CN101891295A - Liquid-phase catalytical processing method for hexavalent chromium in water - Google Patents
Liquid-phase catalytical processing method for hexavalent chromium in water Download PDFInfo
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- CN101891295A CN101891295A CN201010160619.0A CN201010160619A CN101891295A CN 101891295 A CN101891295 A CN 101891295A CN 201010160619 A CN201010160619 A CN 201010160619A CN 101891295 A CN101891295 A CN 101891295A
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- hexavalent chromium
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000007791 liquid phase Substances 0.000 title claims abstract description 17
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 title abstract description 25
- 238000003672 processing method Methods 0.000 title abstract 2
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 11
- 238000006722 reduction reaction Methods 0.000 claims description 12
- 239000010970 precious metal Substances 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims 1
- 239000003344 environmental pollutant Substances 0.000 abstract description 16
- 231100000719 pollutant Toxicity 0.000 abstract description 16
- 238000006731 degradation reaction Methods 0.000 abstract description 15
- 230000015556 catabolic process Effects 0.000 abstract description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000593 degrading effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000004408 titanium dioxide Substances 0.000 abstract description 3
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 38
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000011651 chromium Substances 0.000 description 13
- 229910052804 chromium Inorganic materials 0.000 description 11
- 238000010531 catalytic reduction reaction Methods 0.000 description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 8
- 239000008399 tap water Substances 0.000 description 5
- 235000020679 tap water Nutrition 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 4
- 230000012010 growth Effects 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000007886 mutagenicity Effects 0.000 description 1
- 231100000299 mutagenicity Toxicity 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
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- Treatment Of Water By Oxidation Or Reduction (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a liquid-phase catalytical processing method for hexavalent chromium in water. The method comprises the steps of: adding a supported noble metal titanium dioxide catalyst into water which contains a pollutant, namely hexavalent chromium; adjusting the pH value to be between 1 and 3; and then introducing hydrogen to perform degradation reaction. The liquid-phase hydrogenation catalytical degradation method for the hexavalent chromium has the advantages of remarkable degradation effect, high hexavalent chromium degrading efficiency, high speed, technical feasibility, simple operation and easy implementation.
Description
Technical field
The invention belongs to technical field of drinking water treatment, relate to the removal method of heavy metal ion in the water body, particularly relate to a kind of liquid-phase catalysis and handle chromic method in the water body.
Background technology
Chromium is ubiquitous heavy metal in a kind of natural water body, and the main form that exists has sexavalent chrome and trivalent chromium.Wherein, chromic toxicity is bigger 100 times than trivalent chromium.Studies show that sexavalent chrome has carcinogenesis, is one of 129 kinds of dangerous pollutants of Environmental Protection Agency (EPA) affirmation.The source of chromium mainly is divided into two portions, and the people is mainly derived from the trade effluent that is discharged in the industries such as process hides, plating and weaving for pollution of chromium, and the chromium of occurring in nature is mainly derived from table soil and rock and progressively is discharged into chromium in the water.
Sexavalent chrome all has certain influence to the growth of various biologies.The growth of drop hexavalent chromium energy stimulating plant, excessive sexavalent chrome then can suppress the growth of plant; Chromium also has certain influence to hydrobiological growth, and the sexavalent chrome of high density can be poisoned hydrobiont, and sexavalent chrome also can pass through the food chain enrichment, further influences human beings'health; In a single day sexavalent chrome is absorbed by the body, and can poison each organ of human body, as kidney, liver and stomach etc.In addition, sexavalent chrome also has mutagenicity, the sexavalent chrome of high density even can cause cancer.
For these reasons, countries in the world have been worked out chromic control criterion one after another.Chromic maximum acceptable concentration is 0.05 mg/L in Environmental Protection Agency (EPA) the regulation tap water.And the drinking water sanitary standard of China stipulates that also chromic content can not surpass 0.05 mg/L in the tap water.
Chromic treatment process commonly used at present mainly comprises chemical reduction method, absorption method and ion exchange method etc., and it is big that these methods are handled capacity, and effluent quality is good, but aforesaid each method all has certain limitation, big as energy consumption, speed of reaction is slow, has secondary pollution etc.How to solve hexavalent chromium pollutedly cost-effectively, reach the environmental safety requirement, be still the focus that present research is paid close attention to.
The chromic method of liquid-phase hydrogenatin catalytic reduction that the present invention proposes, to hexavalent chrome reduction efficient height, speed is fast, the feasibility that possesses skills, and simple to operate.This method is used for chromic processing and does not appear in the newspapers as yet.
Summary of the invention
The purpose of this invention is to provide a kind of method of simple, effective hexavalent chrome reduction, can effectively handle in the water body, particularly the hexavalent chromium that exists in the tap water.
The technical solution used in the present invention is as follows:
A kind of liquid-phase catalysis is handled chromic method in the water body, adds the carried noble metal titanium deoxide catalyst in containing chromic water body, regulates pH value to 1～3 of water body, feeds hydrogen then and carry out reduction reaction in water body.After degraded (reduction) reacted completely, the sexavalent chrome in the water was converted into trivalent chromium fully, thereby reached the purpose of handling hexavalent chromium pollutant in the water body.
The present invention can directly handle the water body that contains hexavalent chromium pollutant, particularly contains hexavalent chromium polluted tap water, wherein contains in the water body of hexavalent chromium pollutant, and the starting point concentration of hexavalent chromium pollutant (in chromium metal) is 10～200mg/L.
The catalyzer that the present invention adopts is the carried noble metal titanium deoxide catalyst, and wherein precious metal is Pd, Pt or Rh, is preferably Pd or Pt.The charge capacity of precious metal is 1%～5% of a catalyst quality.The preparation method of carried noble metal titanium deoxide catalyst can adopt the light deposition method, promptly earlier carrier is mixed with precious metal salt solution, reduces under the UV illumination condition then.Precious metal salt solution is generally the aqueous solution of muriate, nitrate or the vitriol of metal.When titanium dioxide mixed with precious metal salt solution, making wherein, the quality of precious metal accounted for 1%～5% of catalyzer total amount; Recovery time is 2～5h, preferred 3～4h; The catalyzer that reduction obtains leaves in the moisture eliminator standby.
The usage quantity of described catalyzer is counted 0.01～0.5g/L with the volume of handling water body, is preferably 0.05～0.5g/L.
DeR needs to carry out under pH value is 1～3 condition, and preferably the pH value is 1～2.Adjusting to the pH value can be adopted acid commonly used or alkali, mineral acid or mineral alkalis such as sodium hydroxide, potassium hydroxide such as example hydrochloric acid, sulfuric acid.
DeR condition of the present invention is simple, only needs usually can carry out at normal temperatures and pressures.Certainly, also can suitably adjust temperature of reaction, as in 20～40 ℃ of scopes, perhaps conditioned reaction pressure suitably can reach purpose of the present invention equally.
The present invention adopts hydrogen as reductive agent, feeds hydrogen with the hexavalent chromium pollutant in the reduction water body in water body.The flow velocity that feeds hydrogen can determine according to actual needs that preferred flow velocity is 20～60ml/min.
The time of DeR can be along with the kind and the usage quantity of pollutent starting point concentration, catalyzer, and the difference of the conditions such as flow velocity of hydrogen is and different, and degradation effect improves along with the growth of time generally speaking, and the preferred time of adopting is 5min～2h.Can adopt spectrophotometer to measure with reacted hexavalent chromium concentration before the reaction.
The present invention is a catalyzer with carried noble metal titanium dioxide, by hexavalent chromium pollutant in the hydrogenation catalyst reduction water body.Under the condition that the titanium deoxide catalyst of noble metal support exists, hydrogen is three prices as reductive agent with hexavalent chrome reduction.The present invention provides a valid approach for chromic degraded, can solve problem hexavalent chromium polluted in the water body effectively.
The chromic method of liquid-phase hydrogenatin catalytic reduction that the present invention proposes shows significant degradation effect, and to six-valent chromium degrading efficient height, speed is fast, the feasibility that possesses skills, and simple to operate, be easy to realize.The sexavalent chrome that the inventive method is used for reducing in the water body, particularly tap water has good economy and environmental benefit.
Describe the present invention below in conjunction with embodiment.Scope of the present invention is not exceeded with embodiment, but is limited by the scope of claim.
Embodiment
Embodiment 1
Pd/TiO with Pd charge capacity 1%
2As catalyzer, the sexavalent chrome in the liquid-phase hydrogenatin catalytic reduction water.Catalyst concn is 0.05g/L, and the starting point concentration of hexavalent chromium pollutant is 20mg/L in the water, and pH value in reaction is 2, and hydrogen flow rate is 40ml/min, and normal temperature and pressure is reaction 30MIN down, and chromic degradation rate reaches 100%.
As seen the catalytic hydrogenating reduction sexavalent chrome is a kind of effective and feasible method.In present embodiment and following Comparative Examples or embodiment, degradation rate is meant the ratio of content of 6-valence Cr ions in content of 6-valence Cr ions that degraded removes and the initial water body.
Embodiment 2
Pd/TiO with Pd charge capacity 1%
2As catalyzer, the sexavalent chrome in the liquid-phase hydrogenatin catalytic reduction water.Catalyst concn is 0.05g/L, and the starting point concentration of hexavalent chromium pollutant is 50mg/L in the water, and pH value in reaction is 2, and hydrogen flow rate is 40ml/min, and normal temperature and pressure is reaction 50MIN down, and chromic degradation rate reaches 100%.
When the sexavalent chrome starting point concentration is higher, can reach degraded fully by prolonging the reaction times.
Embodiment 3
Pd/TiO with Pd charge capacity 1%
2As catalyzer, the sexavalent chrome in the liquid-phase hydrogenatin catalytic reduction water.Catalyst concn is 0.1g/L, and the starting point concentration of hexavalent chromium pollutant is 50mg/L in the water, and pH value in reaction is 2, and hydrogen flow rate is 40ml/min, and normal temperature and pressure is reaction 30MIN down, and chromic degradation rate reaches 100%.
As seen improve with catalyst concn, six-valent chromium degrading speed improves.
Embodiment 4
Pd/TiO with Pd charge capacity 1%
2As catalyzer, the sexavalent chrome in the liquid-phase hydrogenatin catalytic reduction water.Catalyst concn is 0.05g/L, and the starting point concentration of hexavalent chromium pollutant is 100mg/L in the water, and pH value in reaction is 2, and hydrogen flow rate is 40ml/min, and normal temperature and pressure is reaction 70MIN down, and chromic degradation rate reaches 100%.
Embodiment 5
Pt/TiO with Pt charge capacity 1%
2As catalyzer, the sexavalent chrome in the liquid-phase hydrogenatin catalytic reduction water.Catalyst concn is 0.05g/L, and the starting point concentration of hexavalent chromium pollutant is 200mg/L in the water, and pH value in reaction is 1, and hydrogen flow rate is 60ml/min, and normal temperature and pressure is reaction 90MIN down, and chromic degradation rate reaches 100%.
Embodiment 6
Pd/TiO with Pd charge capacity 1%
2As catalyzer, the sexavalent chrome in the liquid-phase hydrogenatin catalytic reduction water.Catalyst concn is 0.05g/L, and the starting point concentration of hexavalent chromium pollutant is 100mg/L in the water, and pH value in reaction is 3, and hydrogen flow rate is 40ml/min, and normal temperature and pressure is reaction 120MIN down, and chromic degradation rate reaches 90%.
Embodiment 7
Pd/TiO with Pd charge capacity 2%
2As catalyzer, the sexavalent chrome in the liquid-phase hydrogenatin catalytic reduction water.Catalyst concn is 0.05g/L, and the starting point concentration of hexavalent chromium pollutant is 100mg/L in the water, and pH value in reaction is 2, and hydrogen flow rate is 40ml/min, and normal temperature and pressure is reaction 50MIN down, and chromic degradation rate reaches 100%.
The noble metal support amount is to the influence of hexavalent chrome reduction process, and usually, charge capacity is high more, and degradation rate is fast more.
Comparative Examples 1
Pd/TiO with Pd charge capacity 1%
2As catalyzer, the sexavalent chrome in the liquid-phase hydrogenatin catalytic reduction water.Catalyst concn is 0.05g/L, and the starting point concentration of hexavalent chromium pollutant is 100mg/L in the water, and pH value in reaction is 4, and hydrogen flow rate is 40ml/min, and normal temperature and pressure is reaction down, and chromic degradation rate reached 20% in two hours.
As seen the pH value is influential to the hexavalent chrome reduction process, and higher pH value is unfavorable for chromic reduction.
Claims (8)
1. a liquid-phase catalysis is handled chromic method in the water body, it is characterized in that adding the carried noble metal titanium deoxide catalyst in containing chromic water body, and regulates pH value to 1～3 of water body, feeds hydrogen then and carry out reduction reaction in water body.
2. method according to claim 1 is characterized in that described containing in the chromic water body, and chromic starting point concentration is 10～200mg/L.
3. method according to claim 1 is characterized in that in the described loaded noble metal catalyst that precious metal is Pd, Pt or Rh, and the charge capacity of precious metal is 1%～5% of a catalyst quality.
4. according to claim 1 or 3 described methods, the preparation method who it is characterized in that described carried noble metal titanium deoxide catalyst is the light deposition method.
5. according to claim 1 or 3 described methods, the usage quantity that it is characterized in that the carried noble metal titanium deoxide catalyst is 0.01～0.5g/L.
6. method according to claim 1 is characterized in that regulating pH value to 1～2 of water body.
7. method according to claim 1, the flow velocity that it is characterized in that feeding hydrogen is 20～60ml/min.
8. method according to claim 1, the time that it is characterized in that described DeR is 5min～2h.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101606190A CN101891295B (en) | 2010-04-30 | 2010-04-30 | Liquid-phase catalytical processing method for hexavalent chromium in water |
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| CN2010101606190A CN101891295B (en) | 2010-04-30 | 2010-04-30 | Liquid-phase catalytical processing method for hexavalent chromium in water |
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| CN101891295A true CN101891295A (en) | 2010-11-24 |
| CN101891295B CN101891295B (en) | 2012-06-27 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107282082A (en) * | 2017-06-15 | 2017-10-24 | 南京大学 | Loaded noble metal catalyst with clad structure and preparation method thereof and in Cr（Ⅵ）Application in liquid phase catalytic reduction |
| CN108970608A (en) * | 2018-07-18 | 2018-12-11 | 南京大学 | Loaded noble metal catalyst with clad structure and preparation method thereof and the application in Cu (II) liquid phase catalytic reduction |
| CN112387277A (en) * | 2020-12-11 | 2021-02-23 | 南京大学 | Method for catalytic hydrogenation reduction of algal toxins in water based on supported noble metal catalyst |
| CN113289690A (en) * | 2021-06-28 | 2021-08-24 | 长春工业大学 | Pd/UiO-66 catalyst and preparation method and application thereof |
| CN114634235A (en) * | 2022-03-19 | 2022-06-17 | 南京大学 | Application of polyaniline embedded Pt/CNT (carbon nanotube) based catalyst in treatment of Cr (VI) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09308891A (en) * | 1996-05-20 | 1997-12-02 | Japan Organo Co Ltd | Removal of selenium oxide in water |
| JPH09327694A (en) * | 1996-06-07 | 1997-12-22 | Japan Organo Co Ltd | Removal of arsenic in water |
-
2010
- 2010-04-30 CN CN2010101606190A patent/CN101891295B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09308891A (en) * | 1996-05-20 | 1997-12-02 | Japan Organo Co Ltd | Removal of selenium oxide in water |
| JPH09327694A (en) * | 1996-06-07 | 1997-12-22 | Japan Organo Co Ltd | Removal of arsenic in water |
Non-Patent Citations (2)
| Title |
|---|
| 《化学学报》 20050131 张青红等 高度分散的Pt/TiO2的制备及光催化活性 65－70 1－8 第63卷, 第1期 2 * |
| 《浙江理工大学学报》 20100131 刘阳等 紫外光原位还原法制备Pt/TiO2及其光催化性能研究 17－21 1-8 第27卷, 第1期 2 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107282082A (en) * | 2017-06-15 | 2017-10-24 | 南京大学 | Loaded noble metal catalyst with clad structure and preparation method thereof and in Cr（Ⅵ）Application in liquid phase catalytic reduction |
| CN107282082B (en) * | 2017-06-15 | 2020-04-28 | 南京大学 | Supported noble metal catalyst with coating structure, preparation method thereof and application thereof in Cr (VI) liquid phase catalytic reduction |
| CN108970608A (en) * | 2018-07-18 | 2018-12-11 | 南京大学 | Loaded noble metal catalyst with clad structure and preparation method thereof and the application in Cu (II) liquid phase catalytic reduction |
| CN112387277A (en) * | 2020-12-11 | 2021-02-23 | 南京大学 | Method for catalytic hydrogenation reduction of algal toxins in water based on supported noble metal catalyst |
| CN113289690A (en) * | 2021-06-28 | 2021-08-24 | 长春工业大学 | Pd/UiO-66 catalyst and preparation method and application thereof |
| CN114634235A (en) * | 2022-03-19 | 2022-06-17 | 南京大学 | Application of polyaniline embedded Pt/CNT (carbon nanotube) based catalyst in treatment of Cr (VI) |
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