CN106830268A - Method for reducing hexavalent chromium by using thiocyanide enhanced sulfite - Google Patents
Method for reducing hexavalent chromium by using thiocyanide enhanced sulfite Download PDFInfo
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- CN106830268A CN106830268A CN201710140522.5A CN201710140522A CN106830268A CN 106830268 A CN106830268 A CN 106830268A CN 201710140522 A CN201710140522 A CN 201710140522A CN 106830268 A CN106830268 A CN 106830268A
- Authority
- CN
- China
- Prior art keywords
- rhodanide
- hexavalent chromium
- sulphite
- sulfite
- strengthens
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 25
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 title claims abstract description 23
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 title claims abstract description 11
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 title claims abstract description 7
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 title abstract description 5
- 239000011651 chromium Substances 0.000 claims abstract description 69
- 239000002351 wastewater Substances 0.000 claims abstract description 16
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 8
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 230000009467 reduction Effects 0.000 claims description 12
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 10
- 235000010265 sodium sulphite Nutrition 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 claims description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052804 chromium Inorganic materials 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 6
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 239000010865 sewage Substances 0.000 abstract description 3
- 239000013067 intermediate product Substances 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 231100000331 toxic Toxicity 0.000 abstract 1
- 230000002588 toxic effect Effects 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- -1 sulfate radical Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000003651 drinking water Substances 0.000 description 3
- 235000020188 drinking water Nutrition 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 231100000315 carcinogenic Toxicity 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- ZVCDLGYNFYZZOK-UHFFFAOYSA-M sodium cyanate Chemical class [Na]OC#N ZVCDLGYNFYZZOK-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- 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
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention relates to the field of hexavalent chromium sewage treatment, in particular to a method for reducing hexavalent chromium by utilizing thiocyanide reinforced sulfite. Adding a proper amount of sulfite reducing agent and trace amount of thiocyanide according to the concentration of the wastewater solution containing Cr (VI), and adding inorganic acid to adjust the pH value, so as to reduce the highly toxic Cr (VI) into Cr (III) at normal temperature and pressure. In the process, SCN‑The complex can be complexed with Cr (VI) and chromium intermediate products, and the complex is beneficial to quickly converting Cr (VI) into Cr (III) and simultaneously inhibits the generation of strong oxidative free radicals in the process, thereby reducing the consumption of sulfite and reducing the treatment cost of Cr (VI) containing wastewater.
Description
Technical field
It is more particularly to a kind of using rhodanide reinforcing sulphite reduction the present invention relates to Cr VI sewage treatment area
The method of Cr VI.
Background technology
The compound of heavy metal chromium is widely used in the industries such as metallurgical, plating, process hides and organic synthesis, due to useless containing chromium
The leakage of water and unreasonable discharge cause serious potential safety hazard to underground water and drinking water source.Chromium is main in water body environment
With Cr (VI) and the existence form of Cr (III).Different its existence form difference of its existence form cause chromium ion physico
Learn the aspects such as characteristic, chemism and bio-toxicity and show greatest differences.For example, Cr (III) is micro unit needed by human
Element, its transfer ability in natural water environment is weaker.However, Cr (VI) have strong oxidizing property, hypertoxicity, strong animal migration and
The features such as carcinogenic aberration inducing acts on strong, its toxicity is 10-100 times of Cr (III), is internationally recognized 3 kinds of carcinogenic metal objects
One of.The water quality standard for drinking water that the World Health Organization and European Union formulate, the greatest contamination limit value of chromium is in regulation drinking water
0.05mg/L.Therefore it is very urgent for the treatment containing high chromium concentration industrial wastewater.
At present, the method that chromate waste water is administered both at home and abroad is more, mainly there is ion exchange technique, membrane separation technique, absorption
Facture, electric flocculation method, photocatalytic method and chemical reduction method etc., wherein chemical reduction method is low for equipment requirements, processes water
It is widely used greatly.Sulphite (E0 (SO42-/SO2)=0.158VNHE) is a kind of strong reductant, is commonly used for containing Cr
(VI) industrial wastewater and the in-situ immobilization of Cr (VI) pollutions.But in the process, sulphite consumption is big, processes it
Expense is of a relatively high.Therefore, in order to realize low cost to the treatment containing Cr (VI) trade effluent, urgent need develop it is a kind of it is cheap,
Efficient Cr (VI) chemical treatment method.
The content of the invention
According to above the deficiencies in the prior art, the present invention provides a kind of using rhodanide reinforcing sulphite reduction sexavalence
The method of chromium, micro rhodanide is added to while adding appropriate sulfite reducing agent in the sewage containing Cr (VI), and
Inorganic acid for adjusting pH value is added, hypertoxicity Cr (VI) is reduced into Cr (III) at normal temperatures and pressures；The presence of the rhodanide can
The also commercial weight of Cr (VI) is greatly improved, while the consumption of sulphite is reduced, so as to reduce being processed into containing Cr (VI) waste water
This.
The technical scheme is that：A kind of method that utilization rhodanide strengthens sulphite reduction of hexavalent chromium, according to
Cr (VI) concentration of waste water solution containing Cr (VI) adds micro rhodanide while adding appropriate sulfite reducing agent,
And inorganic acid for adjusting pH value is added, hypertoxicity Cr (VI) is reduced into Cr (III) by realization at normal temperatures and pressures.
Wherein, preferred scheme is as follows：
Described rhodanide, can be sodium sulfocynanate, potassium rhodanate or ammonium thiocyanate in one or more
Mixture.
Described sulphite, can be sodium sulfite and/or sodium pyrosulfite.
Described Cr (VI) is 1-100 with rhodanide mol ratio.
Described sulphite is 6-20 with Cr (VI) mol ratio.
Described use inorganic acid adjusts to 1-6 pH value, wherein, described inorganic acid is sulfuric acid or hydrochloric acid.
The principle of invention：
Industrially, the chemical agent for being usually used in Cr (VI) reduction treatment is the sulphite with reduction-state, traditional Cr
(VI) treatment is that redox reaction, such as formula occur with 1/2~3/2 ratio under strongly acidic conditions using reducing agent sulphite
(1,2)。
4CrO4-+6NaHSO3+3H2SO4+8H+→2Cr2(SO4)3+3Na2SO4+10H2O (1)
2CrO4-+4HSO3-+6H+→2Cr3++S2O6 2-+6H2O+2SO4 2- (2)
The present invention is improved on traditional Cr (VI) treatment technology, micro containing SCN by adding-Rhodanide
As the hardening agent of sulphite reduction Cr (VI).SCN-Presence can be complexed with the intermediate product of Cr (VI) and chromium, its network
Compound contributes to Cr (VI) to be rapidly converted into Cr (III), while suppress the generation of strong oxidizing property free radical during this, so as to subtract
The consumption of few sulphite, reduces the processing cost containing Cr (VI) waste water.
Advantage for present invention is：
(1) hardening agent of Cr (VI) is reduced as sulphite by adding micro rhodanide, water body will not be produced
Raw secondary pollution.
(2) hardening agent of Cr (VI) is reduced as sulphite by adding micro rhodanide, Cr is greatly improved
(VI) also commercial weight, and the consumption of sulphite is reduced, so as to reduce the processing cost containing Cr (VI) waste water.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
The accompanying drawing to be used needed for having technology description is briefly described.
Fig. 1 is Cr (VI) change in concentration schematic diagram of embodiment 1；
Fig. 2 is Cr (VI) change in concentration schematic diagram of embodiment 2；
Fig. 3 is Cr (VI) change in concentration schematic diagram of embodiment 3；
Fig. 4 is Cr (VI) change in concentration schematic diagram of comparative example 1.
Specific embodiment
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, to the technology in the embodiment of the present invention
Scheme is clearly and completely described, it is clear that described embodiment is a part of embodiment of the invention, rather than whole
Embodiment.Based on the embodiment in the present invention, those of ordinary skill in the art are obtained under the premise of creative work is not made
The every other embodiment for obtaining, belongs to the scope of protection of the invention.
Embodiment 1：
In Cr (VI) concentration is for the waste water solution of 100uM, the sodium sulfite of 600uM and the sodium sulfocyanate of 30uM are added
(SCN), add sulfuric acid to adjust to 3.5 pH value, processed under normal temperature and pressure.Cr in waste water after 30min treatment
(VI) concentration is 9uM, and the consumption of inferior sulfate radical is 460uM, and Δ [inferior sulfate radical]/Δ [Cr (VI)] is 5.1, sulphur during this
Zassol is not consumed, as shown in Figure 1.
Embodiment 2：
In Cr (VI) concentration is for the waste water solution of 100uM, the sodium sulfite of 600uM concentration and the thiocyanic acid of 30uM are added
Sodium, adds sulfuric acid and adjusts to 2.5,3.5,4.5,5.5 pH value, is processed under normal temperature and pressure.After 30min treatment
Cr (VI) concentration is reduced to 0uM, 9uM, 59uM, 48uM respectively in waste water, as shown in Figure 2.
Embodiment 3：
It is 50uM in Cr (VI) concentration, in the waste water solution of 100uM, 200uM, 300uM, adds the sulfurous of 600uM concentration
The sodium sulfocyanate of sour sodium and 30uM, adds sulfuric acid and adjusts to 3.5 pH value, is processed under normal temperature and pressure.At 30min
The treatment effect of Cr (VI) is as shown in Figure 3 in waste water after reason.
Comparative example 1：
In Cr (VI) concentration is for the waste water solution of 100uM, the sodium sulfite of 600uM is added, add sulfuric acid by pH value
Regulation is processed to 3.5 under normal temperature and pressure.Cr (VI) concentration is 63uM, inferior sulfate radical in waste water after 30min treatment
Consumption be 600uM, Δ [inferior sulfate radical]/Δ [Cr (VI)] be 16, as shown in Figure 4.
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example
Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art is not departing from principle of the invention and objective
In the case of above-described embodiment can be changed within the scope of the invention, change, replace and modification.
Claims (6)
1. a kind of method that utilization rhodanide strengthens sulphite reduction of hexavalent chromium, it is characterised in that：According to containing Cr (VI)
Cr (VI) concentration of waste water solution add micro rhodanide while add sulfite reducing agent, and add inorganic acid to adjust
Section pH value, is reduced into Cr (III) by hypertoxicity Cr (VI) at normal temperatures and pressures.
2. the method that a kind of described utilization rhodanide strengthens sulphite reduction of hexavalent chromium, its feature are required according to right 1
It is：Described rhodanide, is one or more the mixture in sodium sulfocynanate, potassium rhodanate or ammonium thiocyanate.
3. the method that a kind of described utilization rhodanide strengthens sulphite reduction of hexavalent chromium, its feature are required according to right 1
It is：Described sulphite, is sodium sulfite or sodium pyrosulfite.
4. the method that a kind of described utilization rhodanide strengthens sulphite reduction of hexavalent chromium, its feature are required according to right 1
It is：Described Cr (VI) is 1-100 with rhodanide mol ratio.
5. the method that a kind of described utilization rhodanide strengthens sulphite reduction of hexavalent chromium, its feature are required according to right 1
It is：Described sulphite is 6-20 with Cr (VI) mol ratio.
6. the method that a kind of described utilization rhodanide strengthens sulphite reduction of hexavalent chromium, its feature are required according to right 1
It is：PH value is adjusted to 1-6 using inorganic acid, wherein, described inorganic acid is sulfuric acid or hydrochloric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710140522.5A CN106830268A (en) | 2017-03-10 | 2017-03-10 | Method for reducing hexavalent chromium by using thiocyanide enhanced sulfite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710140522.5A CN106830268A (en) | 2017-03-10 | 2017-03-10 | Method for reducing hexavalent chromium by using thiocyanide enhanced sulfite |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106830268A true CN106830268A (en) | 2017-06-13 |
Family
ID=59144941
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710140522.5A Pending CN106830268A (en) | 2017-03-10 | 2017-03-10 | Method for reducing hexavalent chromium by using thiocyanide enhanced sulfite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106830268A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109879616A (en) * | 2019-03-25 | 2019-06-14 | 浙江红狮环保股份有限公司 | A kind of method of cement kiln synergic processing waste containing chromium |
| CN110330155A (en) * | 2019-08-13 | 2019-10-15 | 东北大学 | A kind of method of electrolysis-complexing sulfuric acid pickling waste liquid extraction and recovery chromium |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070261A (en) * | 2009-11-24 | 2011-05-25 | 中国航空工业标准件制造有限责任公司 | Hexavalent chromium-containing waste water treatment method |
| CN104310569A (en) * | 2014-11-10 | 2015-01-28 | 中国石油大学(华东) | Method for water treatment oxidation by using Cr (VI)/SO32 |
| CN105776444A (en) * | 2016-04-25 | 2016-07-20 | 青岛理工大学 | Method for strengthening Cr (VI) electroreduction by using small-molecular organic acid |
| CN105858973A (en) * | 2016-06-14 | 2016-08-17 | 沧州泓海化工有限公司 | Hexavalent-chromium wastewater treatment technology |
-
2017
- 2017-03-10 CN CN201710140522.5A patent/CN106830268A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070261A (en) * | 2009-11-24 | 2011-05-25 | 中国航空工业标准件制造有限责任公司 | Hexavalent chromium-containing waste water treatment method |
| CN104310569A (en) * | 2014-11-10 | 2015-01-28 | 中国石油大学(华东) | Method for water treatment oxidation by using Cr (VI)/SO32 |
| CN105776444A (en) * | 2016-04-25 | 2016-07-20 | 青岛理工大学 | Method for strengthening Cr (VI) electroreduction by using small-molecular organic acid |
| CN105858973A (en) * | 2016-06-14 | 2016-08-17 | 沧州泓海化工有限公司 | Hexavalent-chromium wastewater treatment technology |
Non-Patent Citations (2)
| Title |
|---|
| BO JIANG 等: "The roles of polycarboxylates in Cr(VI)/sulfite reaction system:Involvement of reactive oxygen species and intramolecular electrontransfer", 《JOURNAL OF HAZARDOUS MATERIALS》 * |
| KATHARINE A.MUIRHEAD等: "Kinetics and Mechanism of the Oxidation of Thiocyanate Ion by Chromium(VI)", 《INORGANIC CHEMISTRY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109879616A (en) * | 2019-03-25 | 2019-06-14 | 浙江红狮环保股份有限公司 | A kind of method of cement kiln synergic processing waste containing chromium |
| CN110330155A (en) * | 2019-08-13 | 2019-10-15 | 东北大学 | A kind of method of electrolysis-complexing sulfuric acid pickling waste liquid extraction and recovery chromium |
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Application publication date: 20170613 |