CN107349932A - A kind of method that nickel-base catalyst is prepared using charcoal absorption nickel-plating waste water - Google Patents
A kind of method that nickel-base catalyst is prepared using charcoal absorption nickel-plating waste water Download PDFInfo
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- CN107349932A CN107349932A CN201710475907.7A CN201710475907A CN107349932A CN 107349932 A CN107349932 A CN 107349932A CN 201710475907 A CN201710475907 A CN 201710475907A CN 107349932 A CN107349932 A CN 107349932A
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- nickel
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- plating waste
- base catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
Abstract
The present invention relates to a kind of method that nickel-base catalyst is prepared using charcoal absorption nickel-plating waste water, it comprises the following steps：After activated carbon carries out the modifications such as soda acid, pretreatment is added into the nickel-plating waste water of suitable concn, activated carbon is fully adsorbed nickel ion by adjusting wastewater pH and adsorption time, separation of solid and liquid after the completion of absorption, then solid matter is calcined again and reduction treatment, produced.Compared with prior art, beneficial effects of the present invention are to prepare nickel-base catalyst using modified activated carbon absorption nickel-plating waste water, realize the recycling of nickel ion in waste water, while avoid the secondary pollution to caused by environment of the sorbing material containing nickel ion.
Description
Technical field
The invention belongs to nickel-plating waste water recycling field, and in particular to one kind utilizes charcoal absorption nickel-plating waste water system
The method of standby nickel-base catalyst.
Background technology
Nickel-plating technology is a kind of very extensive process for treating surface of application, mainly includes chemical nickel plating and electronickelling.Closely
The fast development of a little year nickel plating industries generates substantial amounts of nickel-plating waste water, if the heavy metal ion such as nickel in waste water is discharged into ring
Health and ecological environment can be caused to seriously endanger in border.Nickel in waste discharge is contained in plating pollutant emission standard
Amount had strict requirements, from 1 day July in 2010, it is desirable to total in all existing and Sewage Water Emissions concentration of newly-built enterprise
Nickel emission limit is 0.5mg/L, and for some Special sections, its limit value is even as low as 0.1mg/L.And nickel in general nickel-plating waste water
Concentration reached more than 500mg/L.Common nickel-plating waste water processing method includes chemical precipitation method, physisorphtion and UF membrane
Method etc., but these methods deposit the problems such as waste material after treatment easily causes secondary pollution and high processing cost.Therefore efficient process
The nickel-plating waste water and recycling of waste material turns into urgent problem after can realizing processing.
Nickel-base catalyst is a kind of common metallic catalyst, is widely used in catalytic hydrogenation, catalytic pyrolysis, catalytic reforming
Etc. in industrial production.Nickel-base catalyst is usually to be made up of nickel, auxiliary agent and carrier, and the presoma of wherein nickel is generally the nitric acid of nickel
Salt, sulfate etc., auxiliary agent are that metal, the carriers such as iron, copper, zinc are typically chosen the bigger serfaces such as aluminum oxide, activated carbon, molecular sieve
Material.Connected if nickel-plating waste water processing and nickel-base catalyst can be prepared, reclaim the nickel in waste water and be used to prepare
Nickel-base catalyst, then just reached processing nickel-plating waste water and prepared the double effectses of nickel-base catalyst, lacked in the prior art
Realize the technical scheme of above-mentioned purpose.
The content of the invention
The present invention provides a kind of method that nickel-base catalyst is prepared using charcoal absorption nickel-plating waste water, it is intended to which nickel plating is given up
Water carries out obtaining commercially valuable nickel-base catalyst while Accumulation with Activated Carbon processing.
The technical scheme that the present invention solves above-mentioned technical problem is as follows：One kind prepares nickel using charcoal absorption nickel-plating waste water
The method of base catalyst, it comprises the following steps：It is 300-1000mg/L that nickel-plating waste water, which is pre-processed to its nickel ion content, is pressed
According to 5-20g:1L rate of charge puts into modified activated carbon into pretreated nickel-plating waste water, adjusts the pH of solution to alkalescence, fills
After dividing absorption, separation of solid and liquid, isolated solid matter through calcining and reduction treatment, produces the nickel-base catalyst successively.
On the basis of above-mentioned technical proposal, the present invention can also have following further specifically chosen.
Specifically, the pretreatment of nickel-plating waste water refers to be evaporated nickel-plating waste water concentration or addition soluble nickel salt
So that the nickel-plating waste water of low nickel-content is changed into the nickel-plating waste water that nickel content reaches 300-1000mg/L high nickel content.Easily reason
Solution, when in the nickel-plating waste water actually obtained nickel content just in 300-1000mg/L when, modified activated carbon can be directly added into
And without remaking pretreatment.
Specifically, in pretreated nickel-plating waste water, in addition to nickel ion, the content of other metal ions is 50-1000mg/
L。
Specifically, other metal ions include at least one of iron ion and copper ion.Under normal circumstances, nickel plating
In waste water in addition to nickel ion, other metal ions include iron, copper, zinc, chromium plasma, its it is more with nitrate, sulfate or
The forms such as complex compound are present.
Specifically, the calcination processing refers to handle 1-3h under conditions of anaerobic and 500-800 DEG C.
Specifically, the reduction treatment refers to the solid matter after calcination under the conditions of reducing atmosphere and 500-800 DEG C
Handle 1-2h.
Specifically, described reducing atmosphere refers to the mixing of the mixed atmosphere or carbon monoxide and nitrogen of hydrogen and nitrogen
Atmosphere.The mixed proportion and carbon monoxide of hydrogen and nitrogen and the mixed proportion of nitrogen can be by one of ordinary skill in the art
Flexibly selection is needed according to reduction.
Specifically, the method for regulation pH value of solution is that sodium hydroxide or potassium hydroxide, solution after regulation are added into solution
PH is 8-12.
Specifically, fully absorption refers to adsorb 6-48h under room temperature and stirring condition.After the completion of absorption, the nickel in solution
Ion application at least more than 95% is adsorbed on activated carbon.
Specifically, the method that separation of solid and liquid uses is normal for the filtering of those skilled in the art's generally use, suction filtration, centrifugation etc.
Advise any of separation method.
Specifically, the modified activated carbon is soda acid modified activated carbon, the load capacity of nickel exists in the nickel-base catalyst
More than 1wt%.The modification of activated carbon surface structure be mainly by either physically or chemically change activated carbon specific surface area and
Pore-size distribution, aperture is expanded or shunk, reach the purpose for changing activated carbon surface structure, so as to improve the energy of adsorption of activated carbon
Power；Soda acid modified activated carbon is using the materials such as acid, alkali processing activated carbon, according to the function for being actually needed adjustment activated carbon surface
Group is to required quantity, so as to improve its adsorption effect to metal ion.
Compared with prior art, the beneficial effects of the invention are as follows：
It can only make solid waste with the sorbing material after the heavy metal such as nickel ion in charcoal absorption nickel-plating waste water in the prior art
Handle and it has secondary pollution risk different to environment, the present invention is first pre-processed nickel-plating waste water to its nickel content appropriate
Concentration, then it is fully adsorbed with modified activated carbon under appropriate pH conditions, most obtained Ni-based through calcination and reduction treatment afterwards
Catalyst, after activated carbon fully adsorbs, in nickel-plating waste water more than 95% nickel ion it is adsorbed remove and obtain Ni-based urge
Agent has preferable catalytic activity, i.e., the present invention prepares nickel-base catalyst using charcoal absorption nickel-plating waste water, realizes useless
The recycling of nickel ion in water, while avoid the secondary pollution to caused by environment of the sorbing material containing nickel ion.
Embodiment
The principle and feature of the present invention are described below in conjunction with specific embodiment, example is served only for explaining this hair
It is bright, it is not intended to limit the scope of the present invention.
The conventional method that the method used in following examples then uses for those skilled in the art unless otherwise noted, use
To medicine be commercially available prod unless otherwise noted.
The nickel-plating waste water used in following examples is nickel ion or other metal ions just in corresponding concentration or warp
Reach corresponding concentration after crossing pretreatment.
Embodiment 1
A kind of method that nickel-base catalyst is prepared using charcoal absorption nickel-plating waste water, particular content are as follows：
1L nickel-plating waste waters, nickel ion concentration 500mg/L are taken, other concentration of metal ions are 300mg/L (wherein iron and copper
Total ion concentration is 100mg/L), 10g modified activated carbons (specific surface area 1000m is added into waste water2/ g), by adding NaOH
Solution regulation is until pH is 9, and stirring at normal temperature 24h is fully to adsorb；Filtering, and activated carbon is collected, in nothing after drying process
Calcined 2 hours under the conditions of oxygen, calcining heat is 700 DEG C, and post-calcination sample is in 50%H2And 50%N2Mixed airflow in 700 DEG C
1 hour is reduced, obtains Ni supported active Pd/carbon catalysts, namely the nickel-base catalyst is made.
Using the nickel-base catalyst of preparation carry out be catalyzed toluene steam reforming performance test, and with the activity of unsupported nickel
Charcoal is contrasted.
Nickel ion concentration only has 4.95mg/L in processed waste water in the present embodiment, and the total content of iron copper ion is
5.15mg/L, the removal efficiency of charcoal absorption nickel reach more than 95%.Ni supported actives Pd/carbon catalyst progress to preparation is micro-
Ripple is cleared up, and determines that the load capacity of nickel is 4.97wt% with AAS (atomic absorption spectrum), the total load amount of iron copper is 0.95wt%.
Contrasted and found by performance test, the activated carbon catalysis toluene conversion for adsorbing nickel reaches 78.5%, and the activity of unadsorbed nickel
Charcoal only has 15.1%.Therefore in waste water more than 90% nickel ion can not only be removed by above method, while passes through activation
Nickel-base catalyst made from method can be applied in the reactions such as catalysis toluene steam reforming, better catalytic activity.
Embodiment 2
A kind of method that nickel-base catalyst is prepared using charcoal absorption nickel-plating waste water, particular content are as follows：
Take 1L nickel-plating waste waters, nickel ion concentration 500mg/L, the concentration of other metal ions for 800mg/L (wherein iron from
The concentration of son is 500mg/L), 10g modified activated carbons (specific surface area 1000m is added into waste water2/ g), by adding NaOH molten
Liquid regulation is until pH is 10, and stirring at normal temperature 30h is fully to adsorb；Filtering, and activated carbon is collected, in anaerobic after drying process
Under the conditions of calcine 2.5 hours, calcining heat be 600 DEG C, post-calcination sample is in 50%H2And 50%N2Mixed airflow in 500 DEG C
3 hours are reduced, obtain Ni supported active Pd/carbon catalysts, namely the nickel-base catalyst is made.
Using the nickel-base catalyst of preparation carry out be catalyzed toluene steam reforming performance test, and with the activity of unsupported nickel
Charcoal is contrasted.
Nickel ion and iron concentration only have 7.11mg/L and 8.15mg/L respectively in processed waste water in the present embodiment, living
Property charcoal absorption nickel removal efficiency all reached more than 95%.Micro-wave digestion is carried out to the Ni-Fe supported actives Pd/carbon catalyst of preparation,
Determine that the load capacity of nickel is 4.93wt% with AAS (atomic absorption spectrum), the load capacity of iron is 4.92wt%.Pass through performance test
Contrast finds that Ni-Fe supported active Pd/carbon catalyst toluene conversions reach more than 86.5%, is lived higher than Ni loads in embodiment 1
Property charcoal and simple activity Pd/carbon catalyst.It is same that other metal ions meeting such as iron contained in nickel-plating waste water is can be seen that from this example
When be tightly held by activated carbon, reach the purpose of processing complex component nickel-plating waste water, while the adsorption of metal ions amount such as iron properly increases
And when suitable with adsorbing the amount of nickel, the catalytic activity of nickel-base catalyst can be effectively improved.
Embodiment 3
A kind of method that nickel-base catalyst is prepared using charcoal absorption nickel-plating waste water, particular content are as follows：
Take 1L nickel-plating waste waters, nickel ion concentration 800mg/L, the concentration of other metal ions for 800mg/L (wherein iron from
The concentration of son be 200mg/L, and the concentration of copper ion is 200mg/L), into waste water, (specific surface area is addition 20g modified activated carbons
1000m2/ g), by adding NaOH solution regulation until pH is 12, stirring at normal temperature 48h is fully to adsorb；Filtering, and collect activity
Charcoal, calcined under anaerobic after drying process 1.5 hours, calcining heat is 700 DEG C, post-calcination sample in 50%CO and
50%N2Mixed airflow in 800 DEG C of 1.5 hours of reduction, obtain Ni supported active Pd/carbon catalysts, namely be made described and Ni-based urge
Agent.
Using the nickel-base catalyst of preparation carry out be catalyzed toluene steam reforming performance test, and with the activity of unsupported nickel
Charcoal is contrasted.
In the present embodiment in processed waste water nickel ion, iron ion and copper ion concentration respectively only have 5.82mg/L,
5.24mg/L and 9.56mg/L, charcoal absorption nickel removal efficiency have reached more than 95%.To the Ni-Fe load type active carbons of preparation
Catalyst carries out micro-wave digestion, and the load capacity that nickel is determined with AAS (atomic absorption spectrum) is 3.82wt%, and the load capacity of iron is
0.93wt%, the load capacity of copper is 0.91wt%.By performance test, nickel-base catalyst catalysis toluene conversion reaches
More than 77.9%.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent substitution and improvements made etc., it should be included in the scope of the protection.
Claims (10)
- A kind of 1. method that nickel-base catalyst is prepared using charcoal absorption nickel-plating waste water, it is characterised in that comprise the following steps： It is 300-1000mg/L that nickel-plating waste water, which is pre-processed to its nickel ion content, according to 5-20g:1L rate of charge is to pretreated Modified activated carbon is put into nickel-plating waste water, adjusts the pH of solution to alkalescence, fully after absorption, separation of solid and liquid, isolated consolidates Body material through calcining and reduction treatment, produces the nickel-base catalyst successively.
- 2. a kind of method that nickel-base catalyst is prepared using charcoal absorption nickel-plating waste water according to claim 1, it is special Sign is that the pretreatment of nickel-plating waste water refers to be evaporated concentration to nickel-plating waste water so that the nickel-plating waste water of low nickel-content turns It is changed into the nickel-plating waste water that nickel content reaches 300-1000mg/L high nickel content.
- 3. a kind of method that nickel-base catalyst is prepared using charcoal absorption nickel-plating waste water according to claim 1, it is special Sign is, in pretreated nickel-plating waste water, in addition to nickel ion, the total content of other metal ions is 50-1000mg/L.
- 4. a kind of method that nickel-base catalyst is prepared using charcoal absorption nickel-plating waste water according to claim 3, it is special Sign is that other metal ions include at least one of iron ion and copper ion.
- 5. a kind of method that nickel-base catalyst is prepared using charcoal absorption nickel-plating waste water according to claim 1, it is special Sign is that the calcination processing refers to handle 1-3h under conditions of anaerobic and 500-800 DEG C.
- 6. a kind of method that nickel-base catalyst is prepared using charcoal absorption nickel-plating waste water according to claim 1, it is special Sign is that the reduction treatment refers to that the solid matter after calcination handles 1-2h under the conditions of reducing atmosphere and 500-800 DEG C.
- 7. a kind of method that nickel-base catalyst is prepared using charcoal absorption nickel-plating waste water according to claim 6, it is special Sign is that described reducing atmosphere refers to the mixed atmosphere or the mixed atmosphere of carbon monoxide and nitrogen of hydrogen and nitrogen.
- 8. a kind of method that nickel-base catalyst is prepared using charcoal absorption nickel-plating waste water according to claim 1, it is special Sign is that the method for adjusting pH value of solution is that sodium hydroxide or potassium hydroxide are added into solution, and the pH of solution is 8-12 after regulation.
- 9. a kind of method that nickel-base catalyst is prepared using charcoal absorption nickel-plating waste water according to claim 1, it is special Sign is that fully absorption refers to adsorb 6-48h under room temperature and stirring condition.
- 10. a kind of according to any one of claim 1 to 9 prepares nickel-base catalyst using charcoal absorption nickel-plating waste water Method, it is characterised in that the modified activated carbon is soda acid modified activated carbon, and the load capacity of nickel exists in the nickel-base catalyst More than 1wt%.
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| CN201710475907.7A CN107349932B (en) | 2017-06-21 | 2017-06-21 | Method for preparing nickel-based catalyst by adsorbing nickel-plating wastewater by using activated carbon |
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| CN201710475907.7A CN107349932B (en) | 2017-06-21 | 2017-06-21 | Method for preparing nickel-based catalyst by adsorbing nickel-plating wastewater by using activated carbon |
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Cited By (4)
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| CN112408477A (en) * | 2020-11-30 | 2021-02-26 | 鞍钢集团北京研究院有限公司 | Method for preparing vanadium dioxide from failure vanadium battery positive electrolyte |
| CN112551580A (en) * | 2020-11-30 | 2021-03-26 | 鞍钢集团北京研究院有限公司 | Method for preparing vanadium trioxide by recycling electrolyte of positive electrode of failure vanadium battery |
| CN112551581A (en) * | 2020-11-30 | 2021-03-26 | 鞍钢集团北京研究院有限公司 | Method for preparing vanadium pentoxide by recovering electrolyte of failed vanadium battery |
| CN114192147A (en) * | 2021-11-30 | 2022-03-18 | 华中科技大学 | Method and system for preparing three-dimensional net-shaped Ni/CA catalyst by comprehensively treating fruit and vegetable waste and nickel plating wastewater |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112408477A (en) * | 2020-11-30 | 2021-02-26 | 鞍钢集团北京研究院有限公司 | Method for preparing vanadium dioxide from failure vanadium battery positive electrolyte |
| CN112551580A (en) * | 2020-11-30 | 2021-03-26 | 鞍钢集团北京研究院有限公司 | Method for preparing vanadium trioxide by recycling electrolyte of positive electrode of failure vanadium battery |
| CN112551581A (en) * | 2020-11-30 | 2021-03-26 | 鞍钢集团北京研究院有限公司 | Method for preparing vanadium pentoxide by recovering electrolyte of failed vanadium battery |
| CN114192147A (en) * | 2021-11-30 | 2022-03-18 | 华中科技大学 | Method and system for preparing three-dimensional net-shaped Ni/CA catalyst by comprehensively treating fruit and vegetable waste and nickel plating wastewater |
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