CN106492886A - A kind of methods for making and using same of mixing rare metal catalyst - Google Patents
A kind of methods for making and using same of mixing rare metal catalyst Download PDFInfo
- Publication number
- CN106492886A CN106492886A CN201610894149.8A CN201610894149A CN106492886A CN 106492886 A CN106492886 A CN 106492886A CN 201610894149 A CN201610894149 A CN 201610894149A CN 106492886 A CN106492886 A CN 106492886A
- Authority
- CN
- China
- Prior art keywords
- metal catalyst
- mixing
- rare metal
- weight portion
- weight
- 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
Links
- 238000002156 mixing Methods 0.000 title claims abstract description 49
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 39
- 239000002184 metal Substances 0.000 title claims abstract description 39
- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000002351 wastewater Substances 0.000 claims abstract description 32
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 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
- 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
- 230000002977 hyperthermial effect Effects 0.000 claims abstract description 8
- 230000004913 activation Effects 0.000 claims abstract description 6
- 238000007493 shaping process Methods 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims description 20
- 230000003647 oxidation Effects 0.000 claims description 16
- 238000007254 oxidation reaction Methods 0.000 claims description 16
- 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
- 239000007787 solid Substances 0.000 claims description 10
- 238000005273 aeration Methods 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 6
- 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
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 229910001404 rare earth metal oxide Inorganic materials 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
- 230000015556 catabolic process Effects 0.000 abstract description 8
- 238000006731 degradation reaction Methods 0.000 abstract description 8
- 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
- 238000003756 stirring Methods 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 230000001413 cellular effect Effects 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
- 238000001556 precipitation Methods 0.000 description 4
- 239000010959 steel Substances 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
- 239000000203 mixture Substances 0.000 description 3
- 230000001590 oxidative effect Effects 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
- 229910052799 carbon Inorganic materials 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
- 238000011049 filling Methods 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
- -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
- 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
- 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
- 238000000354 decomposition reaction Methods 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
- 238000005516 engineering process Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 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
- 238000007639 printing Methods 0.000 description 1
- 230000004224 protection Effects 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
- 239000002699 waste material Substances 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
Classifications
-
- B01J35/60—
-
- 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
Abstract
The invention provides a kind of methods for making and using same of mixing rare metal catalyst.The preparation method of described mixing rare metal catalyst, it is characterised in that include：Step 1：The hydrochloric acid that low-grade Rare Earth Mine and concentrations by weight are 10～60% is compared 1: 1～4 according to weight to mix, 6～12h of post activation is stirred, is obtained rare earths material；Step 2：10～120 weight portion of rare earths material, 0.01～0.021 weight portion of silver granuel, 35～45 weight portion of coke grain and 200～300 weight portion of clay compound that 100 weight portion of pig scrap, 0.1～1 weight portion of copper scale, step 1 are obtained is mixed, add water to thick, put compacting shaping in a mold, taking-up is dried, hyperthermic treatment in Muffle furnace is put into, 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 the organic wastewater of difficult degradation, the present invention.
Description
Technical field
The present invention relates to a kind of method of mixing rare metal catalytic oxidant and its preparation, particularly one kind is applied to
PH2～14 on a large scale interior to organic wastewater with difficult degradation thereby process method.
Background technology
Wet method 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 catalystses have noble metal and base metal configuration, the former be typically platinum,
Silver, rhodium, ruthenium etc.；Non-precious metal catalyst commonly uses copper, iron etc..
It is a kind of the most frequently used method for processing organic wastewater that iron-carbon method processes organic wastewater, actually using light electrolysis
Method, iron are oxidized to iron ion, through effects such as flocculation, bridging, absorption, by organic pollutant degradation, absorption, through precipitation
(or air supporting) carries out gas-liquid separation.Method must be carried out under the strong acidic condition of pH=3 or so, for alkaline waste water needs to use
Acid for adjusting pH, is adjusted with alkali after reaction again and is gone back, and not only processing cost is very high, and produces a large amount of salts by follow-up for impact life
Change is processed.
In wet oxidation with Fenton process oxidation susceptibility preferably, it is with ferrous ion (Fe2+) for catalyst hydrogen peroxide
(H2O2) carry out the method for wastewater treatment of chemical oxidation.It can generate the hydroxyl radical free radical of strong oxidizing property, in aqueous with difficult drop
Solution organic matter generates organic free radical and is allowed to structure destruction, final oxidation Decomposition.Must be strong but Fenton oxidation method has the disadvantage
Carry out under acid condition, have impact on use range.
Content of the invention
It is an object of the invention to provide a kind of rare gold of preparation method and application mixing of mixing rare metal catalyst
The method that metal catalyst processes organic wastewater with difficult degradation thereby, using the composition catalysis of the metals such as low-grade Rare Earth Mine, mixed copper, silver, iron
Oxidant, process refractory organic industrial sewage, the mixing rare metal catalyst have bigger pH to be suitable for model than Fenton reagent
Enclose, and with higher oxidation susceptibility.
In order to achieve the above object, the invention provides a kind of preparation method of mixing rare metal catalyst, its feature
It is, including：
Step 1：The hydrochloric acid that low-grade Rare Earth Mine and concentrations by weight are 10～60% is compared 1: 1～4 according to weight to mix,
Stirring 6～12h of post activation, staticly settles, separation of solid and liquid obtains solids for rare earths material；
Step 2：10～120 weight of rare earths material that 100 weight portion of pig scrap, 0.1～1 weight portion of copper scale, step 1 are obtained
Amount part, 0.01～0.021 weight portion of silver granuel, 35～45 weight portion of coke grain and the mixing of 200～300 weight portion of clay compound
Stirring, adds water to thick, puts compacting shaping in a mold, and taking-up dries, and is put into hyperthermic treatment in Muffle furnace, obtains mixing dilute
There is metallic catalyst module.
Preferably, the rare earth oxide content of described low-grade Rare Earth Mine is 3～5%.More preferably 4%.
Preferably, described low-grade Rare Earth Mine contain neodymia 0.48%, lanthana 0.32%, yittrium oxide 1.24%,
Dysprosia 0.33% and aluminum oxide 0.1%.
Preferably, the particle diameter of described pig scrap is 2～20mm, the 5～15mm of particle diameter of copper scale, the particle diameter of silver granuel is 5～
15mm, the particle diameter of coke grain is 5～15mm.
Preferably, described clay compound contains shale 20-30 weight portions, coal dust 10-20 weight portions, and remaining is viscous
Soil.
Preferably, described hyperthermic treatment includes：First with 5-15 DEG C/h intensification 2.5-3.5h, then heated up with 40-60 DEG C/h
1-3h, then with the speed accelerated warming of 80-100 DEG C/h to 1100～1300 DEG C, be incubated 2h, Temperature fall to 50～60 DEG C,
Take out, natural cooling.
Preferably, described mixing rare metal catalyst module be cuboid, a length of 30～70cm, a width of 10～
40cm, a height of 8～25cm.
Preferably, described mould is welded by steel plate.
Preferably, described mixing rare metal catalyst module surface porosity, in cellular.
Present invention also offers applying the method that above-mentioned mixing rare metal catalyst carries out wastewater treatment, its feature to exist
In, including：Mixing rare metal catalyst module is deposited in catalysis oxidation pond, 1～4 layer is placed, by pH be 2～14 useless
Water is sent in catalysis oxidation pond and is processed, the waste water after being processed.
Preferably, the flow of inlet water of described waste water is carried out according to the requirement after waste strength, difficult degradation degree and process
Adjust.
Preferably, aeration is carried out simultaneously when processing, and gas-water ratio is 3～20: 1.
Preferably, reaction time during described process is 2～6h.
Preferably, in processing procedure, with pipe insert waste water in be added dropwise concentration be 30% hydrogen peroxidase 10 .1～
2vol%.
Compared with prior art, the invention has the beneficial effects as follows：
1st, mixing rare metal catalyst is present invention employs, treatment effeciency and reaction speed can be effectively improved, heavier
Want, reaction condition from iron-carbon method and the pH=3 of Fenton process, bring up to pH2～14 on a large scale interior equal can be dense to high difficult degradation
Degree organic wastewater has good removal effect, it is not necessary to is adjusted with acid, alkali, has expanded significantly range of application, i.e. catalytic more
Hurry up, 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, effectively reduces processing cost.
2nd, the higher organic wastewater of the organic wastewater to extremely difficult degraded, and processing requirement, for example, will be degraded at short notice
Arrive COD≤50mg/L or following, can with pipe intercalation reaction system be added dropwise concentration be 30% hydrogen peroxide, 0.1～2%,
The amount of hydrogen peroxide that now adds typically only has 1/10～1/3 of Fenton process under equal conditions.
3rd, mix rare metal catalyst module after suppressing, meet national standard " GB 18871-2002 ionization radiation protections
With the safe basic standard of radiation source " annex exemption condition.
4th, for high concentration in wastewater from chemical industry and pharmacy waste water the organic wastewater of difficult degradation, the present invention has the present invention
Good treatment effect.
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limit the scope of the present invention.In addition, it is to be understood that after the content for having read instruction of the present invention, people in the art
Member can be made various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Scope.
Embodiment 1
A kind of preparation method of mixing rare metal catalyst, concretely comprises the following steps：
Step 1：By low-grade Rare Earth Mine that rare earth oxide content is 4% (containing neodymia 0.48%, lanthana
0.32%th, the hydrochloric acid that yittrium oxide 1.24%, dysprosia 0.33% and aluminum oxide are 0.1%) and concentrations by weight is 10% is according to weight
Amount compares 1: 1 mixing, stirs post activation 6h, staticly settles, separation of solid and liquid, obtains solids for rare earths material, deposits in Plastic Drum
In standby；
Step 2：By pig scrap 100kg that particle diameter is 2～20mm, the copper scale 0.1kg of 5～15mm of particle diameter,
The coke grain of rare earths material 10kg that step 1 is obtained, the silver granuel 0.01kg that particle diameter is 5～15mm, particle diameter for 5mm
35kg and clay compound 250kg (containing shale 25kg, coal dust 15kg, remaining is clay) is mixed, and is added water to sticky
Shape, is placed in the mould being welded by steel plate compacting shaping, and taking-up is dried, and is put into hyperthermic treatment in Muffle furnace, first with 10 DEG C/
H intensification 3h, then with 50 DEG C/h intensification 2h, then with the speed accelerated warming of 80-100 DEG C/h to 1200 DEG C, be incubated 2h, drop naturally
To 50～60 DEG C after temperature about 24h, take out, natural cooling, obtain mixing rare metal catalyst module, the rare gold of described mixing
Metal catalyst module be cuboid, a length of 30cm, a width of 10cm, a height of 8cm, surface porosity, in cellular.
Embodiment 2
A kind of preparation method of mixing rare metal catalyst, concretely comprises the following steps：
Step 1：By low-grade Rare Earth Mine that rare earth oxide content is 4% (containing neodymia 0.48%, lanthana
0.32%th, the hydrochloric acid that yittrium oxide 1.24%, dysprosia 0.33% and aluminum oxide are 0.1%) and concentrations by weight is 60% is according to weight
Amount compares 1: 4 mixing, stirs post activation 12h, staticly settles, separation of solid and liquid, obtains solids for rare earths material, deposits in Plastic Drum
In standby；
Step 2：By pig scrap 100kg that particle diameter is 2～20mm, the copper scale 1kg of 5～15mm of particle diameter, step 1 obtain dilute
The mixing of native raw material 120kg, the silver granuel 0.021kg that particle diameter is 5～15mm, the coke grain 45kg that particle diameter is 5～15mm and clay
Material 250kg (containing shale 25kg, coal dust 15kg, remaining is clay) is mixed, and adds water to thick, is placed on and is welded by steel plate
Mould in compacting shaping, taking-up dries, and is put into hyperthermic treatment in Muffle furnace, first with 10 DEG C/h intensification 3h, then with 50 DEG C/
H intensification 2h, then with the speed accelerated warming of 80-100 DEG C/h to 1200 DEG C, are incubated 2h, to 50～60 after Temperature fall about 24h
DEG C, taking out, natural cooling, obtain mixing rare metal catalyst module, described mixing rare metal catalyst module is length
Cube, a length of 70cm, a width of 40cm, a height of 25cm, surface porosity, in cellular.
Embodiment 3
A kind of preparation method of mixing rare metal catalyst, concretely comprises the following steps：
Step 1：By the low-grade Rare Earth Mine of rare earth oxide content about 4% (containing neodymia 0.48%, lanthana
0.32%th, the hydrochloric acid that yittrium oxide 1.24%, dysprosia 0.33% and aluminum oxide are 0.1%) and concentrations by weight is 35% is according to weight
Amount compares 1: 2.5 mixing, stirs post activation 8h, staticly settles, separation of solid and liquid, obtains solids for rare earths material, deposits in plastics
Standby in bucket；
Step 2：Pig scrap 100kg that particle diameter is 2～20mm, the copper scale 0.5kg of 5～15mm of particle diameter, step 1 are obtained
Rare earths material 60kg, particle diameter are silver granuel 0.015kg, the coke grain 40kg that particle diameter is 5～15mm of 5～15mm and clay mixing
Material 250kg (containing shale 25kg, coal dust 15kg, remaining is clay) is mixed, and adds water to thick, is placed on and is welded by steel plate
Mould in compacting shaping, taking-up dries, and is put into hyperthermic treatment in Muffle furnace, first with 10 DEG C/h intensification 3h, then with 50 DEG C/
H intensification 2h, then with the speed accelerated warming of 80-100 DEG C/h to 1200 DEG C, are incubated 2h, to 50～60 after Temperature fall about 24h
DEG C, taking out, natural cooling, obtain mixing rare metal catalyst module, described mixing rare metal catalyst module is length
Cube, a length of 50cm, a width of 25cm, a height of 16cm, surface porosity, in cellular.
Application examples 1
Certain dye intermediate wastewater COD about 108000mg/L, pH=4.The mixing rare metal that embodiment 3 is obtained 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%, waste water is sent in catalysis oxidation pond and is processed, and carries out aeration, air water simultaneously during process
Than for 15: 1, aeration 4 hours inserts the hydrogenperoxide steam generator 0.2vol% for being added dropwise in waste water that concentration is 30%, now with pipe
COD drops to 30000mg/L, then aeration 4 hours, plus XSD accelerator (compare 10 by aluminum sulfate, dicyandiamide and formaldehyde according to weight:
Mix at 4: 3) 0.05%, waste water is taken out by aeration 1 hour, add coagulant aluminium chloride 100～300ppm and cloudy from
1～5ppm of sub- PAM flocculation aids, carries out coagulating, precipitation, separates, the waste water after being processed, its COD=2000mg/L.
Application examples 2
Certain dyeing waste water COD=550mg/l, pH=10,300 times of colourity.The mixing rare metal that embodiment 1 is obtained 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%, waste water is sent in catalysis oxidation pond and is processed, and carries out aeration, air water simultaneously during process
Than for 8: 1, waste water is taken out by aeration 4 hours, 100～300ppm of coagulant aluminium chloride and anion PAM flocculation aids is added
1～5ppm coagulatings, precipitation, separation, the waste water after being processed, COD=50mg/L, colourity are less than 80.
If this dyeing waste water directly adds 100～300ppm of aluminium chloride and anion PAM flocculation aid 1～5ppm coagulations
Reaction, precipitation, separation, water outlet COD 250mg/L, 120 times of colourity.
Claims (10)
1. a kind of mixing rare metal catalyst preparation method, it is characterised in that include：
Step 1：The hydrochloric acid that low-grade Rare Earth Mine and concentrations by weight are 10～60% is compared 1: 1～4 according to weight to mix, is stirred
6～12h of post activation, staticly settles, separation of solid and liquid obtains solids for rare earths material；
Step 2：10～120 weight of rare earths material that 100 weight portion of pig scrap, 0.1～1 weight portion of copper scale, step 1 are obtained
Part, 0.01～0.021 weight portion of silver granuel, 35～45 weight portion of coke grain and the mixing of 200～300 weight portion of clay compound are stirred
Mix, add water to thick, put compacting shaping in a mold, taking-up dries, and is put into hyperthermic treatment in Muffle furnace, obtain mixing rare
Metallic catalyst module.
2. as claimed in claim 1 mixing rare metal catalyst preparation method, it is characterised in that described is low-grade dilute
The rare earth oxide content of Tu Kuang is 3～5%.
3. as claimed in claim 1 mixing rare metal catalyst preparation method, it is characterised in that described is low-grade dilute
Tu Kuang contains neodymia 0.48%, lanthana 0.32%, yittrium oxide 1.24%, dysprosia 0.33% and aluminum oxide 0.1%.
4. as claimed in claim 1 mixing rare metal catalyst preparation method, it is characterised in that described pig scrap
Particle diameter is 2～20mm, the 5～15mm of particle diameter of copper scale, and the particle diameter of silver granuel is 5～15mm, and the particle diameter of coke grain is 5～15mm.
5. the preparation method of mixing rare metal catalyst as claimed in claim 1, it is characterised in that described clay mixing
Material contains shale 20-30 weight portions, coal dust 10-20 weight portions, and remaining is clay.
6. as claimed in claim 1 mixing rare metal catalyst preparation method, it is characterised in that described hyperthermic treatment
Including：First with 5-15 DEG C/h intensification 2.5-3.5h, then with 40-60 DEG C/h intensification 1-3h, then added with the speed of 80-100 DEG C/h
Speed is warming up to 1100～1300 DEG C, is incubated 2h, and Temperature fall to 50～60 DEG C takes out, natural cooling.
7. as claimed in claim 1 mixing rare metal catalyst preparation method, it is characterised in that described mixing is rare
Metallic catalyst module be cuboid, a length of 30～70cm, a width of 10～40cm, a height of 8～25cm.
8. the mixing prepared by the preparation method of the mixing rare metal catalyst any one of application claim 1-7 is dilute
The method for having metallic catalyst to carry out wastewater treatment, it is characterised in that include：Mixing rare metal catalyst module is deposited in
In catalysis oxidation pond, 1～4 layer is placed, the waste water that pH is 2～14 is sent in catalysis oxidation pond and is processed, after being processed
Waste water.
9. the method for carrying out wastewater treatment as claimed in claim 8, it is characterised in that carry out aeration, gas simultaneously when processing
Water ratio is 3～20: 1.
10. the method for carrying out wastewater treatment as claimed in claim 8, it is characterised in that in processing procedure, inserted with 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 true CN106492886A (en) | 2017-03-15 |
| CN106492886B 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) |
Cited By (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 |
| CN112337472A (en) * | 2020-11-27 | 2021-02-09 | 湖南湘牛环保实业有限公司 | Catalyst for removing COD (chemical oxygen demand) in wastewater by Fenton oxidation method, preparation method and application |
| CN115487837A (en) * | 2022-10-14 | 2022-12-20 | 吉林大学 | Nano composite material prepared by deep sea rare earth-rich clay loaded titanium dioxide |
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 |
Non-Patent Citations (2)
| Title |
|---|
| 吴向阳等: "《水污染控制工程及设备》", 30 November 2015 * |
| 孙锦宜等: "《含氮废水处理技术与应用》", 30 June 2003 * |
Cited By (5)
| 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 |
| CN112337472A (en) * | 2020-11-27 | 2021-02-09 | 湖南湘牛环保实业有限公司 | Catalyst for removing COD (chemical oxygen demand) in wastewater by Fenton oxidation method, 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 |
| CN115487837A (en) * | 2022-10-14 | 2022-12-20 | 吉林大学 | Nano composite material prepared by deep sea rare earth-rich clay loaded titanium dioxide |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106492886B (en) | 2019-06-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106492886B (en) | A kind of methods for making and using same mixing rare metal catalyst | |
| CN105967266A (en) | Efficient sewage treatment agent and preparation method thereof | |
| CN104724871B (en) | The technique that recycling treatment is carried out to the high-salt wastewater of preparation of hydrazine hydrate by use of ketazine | |
| CN101857325A (en) | Method for treating iron-containing acidic wastewater | |
| JP2009515686A (en) | Rapid non-equilibrium decompression of microbial waste streams | |
| KR102174670B1 (en) | Wastewater treatment system improving T-N quality of effluent water through pre-treatment of reducing nitrogen in returning water from dehydration process at the digestion tank of community sewage disposal plant | |
| 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 | |
| CN109264845A (en) | A kind of device and method of reverse osmosis concentrated water organic matter and ammonia nitrogen removal simultaneously | |
| CN101774673A (en) | Processing method of hardly degraded organic substance | |
| CN108249644A (en) | A kind of removal device and method of waste water phosphite | |
| CN105692717A (en) | Polyferric sulfate and preparation method of polyferric sulfate | |
| CN102583910B (en) | Method for treating waste water in multi-stage catalytic oxidation and microelectrolysis method | |
| JP2020139731A (en) | Method for treating residue and waste acid of industrial furnace | |
| US3927173A (en) | Treatment of acid waste waters to produce ferromagnetic sludges | |
| EP0012476B1 (en) | A process and apparatus for anaerobic conversion of organic material in an aqueous medium | |
| US6080300A (en) | Electrolytic process for generation of low-sulphate ferric hydroxide suspensions to effect purification of wastewater | |
| CN105384286B (en) | A kind of processing method of industrial wastewater recycling | |
| CN105967232A (en) | Method for leaching and simultaneously stabilizing arsenic sulfide slag | |
| CN102616997B (en) | Method for treating wastewater generated in production process of iron oxide pigment | |
| KR101276507B1 (en) | The appuratus of removing total phosphorus in wastewater using oxidaition process | |
| CN109052833A (en) | A kind of recycled water process units | |
| CN210313790U (en) | Ammonia nitrogen oxidation and nitrate nitrogen reduction integrated denitrification device for water body | |
| CN106277654A (en) | A kind of dyeing waste water Zero discharge treatment method | |
| CN107583934B (en) | Treatment process of waste salt mud in sodium chlorate production |
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 |
Granted publication date: 20190604 Termination date: 20211013 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |