstract description 21
- 238000001556 precipitation Methods 0.000 title claims abstract description 18
- 239000000460 chlorine Substances 0.000 claims abstract description 92
- 239000002351 wastewater Substances 0.000 claims abstract description 74
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 40
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 38
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 22
- 239000008103 glucose Substances 0.000 claims abstract description 22
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 28
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical group [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 16
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical group N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 15
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 15
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 15
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 14
- 239000008139 complexing agent Substances 0.000 claims description 8
- 239000007800 oxidant agent Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 238000011085 pressure filtration Methods 0.000 claims 1
- 238000004064 recycling Methods 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 15
- 150000002500 ions Chemical class 0.000 abstract description 14
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 13
- 239000003546 flue gas Substances 0.000 abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 12
- 230000002378 acidificating effect Effects 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 11
- 239000003344 environmental pollutant Substances 0.000 abstract description 10
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- 230000009467 reduction Effects 0.000 abstract description 9
- 238000010828 elution Methods 0.000 abstract description 7
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- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- 239000010949 copper Substances 0.000 description 27
- 239000002244 precipitate Substances 0.000 description 23
- 239000002699 waste material Substances 0.000 description 18
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 12
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
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- 238000001816 cooling Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229960005070 ascorbic acid Drugs 0.000 description 6
- 235000010323 ascorbic acid Nutrition 0.000 description 6
- 239000011668 ascorbic acid Substances 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010865 sewage Substances 0.000 description 6
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 150000001879 copper Chemical class 0.000 description 5
- 238000006298 dechlorination reaction Methods 0.000 description 5
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- -1 cu 2+ Inorganic materials 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 3
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 3
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 3
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- 239000003814 drug Substances 0.000 description 3
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- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
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- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 2
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- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention belongs to the field of industrial acid wastewater treatment and recycling, and relates to a method for efficiently removing chloride ions in polluted acid by using a cuprous chloride precipitation method under high acid. The invention provides a method for efficiently removing chloride ions in polluted acid by using a cuprous chloride precipitation method through glucose reduction under high acidity, which aims to overcome the defects of long reaction time, large using amount of cupric ions and poor chlorine removal effect caused by weak reducing capability of partial reducing agent under high acid (low pH) environment in the traditional cuprous chloride method chlorine removal technology, has short reaction time, low using amount of cupric ions and no copper powder, is suitable for acidic polluted acid wastewater (large application range) comprising pH less than 0 and pH=0-7, has the removing effect of more than 97 percent and can be recycled in the elution process of industrial flue gas pollutants.
Description
Technical Field
The invention belongs to the field of industrial acid wastewater treatment and recycling, and particularly relates to a method for efficiently removing chloride ions in polluted acid by using a cuprous chloride precipitation method for glucose reduction under high acidity.
Background
The copper smelting flue gas washing and purifying process can accumulate extremely polyacid wastewater, and has the main characteristics that the copper smelting flue gas washing and purifying process contains H 2SO4 with a certain concentration (the concentration reaches about 150 g/L), cl - with a concentration reaching 14g/L, as, cu 2+ and other heavy metal ions, and is very difficult to treat. If the waste is easily discharged, the environmental hazard is serious, the waste of dilute acid resources is caused, and even the sustainable development of nonferrous metal smelting enterprises is restricted. In recent years, scholars take acid wastewater recycling treatment as a starting point, and put forward to deeply purify pollutants in acid polluted wastewater and then efficiently recycle dilute sulfuric acid in the acid polluted wastewater, so that the harm to the environment of pollutant discharge is avoided and resources are saved. Efficient removal of Cl - from acidic environments is still difficult today compared to As, cu 2+, and other heavy metal ions.
The most commonly used method for removing Cl - in the waste water of the polluted acid in the industry at present is to react cuprous ions and chloride ions to generate cuprous chloride precipitate for removal, which is further subdivided into: 1) Copper powder and cupric salt are added simultaneously to generate Cu +; 2) Directly adding cuprous oxide to generate Cu +; 3) Adding cupric salt and reducing agent to obtain Cu +.
For the method 1), the method for removing Cl - in the polluted acid wastewater is the most commonly used in the industry at the present stage: copper slag (calculated as Cu 0) and copper sulphate (calculated as Cu 2+). The principle is that Cu 2+ and Cu 0 are subjected to a centering reaction to generate Cu +, and then Cu + and Cl - are subjected to a precipitation reaction to generate CuCl precipitate, so that the aim of removing chlorine from the waste acid and wastewater is fulfilled, but the method is only limited in Cl - removal efficiency (only about 60%), the amount of copper sulfate (calculated by Cu 2+) and the amount of copper slag (calculated by Cu 0) required to be added are 5 times that of Cl - in the wastewater, and the reaction time of 4-5 hours is required, so that the method has the defects in application.
For the method 2), cuprous oxide is directly added to generate cuprous ions, because the cuprous oxide is added in a solid form, the reaction rate is extremely slow, meanwhile, the chlorine removal effect is low due to insufficient non-uniformity of the reaction, and unnecessary resource waste is caused.
For the above method 3), a learner has studied reduction of cupric ions in copper sulfate by ascorbic acid or hydroxylamine sulfate reducing agent to obtain monovalent copper. The method has good effect of removing chloride ions in wastewater only in a limited pH range: when the ascorbic acid is used as a reducing agent of cupric, the pH value is better at 2.4-4.0; when hydroxylamine sulfate is used as a reducing agent for cupric oxide, the pH is preferably 4.4-4.8. However, when treating waste acid and wastewater (sulfuric acid mass concentration 10% -20%, pH < 0) which is known as strong acidity, the reduction of ascorbic acid and hydroxylamine sulfate is significantly reduced with the increase of solution acidity (ascorbic acid and hydroxylamine sulfate are mainly used for reduction in alkaline and weak acidic environments), resulting in a great reduction of chloride ion removal rate (often less than 80%) in highly acidic waste acid. Therefore, it is not suitable for removing chloride ions in the waste acid and water.
In view of the defects of the chlorine removal method, the technology for efficiently removing the Cl - from the acidic wastewater still has a great bottleneck, which greatly limits the smooth implementation of the recycling treatment and recycling technology of the strongly acidic wastewater.
Disclosure of Invention
In view of the above, the invention aims to overcome the defects of long reaction time, large use amount of cupric, poor chlorine removal effect caused by weak reduction capability of ascorbic acid and hydroxylamine sulfate in a high-acid (low pH) environment in the prior art, and the invention aims to provide a method for efficiently removing chloride ions in polluted acid by using a cuprous chloride precipitation method under high acid.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
A method for efficiently removing chloride ions in polluted acid by using a cuprous chloride precipitation method under high acid comprises the steps of taking polluted acid wastewater, adding a chlorine removal agent at 80-100 ℃ and adjusting the acidity of the polluted acid, stirring, and filtering to separate precipitate;
The chlorine removal agent is a mixed reagent consisting of a reducing agent, an oxidizing agent and a complexing agent according to the molar ratio of (1.5-2) (0.25-0.5) (1-10), wherein the reducing agent is glucose, the oxidizing agent is copper sulfate, and the complexing agent is ammonium sulfate.
The chlorine removal method is innovated on the prior chlorine removal technology, and mainly uses ammonium sulfate complexing agent to make cupric ions generate copper ammonia complex ions with lower oxidability. The copper ammonia complex ions can more efficiently perform oxidation-reduction reaction with glucose in an acidic environment, and realize efficient and low-cost purification of chloride ions in the sewage and the acid wastewater under the action of oxidation-reduction precipitation and dechlorination. By utilizing the principle that Cu (NH 3)n]2+ and glucose react more easily to generate Cu + in an acidic environment), cl - can generate CuCl precipitate in the acidic environment more efficiently, so that the aim of chlorine removal is achieved.
The method of the invention can not only remove the chloride ions in the polluted acid efficiently, but also elute the chlorine in the industrial flue gas better, and can regenerate the separated solid, and the separated solid is recycled to the chlorine removal process in the form of copper salt, so the process effect is good and complete.
In addition, the invention has the advantages that the acidity of the waste acid and water is regulated more simply and conveniently, the medicament for removing the chloride ions in the waste acid and water is convenient to use, and the finally obtained chlorine removal efficiency is high and can reach 98.1 percent.
Further, the dirty acid acidity is adjusted to achieve a sulfuric acid environment with a mass concentration of not less than 50%, and the purpose is that: the chlorine is removed in the form of hydrogen chloride gas, meanwhile, the liquid is acid liquid after chlorine removal, and the acid liquid is reused in the washing process of industrial acid making flue gas with high acidity, so that chlorine in the flue gas can be washed out greatly.
In addition, the sulfuric acid environment with the mass concentration of 50 percent saves the cost of the medicament and has better effect; however, when the mass concentration is more than 50%, the chlorine ions become hydrogen chloride gas more easily under the conditions of high temperature and more than 50% acidity, so that a good effect of removing the chlorine ions appears, but more sulfuric acid is consumed simultaneously to adjust the dirty acid, meanwhile, the operation of adjusting the acidity of the dirty acid becomes difficult, and too high acidity causes corrosion of instruments and equipment due to too strong corrosiveness.
Further, the molar ratio of the addition of the reducing agent and the oxidizing agent in the dechlorination medicament to Cl - in the waste acid and water is (1.5-2) 1 and (0.25-0.5) 1 respectively, and the molar ratio of the addition of the complexing agent to Cl - in the waste acid and water is (1-10) 1.
The formation of cuprammonia complex ions reduces the amount of copper powder produced by glucose reduction, so that the oxidation-reduction reaction of Cu (NH 3)n]2+) in the form of ions and glucose can be more effectively carried out, and the molar ratio of the reducing agent to the oxidant to produce proper amount of Cu +,Cu+ and Cl - in the wastewater ensures that Cl - in the wastewater can be fully precipitated.
In addition, the reagent is added in the temperature range of 80-100 ℃ in the technical scheme, so that HCl gas has higher volatilization efficiency in the temperature range, and proper conditions are provided for the volatilization of Cl -.
Further, the stirring mode is any one of magnetic stirring, mechanical stirring or rotary mixing stirring.
The adoption of the further scheme has the beneficial effect that the diversity of stirring modes selected by the chlorine removal method provided by the invention is increased.
Further, the stirring frequency is 180-300r/min, and the stirring time is 110-130min.
The adoption of the further scheme has the beneficial effects that the stirring frequency and the stirring time are determined, so that the reducing agent, the oxidizing agent and the complexing agent are in more sufficient contact with corresponding reactants, the sufficient reaction time is provided for ensuring more thorough removal of Cl - in the wastewater, and meanwhile, oxidation of precipitation and loss of economic cost caused by overlong reaction time are avoided.
Further, the filtering mode is suction filtering or normal pressure filtering.
The filtering mode has the beneficial effects of high filtering speed, high efficiency and low cost.
Compared with the prior art, the invention has the beneficial effects that:
The invention relates to a method for efficiently removing chloride ions in polluted acid by using a cuprous chloride precipitation method under high acid, belonging to the field of industrial acid wastewater treatment and recycling. The invention provides a method for efficiently removing chloride ions in polluted acid by using a cuprous chloride precipitation method through glucose reduction under high acidity, which aims to overcome the defects of long reaction time, large using amount of cupric ions and poor chlorine removal effect caused by weak reducing capability of partial reducing agent under high acid (low pH) environment in the traditional cuprous chloride method chlorine removal technology, has short reaction time, low using amount of cupric ions and no copper powder, is suitable for acidic polluted acid wastewater (large application range) comprising pH less than 0 and pH=0-7, has the removing effect of more than 97 percent and can be recycled in the elution process of industrial flue gas pollutants. In particular, the method comprises the steps of,
1) The invention makes the contaminated acid reach a certain sulfuric acid mass concentration by adding sulfuric acid, and simultaneously uses copper sulfate, ammonium sulfate and glucose to generate cuprous chloride precipitate to reduce chloride ions in the contaminated acid wastewater.
2) According to the invention, an ammonium sulfate complexation mode is adopted, so that cupric [ Cu (NH 3) n]2+ ] is generated, the oxidability of cupric is reduced, and the phenomenon of reduced reaction rate caused by copper powder generation is avoided; meanwhile, glucose with stronger reducibility than ascorbic acid and thiourea is used as a reducing agent, so that a better chlorine removal effect can be achieved in high-acidity sewage and acid wastewater.
3) According to the method, the [ Cu (NH 3)n]2+ and a mode of adopting glucose as a reducing agent ] is generated, and the chloride ion removal rate is high after the reaction is finished; because the regulated acid is strong in acidity, the acid purifying liquid after dechlorination can be reused in the stage of absorbing and eluting pollutants in industrial flue gas, and a foundation is laid for recycling sulfuric acid resources.
4) The method can efficiently remove chloride ions in the polluted acid and simultaneously retain sulfuric acid in the polluted acid, thereby achieving the purpose of enriching and recycling sulfuric acid resources in the polluted acid.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of the principle of the chlorine removal agent provided by the invention for removing Cl - from waste acid and wastewater.
Detailed Description
The following will clearly and completely describe the technical solutions in the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The word "embodiment" as used herein does not necessarily mean that any embodiment described as "exemplary" is preferred or advantageous over other embodiments. Performance index testing in the examples of the present application, unless otherwise specified, was performed using conventional testing methods in the art. It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure.
Unless otherwise defined, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs; other test methods and techniques not specifically mentioned in the present application are those commonly used by those skilled in the art.
In the description of the present invention, it should be understood that the terms "medium," "upper," "lower," "ascending," "descending," "vertical," "face," "top," "bottom," "inner," "outer," and the like indicate or are based on the orientation or positional relationship shown in the drawings, merely to facilitate description of the present invention and simplify the description, and do not indicate or imply that the apparatus or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present invention.
Numerous specific details are set forth in the following examples in order to provide a better understanding of the present application. It will be understood by those skilled in the art that the present application may be practiced without some of these specific details. In the examples, some methods, means, instruments, devices, etc. well known to those skilled in the art are not described in detail in order to highlight the gist of the present application.
On the premise of no conflict, the technical features disclosed by the embodiment of the application can be combined at will, and the obtained technical scheme belongs to the disclosure of the embodiment of the application.
The present invention will be further specifically illustrated by the following examples, which are not to be construed as limiting the invention, but rather as falling within the scope of the present invention, for some non-essential modifications and adaptations of the invention that are apparent to those skilled in the art based on the foregoing disclosure.
Example 1
A method for removing Cl - from simulated acid wastewater, comprising:
Adding sulfuric acid into 500ml simulated acid wastewater with the concentration of 2000mg/L to adjust the acidity of the wastewater to 50% of the mass concentration of H 2SO4, simultaneously adding glucose, copper sulfate and ammonium sulfate according to the molar ratio of 1.5:1, 0.25:1 and 10:1 with the Cl - in the wastewater, magnetically stirring at 80 ℃ with the stirring frequency of 240r/min, reacting for 120min, standing and cooling, sucking and filtering to separate precipitate, wherein the concentration of residual Cl - in the wastewater is 44mg/L, the Cl-removing efficiency is 97.8%, the concentration of residual Cu 2+ in the wastewater is very low, and the mass concentration of residual sulfuric acid is 49%, and recycling the solution in the elution process of industrial flue gas pollutants. The component of the generated precipitate is CuCl precipitate, and the regenerated precipitate is used as copper salt for the chlorine removal procedure.
Example 2
A method for removing Cl - from simulated acid wastewater, comprising:
Adding sulfuric acid into 500ml simulated acid wastewater with the Cl-concentration of 1900mg/L to adjust the acidity of the wastewater to 50% of the mass concentration of H 2SO4, simultaneously adding glucose, copper sulfate and ammonium sulfate according to the molar ratio of 1.5:1, 0.25:1 and 1:1 with the Cl - in the wastewater, magnetically stirring at 90 ℃ with the stirring frequency of 300r/min, reacting for 120min, standing and cooling, sucking and filtering to separate precipitate, wherein the concentration of residual Cl - in the wastewater is 56.7mg/L, the removal efficiency of Cl - is 97.0%, the concentration of residual Cu 2+ in the wastewater is lower, and the mass concentration of residual sulfuric acid is 49.1%, and recycling the solution to the elution process of industrial flue gas pollutants. The component of the generated precipitate is CuCl precipitate, and the regenerated precipitate is used as copper salt for the chlorine removal procedure.
Example 3
A method for removing Cl - in actual acid wastewater, comprising:
Adding sulfuric acid into 500ml of actual waste acid wastewater with the concentration of 2100mg/L to adjust the acidity of the wastewater to 50% of the mass concentration of H 2SO4, simultaneously adding glucose, copper sulfate and ammonium sulfate according to the molar ratio of 1.5:1, 0.5:1 and 5:1 with the Cl - in the wastewater, magnetically stirring at 100 ℃ with the stirring frequency of 180r/min, reacting for 120min, standing and cooling, sucking and filtering to separate precipitate, wherein the concentration of residual Cl - in the wastewater is 39.9mg/L, the removal efficiency of Cl < - > is 98.1%, the concentration of residual Cu 2+ in the wastewater is very low, and the mass concentration of residual sulfuric acid is 48.9%, and recycling the solution to the elution process of industrial flue gas pollutants. The component of the generated precipitate is CuCl precipitate, and the regenerated precipitate is used as copper salt for the chlorine removal procedure.
Example 4
A method for removing Cl - in actual acid wastewater, comprising:
Adding sulfuric acid into 500ml of actual waste acid wastewater with the concentration of 3000mg/L to adjust the acidity of the wastewater to 50% of the mass concentration of H 2SO4, simultaneously adding glucose, copper sulfate and ammonium sulfate according to the molar ratio of 2:1, 0.25:1 and 8:1 with the Cl - in the wastewater, magnetically stirring at 80 ℃ with the stirring frequency of 240r/min, reacting for 120min, standing and cooling, sucking and filtering to separate precipitate, wherein the concentration of residual Cl - in the wastewater is 75mg/L, the removal efficiency of Cl - is 97.5%, the concentration of residual Cu 2+ in the wastewater is very low, and the mass concentration of residual sulfuric acid is 48.6%, and recycling the solution in the elution process of industrial flue gas pollutants. The component of the generated precipitate is CuCl precipitate, and the regenerated precipitate is used as copper salt for the chlorine removal procedure.
In order to further demonstrate the beneficial effects of the present invention for a better understanding of the present invention, the technical features disclosed herein are further illustrated by the following comparative examples, which are not to be construed as limiting the present invention. Other modifications of the invention which do not involve the inventive work, as would occur to those skilled in the art in light of the foregoing teachings, are also considered to be within the scope of the invention.
Comparative example 1
A method for removing Cl - from simulated acid wastewater, comprising:
Adding sulfuric acid into 500ml simulated waste acid water with the Cl-concentration of 2000mg/L to adjust the acidity of the waste water to 50% of the mass concentration of H 2SO4, magnetically stirring at 80 ℃ without adding glucose, copper sulfate and ammonium sulfate, wherein the stirring frequency is 240r/min, standing and cooling after 120min of reaction, sucking and filtering to separate sediment, wherein the concentration of residual Cl - in the waste water is 1060mg/L, and the removal efficiency of Cl - is 47%.
Therefore, the method for improving the reaction acidity is singly adopted, the chlorine removal effect is not good, and the concentration of Cl - in the treated sewage and acid wastewater can not reach the recycling standard.
Comparative example 2
A method for removing Cl - from simulated acid wastewater, comprising:
To 500ml of simulated waste acid wastewater with the Cl - concentration of 2000mg/L, glucose, copper sulfate and ammonium sulfate are simultaneously added according to the molar ratio of 1.5:1, 0.5:1 and 5:1 with Cl - in the wastewater respectively without adding sulfuric acid to adjust the acidity of the wastewater (13% of initial sulfuric acid mass), the stirring frequency is 240r/min under magnetic stirring at 80 ℃, after the reaction is 120min, the mixture is left to stand and cool, suction filtration and separation are carried out, the concentration of residual Cl < - > in the wastewater is 663mg/L, and the Cl < - > removal efficiency is 66.85%.
Therefore, the method for generating cuprous chloride for dechlorination by independently adding glucose, copper sulfate and ammonium sulfate has unsatisfactory dechlorination effect, and the Cl-concentration in the treated sewage and acid wastewater can not reach the recycling standard.
Comparative example 3
A method for removing Cl - from simulated acid wastewater, comprising:
Adding sulfuric acid into 500ml simulated acid wastewater with the concentration of 2000mg/L to adjust the acidity of the wastewater to 30% of the mass concentration of H 2SO4, simultaneously adding glucose, copper sulfate and ammonium sulfate according to the molar ratio of 1.5:1, 0.5:1 and 5:1 with the Cl - in the wastewater, magnetically stirring at 80 ℃ with the stirring frequency of 180r/min, reacting for 120min, standing and cooling, sucking and filtering to separate precipitate, wherein the concentration of residual Cl < - > in the wastewater is 486mg/L, and the Cl < - > removing efficiency is 75.7%.
Therefore, when the adopted reaction acidity is not within the protection range of the invention, the chlorine removal effect is not good, and the concentration of Cl - in the treated sewage and acid wastewater can not reach the recycling standard.
Comparative example 4
A method for removing Cl - from simulated acid wastewater, comprising:
adding sulfuric acid into 500ml simulated acid wastewater with the concentration of 2000mg/L to adjust the acidity of the wastewater to 50% of the mass concentration of H 2SO4, simultaneously adding glucose, copper sulfate and ammonium sulfate according to the molar ratio of 0.5:1 and 0.15:1 to 15:1 with the Cl - in the wastewater, magnetically stirring at 80 ℃ with the stirring frequency of 240r/min, reacting for 120min, standing and cooling, sucking and filtering to separate precipitate, wherein the concentration of residual Cl < - > in the wastewater is 864mg/L, and the Cl < - > removal efficiency is 56.8%.
Therefore, glucose, copper sulfate and ammonium sulfate which are not used in the protection range of the invention are used as chlorine removal agents, the chlorine removal effect is not ideal, and the concentration of Cl - in the treated sewage and acid wastewater can not reach the recycling standard.
From the above analysis, according to the chlorine removal results of examples 1 to 4, the chlorine removal method and the selected reagent according to the present invention can obtain Cl - removal efficiency of 97% or more, regardless of whether they are applied to simulated acid wastewater chlorine removal or actual acid wastewater chlorine removal. The method not only solves the problem of efficiently removing Cl - in the waste acid and water, but also has simple operation, greatly shortens the required reaction time compared with the traditional cuprous chloride method for removing chlorine, and has good application prospect. The method has the advantages that the use amount of bivalent copper is low, copper powder is not used, the method is suitable for acidic waste acid wastewater (the application range is wide) comprising pH < 0 and pH=0-7, and the purified liquid after chlorine removal can be reused in the elution process of industrial flue gas pollutants.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (6)
1. A method for efficiently removing chloride ions in polluted acid by using a cuprous chloride precipitation method under high acid is characterized in that polluted acid wastewater is taken, a chlorine removal agent is added at 80-100 ℃ and the acidity of the polluted acid is adjusted, and the sediment is filtered and separated after stirring;
The chlorine removal agent is a mixed reagent consisting of a reducing agent, an oxidizing agent and a complexing agent according to the molar ratio of (1.5-2) (0.25-0.5) (1-10), wherein the reducing agent is glucose, the oxidizing agent is copper sulfate, and the complexing agent is ammonium sulfate.
2. The method for efficiently removing chloride ions from contaminated acid by using a high-acid cuprous chloride precipitation method as claimed in claim 1, wherein the acidity of the contaminated acid is adjusted to be 50% or more in terms of sulfuric acid concentration by mass.
3. The method for efficiently removing chloride ions from contaminated acid by using a cuprous chloride precipitation method under high acid according to claim 1, wherein the molar ratio of the addition amount of the reducing agent and the oxidizing agent to Cl - in the contaminated acid wastewater is (1.5-2): 1 and (0.25-0.5): 1, respectively, and the molar ratio of the addition amount of the complexing agent to Cl - in the contaminated acid wastewater is (1-10): 1.
4. The method for efficiently removing chloride ions in contaminated acid by using a high-acid cuprous chloride precipitation method according to claim 1, wherein the stirring mode is any one of magnetic stirring, mechanical stirring or rotary mixing stirring.
5. The method for efficiently removing chloride ions in contaminated acid by using a high-acid cuprous chloride precipitation method according to claim 1 or 4, wherein the stirring frequency is 180-300r/min, and the stirring time is 110-130min.
6. The method for efficiently removing chloride ions from polluted acid by using a high-acid cuprous chloride precipitation method as claimed in claim 1, wherein said filtration mode is suction filtration or normal pressure filtration.
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