CN106492886B - A kind of methods for making and using same mixing rare metal catalyst - Google Patents
A kind of methods for making and using same mixing rare metal catalyst Download PDFInfo
- Publication number
- CN106492886B CN106492886B CN201610894149.8A CN201610894149A CN106492886B CN 106492886 B CN106492886 B CN 106492886B CN 201610894149 A CN201610894149 A CN 201610894149A CN 106492886 B CN106492886 B CN 106492886B
- Authority
- CN
- China
- Prior art keywords
- weight
- metal catalyst
- mixing
- parts
- rare metal
- 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.)
- Expired - Fee Related
Links
- 238000002156 mixing Methods 0.000 title claims abstract description 52
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 40
- 239000002184 metal Substances 0.000 title claims abstract description 40
- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000002351 wastewater Substances 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004927 clay Substances 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 10
- 229910052709 silver Inorganic materials 0.000 claims abstract description 10
- 239000004332 silver Substances 0.000 claims abstract description 10
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 9
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 9
- 239000000571 coke Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 230000004913 activation Effects 0.000 claims abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- 230000003647 oxidation Effects 0.000 claims description 15
- 238000007254 oxidation reaction Methods 0.000 claims description 15
- 238000006555 catalytic reaction Methods 0.000 claims description 11
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 6
- 230000001413 cellular effect Effects 0.000 claims description 5
- 239000002817 coal dust Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- GEZAXHSNIQTPMM-UHFFFAOYSA-N dysprosium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Dy+3].[Dy+3] GEZAXHSNIQTPMM-UHFFFAOYSA-N 0.000 claims description 5
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 5
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 5
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 238000004065 wastewater treatment Methods 0.000 claims description 5
- 239000003863 metallic catalyst Substances 0.000 claims description 4
- 101710171243 Peroxidase 10 Proteins 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005189 flocculation Methods 0.000 description 4
- 230000016615 flocculation Effects 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 229960002163 hydrogen peroxide Drugs 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000701 coagulant Substances 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- -1 iron ion Chemical class 0.000 description 2
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000012028 Fenton's reagent Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- MOVRNJGDXREIBM-UHFFFAOYSA-N aid-1 Chemical compound O=C1NC(=O)C(C)=CN1C1OC(COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C(NC(=O)C(C)=C2)=O)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C(NC(=O)C(C)=C2)=O)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C(NC(=O)C(C)=C2)=O)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)CO)C(O)C1 MOVRNJGDXREIBM-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
-
- 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
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of methods for making and using sames for mixing rare metal catalyst.The preparation method of the mixing rare metal catalyst characterized by comprising step 1: low-grade Rare Earth Mine is mixed with the hydrochloric acid that concentrations by weight is 10~60% according to weight ratio 1: 1~4,6~12h of post activation is stirred, obtains rare earths material；Step 2: 10~120 parts by weight of rare earths material, 0.01~0.021 parts by weight of silver granuel, 35~45 parts by weight of coke grain and 200~300 parts by weight of clay mixture that 100 parts by weight of pig scrap, 0.1~1 parts by weight of copper scale, step 1 are obtained are mixed, it adds water to thick, put compacting forming in a mold, taking-up is dried, it is put into heating treatment in Muffle furnace, obtains mixing rare metal catalyst module.The present invention has good treatment effect for high concentration in wastewater from chemical industry and pharmacy waste water and organic wastewater difficult to degrade, the present invention.
Description
Technical field
The present invention relates to a kind of mixing rare metal catalytic oxidants and its method of preparation, especially one kind to be suitable for
To the method for organic wastewater with difficult degradation thereby processing in pH2~14 are a wide range of.
Background technique
Wet process catalytic oxidation treatment organic wastewater with difficult degradation thereby is a kind of effective ways, is mainly used in printing and dyeing, chemical industry, food
The treatment of Organic Wastewater of the industry such as product, medicine.Custom catalysts have noble metal and base metal configuration, the former be typically platinum,
Silver, rhodium, ruthenium etc.；Non-precious metal catalyst often uses copper, iron etc..
Iron-carbon method processing organic wastewater is a kind of most common method for processing organic wastewater, actually utilizes light electrolysis
Method, iron are oxidized to iron ion, by flocculation, bridging, absorption the effects of, by organic pollutant degradation, absorption, through precipitating
(or air bearing) carries out gas-liquid separation.Method must carry out under the strong acidic condition of pH=3 or so, and alkaline waste water is needed to use
Acid for adjusting pH is gone back with alkali adjusting again after reaction, and not only the processing cost is high, and generates a large amount of salts and will affect subsequent life
Change processing.
It is best with Fenton process oxidation susceptibility in wet oxidation, it is with ferrous ion (Fe2+) it is catalyst hydrogen peroxide
(H2O2) carry out chemical oxidation wastewater treatment method.It can generate the hydroxyl radical free radical of strong oxidizing property, drop in aqueous solution with hardly possible
Solution organic matter generates organic free radical and is allowed to structure destruction, final oxygenolysis.But Fenton oxidation method is the disadvantage is that must be strong
It is carried out under acid condition, affects use scope.
Summary of the invention
The object of the present invention is to provide a kind of rare gold of the preparation method and application mixing for mixing rare metal catalyst
The method that metal catalyst handles organic wastewater with difficult degradation thereby utilizes low-grade Rare Earth Mine, the composition catalysis of the metals such as mixed copper, silver, iron
Oxidant, processing refractory organic industrial sewage, the mixing rare metal catalyst have bigger pH to be applicable in model than Fenton reagent
It encloses, and there is stronger oxidation susceptibility.
In order to achieve the above object, the present invention provides a kind of preparation method for mixing rare metal catalyst, features
It is, comprising:
Step 1: low-grade Rare Earth Mine is mixed with the hydrochloric acid that concentrations by weight is 10~60% according to weight ratio 1: 1~4,
6~12h of post activation is stirred, staticly settled, be separated by solid-liquid separation and obtain solids as rare earths material；
Step 2: 10~120 weight of rare earths material that 100 parts by weight of pig scrap, 0.1~1 parts by weight of copper scale, step 1 are obtained
Measure part, 0.01~0.021 parts by weight of silver granuel, 35~45 parts by weight of coke grain and the mixing of 200~300 parts by weight of clay mixture
Stirring, adds water to thick, puts compacting forming in a mold, taking-up dries, be put into heating treatment in Muffle furnace, obtain mixing dilute
There is metallic catalyst module.
Preferably, the rare earth oxide content of the low-grade Rare Earth Mine is 3~5%.More preferably 4%.
Preferably, the low-grade Rare Earth Mine contain neodymia 0.48%, lanthana 0.32%, yttrium oxide 1.24%,
Dysprosia 0.33% and aluminium oxide 0.1%.
Preferably, the partial size of the pig scrap is 2~20mm, 5~15mm of partial size of copper scale, the partial size of silver granuel is 5~
15mm, the partial size of coke grain are 5~15mm.
Preferably, the clay mixture contains shale 20-30 parts by weight, coal dust 10-20 parts by weight, remaining is viscous
Soil.
Preferably, the heating treatment includes: first with 5-15 DEG C/h heating 2.5-3.5h, then with 40-60 DEG C/h heating
1-3h, then with the speed accelerated warming of 80-100 DEG C/h to 1100~1300 DEG C, keep the temperature 2h, Temperature fall to 50~60 DEG C,
It takes out, natural cooling.
Preferably, the mixing rare metal catalyst module be cuboid, a length of 30~70cm, width be 10~
40cm, a height of 8~25cm.
Preferably, the mold is welded by steel plate.
Preferably, the mixing rare metal catalyst module surface porosity is in cellular.
The present invention also provides the method that the above-mentioned mixing rare metal catalyst of application carries out wastewater treatment, feature exists
In, comprising: mixing rare metal catalyst module is deposited in catalysis oxidation pond, places 1~4 layer, by pH be 2~14 it is useless
Water is sent into catalysis oxidation pond and is handled, the waste water that obtains that treated.
Preferably, the flow of inlet water of the waste water according to waste strength, degree difficult to degrade and treated require carry out
It adjusts.
Preferably, it is aerated simultaneously in processing, gas-water ratio is 3~20: 1.
Preferably, the reaction time when processing is 2~6h.
Preferably, during processing, with pipe insertion waste water in be added dropwise concentration be 30% hydrogen peroxidase 10 .1~
2vol%.
Compared with prior art, the beneficial effects of the present invention are:
1, present invention employs mixing rare metal catalyst, treatment effeciency and reaction speed be can effectively improve, it is heavier
It wants, for reaction condition from iron-carbon method and Fenton process pH=3, being increased to pH2~14 can be to high difficult to degrade dense on a large scale
Degree organic wastewater has good removal effect, it is not necessary to be adjusted with acid, alkali, expand application range, i.e. catalytic significantly more
Fastly, compared with Fenton process: Fenton process is only applicable to pH=3, and present invention can be suitably applied to pH2~14, and under effect same, mistake
The dosage of hydrogen oxide only has the 1/3-1/10 of Fenton process, and processing cost is effectively reduced.
2, the organic wastewater to extremely difficult degradation and the higher organic wastewater of processing requirement, such as to degrade in a short time
The hydrogen peroxide that concentration is 30% is added dropwise under pipe intercalation reaction system to COD≤50mg/L or hereinafter, can use, 0.1~2%,
The amount of hydrogen peroxide added at this time generally only has 1/10~1/3 of Fenton process under equal conditions.
3, rare metal catalyst module is mixed after suppressing, and meets national standard " GB 18871-2002 ionization radiation protection
With the safe basic standard of radiation source " annex exemption condition.
4, the present invention is for high concentration in wastewater from chemical industry and pharmacy waste water and organic wastewater difficult to degrade, the present invention have
Good treatment effect.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
A kind of preparation method mixing rare metal catalyst, specific steps are as follows:
Step 1: the low-grade Rare Earth Mine that rare earth oxide content is 4% (is contained into neodymia 0.48%, lanthana
0.32%, yttrium oxide 1.24%, dysprosia 0.33% and aluminium oxide 0.1%) with concentrations by weight be 10% hydrochloric acid according to weight
Amount stirs post activation 6h, staticly settles, is separated by solid-liquid separation than 1: 1 mixing, and obtaining solids is rare earths material, deposits in plastic barrel
In it is spare；
Step 2: by partial size be the pig scrap 100kg of 2~20mm, the copper scale 0.1kg of 5~15mm of partial size,
The coke grain that silver granuel 0.01kg that rare earths material 10kg, the partial size that step 1 obtains are 5~15mm, partial size are 5mm
35kg and clay mixture 250kg (containing shale 25kg, coal dust 15kg, remaining is clay) is mixed, and adds water to sticky
Shape is placed in the mold being welded by steel plate and is compacted forming, and taking-up dries, and is put into heating treatment in Muffle furnace, first with 10 DEG C/
H heating 3h, then 2h is kept the temperature then with the speed accelerated warming of 80-100 DEG C/h to 1200 DEG C with 50 DEG C/h heating 2h, it drops naturally
Temperature is taken out, natural cooling about for 24 hours afterwards to 50~60 DEG C, obtains mixing rare metal catalyst module, the rare gold of the mixing
Metal catalyst module is cuboid, and a length of 30cm, width 10cm, a height of 8cm, surface porosity is in cellular.
Embodiment 2
A kind of preparation method mixing rare metal catalyst, specific steps are as follows:
Step 1: the low-grade Rare Earth Mine that rare earth oxide content is 4% (is contained into neodymia 0.48%, lanthana
0.32%, yttrium oxide 1.24%, dysprosia 0.33% and aluminium oxide 0.1%) with concentrations by weight be 60% hydrochloric acid according to weight
Amount stirs post activation 12h, staticly settles, is separated by solid-liquid separation than 1: 4 mixing, and obtaining solids is rare earths material, deposits in plastic barrel
In it is spare；
Step 2: pig scrap 100kg, the copper scale 1kg of 5~15mm of partial size, step 1 that partial size is 2~20mm being obtained dilute
Coke grain 45kg and the clay mixing that silver granuel 0.021kg that native raw material 120kg, partial size are 5~15mm, partial size are 5~15mm
Expect 250kg (containing shale 25kg, coal dust 15kg, remaining is clay) mixing, adds water to thick, be placed on and welded by steel plate
Made of forming is compacted in mold, taking-up is dried, and heating treatment in Muffle furnace is put into, first heated up 3h with 10 DEG C/h, then with 50 DEG C/
H heating 2h keeps the temperature 2h, Temperature fall is about for 24 hours afterwards to 50~60 then with the speed accelerated warming of 80-100 DEG C/h to 1200 DEG C
DEG C, it takes out, natural cooling, obtains mixing rare metal catalyst module, the mixing rare metal catalyst module is length
Cube, a length of 70cm, width 40cm, a height of 25cm, surface porosity is in cellular.
Embodiment 3
A kind of preparation method mixing rare metal catalyst, specific steps are as follows:
Step 1: by rare earth oxide content be about 4% low-grade Rare Earth Mine (containing neodymia 0.48%, lanthana
0.32%, yttrium oxide 1.24%, dysprosia 0.33% and aluminium oxide 0.1%) with concentrations by weight be 35% hydrochloric acid according to weight
Amount stirs post activation 8h, staticly settles, is separated by solid-liquid separation than 1: 2.5 mixing, and obtaining solids is rare earths material, deposits in plastics
It is spare in bucket；
Step 2: pig scrap 100kg, the copper scale 0.5kg of 5~15mm of partial size, step 1 that partial size is 2~20mm are obtained
Coke grain 40kg and the clay mixing that silver granuel 0.015kg that rare earths material 60kg, partial size are 5~15mm, partial size are 5~15mm
Expect 250kg (containing shale 25kg, coal dust 15kg, remaining is clay) mixing, adds water to thick, be placed on and welded by steel plate
Made of forming is compacted in mold, taking-up is dried, and heating treatment in Muffle furnace is put into, first heated up 3h with 10 DEG C/h, then with 50 DEG C/
H heating 2h keeps the temperature 2h, Temperature fall is about for 24 hours afterwards to 50~60 then with the speed accelerated warming of 80-100 DEG C/h to 1200 DEG C
DEG C, it takes out, natural cooling, obtains mixing rare metal catalyst module, the mixing rare metal catalyst module is length
Cube, a length of 50cm, width 25cm, a height of 16cm, surface porosity is in cellular.
Application examples 1
Certain dye intermediate wastewater COD about 108000mg/L, pH=4.The mixing rare metal that embodiment 3 obtains is urged
Agent module is deposited in catalysis oxidation pond, places 2 layers, the filling of the mixing rare metal catalyst module in catalysis oxidation pond
Percent by volume is 30%-50%, and waste water is sent into catalysis oxidation pond and be handled, is aerated when processing simultaneously, air water
Than being 15: 1, it is aerated 4 hours, the hydrogenperoxide steam generator 0.2vol% that concentration is 30% is added dropwise in pipe insertion waste water, at this time
COD drops to 30000mg/L, then is aerated 4 hours, add XSD promotor (by aluminum sulfate, dicyandiamide and formaldehyde according to weight ratio 10:
Mix at 4: 3) 0.05%, be aerated 1 hour, waste water is taken out, be added 100~300ppm of coagulant aluminium chloride and yin from
1~5ppm of sub- PAM flocculation aid carries out coagulating, precipitating, separation, obtain that treated waste water, COD=2000mg/L.
Application examples 2
300 times of certain dyeing waste water COD=550mg/l, pH=10, coloration.The mixing rare metal that embodiment 1 obtains is urged
Agent module is deposited in catalysis oxidation pond, places 2 layers, the filling of the mixing rare metal catalyst module in catalysis oxidation pond
Percent by volume is 25%-45%, and waste water is sent into catalysis oxidation pond and be handled, is aerated when processing simultaneously, air water
Than being 8: 1, it is aerated 4 hours, waste water is taken out, 100~300ppm of coagulant aluminium chloride and anion PAM flocculation aid is added
1~5ppm coagulating, precipitating, separation, the waste water that obtains that treated, COD=50mg/L, coloration is less than 80.
If this dyeing waste water directly adds 100~300ppm of aluminium chloride and anion PAM flocculation aid 1~5ppm coagulation
Reaction, precipitating, separation, be discharged COD 250mg/L, 120 times of coloration.
Claims (10)
1. a kind of preparation method for mixing rare metal catalyst characterized by comprising
Step 1: low-grade Rare Earth Mine being mixed with the hydrochloric acid that concentrations by weight is 10~60% according to weight ratio 1:1~4, is stirred
6~12h of post activation, staticly settle, be separated by solid-liquid separation obtain solids be rare earths material；
Step 2: 10~120 weight of rare earths material that 100 parts by weight of pig scrap, 0.1~1 parts by weight of copper scale, step 1 are obtained
Part, 0.01~0.021 parts by weight of silver granuel, 35~45 parts by weight of coke grain and the mixing of 200~300 parts by weight of clay mixture are stirred
It mixes, adds water to thick, put compacting forming in a mold, taking-up dries, be put into heating treatment in Muffle furnace, obtain mixing rare
Metallic catalyst module；The mixing rare metal catalyst module surface porosity is in cellular.
2. the preparation method of mixing rare metal catalyst as described in claim 1, which is characterized in that described is low-grade dilute
The rare earth oxide content of Tu Kuang is 3~5%.
3. the preparation method of mixing rare metal catalyst as described in claim 1, which is characterized in that described is low-grade dilute
Tu Kuang contains neodymia 0.48%, lanthana 0.32%, yttrium oxide 1.24%, dysprosia 0.33% and aluminium oxide 0.1%.
4. the preparation method of mixing rare metal catalyst as described in claim 1, which is characterized in that the pig scrap
Partial size is 2~20mm, and 5~15mm of partial size of copper scale, the partial size of silver granuel is 5~15mm, and the partial size of coke grain is 5~15mm.
5. the preparation method of mixing rare metal catalyst as described in claim 1, which is characterized in that the clay mixing
Material contains shale 20-30 parts by weight, coal dust 10-20 parts by weight, remaining is clay.
6. the preparation method of mixing rare metal catalyst as described in claim 1, which is characterized in that the heating treatment
Include: first with 5-15 DEG C/h heating 2.5-3.5h, then with 40-60 DEG C/h heating 1-3h, is then added with the speed of 80-100 DEG C/h
Speed is warming up to 1100~1300 DEG C, keeps the temperature 2h, and Temperature fall takes out, natural cooling to 50~60 DEG C.
7. the preparation method of mixing rare metal catalyst as described in claim 1, which is characterized in that the mixing is rare
Metallic catalyst module is cuboid, and a length of 30~70cm, width is 10~40cm, a height of 8~25cm.
8. mixing prepared by the preparation method of application mixing rare metal catalyst of any of claims 1-7 is dilute
The method for thering is metallic catalyst to carry out wastewater treatment characterized by comprising be deposited in mixing rare metal catalyst module
In catalysis oxidation pond, 1~4 layer is placed, the waste water that pH is 2~14 is sent into catalysis oxidation pond and is handled, after obtaining processing
Waste water.
9. carrying out the method for wastewater treatment as claimed in claim 8, which is characterized in that be aerated simultaneously in processing, gas
Water ratio is 3~20:1.
10. carrying out the method for wastewater treatment as claimed in claim 8, which is characterized in that during processing, be inserted into pipe
Hydrogen peroxidase 10 .1~2vol% that concentration is 30% is added dropwise in waste water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610894149.8A CN106492886B (en) | 2016-10-13 | 2016-10-13 | A kind of methods for making and using same mixing rare metal catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610894149.8A CN106492886B (en) | 2016-10-13 | 2016-10-13 | A kind of methods for making and using same mixing rare metal catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106492886A CN106492886A (en) | 2017-03-15 |
| CN106492886B true CN106492886B (en) | 2019-06-04 |
Family
ID=58295353
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610894149.8A Expired - Fee Related CN106492886B (en) | 2016-10-13 | 2016-10-13 | A kind of methods for making and using same mixing rare metal catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106492886B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107029729A (en) * | 2017-04-29 | 2017-08-11 | 张仕林 | A kind of ceramic catalyst and its preparation method and application |
| CN112337472B (en) * | 2020-11-27 | 2023-08-11 | 湖南湘牛环保实业有限公司 | Catalyst for removing COD in wastewater by Fenton oxidation method, preparation method and application |
| CN115487837B (en) * | 2022-10-14 | 2023-10-20 | 吉林大学 | Nanocomposite prepared by loading titanium dioxide on deep sea rare earth-rich clay |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07185569A (en) * | 1993-12-28 | 1995-07-25 | Nippon Shokubai Co Ltd | Treatment of nitrate radical-containing waste water |
| CN1045398C (en) * | 1991-02-05 | 1999-10-06 | 株式会社日本触媒 | Catalyst for treating waste water, process for producing it, and process for treating waste water with catalyst |
| CN101654297A (en) * | 2008-08-18 | 2010-02-24 | 武钦佩 | Method and equipment for mineralizing and degrading organic wastewater |
| CN103058347A (en) * | 2013-01-06 | 2013-04-24 | 东华大学 | Method for processing high-concentration refractory organic wastewater by using mixed rare earth-brass-iron-carbon catalytic oxidation method |
| CN104030428A (en) * | 2014-06-19 | 2014-09-10 | 同济大学 | Industrial wastewater advanced treatment method by catalytic oxidation of hydrogen peroxide |
| CN104386800A (en) * | 2014-11-25 | 2015-03-04 | 东华大学 | Rare-earth catalytic oxidation device and method for printing and dyeing wastewater |
-
2016
- 2016-10-13 CN CN201610894149.8A patent/CN106492886B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1045398C (en) * | 1991-02-05 | 1999-10-06 | 株式会社日本触媒 | Catalyst for treating waste water, process for producing it, and process for treating waste water with catalyst |
| JPH07185569A (en) * | 1993-12-28 | 1995-07-25 | Nippon Shokubai Co Ltd | Treatment of nitrate radical-containing waste water |
| CN101654297A (en) * | 2008-08-18 | 2010-02-24 | 武钦佩 | Method and equipment for mineralizing and degrading organic wastewater |
| CN103058347A (en) * | 2013-01-06 | 2013-04-24 | 东华大学 | Method for processing high-concentration refractory organic wastewater by using mixed rare earth-brass-iron-carbon catalytic oxidation method |
| CN104030428A (en) * | 2014-06-19 | 2014-09-10 | 同济大学 | Industrial wastewater advanced treatment method by catalytic oxidation of hydrogen peroxide |
| CN104386800A (en) * | 2014-11-25 | 2015-03-04 | 东华大学 | Rare-earth catalytic oxidation device and method for printing and dyeing wastewater |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106492886A (en) | 2017-03-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106492886B (en) | A kind of methods for making and using same mixing rare metal catalyst | |
| CN105621809B (en) | A kind of processing method of shale gas fracturing outlet liquid | |
| CN109052445A (en) | A kind of method of Quadratic aluminum dust innoxious use | |
| EP2927197A1 (en) | System for treating coal gasification wastewater, and method for treating coal gasification wastewater | |
| CN106745613B (en) | A kind of processing method of organic phosphine precipitating reagent and the waste water of organic phosphine containing high concentration | |
| CN101172684A (en) | Method for industrial production of polymeric aluminum ferric chloride water purification agent with coal ash | |
| CN105692717B (en) | A kind of bodied ferric sulfate and preparation method thereof | |
| CN107098518A (en) | The processing method and processing system of chemical nickle-plating wastewater | |
| CN104193058B (en) | A kind of gold mine cyanide wastewater comprehensive processing method | |
| CN104176884B (en) | A kind of cyanide wastewater integrated conduct method | |
| CN109264845A (en) | A kind of device and method of reverse osmosis concentrated water organic matter and ammonia nitrogen removal simultaneously | |
| CN108249644A (en) | A kind of removal device and method of waste water phosphite | |
| CN110467251A (en) | A kind of composite water treatment agent and the preparation method and application thereof | |
| CN107188292B (en) | Method for purifying arsenic-containing waste liquid by utilizing cyaniding silver extraction waste residues | |
| CN109354314B (en) | Combined biological bed treatment process for low-carbon-source high-ammonia-nitrogen high-organophosphorus wastewater | |
| US3927173A (en) | Treatment of acid waste waters to produce ferromagnetic sludges | |
| Moldoveanu et al. | Strategies for calcium sulphate scale control in hydrometallurgical processes at 80° C | |
| CN106006926B (en) | Efficient catalytic ozone water treatment technology based on composite oxides | |
| CN105384286B (en) | A kind of processing method of industrial wastewater recycling | |
| CN106698890A (en) | Method for preparing sludge treating agent through waste acid containing ferrous ions | |
| CN103058348B (en) | Method for processing high-concentration refractory organic wastewater by using mixed rare earth-iron-carbon catalytic oxidant | |
| CN105906014A (en) | Production technology for polymeric aluminum magnesium water purifying agent and water purifying method | |
| CN105967232A (en) | Method for leaching and simultaneously stabilizing arsenic sulfide slag | |
| KR101276507B1 (en) | The appuratus of removing total phosphorus in wastewater using oxidaition process | |
| CN108557973A (en) | A kind of polyacrylamide flocculant and preparation method for sewage disposal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | 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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190604 Termination date: 20211013 |