CN109647410A - For handling the preparation method of the support type expandable graphite catalyst of EDTA-Cu waste water - Google Patents

For handling the preparation method of the support type expandable graphite catalyst of EDTA-Cu waste water Download PDF

Info

Publication number
CN109647410A
CN109647410A CN201910014854.8A CN201910014854A CN109647410A CN 109647410 A CN109647410 A CN 109647410A CN 201910014854 A CN201910014854 A CN 201910014854A CN 109647410 A CN109647410 A CN 109647410A
Authority
CN
China
Prior art keywords
expanded graphite
graphite
catalyst
support type
edta
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.)
Granted
Application number
CN201910014854.8A
Other languages
Chinese (zh)
Other versions
CN109647410B (en
Inventor
贺君
邢丽飞
宋来洲
陈思琦
宋文超
田晶
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yanshan University
Original Assignee
Yanshan University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Yanshan University filed Critical Yanshan University
Priority to CN201910014854.8A priority Critical patent/CN109647410B/en
Publication of CN109647410A publication Critical patent/CN109647410A/en
Application granted granted Critical
Publication of CN109647410B publication Critical patent/CN109647410B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/10—Magnesium; Oxides or hydroxides thereof
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • 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
    • B01J23/745—Iron
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Catalysts (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The present invention provide it is a kind of for handling the preparation method of the support type expandable graphite catalyst of EDTA-Cu waste water, first to natural flake graphite carry out chemical oxidation intercalation, high temperature puffing, preparation without sulphur without manganese expanded graphite；Then surface carboxylation, amination processing are carried out without manganese expanded graphite to made no sulphur, obtains functionalization expanded graphite carrier；Using iron, nickel and magnesium as active component, through dip loading, high temperature sintering is finally prepared for support type expandable graphite catalyst, i.e. Fe2O3- EG, MgO-EG or NiO-EG.Preparation process of the present invention is simple, low in cost, is easy to be engineered popularization；The catalytic performance efficient stable of the support type expandable graphite catalyst, can be greatly improved reaction system oxidisability, and quick contact break while realizes that the efficient removal of copper ion, the improvement for EDTA-Cu waste water provide technological borrowing.

Description

For handling the preparation method of the support type expandable graphite catalyst of EDTA-Cu waste water
Technical field
The invention belongs to catalyst technical fields, are related to a kind of for handling the support type expanded graphite of EDTA-Cu waste water The preparation method of catalyst.
Background technique
EDTA-Cu waste water is typical electroplating wastewater, heavy metal Cu2+Content is high, difficult for biological degradation, and is complexed with EDTA etc. Agent easily forms soluble complexes, and the Stability of Metal Complexes is high, and processing difficulty is big, very harmful to environmental and human health impacts.It is public The number of opening is that the patent of CN104071932A discloses the processing method and electric flocculation device of a kind of Cu-EDTA complexing waste water, processing Method is that Cu-EDTA complexing waste water is put into reactive tank, and using aluminium electrode as anode, ferroelectricity extremely cathode carries out electric flocculation reaction 30~50min；Then change current direction, with ferroelectricity extremely anode, aluminium electrode be cathode carry out electric flocculation reaction 30~ 50min completes the processing to Cu-EDTA complexing waste water.Although this patent is during handling waste water that chemical agent is not added And adsorbent, it is easy to operate, but organic matter degradation is not thorough, it consumes energy larger, it is big and highly concentrated to be not suitable for processing flow Waste water is complexed in Cu-EDTA, is unfavorable for engineering application.The patent of Publication No. CN102910762A discloses another processing Cu (II) method of-EDTA waste water, i.e., the COD and Cu of preceding Cu (the II)-EDTA waste water of measurement processing first2+Concentration；Adjust reaction tank Cu (II)-EDTA pH value of waste water in one is added catalyst and oxidant, 0.5~3h is stirred to react, after obtaining reaction to 3~6 Cu (II)-EDTA waste water；After Cu (II)-EDTA waste water after reaction is stood, wastewater supernatant fluid is emitted into reaction tank two, NaOH is added in wastewater supernatant fluid and adjusts pH value to 11~12, standing takes precipitating, be filtered, washed, calcine after obtain copper oxide；Instead Sediment in Ying Chiyi after drying, is reused as catalyst.Method treatment process in this patent is cumbersome, processing dress It is larger to set occupied area, and joined a large amount of chemical reagent, easily causes secondary pollution.In conclusion conventional method is to processing EDTA-Cu waste water has certain effect, while there is also many drawbacks, limiting its engineer application.
Summary of the invention
In view of the deficiencies of the prior art, the support type that the present invention provides a kind of for handling EDTA-Cu waste water expands stone The preparation method of black catalyst prepares no sulphur without manganese expanded graphite carrier, and then carry out surface-functionalized processing to it first, warp Dip loading, high temperature sintering finally obtain the support type expandable graphite catalyst composite material of load iron, magnesium or nickel, preparation Simple process, low production cost, and the catalytic performance efficient stable of support type graphite catalyst obtained.
Technical scheme is as follows:
It is a kind of for handling the preparation method of the support type expandable graphite catalyst of EDTA-Cu waste water, specifically include with Lower step:
The expanded graphite of S1, preparation catalyst carrier without sulphur without manganese:
S11, expansible graphite is prepared:
Ammonium nitrate solid is added in perchloric acid, natural flake graphite is added after stirring and dissolving, constant temperature water bath adds after sealing Heat simultaneously stirs, and bath temperature is 30~50 DEG C, and revolving speed is 200~300r/min, and mixing time is 45~75min, and reaction obtains Mixture；
After the reaction was completed, depressurization, after being cooled to room temperature, the mixture repeatedly rinsed with deionized water, until The pH of flushing water is 5~7；The mixture of washes clean is filtered, by filtered mixture dry 4 at 60~80 DEG C Expansible graphite is made in~6h；
The high-temperature expansion of S12, expansible graphite prepare the expanded graphite without sulphur without manganese:
Expansible graphite made from step S11 is weighed, calcination is carried out with 900~1000 DEG C of temperature, until not being expanded to Only, expanded graphite of no sulphur without manganese is obtained；
S2, functional modification expanded graphite:
The carboxylated of S21, expanded graphite:
The expanded graphite made from step S1 without sulphur without manganese is added in ethanol water, is ultrasonically treated to obtain uniform Expanded graphite dispersion liquid, is successively added sodium carbonate liquor that concentration is 5mol/L in expanded graphite dispersion liquid and concentration is Monoxone, sodium chloroacetate or the bromoacetic acid solution of 3mol/L is vibrated after ultrasonic treatment, and oscillation revolving speed is 150~200r/ Min, duration of oscillation are 3~5h；After oscillation treatment, with sodium carbonate remaining in solution in addition 2mol/L hydrochloric acid solution, diafiltration is crossed It washs, is repeatedly washed with deionized water, until filtrate pH is 6~7, is filtered by vacuum, is dry, after cooled to room temperature, carboxylic is made Base expanded graphite；
The secondary modification of S22, expanded graphite amino:
The expanded graphite of step S21 carboxylated is added in ethanol water, it is swollen that ultrasonic treatment obtains uniform carboxylated Swollen graphite alcohol dispersion liquid, the carboxylated expanded graphite alcohol dispersion liquid and concentration that measurement concentration is 10g/L respectively are 1g/L's Beet alkali surface activator solution, is sufficiently mixed, 70~80 DEG C of return stirrings, and sufficiently 6~8h of reaction, reaction terminates, be cooled to Room temperature stands for 24 hours, obtains mixed liquor, mixed liquor is filtered washing, is first washed repeatedly with dehydrated alcohol, then use deionization Water washing is multiple, is filtered by vacuum and dry, after cooled to room temperature, obtains the expanded graphite of amino secondary modification, complete to urge The functional modification of agent carrier expanded graphite；
S3, support type expandable graphite catalyst is prepared:
The metal-nitrate solutions that metal ion concentration is 1mol/L are added in ethanol water, after mixing, The functionalization expanded graphite of step S2 preparation is added, is ultrasonically treated, vibrates, stands filtering, filter residue is dried, it is natural It is cooled to room temperature, obtains catalyst precursor；Catalyst precursor is calcined, heating rate is 10 DEG C/min, calcining temperature Degree is 500~600 DEG C, and calcination time is 2~3h, and support type expandable graphite catalyst is made in cooled to room temperature.
Preferably, the amount ratio of natural flake graphite, ammonium nitrate and perchloric acid are as follows: 1g~2.5g:0.5g~2.5g:3mL ~9mL.
Preferably, expanded graphite of no sulphur without manganese, natrium carbonicum calcinatum, the mass ratio of monoxone, sodium chloroacetate or bromoacetic acid For 0.1~0.5:6~30:5~25.
Preferably, the volume ratio of second alcohol and water is 1:3 in ethanol water.
Preferably, the ultrasound condition of step S21 are as follows: ultrasonic power 40kHz, ultrasonic time are 10~20min, ultrasonic water Bath temperature is 25~35 DEG C；In step S22, the condition of ultrasonic treatment are as follows: ultrasonic power 40kHz, ultrasonic water bath temperature are 25 ~35 DEG C, ultrasonic time is 5~15min；The vacuum drying condition of step S21 and S22 are as follows: vacuum degree 0.05MPa, temperature are 60~70 DEG C, drying time is 6~8h.
Preferably, the beet alkali surface activator is carboxylic acid group's glycine betaine, alkyl dimethyl sulfoethyl glycine betaine or alkane Base dimethyl sulfopropyl betaine.
Preferably, the mass ratio of carboxylated expanded graphite and beet alkali surface activator is 1:0.02~0.03.
Preferably, the metal nitrate is Fe(NO3)39H2O, magnesium nitrate hexahydrate or Nickelous nitrate hexahydrate.
Preferably, the mass ratio of functional modification expanded graphite and metal nitrate is 1:1.5~3.5.
Preferably, the condition being ultrasonically treated in step S3 are as follows: ultrasonic power 40kHz, ultrasonic water bath temperature are 25~35 DEG C, ultrasonic time is 5~15min；The condition of oscillation are as follows: hunting speed is 100~150r/min, and duration of oscillation is 9~12h； Dry condition are as follows: drying temperature is 70~80 DEG C, and drying time is 3~5h.
Compared with prior art, the invention has the following advantages:
1, the present invention using no sulphur without manganese expanded graphite as catalyst carrier, relative to commercially available expanded graphite, not sulfur-bearing It is environmentally friendly with heavy metal manganese, while high magnification expands, specific surface area is larger, stability with higher, contains abundant hole Gap structure can provide enough load spaces for active component, and make its high degree of dispersion, increase active site, can make load Catalyst activity component is uniformly dispersed, in addition, carrying out surface-functionalized processing to it, not only has with catalyst activity component stronger Binding force, also enhance active catalyst sites quantity, meanwhile, no sulphur is without manganese expanded graphite production cost is low and preparation process Simply, convenient for engineering production.
2, the method comprises the steps of firstly, preparing going out without sulphur to carry out carboxyl and amination functionalized modification without manganese expanded graphite, and to it, then Using Fe2+、Mg2+And Ni2+As active component, expanded graphite is loaded, most obtains excellent bear through high-temperature calcination afterwards Load type expandable graphite catalyst, the catalyst is low in cost, and preparation process is simple, environmental-friendly, and low toxicity is harmless, and active component is negative It is high to carry content, and catalytic performance is excellent, stablizes, and can ozonize with efficient catalytic and generate a large amount of OH, thus in high concentration, high poison Property, difficult for biological degradation electroplating wastewater industry have a vast application prospect, and recycle convenient, can repeatedly use, be convenient for engineering Change application.
3, support type expandable graphite catalyst high degree of dispersion in waste water, and do not influenced by wastewater pH, efficient catalytic is smelly Oxygen generates OH, is greatly improved hardly degraded organic substance mineralization rate, and quick contact break while realizes the efficient removal of copper ion, is The improvement of EDTA-Cu waste water provides technological borrowing.
Detailed description of the invention
Fig. 1 is the infrared spectrum of functionalization expanded graphite and support type expandable graphite catalyst of the invention；
Fig. 2 is the Cu of support type expandable graphite catalyst Catalytic Ozonation Cu-EDTA waste water2+Removal rate；And
Fig. 3 is the EDTA mineralization rate of support type expandable graphite catalyst Catalytic Ozonation Cu-EDTA waste water.
Specific embodiment
Below with reference to the attached drawing exemplary embodiment that the present invention will be described in detail, feature and aspect of performance.It is identical in attached drawing Appended drawing reference indicate element functionally identical or similar.Although the various aspects of embodiment are shown in the attached drawings, remove It non-specifically points out, it is not necessary to attached drawing drawn to scale.
The present invention chooses new carbon-and is used as catalyst carrier without manganese expanded graphite without sulphur, with compared with high stable Property, containing abundant pore structure, enough load spaces can be provided for active component, and make its high degree of dispersion, increase active sites Point, while sulphur-free expanded graphite production cost is low and preparation process is simple, convenient for engineering production.
Iron oxide, magnesia and raw material of nickel oxide source are wide, and production cost is low, and catalytic performance efficient stable is generally acknowledged The excellent catalyst that catalysis ozone decomposes, but it is easy to reunite, and subsequent recovery is difficult, limits its application.Expanded graphite is as new Type Carbon Materials, structure have abundant hole and special surface group similar to vermiform, provide for catalyst activity component attachment Sufficient space, and make its high degree of dispersion.
The preparation method of support type expandable graphite catalyst for handling EDTA-Cu waste water of the invention, prepares first Out without sulphur without manganese expanded graphite, and carboxyl and amination functionalized modification are carried out to it, then use Fe2+、Mg2+And Ni2+As activity Component loads expanded graphite, most obtains excellent support type expandable graphite catalyst through high-temperature calcination afterwards, specific The following steps are included:
The expanded graphite of S1, preparation catalyst carrier without sulphur without manganese:
It is raw materials used are as follows: natural flake graphite (32 mesh, phosphorus content >=99.99%), ammonium nitrate (content >=98.5%) are high Chloric acid (mass fraction 72%)；The amount ratio of above-mentioned raw materials are as follows: natural flake graphite: ammonium nitrate: perchloric acid=1~2.5 (g): 0.5~2.5 (g): 3~9 (mL)；
S11, expansible graphite is prepared:
Ammonium nitrate solid is added in perchloric acid, natural flake graphite is added after stirring and dissolving, constant temperature water bath adds after sealing Heat simultaneously stirs, and bath temperature is 30~50 DEG C, and revolving speed is 200~300r/min, and mixing time is 45~75min, and reaction obtains Mixture；
After the reaction was completed, depressurization, after being cooled to room temperature, the mixture repeatedly rinsed with deionized water, until The pH of flushing water is 5~7；The mixture of washes clean is filtered, by filtered mixture dry 4 at 60~80 DEG C Expansible graphite is made in~6h；
The high-temperature expansion of S12, expansible graphite prepare the expanded graphite without sulphur without manganese:
Expansible graphite made from step S11 is weighed, calcination is carried out with 900~1000 DEG C of temperature, until not being expanded to Only, expanded graphite of no sulphur without manganese is obtained；
Under same experimental conditions, parallel laboratory test three times is done, parallel laboratory test allowance for expansion average value three times is sought, is computed Show that allowance for expansion is 300~400mL/g；
S2, functional modification expanded graphite:
It is raw materials used are as follows: without sulphur without manganese expanded graphite, dehydrated alcohol (content >=99.7%), anhydrous carbon made from step S1 Sour sodium (content >=99.8%), monoxone (content >=98%), sodium chloroacetate (content >=98%), bromoacetic acid (content >= 99.5%) one such；The mass ratio of above-mentioned raw materials are as follows: without sulphur without manganese expanded graphite: natrium carbonicum calcinatum: monoxone, chloroethene Sour sodium or bromoacetic acid=0.1~0.5:6~30:5~25；
The carboxylated of S21, expanded graphite:
The expanded graphite made from step S1 without sulphur without manganese is added in ethanol water, is ultrasonically treated to obtain uniform Expanded graphite dispersion liquid, ultrasonic power 40kHz, ultrasonic time are 10~20min, and ultrasonic water bath temperature is 25~35 DEG C, The sodium carbonate liquor that concentration is 5mol/L and the monoxone that concentration is 3mol/L, monoxone are successively added in expanded graphite dispersion liquid Sodium or bromoacetic acid solution, after being ultrasonically treated with identical ultrasound condition sealing vibrated, oscillation revolving speed be 150~ 200r/min, duration of oscillation are 3~5h；After oscillation treatment, it is added in 2mol/L hydrochloric acid solution and sodium carbonate remaining in solution, mistake Filter washing is repeatedly washed with deionized water, until filtrate pH is 6~7, after vacuum filtration, it is 0.05MPa with vacuum degree, temperature For the dry 6~8h of 60~70 DEG C of conditions, after cooled to room temperature, carboxylated expanded graphite is made；
The secondary modification of S22, expanded graphite amino:
The expanded graphite of step S21 carboxylated is added in ethanol water, is ultrasonically treated, the condition of ultrasonic treatment Are as follows: ultrasonic power 40kHz, ultrasonic water bath temperature are 25~35 DEG C, and ultrasonic time is 5~15min, obtains uniform carboxylated Expanded graphite dispersion liquid measures the carboxylated expanded graphite alcohol dispersion liquid that concentration is 10g/L and the sweet tea that concentration is 1g/L respectively The mass ratio of dish alkali surfactant solution, carboxylated expanded graphite and beet alkali surface activator is 1:0.02~0.03, is filled Dividing mixing, 70~80 DEG C of return stirrings, sufficiently 6~8h of reaction, reaction terminate, are cooled to room temperature, stand for 24 hours, obtain mixed liquor, Mixed liquor is filtered washing, is first washed repeatedly with dehydrated alcohol, then is washed with deionized repeatedly, vacuum filtration, and When vacuum degree is 0.05MPa, 60~70 DEG C of dry 6~8h after cooled to room temperature, obtain the expansion stone of amino secondary modification Ink completes the functional modification of catalyst carrier expanded graphite；
S3, support type expandable graphite catalyst is prepared:
The metal-nitrate solutions that metal ion concentration is 1mol/L are added in ethanol water, after mixing, The mass ratio of the functionalization expanded graphite of addition step S2 preparation, functional modification expanded graphite and metal nitrate is 1:1.5 ~3.5, it is ultrasonically treated, ultrasonic power 40kHz, ultrasonic water bath temperature is 25~35 DEG C, and ultrasonic time is 5~15min, It after ultrasound, is vibrated, hunting speed is 100~150r/min, and duration of oscillation is 9~12h, after reaction, is stood Filtering, by filter residue, dry 3~5h, cooled to room temperature obtain catalyst precursor at a temperature of 70~80 DEG C；By catalyst Presoma is calcined, and heating rate is 10 DEG C/min, and calcination temperature is 500~600 DEG C, and calcination time is 2~3h, naturally cold But to room temperature, support type expandable graphite catalyst is made.
Preferably, the volume ratio of second alcohol and water is 1:3 in ethanol water.
Preferably, beet alkali surface activator is carboxylic acid group's glycine betaine, alkyl dimethyl sulfoethyl glycine betaine or alkyl two Methyl azochlorosulfonate propyl lycine, carboxylic acid group's glycine betaine are alkyl dimethyl betaine, and alkyl dimethyl azochlorosulfonate propyl lycine is 12 Alkyl hydroxypropyl base sulfobetaines, dodecyl azochlorosulfonate propyl lycine, myristamide propyl hydroxypropyl sulfobetaines or the last of the ten Heavenly stems Alkyl hydroxypropyl base sulfobetaines.
Preferably, metal nitrate be Fe(NO3)39H2O, magnesium nitrate hexahydrate or Nickelous nitrate hexahydrate, so, preparation Support type expandable graphite catalyst be Fe2O3- EG, MgO-EG or NiO-EG.
Embodiment 1
The expanded graphite of S1, preparation catalyst carrier without sulphur without manganese:
S11, expansible graphite is prepared:
3mL perchloric acid is pipetted in the 250mL beaker of clean dried, 0.5g ammonium nitrate solid is slowly added to, uses glass bar After stirring and dissolving, 1g natural flake graphite is added, magnetic rotor is put into, beaker is sealed with sealed membrane, is subsequently placed at thermal-arrest In formula constant-temperature heating magnetic stirring apparatus, 30 DEG C of bath temperature are set, adjusts revolving speed 200r/min, mixing time 75min；Wait react After the completion, beaker is taken out at once, is placed in draught cupboard, beaker sealed membrane is opened, and after being cooled to room temperature, takes out magnetic force using tweezers Rotor repeatedly rinses mixture with deionized water later, until flushing water pH is about 6；It is dry to washing using vacuum pump using circulatory water Net mixture is filtered, and is then transferred to the mixture retained on filter paper in clean culture dish, is placed in drying box, Dry 6h, is made expansible graphite at 60 DEG C；
The high-temperature expansion of S12, expansible graphite prepare the expanded graphite without sulphur without manganese:
1g expansible graphite obtained above is weighed, the calcination 5min in 900~1000 DEG C of high temperature Muffle furnace is placed in Quartz beaker in, then quartz beaker is immediately placed in 900~1000 DEG C of high temperature Muffle furnace, is not related to fire door, depending on not swollen Until swollen, take out immediately, it is final to be made without sulphur without manganese expanded graphite；
Under same experimental conditions, parallel laboratory test three times is done, every time when reading, reads quartz beaker top surface highest point and most Low spot corresponds to the average value of scale, seeks parallel laboratory test allowance for expansion average value three times, is computed and show that allowance for expansion is 300mL/g。
S2, functional modification expanded graphite:
The carboxylated of S21, expanded graphite:
0.5g is taken, without manganese expanded graphite, to be added in the beaker for filling 100mL ethanol water without sulphur, place the beaker numerical control It is ultrasonically treated in ultrasonic cleaner, obtains uniform expanded graphite dispersion liquid, set ultrasonic power as 40kHz, ultrasound Time is 10min, and ultrasonic water bath temperature is 25 DEG C.It is molten that the sodium carbonate that 11.3mL concentration is 5mol/L is successively added into dispersion liquid The chloroacetic acid solution that liquid and 17.6mL concentration are 3mol/L, ultrasound condition is constant, handles 20min again.After ultrasound, with envelope Membrana oralis sealed beaker is transferred on cyclotron oscillation device, and adjusting oscillation revolving speed is 150r/min, duration of oscillation 5h；Fully reacting Afterwards, it is slowly added in 2mol/L hydrochloric acid solution repeatedly be washed with sodium carbonate remaining in solution, subsequent filtration washing with deionized water It washs, until filtrate pH is not less than 6, reuses vacuum pump using circulatory water and be filtered by vacuum, by the solid retained on filter paper and filter paper one And be transferred in the culture dish of dried and clean, juxtaposition in a vacuum drying oven, set the vacuum degree of vacuum oven as 0.05MPa, temperature are 60 DEG C, dry 8h, and after cooled to room temperature, carboxylated expanded graphite is made.
The secondary modification of S22, expanded graphite amino:
It takes 1g carboxylated expanded graphite to be added in the beaker for filling 100mL ethanol water, is ultrasonically treated, set Ultrasonic power is 40kHz, and ultrasonic water bath temperature is 25 DEG C, ultrasonic time 15min, obtains uniform carboxylated expanded graphite point Dispersion liquid；The carboxylated expanded graphite uniform dispersion that 100mL concentration is 10g/L and the beet that 30mL concentration is 1g/L are measured respectively Alkali surfactant solution, is successively transferred in three-necked flask, and sufficiently, pH of mixed is neutrality at this time for mixing, and 70 DEG C of reflux are stirred Mixing sufficiently reaction 8h, reaction terminates, is cooled to room temperature, and stands for 24 hours；Washing is filtered to obtained mixed liquor, first with anhydrous Ethanol washing 3 times, then be washed with deionized 3 times, it is finally filtered by vacuum, will be retained on filter paper using vacuum pump using circulatory water Solid and filter paper be transferred in the culture dish of dried and clean together, juxtaposition in a vacuum drying oven, vacuum degree be 0.05MPa When, 60 DEG C of dry 8h after cooled to room temperature, obtain the expanded graphite of amino secondary modification, the i.e. catalysis of functional modification Agent carrier expanded graphite.
S3, support type expandable graphite catalyst is prepared:
The iron nitrate solution that 5.36mL is 1mol/L containing iron concentration is pipetted, is slowly added into and fills 100mL ethanol water In the beaker of solution, be uniformly mixed, then be added 1g functionalization expanded graphite, place the beaker in numerical control ultrasonic cleaner into Row ultrasonic treatment, ultrasonic power 40kHz, ultrasonic water bath temperature are 25 DEG C, ultrasonic time 15min.After ultrasound, it will burn Cup is sealed with sealed membrane, is transferred on cyclotron oscillation device, and adjusting hunting speed is 100r/min, duration of oscillation 12h, reaction knot Shu Hou stands filtering, filter residue is transferred in the culture dish of dried and clean, is put into drying box, 70 DEG C of dry 5h, natural cooling To room temperature, catalyst precursor is obtained；
Corundum straight tube crucible first is wiped with alcohol swab, is placed into drying box, 70 DEG C of dry 2h, after being cooled to room temperature, then It is put into catalyst precursor obtained, is finally putting into numerical control Muffle furnace and is calcined, heating rate is set as 10 DEG C/min, forges Burning temperature is 500 DEG C, calcination time 3h, and support type expandable graphite catalyst, i.e. Fe is made in cooled to room temperature2O3-EG。
To functionalization expanded graphite prepared by the implementation case and support type expandable graphite catalyst (Fe2O3- EG) it carries out Infrared test, result are as shown in Figure 1.When preparing functionalization expanded graphite, functional group is successively introduced on expanded graphite Group carboxyl (- COOH) and amino (- NH-CO-), wave number 1382cm-1For-COOH stretching vibration peak, wave number 1650cm-1For-NH- CO- stretching vibration peak illustrates that functionalization expanded graphite has been made in the implementation case.Wave number 563cm-1For Fe-O key, it was demonstrated that this reality It applies case and has successfully prepared support type expandable graphite catalyst (Fe2O3-EG)。
Weigh 0.4030g CuSO4·5H2O and 0.6000g C10H16N2O8Na2(analysis is pure) is dissolved in 1L deionized water, 1.6mmol/L EDTA-Cu simulated wastewater is prepared, wherein the molar ratio of Cu (II) and EDTA is 1:1, and TOC concentration is 200mg/L, PH is about 3.Under room temperature, ozone concentration 9mg/L, the catalyst (Fe of the implementation case preparation2O3- EG) concentration be 1g/L, Catalytic ozonation handles Cu-EDTA simulated wastewater, reacts under 120min, with the same terms, independent ozone treatment Cu-EDTA simulation The Cu of waste water2+The comparison diagram of removal rate is as shown in Fig. 2, the comparison diagram of EDTA mineralization rate is as shown in Figure 3.Catalyst is added (Fe2O3- EG), after reacting 75min, Cu2+Removal rate is higher by 35% than independent ozone treatment close to 100%；Entirely reacting In, catalyst (Fe is added2O3- EG) afterwards EDTA mineralization rate than independent ozone treatment improve 13%.It can be seen that this implementation Made catalyst (the Fe of example2O3- EG) catalytic ozonation handles EDTA-Cu waste water, and significant effect, catalytic performance is excellent.
Embodiment 2
The expanded graphite of S1, preparation catalyst carrier without sulphur without manganese:
S11, expansible graphite is prepared:
6mL perchloric acid is pipetted in the 250mL beaker of clean dried, 0.15g ammonium nitrate solid is slowly added to, uses glass bar After stirring and dissolving, 2g natural flake graphite is added, magnetic rotor is put into, beaker is sealed with sealed membrane, is subsequently placed at thermal-arrest In formula constant-temperature heating magnetic stirring apparatus, 40 DEG C of bath temperature are set, adjusts revolving speed 250r/min, mixing time 60min；Wait react After the completion, beaker is taken out at once, is placed in draught cupboard, beaker sealed membrane is opened, and after being cooled to room temperature, takes out magnetic force using tweezers Rotor repeatedly rinses mixture with deionized water later, until flushing water pH is about 6；It is dry to washing using vacuum pump using circulatory water Net mixture is filtered, and is then transferred to the mixture retained on filter paper in clean culture dish, is placed in drying box, Dry 5h, is made expansible graphite at 70 DEG C；
The high-temperature expansion of S12, expansible graphite prepare the expanded graphite without sulphur without manganese:
1g expansible graphite obtained above is weighed, the calcination 5min in 900~1000 DEG C of high temperature Muffle furnace is placed in Quartz beaker in, then quartz beaker is immediately placed in 900~1000 DEG C of high temperature Muffle furnace, is not related to fire door, depending on not swollen Until swollen, take out immediately, it is final to be made without sulphur without manganese expanded graphite；
Under same experimental conditions, parallel laboratory test three times is done, every time when reading, reads quartz beaker top surface highest point and most Low spot corresponds to the average value of scale, seeks parallel laboratory test allowance for expansion average value three times, is computed and show that allowance for expansion is 350mL/g。
S2, functional modification expanded graphite:
The carboxylated of S21, expanded graphite:
Take 0.5g without sulphur without manganese expanded graphite, be added in the beaker for filling 100mL ethanol water (volume ratio is ethyl alcohol: Water=1:3), it places the beaker in numerical control ultrasonic cleaner and is ultrasonically treated, obtain uniform expanded graphite dispersion liquid, if Determining ultrasonic power is 40kHz, and ultrasonic time 15min, ultrasonic water bath temperature is 30 DEG C.28.3mL is successively added into dispersion liquid The chloroacetic acid solution that the sodium carbonate liquor and 61.7mL concentration that concentration is 5mol/L are 3mol/L, ultrasound condition is constant, locates again Manage 15min.It after ultrasound, with sealed membrane sealed beaker, is transferred on cyclotron oscillation device, adjusting oscillation revolving speed is 175r/ Min, duration of oscillation 4h；After fully reacting, it is slowly added in 2mol/L hydrochloric acid solution and sodium carbonate remaining in solution, subsequent mistake Filter washing is repeatedly washed with deionized water, until filtrate pH is 6~7, is reused vacuum pump using circulatory water and is filtered by vacuum, will be filtered The solid and filter paper retained on paper is transferred to together in the culture dish of dried and clean, and juxtaposition in a vacuum drying oven, sets vacuum The vacuum degree of drying box is 0.05MPa, and temperature is 65 DEG C, dry 7h, after cooled to room temperature, carboxylated is made and expands stone Ink.
The secondary modification of S22, expanded graphite amino:
Taking 1.5g carboxylated expanded graphite to be added in the beaker for filling 100mL ethanol water, (volume ratio is ethyl alcohol: water =1:3), it is ultrasonically treated, sets ultrasonic power as 40kHz, ultrasonic water bath temperature is 30 DEG C, and ultrasonic time 10min is obtained To uniform carboxylated expanded graphite dispersion liquid；It is evenly dispersed that the carboxylated expanded graphite that 150mL concentration is 10g/L is measured respectively The beet alkali surface activator solution that liquid and 65mL concentration are 1g/L, is successively transferred in three-necked flask, and mixing sufficiently, mixes at this time Closing liquid pH is neutrality, and 75 DEG C of return stirrings sufficiently react 7h, and reaction terminates, and is cooled to room temperature, and is stood for 24 hours；Mixing to obtaining Liquid is filtered washing, is first washed 3 times with dehydrated alcohol, then is washed with deionized 3 times, finally using vacuum pump using circulatory water into Row vacuum filtration, the solid retained on filter paper and filter paper are transferred to together in the culture dish of dried and clean, and it is dry to be placed in vacuum In dry case, when vacuum degree is 0.05MPa, 65 DEG C of dry 7h after cooled to room temperature, obtain the expansion of amino secondary modification Graphite, i.e. the catalyst carrier expanded graphite of functional modification.
S3, support type expandable graphite catalyst is prepared:
The magnesium nitrate solution that 12.5mL is 1mol/L containing magnesium ion concentration is pipetted, is slowly added into and fills 100mL ethanol water In the beaker of solution, be uniformly mixed, then be added 1g functionalization expanded graphite, place the beaker in numerical control ultrasonic cleaner into Row ultrasonic treatment, ultrasonic power 40kHz, ultrasonic water bath temperature are 30 DEG C, ultrasonic time 10min.After ultrasound, it will burn Cup is sealed with sealed membrane, is transferred on cyclotron oscillation device, and adjusting hunting speed is duration of oscillation 10.5h under 125r/min, instead After answering, filtering is stood, filter residue is transferred in the culture dish of dried and clean, is put into drying box, 75 DEG C of dry 4h are natural After being cooled to room temperature, catalyst precursor is obtained；
Corundum straight tube crucible first is wiped with alcohol swab, is placed into drying box, 75 DEG C of dry 1.5h, after being cooled to room temperature, Catalyst precursor obtained is placed into, is finally putting into numerical control Muffle furnace and is calcined, sets heating rate as 10 DEG C/min, Calcination temperature is 550 DEG C, calcination time 2.5h, and support type expandable graphite catalyst (MgO- is made in cooled to room temperature EG)。
Embodiment 3
The expanded graphite of S1, preparation catalyst carrier without sulphur without manganese:
S11, expansible graphite is prepared:
9mL perchloric acid is pipetted in the 250mL beaker of clean dried, 2.5g ammonium nitrate solid is slowly added to, uses glass bar After stirring and dissolving, 2.5g natural flake graphite is added, magnetic rotor is put into, beaker is sealed with sealed membrane, is subsequently placed at collection In hot type constant-temperature heating magnetic stirring apparatus, 50 DEG C of bath temperature are set, adjusts revolving speed 300r/min, mixing time 45min；To anti- After the completion of answering, beaker is taken out at once, is placed in draught cupboard, beaker sealed membrane is opened, and after being cooled to room temperature, takes out magnetic using tweezers Power rotor, repeatedly rinses mixture with deionized water later, until flushing water pH is about 6；Using vacuum pump using circulatory water, to washing Clean mixture is filtered, and is then transferred to the mixture retained on filter paper in clean culture dish, is placed in drying box In, dry 4h, is made expansible graphite at 80 DEG C；
The high-temperature expansion of S12, expansible graphite prepare the expanded graphite without sulphur without manganese:
1g expansible graphite obtained above is weighed, the calcination 5min in 900~1000 DEG C of high temperature Muffle furnace is placed in Quartz beaker in, then quartz beaker is immediately placed in 900~1000 DEG C of high temperature Muffle furnace, is not related to fire door, depending on not swollen Until swollen, take out immediately, it is final to be made without sulphur without manganese expanded graphite；
Under same experimental conditions, parallel laboratory test three times is done, every time when reading, reads quartz beaker top surface highest point and most Low spot corresponds to the average value of scale, seeks parallel laboratory test allowance for expansion average value three times, is computed and show that allowance for expansion is 400mL/g。
S2, functional modification expanded graphite:
The carboxylated of S21, expanded graphite:
Take 0.5g without sulphur without manganese expanded graphite, be added in the beaker for filling 100mL ethanol water, place the beaker number It is ultrasonically treated in control ultrasonic cleaner, obtains uniform expanded graphite dispersion liquid, set ultrasonic power as 40kHz, surpass The sound time is 10min, and ultrasonic water bath temperature is 35 DEG C.The sodium carbonate that 56.6mL concentration is 5mol/L is successively added into dispersion liquid The chloroacetic acid solution that solution and 88.2mL concentration are 3mol/L, ultrasound condition is constant, handles 10min again.After ultrasound, use Sealed membrane sealed beaker is transferred on cyclotron oscillation device, and adjusting oscillation revolving speed is 200r/min, duration of oscillation 3h；It has reacted Quan Hou is slowly added in 2mol/L hydrochloric acid solution repeatedly be washed with sodium carbonate remaining in solution, subsequent filtration washing with deionized water It washs, until filtrate pH is not less than 6, reuses vacuum pump using circulatory water and be filtered by vacuum, by the solid retained on filter paper and filter paper one And be transferred in the culture dish of dried and clean, juxtaposition in a vacuum drying oven, set the vacuum degree of vacuum oven as 0.05MPa, temperature are 70 DEG C, dry 6h, and after cooled to room temperature, carboxylated expanded graphite is made.
The secondary modification of S22, expanded graphite amino:
It takes 1g carboxylated expanded graphite to be added in the beaker for filling 100mL ethanol water, is ultrasonically treated, set Ultrasonic power is 40kHz, and ultrasonic water bath temperature is 35 DEG C, ultrasonic time 5min, obtains uniform carboxylated expanded graphite point Dispersion liquid；The carboxylated expanded graphite uniform dispersion that 100mL concentration is 10g/L and the beet that 10mL concentration is 2g/L are measured respectively Alkali surfactant solution, is successively transferred in three-necked flask, and sufficiently, pH of mixed is neutrality at this time for mixing, and 80 DEG C of reflux are stirred Mixing sufficiently reaction 6h, reaction terminates, is cooled to room temperature, and stands for 24 hours；Washing is filtered to obtained mixed liquor, first with anhydrous Ethanol washing 3 times, then be washed with deionized 3 times, it is finally filtered by vacuum, will be retained on filter paper using vacuum pump using circulatory water Solid and filter paper be transferred in the culture dish of dried and clean together, juxtaposition in a vacuum drying oven, vacuum degree be 0.05MPa When, 70 DEG C of dry 6h after cooled to room temperature, obtain the expanded graphite of amino secondary modification, the i.e. catalysis of functional modification Agent carrier expanded graphite.
S3, support type expandable graphite catalyst is prepared:
The nickel nitrate solution that 5.1mL is 1mol/L containing nickel ion concentration is pipetted, is slowly added into that fill 100mL ethyl alcohol water-soluble It in the beaker of liquid, is uniformly mixed, 1g functionalization expanded graphite is then added, places the beaker in numerical control ultrasonic cleaner and carries out Ultrasonic treatment, ultrasonic power 40kHz, ultrasonic water bath temperature are 35 DEG C, ultrasonic time 5min.After ultrasound, by beaker It is sealed, is transferred on cyclotron oscillation device with sealed membrane, adjusting hunting speed is duration of oscillation 9h under 150r/min, reaction knot Shu Hou stands filtering, filter residue is transferred in the culture dish of dried and clean, is put into drying box, 80 DEG C of dry 3h, natural cooling To room temperature, catalyst precursor is obtained；
Corundum straight tube crucible first is wiped with alcohol swab, is placed into drying box, 80 DEG C of dry 1h, after being cooled to room temperature, then It is put into catalyst precursor obtained, is finally putting into numerical control Muffle furnace and is calcined, heating rate is set as 10 DEG C/min, forges Burning temperature is 600 DEG C, calcination time 2h, and support type expandable graphite catalyst, i.e. NiO-EG is made in cooled to room temperature.
The present invention is prepared for surface-functionalized expanded graphite, on the basis of original, and considerably increases active site quantity. Surface-functionalized expanded graphite successively carries out dip loading as carrier, and support type expanded graphite is prepared in high-temperature calcination processing Catalyst composite, can be greatly improved reaction system oxidisability, and quick contact break while realizes the efficient removal of copper ion, Support type expandable graphite catalyst catalytic ozonation processing EDTA-Cu waste water, significant effect, catalytic performance are excellent.
Finally, it should be noted that above-described each embodiment is merely to illustrate technical solution of the present invention, rather than it is limited System；Although the present invention is described in detail referring to the foregoing embodiments, those skilled in the art should understand that: its It can still modify to technical solution documented by previous embodiment, or part of or all technical features are carried out Equivalent replacement；And these modifications or substitutions, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution Range.

Claims (10)

1. a kind of for handling the preparation method of the support type expandable graphite catalyst of EDTA-Cu waste water, it is characterised in that: it has Body the following steps are included:
The expanded graphite of S1, preparation catalyst carrier without sulphur without manganese:
S11, expansible graphite is prepared:
Ammonium nitrate solid is added in perchloric acid, natural flake graphite is added after stirring and dissolving, constant temperature water bath heats simultaneously after sealing Stirring, bath temperature are 30~50 DEG C, and revolving speed is 200~300r/min, and mixing time is 45~75min, and reaction is mixed Object；
After the reaction was completed, depressurization, after being cooled to room temperature, the mixture repeatedly rinsed with deionized water, until rinsing The pH of water is 5~7；The mixture of washes clean is filtered, by filtered mixture dry 4 at 60~80 DEG C~ Expansible graphite is made in 6h；
The high-temperature expansion of S12, expansible graphite prepare the expanded graphite without sulphur without manganese:
Expansible graphite made from step S11 is weighed, calcination is carried out with 900~1000 DEG C of temperature and is obtained until not expanding Expanded graphite to no sulphur without manganese；
S2, functional modification expanded graphite:
The carboxylated of S21, expanded graphite:
The expanded graphite made from step S1 without sulphur without manganese is added in ethanol water, is ultrasonically treated and is uniformly expanded Graphite dispersing solution, it is 3mol/L's that sodium carbonate liquor that concentration is 5mol/L and concentration are successively added in expanded graphite dispersion liquid Monoxone, sodium chloroacetate or bromoacetic acid solution are vibrated after ultrasonic treatment, and oscillation revolving speed is 150~200r/min, when oscillation Between be 3~5h；After oscillation treatment, it is added in 2mol/L hydrochloric acid solution and remaining sodium carbonate in solution, filtration washing uses deionization Water repeatedly washs, until filtrate pH is 6~7, is filtered by vacuum, is dry, after cooled to room temperature, carboxylated is made and expands stone Ink；
The secondary modification of S22, expanded graphite amino:
The expanded graphite of step S21 carboxylated is added in ethanol water, ultrasonic treatment obtains uniform carboxylated expansion stone Black alcohol dispersion liquid measures the carboxylated expanded graphite alcohol dispersion liquid that concentration is 10g/L and the beet that concentration is 1g/L respectively Alkali surfactant solution, is sufficiently mixed, 70~80 DEG C of return stirrings, and sufficiently 6~8h of reaction, reaction terminates, be cooled to room temperature, It stands for 24 hours, obtains mixed liquor, mixed liquor is filtered washing, is first washed repeatedly with dehydrated alcohol, then be washed with deionized Repeatedly, it is filtered by vacuum and dry, after cooled to room temperature, obtains the expanded graphite of amino secondary modification, complete catalyst and carry The functional modification of body expanded graphite；
S3, support type expandable graphite catalyst is prepared:
The metal-nitrate solutions that metal ion concentration is 1mol/L are added in ethanol water, after mixing, are added The functionalization expanded graphite of step S2 preparation, is ultrasonically treated, and is vibrated, and is stood filtering, filter residue is dried, natural cooling To room temperature, catalyst precursor is obtained；Catalyst precursor is calcined, heating rate is 10 DEG C/min, and calcination temperature is 500~600 DEG C, calcination time is 2~3h, and support type expandable graphite catalyst is made in cooled to room temperature.
2. it is according to claim 1 for handling the preparation method of the support type expandable graphite catalyst of EDTA-Cu waste water, It is characterized by: the amount ratio of natural flake graphite, ammonium nitrate and perchloric acid are as follows: 1g~2.5g:0.5g~2.5g:3mL~ 9mL。
3. it is according to claim 1 for handling the preparation method of the support type expandable graphite catalyst of EDTA-Cu waste water, It is characterized by: the expanded graphite without sulphur without manganese, natrium carbonicum calcinatum, the mass ratio of monoxone, sodium chloroacetate or bromoacetic acid are 0.1 ~0.5:6~30:5~25.
4. it is according to claim 1 for handling the preparation method of the support type expandable graphite catalyst of EDTA-Cu waste water, It is characterized by: the volume ratio of second alcohol and water is 1:3 in ethanol water.
5. it is according to claim 1 for handling the preparation method of the support type expandable graphite catalyst of EDTA-Cu waste water, It is characterized by: the ultrasound condition of step S21 are as follows: ultrasonic power 40kHz, ultrasonic time are 10~20min, ultrasonic water bath temperature Degree is 25~35 DEG C；In step S22, the condition of ultrasonic treatment are as follows: ultrasonic power 40kHz, ultrasonic water bath temperature are 25~35 DEG C, ultrasonic time is 5~15min；The vacuum drying condition of step S21 and S22 are as follows: vacuum degree 0.05MPa, temperature be 60~ 70 DEG C, drying time is 6~8h.
6. it is according to claim 1 for handling the preparation method of the support type expandable graphite catalyst of EDTA-Cu waste water, It is characterized by: the beet alkali surface activator is carboxylic acid group's glycine betaine, alkyl dimethyl sulfoethyl glycine betaine or alkyl two Methyl azochlorosulfonate propyl lycine.
7. it is according to claim 6 for handling the preparation method of the support type expandable graphite catalyst of EDTA-Cu waste water, It is characterized by: the mass ratio of carboxylated expanded graphite and beet alkali surface activator is 1:0.02~0.03.
8. it is according to claim 1 for handling the preparation method of the support type expandable graphite catalyst of EDTA-Cu waste water, It is characterized by: the metal nitrate is Fe(NO3)39H2O, magnesium nitrate hexahydrate or Nickelous nitrate hexahydrate.
9. it is according to claim 8 for handling the preparation method of the support type expandable graphite catalyst of EDTA-Cu waste water, It is characterized by: the mass ratio of functional modification expanded graphite and metal nitrate is 1:1.5~3.5.
10. according to claim 1 for handling the preparation side of the support type expandable graphite catalyst of EDTA-Cu waste water Method, it is characterised in that: the condition being ultrasonically treated in step S3 are as follows: ultrasonic power 40kHz, ultrasonic water bath temperature are 25~35 DEG C, ultrasonic time is 5~15min；The condition of oscillation are as follows: hunting speed is 100~150r/min, and duration of oscillation is 9~12h； Dry condition are as follows: drying temperature is 70~80 DEG C, and drying time is 3~5h.
CN201910014854.8A 2019-01-08 2019-01-08 Preparation method of supported expanded graphite catalyst for treating EDTA-Cu wastewater Active CN109647410B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910014854.8A CN109647410B (en) 2019-01-08 2019-01-08 Preparation method of supported expanded graphite catalyst for treating EDTA-Cu wastewater

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910014854.8A CN109647410B (en) 2019-01-08 2019-01-08 Preparation method of supported expanded graphite catalyst for treating EDTA-Cu wastewater

Publications (2)

Publication Number Publication Date
CN109647410A true CN109647410A (en) 2019-04-19
CN109647410B CN109647410B (en) 2020-04-21

Family

ID=66119553

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910014854.8A Active CN109647410B (en) 2019-01-08 2019-01-08 Preparation method of supported expanded graphite catalyst for treating EDTA-Cu wastewater

Country Status (1)

Country Link
CN (1) CN109647410B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110039182A (en) * 2019-05-27 2019-07-23 华侨大学 A kind of method and device preparing Electrolyzed Processing Flexible cathodes

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1911513A2 (en) * 2006-10-02 2008-04-16 Dieter Dr. Girlich Ozone catalytic converter
US20120027670A1 (en) * 2009-04-09 2012-02-02 University Of Miami Self sustained electrochemical promotion catalysts
CN105502360A (en) * 2015-12-25 2016-04-20 燕山大学 Preparation method of sulfur-free expansible graphite
CN106694007A (en) * 2016-12-19 2017-05-24 中国科学院山西煤炭化学研究所 Monodisperse metal atom/graphene composite catalyst and preparation method and application thereof
CN107226520A (en) * 2017-07-14 2017-10-03 哈尔滨工业大学 A kind of method that catalytic ozonation removes Organic substance in water
CN107252682A (en) * 2017-06-10 2017-10-17 陈永 A kind of preparation method and applications for being used for organic carbon vapor phase growth for the catalyst of carbide
CN107744806A (en) * 2017-10-16 2018-03-02 燕山大学 A kind of preparation method of catalyst using expanded graphite as carrier catalysis ozone decomposition
CN109107582A (en) * 2018-09-19 2019-01-01 江西萍乡市成宇陶瓷有限责任公司 A kind of preparation method of efficient ozone catalyst

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1911513A2 (en) * 2006-10-02 2008-04-16 Dieter Dr. Girlich Ozone catalytic converter
US20120027670A1 (en) * 2009-04-09 2012-02-02 University Of Miami Self sustained electrochemical promotion catalysts
CN105502360A (en) * 2015-12-25 2016-04-20 燕山大学 Preparation method of sulfur-free expansible graphite
CN106694007A (en) * 2016-12-19 2017-05-24 中国科学院山西煤炭化学研究所 Monodisperse metal atom/graphene composite catalyst and preparation method and application thereof
CN107252682A (en) * 2017-06-10 2017-10-17 陈永 A kind of preparation method and applications for being used for organic carbon vapor phase growth for the catalyst of carbide
CN107226520A (en) * 2017-07-14 2017-10-03 哈尔滨工业大学 A kind of method that catalytic ozonation removes Organic substance in water
CN107744806A (en) * 2017-10-16 2018-03-02 燕山大学 A kind of preparation method of catalyst using expanded graphite as carrier catalysis ozone decomposition
CN109107582A (en) * 2018-09-19 2019-01-01 江西萍乡市成宇陶瓷有限责任公司 A kind of preparation method of efficient ozone catalyst

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110039182A (en) * 2019-05-27 2019-07-23 华侨大学 A kind of method and device preparing Electrolyzed Processing Flexible cathodes
CN110039182B (en) * 2019-05-27 2024-02-27 华侨大学 Method and device for preparing flexible cathode for electrolytic machining

Also Published As

Publication number Publication date
CN109647410B (en) 2020-04-21

Similar Documents

Publication Publication Date Title
CN110170295A (en) A kind of dephosphorization adsorbent and preparation method thereof
CN113877581B (en) Copper ferrite spinel material and preparation method and application thereof
CN103706328B (en) The order mesoporous carbon adsorbent of aza magnetic, preparation method and application
CN105032375B (en) Preparation method of magnetic graphite-based heavy metal adsorbing material
CN109482188A (en) A kind of mesoporous iron cobalt class fenton catalyst of low price and preparation method thereof
CN110280308A (en) A kind of sodium tartrate Modified Cu ferro-cobalt houghite load carbon quantum dot nanocomposite and its preparation method and application
CN107308922A (en) A kind of water process is with Ni-based from growth three-dimensional material and preparation method thereof
CN109336225A (en) The mosaic electrode and preparation method thereof removed for nitrate nitrogen in sewage treatment plant tail water
CN109665525A (en) A kind of preparation method of " dumbbell shape " iron nitrogen codope porous carbon
CN108722445B (en) A kind of ultra-thin BiOX based solid solution photochemical catalyst and its preparation method and application
CN109647410A (en) For handling the preparation method of the support type expandable graphite catalyst of EDTA-Cu waste water
CN106964333A (en) The method that rare earth loaded catalyst for handling sewage and its preparation method and application and catalytic ozonation handle sewage
WO2020093517A1 (en) Photocatalytic material for efficient and selective reduction and removal of nitrate nitrogen in water, and preparation method thereof
CN105413697B (en) The preparation method of magnetic rare earth barium ferrite nanometer cleaning catalyst
CN107159094B (en) The method of tetracycline in magnetic magnesium hydroxide adsorbent removal waste water
CN105460979A (en) Preparation method and use method of FeS particles used for repairing hexavalent chromium contaminated soil
CN105271443A (en) Method for preparing flaky nano CoO or Co3O4 through assistant microwave heating
CN107866226A (en) A kind of NiFe2O4/Fe2O3The preparation method of magnetic composite
CN111151251A (en) Fe-Ni-Co composite Fenton-like catalyst and preparation method thereof
CN106744687B (en) A method of titanium hydride powders are prepared using chemical method
CN105883847A (en) Preparation method of iron-containing Y-shaped zeolite
CN113457709B (en) Preparation method and application of magnetic Co@CN nano material
CN109650515A (en) Utilize the method for sulfur doping ordered mesoporous carbon material activation persulfate processing 4- nitrophenol
CN102392270B (en) Method for preparing dendritic Ni nanocrystalline
CN107758723A (en) A kind of copper acid samarium nano-photo catalytic raw powder's production technology and its application

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant