CN110404543A - The VOC catalyst and preparation method thereof that metal composite oxide and ferroso-ferric oxide ordered arrangement are characterized - Google Patents
The VOC catalyst and preparation method thereof that metal composite oxide and ferroso-ferric oxide ordered arrangement are characterized Download PDFInfo
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- CN110404543A CN110404543A CN201910627336.3A CN201910627336A CN110404543A CN 110404543 A CN110404543 A CN 110404543A CN 201910627336 A CN201910627336 A CN 201910627336A CN 110404543 A CN110404543 A CN 110404543A
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- metal composite
- ferroso
- composite oxide
- reagent
- electroplating sludge
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- 239000002905 metal composite material Substances 0.000 title claims abstract description 25
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229940056319 ferrosoferric oxide Drugs 0.000 title claims abstract description 17
- 239000003054 catalyst Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 238000009713 electroplating Methods 0.000 claims abstract description 40
- 239000010802 sludge Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 5
- 239000002086 nanomaterial Substances 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 43
- 229910052742 iron Inorganic materials 0.000 claims description 24
- 239000003153 chemical reaction reagent Substances 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 10
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 229960000583 acetic acid Drugs 0.000 claims description 7
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 235000010265 sodium sulphite Nutrition 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 229910052596 spinel Inorganic materials 0.000 claims description 2
- 239000011029 spinel Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- WTFXARWRTYJXII-UHFFFAOYSA-N iron(2+);iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+2].[Fe+3].[Fe+3] WTFXARWRTYJXII-UHFFFAOYSA-N 0.000 abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000002386 leaching Methods 0.000 abstract description 3
- 239000002910 solid waste Substances 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 231100001261 hazardous Toxicity 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 abstract 1
- 238000003672 processing method Methods 0.000 abstract 1
- 229920002994 synthetic fiber Polymers 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 6
- 239000011651 chromium Substances 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- 150000002505 iron Chemical class 0.000 description 3
- 239000011268 mixed slurry Substances 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002361 compost Substances 0.000 description 1
- 238000009264 composting Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/864—Removing carbon monoxide or hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
-
- 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
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/862—Iron and chromium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/008—Sludge treatment by fixation or solidification
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/10—Treatment of sludge; Devices therefor by pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Catalysts (AREA)
- Compounds Of Iron (AREA)
Abstract
A kind of VOC catalyst and preparation method thereof that metal composite oxide is characterized with ferroso-ferric oxide ordered arrangement.The present invention is using electroplating sludge as synthetic material, in acidic environment down conversion temperature, pressure, the metallic element dissolution calcined in electroplating sludge under air and the nitrogen alternately atmosphere of variation sufficiently reacts into solution, forms the nano material of stable metal composite oxide and ferroso-ferric oxide ordered arrangement.The processing method minimizing that this method compares traditional electroplating sludge is obvious, and Leaching is extremely low；Calcination time is shorter, and temperature is lower, relatively large number of saving energy consumption；The amount of consumed metal salt reduces nearly half, it is reacted in acid condition, the metal ion for being easy to leach loss can be made sufficiently to react, in addition process flow is relatively simple, and reaction condition is more mild, the treatment process as hazardous solid waste, while guaranteeing innoxious, minimizing is obvious, and resource therein is greatly utilized, and reduces enterprise operation cost.
Description
Technical field
It is special the present invention relates to a kind of synthesized with electroplating sludge with metal composite oxide and ferroso-ferric oxide ordered arrangement
VOC catalyst of sign and preparation method thereof belongs to solid waste control technology field.
Background technique
Electroplating sludge is the emission for being handled in plating production process the waste water containing heavy metal and being generated.Plating,
Electronics industry generates a large amount of Cu, Ni, Cr, Fe, and due to electroplate technology, plating piece type, the difference of waste water treatment process is each
Variant, composition is sufficiently complex.
Final state object of the electroplating sludge as electroplating wastewater, although its amount much less than waste water, due in waste water
The heavy metals such as Cu, Ni, Cr, Zn, Fe are shifted and are enriched in sludge, in a sense, harm of the electroplating sludge to environment
It is more serious than electroplating wastewater.If not making any disposition to the great electroplating sludge of this harmfulness, ecological environment is broken
It badly will be even more serious.On the other hand, it if the heavy metal substance high to grade in electroplating sludge is not recycled, also anticipates
Taste the huge waste of resource.
The characteristics of for electroplating sludge and its harmfulness, from the point of view of environmental pollution prevention and control and resource circulation utilization,
Following two processing mode is mainly used, first is that after treatment, making sludge not cause secondary pollution and abandon and store, i.e.,
Harmlessness disposing；Second is that making to carry out synthetical recovery, i.e. resource utilization to the heavy metal resources in sludge.
The recycling treatment of electroplating sludge is broadly divided into solution leaching beneficiation technologies, and Ferrite method is handled, at composting organisms
Three kinds of reason, the above two need to add a large amount of medicament, and compost then occupies biggish space, and resource utilization is relatively low in preceding two
Person.Therefore it is badly in need of a kind of method of inexpensive high usage, while minimizing that electroplating sludge is innoxious, to greatest extent
Utilize resource therein.
Summary of the invention
One of the objects of the present invention is to provide a kind of metal composite oxides and ferroso-ferric oxide ordered arrangement to be characterized
VOC catalyst.
The second object of the present invention is to provide what the metal composite oxide was characterized with ferroso-ferric oxide ordered arrangement
The preparation method of VOC catalyst.
In order to achieve the above objectives, the present invention adopts the following technical scheme:
A kind of VOC catalyst that metal composite oxide is characterized with ferroso-ferric oxide ordered arrangement, it is characterised in that the catalysis
The structure of agent are as follows: the metal composite oxide and the equally distributed nano material of ferroso-ferric oxide of spinel structure, composition metal
The particle size of oxide is between 200-500nm, and the particle size of ferroso-ferric oxide is between 20-90nm, wherein four oxidations
Three weight of iron accountings are the 5~20% of totality.
A kind of side preparing the VOC catalyst that above-mentioned metal composite oxide and ferroso-ferric oxide ordered arrangement are characterized
Method, it is characterised in that:
A. by 0.2~0.25mol/L glacial acetic acid solution, 0.1~0.2mol/L citric acid solution according to 1:1~1:1.5 volume
Than being mixed and made into reagent a；Again by 0.025~-0.05mol/L potassium sodium tartrate solution and 0.01~0.02mol/L ethylenediamine tetraacetic
Acetic acid solution is mixed and made into reagent b according to the volume ratio between 1:1~1:2；Again by the reagent a and the reagent b according to 1:
The volume ratio of 0.2~1:0.5 uniformly mixes, and dehydrated alcohol is added after mixing, and dehydrated alcohol volume is less than mixed liquor volume
2%, structure-forming agent is made；
B. electroplating sludge and step a resulting structures forming agent mixed according to the ratio of solid-to-liquid ratio 1g:10ml~1g:12ml and,
Prepare metal composite oxide idiosome；
C. 0.1-0.15mol/L sodium carbonate liquor, 0.05-0.075mol/L sodium sulfite solution, by above two solution are prepared
Reagent c is mixed and made into according to the volume ratio of 1:0.2~1:0.5；
D. a kind of iron content electroplating sludge is taken, metal member of the iron content therein in 20g/100g or more, in addition to iron and calcium
Cellulose content in 10g/100g hereinafter, later by reagent c obtained by the iron content electroplating sludge and step c according to solid-to-liquid ratio 1g:7.5ml~
The ratio of 1g:10ml mixes, and is cooled to room temperature after being stirred and heated to 80~100 DEG C of heat preservations 30~45 minutes, and crystal form guiding is made
Agent；
E. by crystal form directed agents obtained by metal composite oxide idiosome obtained by step b and step d according to 1:1.5g~1:1.75g's
Ratio uniform mixing is warming up to 190 DEG C~220 DEG C under the atmosphere of the air under the pressure of 120-150KPa and calcines 60~90 points
Clock is warming up to 400~450 DEG C later and calcines 60~90 minutes under nitrogen atmosphere under normal pressure, heating rate controls when calcining
In 1~5 DEG C/min, the VOC catalyst that metal composite oxide and ferroso-ferric oxide ordered arrangement are characterized is obtained after cooling.
The present invention compared with prior art, has obvious prominent substantive distinguishing features and remarkable advantage:
(1) general curing/stabilizing technology is compared, the minimizing of this technique is obvious, and Leaching is extremely low；
(2) general heat treatment technics is compared, the control of this technique calcination temperature is at 450 DEG C hereinafter, calcination time is shorter, relatively
More saving energy consumptions；
(3) various electroplating sludge Ferrite method technologies are compared, the amount of metal salt consumed by this technique reduces nearly half, in acidity
Under the conditions of reacted, can make be easy leach be lost metal ion sufficiently react, in addition process flow is relatively simple,
Reaction condition is more mild；
It can be seen that the present invention has breakthrough advantage, it is innoxious in guarantee as the treatment process of hazardous solid waste
Meanwhile minimizing is obvious, and resource therein is greatly utilized, and reduces enterprise operation cost.
Detailed description of the invention
Fig. 1: the XRD characterization figure of material synthesized by embodiment 1.
Fig. 2: material synthesized by embodiment 1 is to the catalytic effect diagram of toluene, and toluene concentration is 1000ppm, air speed in figure
GHSV=9600h-1。
Specific embodiment
Embodiment 1
A method of metal composite oxide being synthesized using chromium containing electroplating sludge, wherein the content of Cr element is 25.40g/
100g, iron content electroplating sludge iron content are 23.16 g/100g, are comprised the following steps that
A. 0.2mol/L glacial acetic acid solution and 0.1mol/L citric acid solution are prepared, both solution 1:1 is mixed, is mixed
Reagent a, then 0.025mol/L potassium sodium tartrate solution and 0.01mol/L edta solution are prepared, according to the ratio of 1:2
It is mixed and made into reagent b, inwardly adds dehydrated alcohol later, structure-forming agent is made.
B. 5g chromium containing electroplating sludge is taken, is mixed with the structure-forming agent of 50ml, metal composite oxide idiosome is prepared.
C. 7.5g iron content electroplating sludge is weighed, and prepares 0.125mol/L sodium carbonate liquor, 0.05mol/L sodium sulfite is molten
Above two solution is mixed and made into reagent c according to the ratio of 1:0.25 by liquid, by the reagent of this iron content electroplating sludge and 57ml
C mixing, is cooled to room temperature after being stirred and heated to 100 DEG C, crystal form directed agents is made.
D. it takes the idiosome of 20ml uniformly to mix with the crystal form directed agents of 35ml, mixed slurries is placed in transformation program liter
In warm device, 200 DEG C of calcinings 90 minutes are warming up under the atmosphere of the air under the pressure of 140KPa, later nitrogen under normal pressure
Atmosphere is warming up to 450 DEG C and calcines 90 minutes under enclosing, heating rate is 2 DEG C/min when calcining, and electroplating sludge solidification is obtained after cooling
Object.
Embodiment 2
A method of metal composite oxide being synthesized using nickeliferous electroplating sludge, wherein the content of Ni element is 24.18g/
100g, iron content electroplating sludge iron content are 23.16 g/100g, are comprised the following steps that
A. 0.25mol/L glacial acetic acid solution and 0.1mol/L citric acid solution are prepared, both solution 1:1.5 is mixed, mixing
Reagent a is made, then prepares 0.04mol/L potassium sodium tartrate solution and 0.02mol/L edta solution, according to 1:1's
Ratio is mixed and made into reagent b, inwardly adds dehydrated alcohol later, structure-forming agent is made.
B. 10g copper-contained electroplating sludge is taken, is mixed with the structure-forming agent of 100ml, metal composite oxide idiosome is prepared.
C. 15g iron content electroplating sludge is weighed, and prepares 0.75mol/L sodium carbonate liquor, 0.05mol/L sodium sulfite is molten
Above two solution is mixed and made into reagent c according to the ratio of 1:0.4 by liquid, by the examination of this iron content electroplating sludge and 112.5ml
Agent c mixing, is cooled to room temperature after being stirred and heated to 80 DEG C, crystal form directed agents is made.
D. it takes the idiosome of 40ml uniformly to mix with the crystal form directed agents of 70ml, mixed slurries is placed in transformation program liter
In warm device, 200 DEG C of calcinings 90 minutes are warming up under the atmosphere of the air under the pressure of 120KPa, later nitrogen under normal pressure
Atmosphere is warming up to 450 DEG C and calcines 60 minutes under enclosing, heating rate is 5 DEG C/min when calcining, and electroplating sludge solidification is obtained after cooling
Object.
Embodiment 3
A method of metal composite oxide being synthesized using copper-contained electroplating sludge, wherein the content of Cu element is 39.84g/
100g, iron content electroplating sludge iron content are 23.16 g/100g, are comprised the following steps that
A. 0.2mol/L glacial acetic acid solution and 0.1mol/L citric acid solution are prepared, both solution 1:1 is mixed, is mixed
Reagent a, then 0.025mol/L potassium sodium tartrate solution and 0.01mol/L edta solution are prepared, according to the ratio of 1:1
It is mixed and made into reagent b, inwardly adds dehydrated alcohol later, structure-forming agent is made.
B. 5g copper-contained electroplating sludge is taken, is mixed with the structure-forming agent of 50ml, metal composite oxide idiosome is prepared.
C. 7.5g iron content electroplating sludge is weighed, and prepares 0.1mol/L sodium carbonate liquor, 0.05mol/L sodium sulfite is molten
Above two solution is mixed and made into reagent c according to the ratio of 1:0.2 by liquid, by the reagent c of this iron content electroplating sludge and 57ml
Mixing, is cooled to room temperature after being stirred and heated to 80 DEG C, crystal form directed agents is made.
D. it takes the idiosome of 20ml uniformly to mix with the crystal form directed agents of 30ml, mixed slurries is placed in transformation program liter
In warm device, 200 DEG C of calcinings 60 minutes are warming up under the atmosphere of the air under the pressure of 120KPa, later nitrogen under normal pressure
Atmosphere is warming up to 400 DEG C and calcines 60 minutes under enclosing, heating rate is 5 DEG C/min when calcining, and electroplating sludge solidification is obtained after cooling
Object.
The embodiment of the present invention is illustrated above, but the present invention is not limited to the above embodiments, it can also be according to this hair
The purpose of bright innovation and creation makes a variety of variations, and that does under the Spirit Essence and principle of all technical solutions according to the present invention changes
Become, modification, substitution, combination or simplified, should be equivalent substitute mode, as long as meeting goal of the invention of the invention, as long as not
Away from the method and technology principle and inventive concept of electroplating wastewater modified activated carbon of the present invention, protection scope of the present invention is belonged to.
Claims (2)
1. the VOC catalyst that a kind of metal composite oxide and ferroso-ferric oxide ordered arrangement are characterized, it is characterised in that this is urged
The structure of agent are as follows: the metal composite oxide and the equally distributed nano material of ferroso-ferric oxide of spinel structure, compound gold
Belong to the particle size of oxide between 200-500nm, the particle size of ferroso-ferric oxide is between 20-90nm, wherein four oxygen
Changing three weight of iron accountings is overall 5-20%.
2. a kind of prepare what metal composite oxide according to claim 1 was characterized with ferroso-ferric oxide ordered arrangement
The method of VOC catalyst, it is characterised in that:
A. by 0.2~0.25mol/L glacial acetic acid solution, 0.1~0.2mol/L citric acid solution according to 1:1~1:1.5 volume
Than being mixed and made into reagent a；Again by 0.025~-0.05mol/L potassium sodium tartrate solution and 0.01~0.02mol/L ethylenediamine tetraacetic
Acetic acid solution is mixed and made into reagent b according to the volume ratio between 1:1~1:2；Again by the reagent a and the reagent b according to 1:
The volume ratio of 0.2~1:0.5 uniformly mixes, and dehydrated alcohol is added after mixing, and dehydrated alcohol volume is less than mixed liquor volume
2%, structure-forming agent is made；
B. electroplating sludge and step a resulting structures forming agent mixed according to the ratio of solid-to-liquid ratio 1g:10ml~1g:12ml and,
Prepare metal composite oxide idiosome；
C. 0.1-0.15mol/L sodium carbonate liquor, 0.05-0.075mol/L sodium sulfite solution, by above two solution are prepared
Reagent c is mixed and made into according to the volume ratio of 1:0.2~1:0.5；
D. a kind of iron content electroplating sludge is taken, metal member of the iron content therein in 20g/100g or more, in addition to iron and calcium
Cellulose content in 10g/100g hereinafter, later by reagent c obtained by the iron content electroplating sludge and step c according to solid-to-liquid ratio 1g:7.5ml~
The ratio of 1g:10ml mixes, and is stirred and heated to 80~100 DEG C of heat preservations 30~be cooled to room temperature after forty minutes, crystal form guiding is made
Agent；
E. by crystal form directed agents obtained by metal composite oxide idiosome obtained by step b and step d according to 1:1.5g~1:1.75g's
Ratio uniform mixing is warming up to 190 DEG C~220 DEG C under the atmosphere of the air under the pressure of 120-150KPa and calcines 60~90 points
Clock is warming up to 400~450 DEG C later and calcines 60~90 minutes under nitrogen atmosphere under normal pressure, heating rate controls when calcining
In 1~5 DEG C/min, the VOC catalyst that metal composite oxide and ferroso-ferric oxide ordered arrangement are characterized is obtained after cooling.
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