CN107459164A - The recovery method of catalyst in a kind of CWO waste water - Google Patents
The recovery method of catalyst in a kind of CWO waste water Download PDFInfo
- Publication number
- CN107459164A CN107459164A CN201710641516.8A CN201710641516A CN107459164A CN 107459164 A CN107459164 A CN 107459164A CN 201710641516 A CN201710641516 A CN 201710641516A CN 107459164 A CN107459164 A CN 107459164A
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- Prior art keywords
- catalyst
- cwo
- recovery method
- waste water
- water according
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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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/18—Removal of treatment agents after treatment
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- 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)
- Catalysts (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a kind of recovery method of catalyst in CWO waste water, it is related to catalyst recovery technology field, comprises the following steps：Comprise the following steps：1. vulcanize：Water outlet to wet oxidation carries out vulcanizing treatment, generates sulfide precipitation and treatment fluid 1；2. adsorb：Treatment fluid 1 is adsorbed using resin, obtains polymeric adsorbent and treatment fluid 2；3. dissolve：Sulfide precipitation is put into acid solution and dissolved, it is stand-by to obtain lysate；4. elute：Polymeric adsorbent is eluted, it is stand-by to obtain eluent.Transition-metal catalyst, the rate of recovery such as the copper of the recyclable high concentration of the recovery method, manganese, zinc, cobalt, iron, nickel reduce heavy metal pollution up to more than 99%, save processing cost, and catalyst is regenerated in a manner of soluble-salt, convenient to recycle.
Description
Technical field
The present invention relates to catalyst recovery technology field, in particular to a kind of time of catalyst in CWO waste water
Receiving method.
Background technology
CWO refers under high temperature (200~280 DEG C), high pressure (2~8 MPa), with oxygen rich gas or oxygen
For oxidant, using the catalytic action of catalyst, accelerate useless haptoreaction between Organic substance in water and oxidant, make in waste water
Organic matter and it is oxidized to CO containing poisonous substances such as N, S2、N2、SO2、H2O, reach a kind of method of wastewater treatment of the purpose of purification.
CWO often by the use of transition metal such as copper, manganese, zinc, cobalt, iron, nickel as catalyst, is processed into reduce
Originally and heavy metal pollution is prevented, catalyst needs to be reclaimed, and traditional recovery method is alkali soluble dipping or strong acid after calcining
Adsorption/desorption is carried out with resin again after dissolving, its rate of recovery is relatively low, wherein simple resin adsorption desorption is not suitable for high concentration
The recovery of catalyst, adsorption-desorption operation are more frequent.
Applicant carried out beneficial exploration with regard to catalyst recovery, and had applied for Patents, if application publication number is CN
104876380 A Chinese invention patent discloses the recovery method of a kind of organic copper-containing wastewater processing of high concentration and copper, and it is adopted
Catalyst copper further is reclaimed with resin after being precipitated with liquid caustic soda and/or sulfide, but is reclaimed without specific description
The operating condition of method；And to disclose a kind of high concentration organic for the Chinese invention patent that application publication number is the A of CN 105858954
The processing method of waste water, copper catalyst is reclaimed after resin with after sulfide removal after wet oxidation, resin selects HYC-100, satisfies
Parsed with resin with dilute sulfuric acid, desorbed solution regeneration mantoquita, also without the specific regeneration of explanation.
The content of the invention
Present invention aim to provide a kind of recovery method of catalyst, for reclaiming in CWO waste water
Copper, manganese, zinc, cobalt, iron, the transition-metal catalyst such as nickel, the present invention can reclaim more than 99% copper in wet oxidation water outlet,
The transition metal such as manganese, zinc, cobalt, iron, nickel, and the content of transition metal can be reduced to below discharge standard, catalyst regeneration
Recycled for soluble-salt, economized on resources while reducing heavy metal pollution.
The recovery method of catalyst, comprises the following steps in a kind of CWO waste water：
1. vulcanize：Water outlet to CWO carries out vulcanizing treatment, generates sulfide precipitation and treatment fluid 1；
2. adsorb：Treatment fluid 1 is adsorbed using resin, obtains the resin and treatment fluid 2 of adsorption saturation；
3. dissolve：Sulfide precipitation is put into acid solution and dissolved, it is stand-by to obtain lysate；
4. elute：The resin of adsorption saturation is eluted, it is stand-by to obtain eluent；
Step sequencing in the application also can be：Vulcanization, dissolving, absorption, elution or vulcanization, absorption, elution, dissolving, should
Order is to the effect of recovery method without materially affect.
Levels of transition metals is about 200 ~ 2000ppm in the water outlet of usual wet oxidation, the mistake of the treatment fluid 1 after vulcanization
Cross tenor and be typically about 10 ~ 50ppm, the levels of transition metals for the treatment of fluid 2 through absorption can then be down to below 0.5ppm, reach
Discharge standard.
As the preferred of above-mentioned technical proposal, step 1. in, the water outlet of wet oxidation is carried out using dissolvable sulfide
The mol ratio of vulcanizing treatment, dissolvable sulfide and transition metal in water outlet is 0.5:1~2:1.As the excellent of above-mentioned technical proposal
Choosing, step 1. in obtained sulfide precipitation before being dissolved, be rinsed first with water.
As the preferred of above-mentioned technical proposal, step 2. in, adsorbed using macroreticular resin.
As the preferred of above-mentioned technical proposal, step 2. in, flow velocity during absorption is 0.5 ~ 5Bv/h.
As the preferred of above-mentioned technical proposal, step 3. in, the acid solution is that the mixing of sulfuric acid and hydrogen peroxide is molten
Liquid.
As the preferred of above-mentioned technical proposal, step 3. in, the sulfide precipitation and the acid solution reclaimed water, sulphur
The molar ratio of acid and hydrogen peroxide is 1:18:1:2~1:21:3:4.
As the preferred of above-mentioned technical proposal, step 3. in, the sulfide precipitation thing is put into the aqueous solution of sulfuric acid
Dissolved, solution temperature is 10 ~ 90 DEG C；When solution temperature is risen to, hydrogen peroxide is put into the aqueous solution of sulfuric acid in batches,
Every batch of dosage is not higher than the 10% of the total dosage of hydrogen peroxide, until the sulfide precipitation thing dissolves.
As the preferred of above-mentioned technical proposal, step 4. in, polymeric adsorbent is eluted using acidic aqueous solution.
As the preferred of above-mentioned technical proposal, step 4. in, use mass fraction for 2 ~ 30% sulfuric acid, hydrochloric acid or nitric acid
In a kind of polymeric adsorbent is eluted.
The present invention compared with prior art, has advantages below and beneficial effect：
（1）The transition metal such as the copper of the recyclable high concentration of recovery method of catalyst of the present invention, manganese, zinc, cobalt, iron, nickel
Catalyst, the rate of recovery is up to more than 99%；
（2）The recovery method of catalyst of the present invention reduces heavy metal pollution, while saves processing cost；
（3）The recovery method of catalyst of the present invention is by transition metal such as catalyst copper, manganese, zinc, cobalt, iron, nickel through processing
After be converted into soluble-salt, be easy to reuse.
Embodiment
With reference to specific embodiment, the present invention is described in further detail（Catalyst is represented with M in form）：
In water outlet after CWO processing, the copper content of embodiment 1 ~ 3 is about 500ppm；The copper content of embodiment 4 and 5
For 2000ppm；The iron-holder of embodiment 6 is 1000ppm；The zinc content of embodiment 7 is 1000ppm.
Embodiment 1 ~ 7 is using deionized water cleaning sulfide precipitation, and adsorbed using macroreticular resin, every batch of dioxygen
Water interval of adding is 10 minutes.
The technological parameter of 1 ~ embodiment of embodiment 7 is shown in Table 1：
The technological parameter of the 1 ~ embodiment of embodiment 7 of table 1
The treatment fluid index of 1 ~ embodiment of embodiment 7 is shown in Table 2：
The treatment fluid index of the 1 ~ embodiment of embodiment 7 of table 2
As shown in Table 2, in the recovery method of herein described catalyst, the recovery of the transition metal such as copper, manganese, zinc, cobalt, iron, nickel
Rate is up to more than 99%, and the content of the transition metal such as copper, manganese, zinc, cobalt, iron, nickel is reachable respectively in lysate and eluent
54000 ~ 60000ppm and 24000 ~ 28000ppm, the rate of recovery is high and recovery is convenient and swift；Simultaneously the copper for the treatment of fluid 2, manganese, zinc,
The levels of transition metals such as cobalt, iron, nickel are less than 0.5ppm, meet discharge standard.
Claims (10)
1. the recovery method of catalyst in a kind of CWO waste water, it is characterised in that comprise the following steps：
1. vulcanize：Water outlet to CWO carries out vulcanizing treatment, generates sulfide precipitation and treatment fluid 1；
2. adsorb：Treatment fluid 1 is adsorbed using resin, obtains the resin and treatment fluid 2 of adsorption saturation；
3. dissolve：Sulfide precipitation is put into acid solution and dissolved, it is stand-by to obtain lysate；
4. elute：The resin of adsorption saturation is eluted, it is stand-by to obtain eluent；
Step sequencing in the application also can be：Vulcanization, dissolving, absorption, elution or vulcanization, absorption, elution, dissolving, should
Order is to the effect of recovery method without materially affect.
2. the recovery method of catalyst in a kind of CWO waste water according to claim 1, it is characterised in that：Step
Suddenly 1. in, vulcanizing treatment, dissolvable sulfide and transition in water outlet are carried out to the water outlet of wet oxidation using dissolvable sulfide
The mol ratio of metal is 0.5:1~2:1, vulcanized sodium, NaHS, potassium sulfide, sulphur hydrogenation may be selected in the dissolvable sulfide
One or more in potassium, vulcanization ammonia.
3. the recovery method of catalyst, its feature exist in a kind of CWO waste water according to claim 1 or 2
In：Step 1. in obtained sulfide precipitation before being dissolved, be rinsed first with water.
4. the recovery method of catalyst in a kind of CWO waste water according to claim 1, it is characterised in that：Step
Suddenly 2. in, adsorbed using macroreticular resin.
5. the recovery method of catalyst in a kind of CWO waste water according to claim 4, it is characterised in that：Step
Suddenly 2. in, flow velocity during absorption is 0.5-5Bv/h.
6. the recovery method of catalyst in a kind of CWO waste water according to claim 1, it is characterised in that：Step
Suddenly 3. in, the acid solution is the mixed solution of sulfuric acid and hydrogen peroxide.
7. the recovery method of catalyst in a kind of CWO waste water according to claim 6, it is characterised in that：Step
Suddenly 3. in, the molar ratio of the sulfide precipitation and the acid solution reclaimed water, sulfuric acid and hydrogen peroxide is 1:18:1:2~1:
21:3:4。
8. the recovery method of catalyst, its feature exist in a kind of CWO waste water according to claim 6 or 7
In：Step 3. in, the sulfide precipitation thing is put into the aqueous solution of sulfuric acid and dissolved, solution temperature be 10 ~ 90 DEG C；Treat
When rising to solution temperature, hydrogen peroxide is put into the aqueous solution of sulfuric acid in batches, every batch of dosage always adds not higher than hydrogen peroxide
The 10% of amount, until the sulfide precipitation thing dissolves.
9. the recovery method of catalyst in a kind of CWO waste water according to claim 1, it is characterised in that：Step
Suddenly 4. in, polymeric adsorbent is eluted using acidic aqueous solution.
10. the recovery method of catalyst in a kind of CWO waste water according to claim 9, it is characterised in that：
Step 4. in, use mass fraction to be eluted for a kind of in 2 ~ 30% sulfuric acid, hydrochloric acid or nitric acid to polymeric adsorbent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710641516.8A CN107459164A (en) | 2017-07-31 | 2017-07-31 | The recovery method of catalyst in a kind of CWO waste water |
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| CN201710641516.8A CN107459164A (en) | 2017-07-31 | 2017-07-31 | The recovery method of catalyst in a kind of CWO waste water |
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| CN107459164A true CN107459164A (en) | 2017-12-12 |
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| CN201710641516.8A Pending CN107459164A (en) | 2017-07-31 | 2017-07-31 | The recovery method of catalyst in a kind of CWO waste water |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109879476A (en) * | 2019-03-06 | 2019-06-14 | 浙江德强科技有限公司 | The method of the processing and resource recycling of electroplating wastewater |
| CN112441678A (en) * | 2019-09-03 | 2021-03-05 | 中国石油化工股份有限公司 | Method for treating saccharin production wastewater |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103946401A (en) * | 2011-11-22 | 2014-07-23 | 住友金属矿山株式会社 | Method for producing high-purity nickel sulfate |
| CN104876380A (en) * | 2015-05-26 | 2015-09-02 | 浙江奇彩环境科技有限公司 | Method for treating high-concentration organic copper-containing wastewater and recycling copper |
| CN105858954A (en) * | 2016-04-26 | 2016-08-17 | 浙江奇彩环境科技股份有限公司 | Treatment method of high-concentration organic wastewater |
-
2017
- 2017-07-31 CN CN201710641516.8A patent/CN107459164A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103946401A (en) * | 2011-11-22 | 2014-07-23 | 住友金属矿山株式会社 | Method for producing high-purity nickel sulfate |
| CN104876380A (en) * | 2015-05-26 | 2015-09-02 | 浙江奇彩环境科技有限公司 | Method for treating high-concentration organic copper-containing wastewater and recycling copper |
| CN105858954A (en) * | 2016-04-26 | 2016-08-17 | 浙江奇彩环境科技股份有限公司 | Treatment method of high-concentration organic wastewater |
Non-Patent Citations (1)
| Title |
|---|
| 畅飞等: "微电解-Fenton耦合处理废水的反应机理与研究进展", 《西安文理学院学报：自然科学版》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109879476A (en) * | 2019-03-06 | 2019-06-14 | 浙江德强科技有限公司 | The method of the processing and resource recycling of electroplating wastewater |
| CN112441678A (en) * | 2019-09-03 | 2021-03-05 | 中国石油化工股份有限公司 | Method for treating saccharin production wastewater |
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