CN109133296A - Application of N, N- diethyl-N '-fluorine substituted benzoyl thiocarbamide in nickel waste water processing - Google Patents
Application of N, N- diethyl-N '-fluorine substituted benzoyl thiocarbamide in nickel waste water processing Download PDFInfo
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- CN109133296A CN109133296A CN201810734079.9A CN201810734079A CN109133296A CN 109133296 A CN109133296 A CN 109133296A CN 201810734079 A CN201810734079 A CN 201810734079A CN 109133296 A CN109133296 A CN 109133296A
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- Prior art keywords
- thiocarbamide
- diethyl
- nickel
- substituted benzoyl
- fluorine substituted
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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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
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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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a kind of N; application of N- diethyl-N '-fluorine substituted benzoyl thiocarbamide in nickel waste water processing; utilize N; the strong coordinating processing to nickel ion in waste water of N- diethyl-N '-fluorine substituted benzoyl thiocarbamide acts on, and is measured using flame atomic absorption method to residual nickel ion content.The result shows that in the simulated wastewater for containing Ni (II) 500mg/L; in the presence of flocculant poly aluminium chloride and polyacrylamide; acylthioureas can be complete by Ni (II) ion precipitation in 7~8 range of pH, and residual nickel content is far below national emission standard.The present invention has the advantages that can precipitate nickel ion completely under conditions of close to neutral, treated, and waste liquid can be without adjusting pH direct emission；Acylthioureas Ni (II) complex compound sediment of generation filtered, is acidified and can be released nickel ion and thiocarbamide precipitating again; fast implement the enrichment of Ni (II) and the recycling of precipitating reagent; the precipitating reagent rate of recovery reduces cost for wastewater treatment up to 72.1%.
Description
Technical field
The invention belongs to technical field of waste water processing, and in particular to N, N- diethyl-N '-fluorine substituted benzoyl thiocarbamide
Application in nickel waste water processing.
Background technique
The toxicity of heavy metal ion has the characteristics that long-term accumulated is difficult to degrade and destroy again, can only pass through valence state and chemical combination
The change of species handles its enrichment method.Ni2+It is common one of heavy metal contaminants, at nickel waste water reported at present
Reason method mainly has chemical precipitation method, ion-exchange, oxidizing process, electrolysis method etc..Traditional hydroxide precipitation method: after processing
Waste water often pH value is high, need in acid adding and just discharge, and for weak amphoteric metal as Ni, pH value is higher, precipitate
Object may be redissolved, therefore pH value control wants very strict, and nickel residual concentration is smaller than 1mg/L in water after the processing of this method；Sulphur
The compound precipitation method: since the solubility of sulfide is smaller than the solubility of hydroxide, treatment effect is than hydroxide neutralization precipitation
Method is more preferable, and is convenient for metal recovery, but vulcanizing agent price is high, and processing cost is higher and sulfide precipitation particle is relatively fine, holds
Colloid is easily formed, precipitating is relatively difficult, and hydrogen sulfide gas easily generated during processing, causes secondary pollution；Ion exchange
Method: both can remove the metal cation in waste water, also can remove anion, and remaining nickel ion concentration after wastewater treatment
It is low, high treating effect, but ion exchange resin cost is relatively high, and acid, alkali or salt are needed when resin regeneration, thus running cost
With relatively high, regenerated liquid needs are further processed；Ferrite process: improved ferrite process, removal rate is good, the sediment sedimentation time
Short, treatment effect is preferable, and cost is relatively low, but ferrous sulfate and sodium hydroxide dosage are larger, and water outlet sodium sulphate content is more,
Complex procedures, energy consumption is higher, and operating cost is higher, is not suitable for a large amount of wastewater treatments；Electrolysis method treatment effeciency is higher, is also convenient for
Control management, but equipment loss is serious, and power consumption is more, and water treatment effect is not ideal enough and stablizes, thus fails to be widely applied.
Summary of the invention
N is utilized the purpose of the present invention is to provide a kind of, N- diethyl-N '-fluorine substituted benzoyl thiocarbamide handles nickel
The new method of waste water.
The present invention relates to N, application of N- diethyl-N '-fluorine substituted benzoyl thiocarbamide in nickel waste water is handled, specifically
Processing mode are as follows: be added to N after N- diethyl-N '-fluorine substituted benzoyl thiocarbamide is completely dissolved with NaOH aqueous solution
In nickel waste water, 20~40min of stirring reacts fully progresss, then addition flocculant poly aluminium chloride and polyacrylamide, then
20~40min of stirring makes fully reacting；Reaction solution is then stood 10~20 hours, filtering, filtrate direct emission, filter residue acid
It will be dissociated into nickel ion and N, N- diethyl-N '-fluorine substituted benzoyl thiocarbamide, dissociation again after adjusting pH to 1.5~2.5
Nickel ion recycling out, the N dissociateed, N- diethyl-N '-fluorine substituted benzoyl thiocarbamide are insoluble in water and are analysed with precipitating
Out, it is reused after filtering.
The structural formula of N of the invention, N- diethyl-N '-fluorine substituted benzoyl thiocarbamide is as follows:
In above-mentioned processing mode, the N of the quality of nickel ion and addition in the nickel waste water, N- diethyl-N '-fluorine substituted benzene
The mass ratio of formoxyl thiocarbamide be 1:7~15, the N of the quality of nickel ion and addition preferably in nickel waste water, N- diethyl-N '-
The mass ratio of fluorine substituted benzoyl thiocarbamide is 1:9~12.
In above-mentioned processing mode, the quality of nickel ion and the aluminium polychloride of addition and polyacrylamide preferably in nickel waste water
The ratio between gross mass be 1:1 × 10-5~3 × 10-5, wherein the mass ratio of aluminium polychloride and polyacrylamide is 1:0.5~2.
In above-mentioned processing mode, the acid is hydrochloric acid.
The present invention is precipitating reagent with N, N- diethyl-N '-fluorine substituted benzoyl thiocarbamide, utilizes matching by force for acylthioureas
Position property removes the nickel ion in complexing waste water, can in neutral conditions precipitate nickel ion completely, again can after the precipitating acid adding of generation
Reach enrichment and the N of nickel ion, the recycling of N- diethyl-N '-fluorine substituted benzoyl thiocarbamide, to establish a kind of operation
Simplicity, cost are relatively cheap, and filth-discharging effect more preferably handles the new method of nickel-containing waste water.
Relative to the processing method of other nickel waste waters, the specific following advantage of the present invention:
1, nickel ion significant effect is removed, nickel ion concentration is in 0.01mg/L hereinafter, being far below state in treated waste water
Family nickel discharge standard 1mg/L；
2, remove nickel ion after filtrate pH value between 7~8, can direct emission, avoid many and diverse program of post-processing；
3, by after filter residue acid processing, nickel ion can be released, is recycled convenient for nickel ion, simultaneously as the N dissociateed,
N- diethyl-N '-fluorine substituted benzoyl thiocarbamide is insoluble in water and Precipitation in acid condition, can recycle, from
And greatly reduce cost for wastewater treatment.
Detailed description of the invention
Fig. 1 is the canonical plotting that absorbance changes with nickel ion concentration.
Specific embodiment
The present invention is described in more detail with reference to the accompanying drawings and examples, but protection scope of the present invention is not limited only to
These embodiments.
Embodiment 1
1, standard curve is drawn
It takes the Ni standard solution of 1000 μ g/mL to be configured to the standard solution of series of concentrations gradient with deionized water, uses
TAS-990 atomic absorption spectrophotometer successively tests various concentration standard solution, records test data, draws extinction
The standard curve changed with nickel ion concentration is spent, as a result as shown in table 1 and Fig. 1.
1 nickel ion normal concentration of table
2, nickel ion removal effect detects
By 8.8706g N, N- diethyl-N '-fluorine substituted benzoyl sulfocarbamide crystallization is complete with 1mol/LNaOH aqueous solution
After fully dissolved, it is transferred to constant volume in the volumetric flask of 100mL, obtains thiourea ligand solution.7 clean 250mL conical flasks are taken, according to
Secondary number 1,2,3,4,5,6,7, by table 2 be separately added into 100mL nickel ion concentration be 500mg/L nickel waste water, with pipette according to
It is secondary that 3,4,5,6,7,8,9mL thiourea ligand solution are added according to label, less than being supplied with distilled water for 9mL thiourea ligand solution,
Concussion conical flask 30min to react abundant progress, be then respectively adding 0.5mL1mg/L polyaluminum chloride aqueous solution and
The polyacrylamide solution of 0.5mL1mg/L, then shake 30min and make fully reacting.Then, reaction solution is stood 10 hours, it
It successively sequentially filters afterwards, filter residue and filtrate are saved respectively by reference numeral, and filtrate carries out the measurement of nickel ion removal effect, measurement knot
Fruit is shown in Table 3.
2 waste water composition of table and precipitating reagent dosage
Nickel ion content is remained in 3 waste liquid of table
Known by 3 experimental measurements of table, N, the quality of N- diethyl-N '-fluorine substituted benzoyl thiocarbamide and nickel ion
Than in 7:1~14:1 or so, the sedimentation effect of nickel ion is well, to remain nickel ion concentration most in filtrate in 10.6:1
It is low.This is primarily due to N, and N- diethyl-N '-fluorine substituted benzoyl thiocarbamide and nickel ion form complex compound, when addition sulphur
When the amount deficiency of urea derivative, complexing result is not fine；But when thiourea derivative excess is added since the amount of NaOH also increases
Add, the alkalinity of solution influences the stability of complex instead, so that nickel ion content starts to increase in raffinate.So this hair
In the complexation process of bright selection N, N- diethyl-N '-fluorine substituted benzoyl thiocarbamide and nickel ion, N, N- diethyl-is added
The quality and nickel ion mass ratio of N '-fluorine substituted benzoyl thiocarbamide are 7~15:1, preferably 9~12:1.
3, the measurement of N, N- diethyl-N '-fluorine substituted benzoyl thiocarbamide rate of recovery
6mol/L hydrochloric acid will be sequentially added in filter residue obtained in test 2, complex is substantially complete when pH value of solution is lower than 2.5
Complete solution is from the nickel ion after dissociation enters solution, can further concentration and recovery nickel.And N, N- diethyl-N '-fluorine substituted benzoyl
The acylthioureas precipitating reagent then Precipitation again due to being insoluble in water in acid condition, is filtered, is dried, is weighed,
Calculate the rate of recovery of precipitating reagent:
The rate of recovery=(recycling acylthioureas quality/addition acylthioureas quality) × 100%
It the results are shown in Table 4.
The 4 acylthioureas rate of recovery of table
It can be seen that N in each group experiment, N- diethyl-N '-fluorine substituted benzoyl from the data collection of 4 acylthioureas of table
The rate of recovery of acylthioureas is more satisfactory, reaches as high as 76.6%, minimum also to reach 61.8%, comprehensively considers precipitating reagent use
More excellent, the rate of recovery base of acylthioureas precipitating reagent is matched in amount, removal effect, the acid-base property of waste liquid after processing, 3,4,5 groups of experiments
This stabilization illustrates that the method can not only handle nickel-containing waste water well 70% or so, but also can realize nickel and precipitating reagent very
Good separation, can substantially reduce operating cost.
4, the influence of acidity
Due to N, N- diethyl-N '-fluorine substituted benzoyl thiocarbamide is soluble in alkali, pH higher, after being mixed with nickel waste water,
The variation of N-H proton can all make pH of mixed relative reduction, this point on thiourea group when solution is diluted and is complexed with nickel
Has embodiment in table 3, and as can be seen from Table 3: the amount ratio of acylthioureas and nickel ion filtrate within the scope of 7~14:1
Middle residual nickel ion concentration is far below national emission standard, and at this time the pH of mixed liquor between 7.0~8.5, peracid or
It is all less desirable for sedimentation effect to cross alkali, pH is too low, and not exclusively, pH is too high for complexing, and Stability of Metal Complexes reduces, therefore,
It can be concluded that the Optimal pH of N, N- diethyl-N '-fluorine substituted benzoyl thiocarbamide precipitating nickel ions is between 7.0~8.5, and
The treatment fluid of the range can not acidified direct emission.
Claims (7)
- Application of 1.N, N- diethyl-N '-fluorine substituted benzoyl thiocarbamide in nickel waste water processing, the N, N- diethyl- The structural formula of N '-fluorine substituted benzoyl thiocarbamide are as follows:
- 2. N according to claim 1, N- diethyl-N '-fluorine substituted benzoyl thiocarbamide answering in nickel waste water processing With, it is characterised in that: by N, after N- diethyl-N '-fluorine substituted benzoyl thiocarbamide is completely dissolved with NaOH aqueous solution, it is added Into nickel waste water, 20~40min is stirred, aluminium polychloride and polyacrylamide is then added, is stirred for 20~40min；Then Reaction solution is stood 10~20 hours, filtering, filtrate direct emission, filter residue will dissociate again after being adjusted with acid pH to 1.5~2.5 For nickel ion and N, N- diethyl-N '-fluorine substituted benzoyl thiocarbamide, the nickel ion recycling dissociateed, the N dissociateed, N- Diethyl-N '-fluorine substituted benzoyl thiocarbamide is insoluble in water and Precipitation, is reused after filtering.
- 3. N according to claim 2, N- diethyl-N '-fluorine substituted benzoyl thiocarbamide answering in nickel waste water processing With, it is characterised in that: the N of the quality of nickel ion and addition in the nickel waste water, N- diethyl-N '-fluorine substituted benzoyl sulphur The mass ratio of urea is 1:7~15.
- 4. N according to claim 3, N- diethyl-N '-fluorine substituted benzoyl thiocarbamide answering in nickel waste water processing With, it is characterised in that: the N of the quality of nickel ion and addition in the nickel waste water, N- diethyl-N '-fluorine substituted benzoyl The mass ratio of thiocarbamide is 1:9~12.
- 5. N- diethyl-N '-fluorine substituted benzoyl thiocarbamide is useless in nickel according to N described in claim 2~4 any one Application in water process, it is characterised in that: the quality of nickel ion and the aluminium polychloride of addition and polypropylene in the nickel waste water The ratio between gross mass of amide is 1:1 × 10-5~3 × 10-5。
- 6. N according to claim 5, N- diethyl-N '-fluorine substituted benzoyl thiocarbamide answering in nickel waste water processing With, it is characterised in that: the mass ratio of the aluminium polychloride and polyacrylamide is 1:0.5~2.
- 7. N according to claim 2, N- diethyl-N '-fluorine substituted benzoyl thiocarbamide answering in nickel waste water processing With, it is characterised in that: the acid is hydrochloric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810734079.9A CN109133296B (en) | 2018-07-06 | 2018-07-06 | Application of N, N-diethyl-N' -m-fluoro substituted benzoyl thiourea in nickel wastewater treatment |
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|---|---|---|---|
| CN201810734079.9A CN109133296B (en) | 2018-07-06 | 2018-07-06 | Application of N, N-diethyl-N' -m-fluoro substituted benzoyl thiourea in nickel wastewater treatment |
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| CN109133296A true CN109133296A (en) | 2019-01-04 |
| CN109133296B CN109133296B (en) | 2023-08-15 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4571265A (en) * | 1983-11-05 | 1986-02-18 | Degussa Aktiengesellschaft | Process for separation and purification of platinum group metals (II) |
| US4980071A (en) * | 1988-11-19 | 1990-12-25 | Degussa Aktiengesellschaft | Substituted thioureas for the separation of complexly bound heavy-metal ions |
| WO2000047556A1 (en) * | 1999-02-08 | 2000-08-17 | University College Cork | Complexing agents |
-
2018
- 2018-07-06 CN CN201810734079.9A patent/CN109133296B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4571265A (en) * | 1983-11-05 | 1986-02-18 | Degussa Aktiengesellschaft | Process for separation and purification of platinum group metals (II) |
| US4980071A (en) * | 1988-11-19 | 1990-12-25 | Degussa Aktiengesellschaft | Substituted thioureas for the separation of complexly bound heavy-metal ions |
| WO2000047556A1 (en) * | 1999-02-08 | 2000-08-17 | University College Cork | Complexing agents |
Non-Patent Citations (1)
| Title |
|---|
| 庞海霞: "酰基硫脲及其配合物的合成、晶体结构及阴离子识别研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
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