CN109513439A - A kind of catalyst for waste water debirs advanced oxidation degradation - Google Patents
A kind of catalyst for waste water debirs advanced oxidation degradation Download PDFInfo
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- CN109513439A CN109513439A CN201810607904.9A CN201810607904A CN109513439A CN 109513439 A CN109513439 A CN 109513439A CN 201810607904 A CN201810607904 A CN 201810607904A CN 109513439 A CN109513439 A CN 109513439A
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- Prior art keywords
- solution
- catalyst
- waste water
- debirs
- sediment
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- 239000003054 catalyst Substances 0.000 title claims abstract description 28
- 239000002351 wastewater Substances 0.000 title claims abstract description 18
- 230000003647 oxidation Effects 0.000 title claims abstract description 17
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 17
- 230000015556 catabolic process Effects 0.000 title claims abstract description 10
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 10
- 239000000243 solution Substances 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 21
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 21
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000013049 sediment Substances 0.000 claims abstract description 14
- 239000012266 salt solution Substances 0.000 claims abstract description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000032683 aging Effects 0.000 claims abstract description 11
- 238000011049 filling Methods 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000000853 adhesive Substances 0.000 claims abstract description 5
- 230000001070 adhesive effect Effects 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 3
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 3
- 238000001556 precipitation Methods 0.000 claims abstract description 3
- 230000003197 catalytic effect Effects 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- -1 hydroxybutyl Chemical group 0.000 claims description 6
- 229920000609 methyl cellulose Polymers 0.000 claims description 6
- 239000001923 methylcellulose Substances 0.000 claims description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 claims description 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N alpha-methyl toluene Natural products CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 2
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 2
- 238000009938 salting Methods 0.000 claims 2
- 230000000694 effects Effects 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000741 silica gel Substances 0.000 abstract description 7
- 229910002027 silica gel Inorganic materials 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000012267 brine Substances 0.000 abstract description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 abstract description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 32
- 229910052763 palladium Inorganic materials 0.000 description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229960001866 silicon dioxide Drugs 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 235000010981 methylcellulose Nutrition 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- YNTCDWYDVCVNPF-UHFFFAOYSA-N [C-]#N.[Na+].S(=O)(=O)(O)O Chemical compound [C-]#N.[Na+].S(=O)(=O)(O)O YNTCDWYDVCVNPF-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NXJCBFBQEVOTOW-UHFFFAOYSA-L palladium(2+);dihydroxide Chemical compound O[Pd]O NXJCBFBQEVOTOW-UHFFFAOYSA-L 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- PANBYUAFMMOFOV-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [Na].OS(O)(=O)=O PANBYUAFMMOFOV-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- 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
- B01J23/8933—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8946—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
-
- B01J35/56—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
Abstract
The invention discloses a kind of catalyst for waste water debirs advanced oxidation degradation, preparation method includes: range of the sodium silicate solution by sulfuric acid or sodium hydroxide adjusting pH value in 12-13, formation clear solution；Soluble metal salt solution is mixed with sodium silicate solution, carries out neutralization-precipitation reaction, generation obtains the doping sediment of silica gel and metal hydroxides, then the pH value for adjusting mixed liquor by dilute sulfuric acid keeps mixing to continue aging reaction in 6-8；Sediment after reaction aging is separated by filtration and is dried, then the adhesive mixing of sediment 5-12% mass is added, and after being squeezed by mold and forming the body drying of honeycomb, is roasted at a temperature of 400~600 DEG C, obtain the catalyst monolith filling body of high specific area.The present invention efficiently can carry out catalysis oxidation to such as phenol of hardly degraded organic substance in waste water etc., recycle the salt in brine waste.
Description
Technical field
The invention belongs to the catalyst for catalytic oxidation of hardly degraded organic substance in technical field of environmental protection in chemical industry more particularly to waste water
And preparation method thereof.
Background technique
As China's industry is grown rapidly, sewage discharge increasingly increases, and is difficult to biodegradable chemicals largely with waste water
Form is discharged into environment, causes the serious pollution of water resource, has become the pain spot of social development and the hot spot of concern.Especially exist
That discharges in the industrial processes such as coking, petrochemical industry, printing and dyeing, pharmacy, organic synthesis is anhydrous containing a large amount of toxic organic compounds and height
Concentration salt, such as sodium sulphate, sodium chloride, sodium nitrate, copper sulphate etc. need pair so that can not directly pass through biochemical treatment means
After Nacl carries out Crystallization Separation in waste water, then biochemical treatment is carried out, to generate toxic industrial waste salt, can not accomplish industry
Salt recycling treatment；Simultaneously because useless Organic substance in water contains such as formaldehyde, alcohols and difficult to degrade and high boiling phenolic material
Matter, at present Conventional catalytic oxidation can not also be handled, and be abraum salt by the salt that distillation crystallization obtains for brine waste,
It can not recycling treatment.Oxidation means of the advanced oxidation as new development obtain extremely strong energy of oxidation by screening suitable catalyst
The macromolecular debirs of bond energy high in water body are oxidized to degradable, hypotoxicity small molecule by the free radical of power, but it is catalyzed
Agent and core process technology be all from external import, it is at high cost, be unfavorable for the development of domestic sewage disposal technology.
Summary of the invention
Goal of the invention: being directed to above-mentioned existing problem and shortage, and the object of the present invention is to provide one kind to be used for waste water
The catalyst of debirs advanced oxidation degradation efficiently can carry out catalysis oxygen to such as phenol of hardly degraded organic substance in waste water etc.
Change, recycles the salt in brine waste.
Technical solution: in order to solve the above-mentioned technical problem, the invention adopts the following technical scheme: a kind of organic for waste water
The catalyst of waste advanced oxidation degradation, preparation method includes the following steps:
Step 1: raw material is prepared:
(1) it weighs sodium metasilicate and is dissolved in pure water, obtain the sodium silicate solution of 15-25% mass percentage concentration, and pass through
Sulfuric acid or sodium hydroxide adjust pH value in the range of 12-13, form clear solution, spare；
(2) soluble metal salt solution with catalytic activity is chosen
Salt, and soluble metal salt solution is prepared by being dissolved in acid, it is spare；
(3) methylcellulose, hydroxybutyl cellulose, hydroxyethylmethylcellulose, hydroxypropyl cellulose or hydroxypropyl are selected from
The adhesive of methylcellulose and its a variety of mixtures；
Step 2: soluble metal salt solution is mixed with sodium silicate solution, is carried out neutralization-precipitation reaction, is generated
To the doping sediment of silica gel and metal hydroxides, then the pH value for adjusting mixed liquor by dilute sulfuric acid keeps mixing in 6-8
Continue aging reaction；
Step 3: the sediment after reaction aging is separated by filtration and is dried, and sediment 5-12% is then added
The adhesive of quality mixes, and the green body to form honeycomb is squeezed by mold, and green body is by at least above for 24 hours drying；
Step 4: the green body that step 3 obtains is roasted at a temperature of 400~600 DEG C, obtains urging for high specific area
Agent honeycomb filling body.
Preferably, the soluble metal salt solution is hydrochloric acid solution, palladium nitrate solution, the ferric chloride solution of palladium chloride
Or the first in silver nitrate solution or a variety of mixing.
Preferably, the soluble metal salt solution is the solution that tetra-triphenylphosphine palladium is dissolved in ethyl alcohol or benzene, preferably benzene
Solution.
Preferably, the mass ratio of sodium metasilicate and soluble metal salt solution is in step 2 in terms of active metal quality
10:1~4.
Preferably, the mass ratio of sodium metasilicate and soluble metal salt solution is in step 2 in terms of active metal quality
10:2~2.5.
Specific embodiment
Combined with specific embodiments below, the present invention is furture elucidated, it should be understood that these embodiments are merely to illustrate the present invention
Rather than limit the scope of the invention, after the present invention has been read, those skilled in the art are to various equivalences of the invention
The modification of form falls within the application range as defined in the appended claims.
Embodiment 1
Firstly, the sodium silicate solution of 20% mass concentration is prepared, and with sodium hydroxide adjust pH value 12~13 it
Between, formation obtains weighing solution；Then tetra-triphenylphosphine palladium is dissolved in 1:1 ethanol water obtain mass concentration 10~
20% organic palladium solution then under stiring is slowly added to the organic palladium solution to carry out hybrid reaction in sodium silicate solution,
The sediment of silica gel Yu Metal Palladium hydroxide codope is obtained, during being somebody's turn to do, the mass ratio of sodium metasilicate and Metal Palladium is 10:2.
Then, ph value is adjusted in the range of 6-8, continues to keep aging reaction at least 2h or more, then by filtering point
From, and organic palladium catalyst is dried to obtain at 50~80 DEG C；Then organic palladium catalyst is pressed with methyl cellulose binder
It is mixed according to the mass ratio of 1:0.1~0.5, forms honeycomb green body, and dry 24 or more under mould action, reduce base
Body fluid phase component content avoids the chap for causing filling body when high-temperature roasting and surface layer oversintering, influences catalytic activity.Finally,
After carrying out 0.5~2h of roasting at a temperature of green body is placed in 400~600 DEG C, the catalyst monolith filling body of high-specific surface area is obtained.
Embodiment 2
Firstly, the sodium silicate solution of 20% mass concentration is prepared, and with sodium hydroxide adjust pH value 12~13 it
Between, formation obtains weighing solution；In addition palladium chloride is dissolved in 20~30% dilute hydrochloric acid and obtains palladium chloride solution, then stirred
It mixes down, which is slowly added to carry out hybrid reaction in sodium silicate solution, the hydroxide for obtaining silica gel and palladium is total
The sediment of doping, during being somebody's turn to do, the mass ratio of sodium metasilicate and Metal Palladium is 10:2.5.
Then, ph value is adjusted in the range of 6-8, continues to keep aging reaction at least 2h or more, to ensure that Metal Palladium exists
Load and uniformly bonding are consolidated in silica-gel carrier, the loss of Metal Palladium in catalytic reaction process are reduced, to improve catalyst
The tolerance of catalytic activity, especially catalyst.
Then sediment after aging is filtered separation, and is dried to obtain organic palladium catalyst at 50~60 DEG C；It connects
Organic palladium catalyst is mixed with methyl cellulose binder according to the mass ratio of 1:0.2, formed under mould action
Honeycomb green body, and dry 24 or more, green body liquid phase component content is reduced, the chap for causing filling body when high-temperature roasting is avoided
With surface layer oversintering, catalytic activity is influenced.Finally, being obtained after carrying out 0.5~2h of roasting at a temperature of green body is placed in 400~600 DEG C
To the catalyst monolith filling body of high-specific surface area.
Embodiment 3
Firstly, the sodium silicate solution of 20% mass concentration is prepared, and with sodium hydroxide adjust pH value 12~13 it
Between, formation obtains weighing solution；In addition the dilute hydrochloric acid that palladium chloride and iron chloride are dissolved in 20~30% according to the mass ratio of 2:1 is weighed
In obtain the mixed solution of palladium chloride and iron chloride, then under stiring, by mixed solution be slowly added in sodium silicate solution into
Row hybrid reaction obtains the sediment of the hydroxide codope of silica gel and palladium and iron, should during, sodium metasilicate and Metal Palladium and
The mass ratio of iron is 10:2:1.
Then, adjust ph value in the range of 6-8, continue keep aging reaction at least 2h or more, with ensure Metal Palladium and
Iron firm load in silica-gel carrier is bonded with uniform, and active metal is in catalytic reaction process in reduction catalytic reaction process
It is lost, to improve the catalytic activity of catalyst, the especially tolerance of catalyst.
Then sediment after aging is filtered separation, and is dried to obtain organic palladium catalyst at 50~60 DEG C；It connects
Organic palladium catalyst is mixed with methyl cellulose binder according to the mass ratio of 1:0.2, formed under mould action
Honeycomb green body, and dry 24 or more, green body liquid phase component content is reduced, the chap for causing filling body when high-temperature roasting is avoided
With surface layer oversintering, catalytic activity is influenced.Finally, being obtained after carrying out 0.5~2h of roasting at a temperature of green body is placed in 400~600 DEG C
To the catalyst monolith filling body of high-specific surface area.
It is handled for Jiangxi petrochemical industry synthesis factory's waste water, the water quality of waste water is as follows: sodium sulphate salt content about 7%, COD
Content is 224ppm, and ammonia-nitrogen content is 4~5ppm, and sodium phenolate is 2~4%, also containing the cyanide of 0.1~0.2ppm.With solid
Fixed bed catalytic tower loads above-described embodiment catalyst as wastewater treatment reaction tower in reaction tower, and with ozone and dioxygen
After water carries out catalysis oxidation as strong oxidizer, it is re-fed into waste water after biochemical device carries out biochemical treatment and is evaporated crystallization recycling
Technical grade sulfuric acid sodium is obtained, it is the wastewater treatment rear impurity content of each embodiment below that liquid phase water, which meets discharge standard:
| Sodium phenolate | COD | Ammonia-nitrogen content | Cyanide | Sodium sulfate salt | |
| Embodiment 1 | <5ppm | 18ppm | <1ppm | 0 | It is colourless, technical grade |
| Embodiment 2 | <5ppm | 12ppm | <1ppm | 0 | It is colourless, technical grade |
| Embodiment 3 | <5ppm | 27ppm | <1ppm | 0 | It is colourless, technical grade |
And in the prior art, the hardly degraded organic substances such as sodium phenolate can not degrade, and further across biochemical treatment, and COD
Content is still higher, and multistep treatment is needed to can be only achieved discharge standard.
Claims (5)
1. a kind of catalyst for waste water debirs advanced oxidation degradation, preparation method includes the following steps:
Step 1: raw material is prepared:
(1) it weighs sodium metasilicate and is dissolved in pure water, obtain the sodium silicate solution of 15-25% mass percentage concentration, and pass through sulfuric acid
Or sodium hydroxide adjusts pH value in the range of 12-13, forms clear solution, it is spare；
(2) soluble metal salt solution with catalytic activity is chosen
Salt, and soluble metal salt solution is prepared by being dissolved in acid, it is spare；
(3) methylcellulose, hydroxybutyl cellulose, hydroxyethylmethylcellulose, hydroxypropyl cellulose or hydroxypropyl methyl are selected from
The adhesive of cellulose and its a variety of mixtures；
Step 2: soluble metal salt solution is mixed with sodium silicate solution, carries out neutralization-precipitation reaction, and generation obtains silicon
Then the doping sediment of glue and metal hydroxides, the pH value for adjusting mixed liquor by dilute sulfuric acid keep mixing to continue in 6-8
Aging reaction；
Step 3: the sediment after reaction aging is separated by filtration and is dried, and sediment 5-12% mass is then added
Adhesive mixing, and the green body to form honeycomb is squeezed by mold, green body by least for 24 hours more than drying；
Step 4: the green body that step 3 obtains is roasted at a temperature of 400~600 DEG C, obtains the catalyst of high specific area
Honeycomb filling body.
2. according to claim 1 be used for waste water debirs advanced oxidation degradation catalyst, it is characterised in that: it is described can
Solube metallic salting liquid be the first in the hydrochloric acid solution of palladium chloride, palladium nitrate solution, ferric chloride solution or silver nitrate solution or
A variety of mixing.
3. according to claim 1 be used for waste water debirs advanced oxidation degradation catalyst, it is characterised in that: it is described can
Solube metallic salting liquid is the solution that tetra-triphenylphosphine palladium is dissolved in ethyl alcohol or benzene, preferably benzole soln.
4. being used for the catalyst of waste water debirs advanced oxidation degradation according to Claims 2 or 3, it is characterised in that: with
Active metal quality meter, the mass ratio of sodium metasilicate and soluble metal salt solution is 10:1~4 in step 2.
5. being used for the catalyst of waste water debirs advanced oxidation degradation according to claim 4, it is characterised in that: with activity
Metallic meter, the mass ratio of sodium metasilicate and soluble metal salt solution is 10:2~2.5 in step 2.
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