CN1326616C - Nano grade transition metal oxidation catalyst and its preparing method and use - Google Patents
Nano grade transition metal oxidation catalyst and its preparing method and use Download PDFInfo
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- CN1326616C CN1326616C CNB2005100168592A CN200510016859A CN1326616C CN 1326616 C CN1326616 C CN 1326616C CN B2005100168592 A CNB2005100168592 A CN B2005100168592A CN 200510016859 A CN200510016859 A CN 200510016859A CN 1326616 C CN1326616 C CN 1326616C
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Abstract
The present invention relates to a high-efficiency oxidation catalyst in organic waste water treatment, and a manufacturing method and the application thereof. The composite powder of the oxide of Ti, Si, Al and rare earth metal of which the mean particle size is smaller than 100 nm is manufactured into carriers, and at least two kinds of transition metal are loaded on the carriers. By weight, the catalyst occupies 100 portions, wherein TiO2-SiO2-Al2O3 occupies 65 to 85 portions, rare earth oxide occupies 5 to 15 portions, and transition metal element oxide occupies 5 to 30 portions. The components which are formed into the carriers are fluidized to shed associated water under supercriticality through precipitating, homogenizing, aging, filtering, washing, mashing and dispersively homogenizing, are activated to obtain nanometer composite powder, and are activated to manufacture the catalyst through molding, impregnating, fluidizing and drying. The present invention is used for the oxidation treatment of acidic organic waste water containing naphthaline sulphonate components, and the acidic organic waste water has high concentration, high chroma and high ammonia-nitrogen content. COD degradation rate is larger than 95%, ammonia-nitrogen oxidizing conversion rate is larger than 99%, chroma removing rate is larger than 95%, reaction is mild and cost is low.
Description
Technical field
The present invention relates to efficient oxidation catalyst in a kind of treatment of Organic Wastewater, relate in particular to and be used for the needed catalyst of catalytic oxidation treatment that highly acid, high concentration amount, high chroma, high ammonia nitrogen contain the bio-refractory organic wastewater of naphthalene sulfonic salt component.
Background technology
High concentrated organic wastewater deep oxidation oxidation catalyst is a kind of highly active multi-functional catalysis material, can make oxidant such as O
2, H
2O
2, O
3, ClO
2Deng under given operating condition, isolating fast and discharging the strong oxide group of OH, adsorbing oxicracking organic matter and ammonia nitrogen on the catalyst inner surface of organic matter or ammonia-nitrogen simultaneously, remove the purpose that organic component and ammonia nitrogen reduce waste water COD thereby reach.Oxidation activity is provided by metal in catalyst system and catalyzing, and carrier not only provides its inner surface that is used for high degree of dispersion and acid centre for reactive metal, and provide the space, duct for oxidative cracking reaction, can make oxidant separate to transform discharge the reaction of OH and oxicracking organic matter or ammonia nitrogen reaction coupling more in catalyst inner surface duct simultaneously, in the utilization rate that has improved oxidant, present the oxidation reaction high activity.But at present used non-precious metal catalyst and all can not well embody function match because the shortcoming of preparation aspect in the treatment of Organic Wastewater of bibliographical information or patent disclosure in real reaction.Thereby make operating temperature height (＞100 ℃), reaction pressure big (＞3.0Mpa), consersion unit requires harsh, water treatment operating cost height.
Based on the importance of oxidation catalyst in catalytic oxidation treatment organic wastewater, thereby develop inexpensively, efficient base metal oxidation catalyst is the key that reduces the wastewater treatment expense.
Catalytic oxidation is handled in the organic wastewater process, COD
CrAnd the economy of the up to standard and operating cost of chroma removal rate, depend primarily on the active and stable of core technology oxidation catalyst, because catalyst is to reduce reaction activity to improve reaction speed, improve the core means of oxidant utilization rate.Handle in the waste water at heterogeneous catalytic oxidation, the kind of catalyst mainly contains noble metal series, transition metal series and rare earth metal series three major types.Oxidation reaction is had high activity with noble metal (Pt, Ru, Ph, Pd, Os) catalyst and stability has been widely used in petrochemical industry, fine chemistry industry and waste water treatment industry.Aspect the catalytic oxidation treatment waste water, Preparation of catalysts and application are quite ripe as Osaka, Japan gas company, and they are with TiO
2Or ZrO
2Be carrier, one or more components among carried noble metal Ru, Rh, Pt, the Ph, administer pharmacy, papermaking, alcohol, dyeing waste water are obtained very ten-strike, take the lead in realizing the through engineering approaches application, it is several among Ru, Rh, Pd, Ir, the Pt that Nippon Shokubai Kagaku Kogyo Co., Ltd makes the noble metal catalyst component, handles COD under 240 ℃, 5Mpa
CrThe waste water of=40000mg/l, SS=10g/l, total nitrogen=25000mg/l, clearance are respectively 99.9%, 99.2%, 99.9%.France Gallezot uses the platinum group noble metal to be carried on the active carbon to handle little carboxylic acids as catalyst oxidation and is oxidized to CO 53 ℃ the time
2+ H
2O, some researchers of R﹠D institution of China in the world the noble metal catalyst series of practicability study, people such as Du Hongzhang adopt Ru/TiO
2280 ℃ of catalyst, 8Mpa are handled COD down
CR=6305mg/l, the high-concentration waste water of ammonia nitrogen=3775mg/l adopts air speed 1h
-1, handle water outlet COD
Cr＜50mg/l, ammonia nitrogen＜10mg/L.Catalyst activity, stability are all very high.But in the processing engineering of organic wastewater, both required COD at present
Cr, colourity, BOD
5Can be up to standard etc. the index removal efficiency, but consider to require operating cost low from economic angle, and its direct benefit is can't see in efforts at environmental protection at single enterprise, but under national legislation requires, must carry out the wastewater treatment qualified discharge, thereby efficient, economic treatment technology is unique practical means.(the catalyst price of noble metal catalyst price such as supporting Pt, Pd, Rh is all 10 because the noble metal costliness is rare
6Yuan/ton), impel domestic and international scientist then the exploiting economy practicality, high activity, the catalyst of high stability.The Li Tian of Tongji University fine jade etc. has been developed CuO/ solid carrier oxidation catalyst and has been handled high dense (COD
Cr=40g/l) BATA sodium naphthalene sulfonate waste water (under 0.6Mpa, 164-180 ℃) COD
CrClearance reaches 93.6%.The prosperous Fe-Cu/AL that waits of the Yang Run of University Of Xiangtan
2O
3Or all COD is handled in the phase reagent examination
Cr=14350mg/l contains phenol water sample, reaction condition: 0.6Mpa, 165 ℃, COD
CrClearance＞80%.People such as the Tan second place of Tsing-Hua University are with SiO
2, Al
2O
3Active carbon is that carrier loaded Cu, Fe, Zn have prepared oxidation catalyst processing COD
CrThe H acid waste water of＞10g/l, 200 ℃ of reaction conditions, 4.1Mpa, COD
CrClearance reaches more than 80%.Tsing-Hua University wishes that people such as Wan Peng have prepared FeMnNi/AL
2O
3Catalyst treatment tobias acid waste water clearance greater than 60%, BOD/COD＞0.35, possesses biodegradability, Zhejiang University in addition, East China University of Science, Xiamen University, also at the catalyst of active development catalytic oxidation treatment organic wastewater, Japan is dense at the catalytic oxidation treatment height in R﹠D institutions such as the Dalian Chemistry and Physics Institute, and poisonous difficult for biological degradation organic wastewater field is in rank first.Japan catalyst (catalyst) the chemical industry TiO of Co., Ltd.
2, SiO
2Superfines is made carrier, and Co, Ni, W, Zn make metal component, make honeycombed catalyst, handles COD
CrClearance is respectively 99.9%, 99.2%, 99.9% under=4000mg/l, total nitrogen 2500mg/l, 240 ℃ of SS=10000mg/l waste water, the 4.9Mpa.The Osaka, Japan gas TiO of company
2Nano material is made carrier, makes catalyst behind load Fe, CO, the Ni, 250 ℃, 7.0Mpa, moves 11000 hours continuously and handles COD
Cr=17500mg/l, ammonia-nitrogen content 3750mg/l waste water, COD
CrClearance 99.9%.Ammonia nitrogen removal rate 99.8%, qualified discharge.U.S. MODAR utilizes the long chain hydrocarbon of catalysis and supercritical water oxidative treatment content of organics 10% and amine to handle back COD
Cr＜5ppm, ammonia nitrogen concentration＜1ppm.In addition, U.S. MODEC company is that Bayer A.G has set up efficiently catalyzing and oxidizing method processing medicine and Intermediate Wastewater technology.Disposal ability 5-30 ton/sky, Britain scientist Mantzavinos heterogeneous catalyst CuO-ZnO/Al
2O
3, 130 ℃-170 ℃, 3.23Mpa handle down and contain P-cumarin waste water, 30 minutes COD
CrClearance＞90%.On the whole, the present both at home and abroad base metal water treatment of developing oxidation catalyst reaction temperature height (＞100 ℃), reaction pressure height (3.0-10.0MPa) thereby equipment investment are big, the operating cost height.
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists, a kind of suitable bigger serface is provided, the composite nano materials of large pore volume is a carrier, and transition metal is efficient oxidation catalyst of active component and preparation method thereof and this Application of Catalyst.
A kind of nano grade transition metal efficient oxidation catalyst is characterized in that: the oxide composite end with Ti, Si, Al and the metal M of particle mean size＜100nm makes specific area 380～500m
2/ g, pore volume 0.9～1.4ml/g, infrared acidity 0.35～0.50mmol/g complex carrier is by at least two kinds of active transition metallic elements of infusion process load; By weight, the catalyst that makes is 100 parts, wherein, and TiO
2-SiO
2-Al
2O
3Account for 65～85 parts, the oxide of metal M accounts for 5～15 parts, and oxidation of interim metal accounts for 5～30 parts; SiO by weight in the carrier
2Be 15～30%, TiO
2Be 15～30%, Al
2O
3Be 15～25%, the metal M oxide is 5～15%, and each component sum is 100% in the carrier; Described metal M is selected among rare earth element and the Nb at least a.
Above-mentioned catalyst, its described carrier specific area 400～500m
2/ g, pore volume 1.1～1.4ml/g, infrared acidity 0.35～0.45mmol/g.
Above-mentioned catalyst, it is at least a among La, Ce, the Nd that its described carrier is formed the middle rare earth element.
Above-mentioned catalyst, its described active transition metal are selected among Fe, Co, Zn, Cu, Ni, W, V, the Mn at least two kinds.
Above-mentioned catalyst, its specific area are 180～300m
2/ g, pore volume 0.48～0.60, infrared acidity 0.35～0.40mmol/g.
The preparation method of nano grade transition metal oxidation catalyst is characterized in that: this method is made up of following process:
(1) preparing carriers
1. be to be selected from the nitrate of rare earth element and Nb and silicate and another kind of alkaline precipitating agent to add in the reactor that fills the deionized water that has dissolved certain density organic dispersing agent with acid aluminium salt, titanium salt, the metal M of requirement, in pH=6～7,55～85 ℃ of temperature, form colloidal sol, neutralization reaction time 1.5～2.5h.
2. incite somebody to action 1. homogenizing 40～80min under pH=7～8 conditions.
3. in pH=8～9, temperature is aging 60～100min under 50～70 ℃ of conditions.
4. filter and spend deionised water 4～6 times.
5. will add the organic dispersing agent homogenizing of requirement, pH=7～8,50～70 ℃ of temperature 4. with the deionized water making beating.
6. will in temperature 375-400 ℃, take off associated water 6-10h under pressure 22.1～22.8Mpa 5. under super critical condition, the nano composite powder that obtains in 550 ℃ of activation 2h, makes needed rerum natura butt powder again.
In the carrier sial titanium rare earth element Composite Preparation involved in the present invention, 1. acidic aluminum can be Al
2(SO
4)
3, AlCl
3, Al (NO
3)
3In a kind of, titanium salt can be Ti (SO
4)
2, TiCl
4In a kind of, metal M (being selected from rare earth element and Nb) nitrate is La (NO
3)
3, Nd (NO
3)
3, Ce (NO
3)
3And Nb (NO
3)
3In a kind of, alkaline precipitating agent is NH
4OH, NaAiO
2, Na
2CO
3In a kind of, but in commercial Application Al
2(SO
4)
3And AlCl
3Be commonly used, and use the different salting liquids of metal of the same race or all can make 6. with the Different Alkali precipitating reagent in obtain composite matrix difference to some extent, the micelle size also has difference.
Aging back process " 5. " and 4. routinely the method for finishing, with the compound gel detergent that obtains to remove impurity such as de-iron, sodium, sulfate radical or chlorine root, deviating from the impurity purpose is reactivity or the stability that does not influence catalyst of the present invention, solid gel deionized water pulp after washing finishes, add organic dispersing agent, rare nitric acid is transferred pH=6.0～6.5, and under supercriticality, carry out fluidized drying, at 375～400 ℃, 22.05Mpa fluidized drying is 6～10 hours under the～22.6Mpa, dry back material 90% above particle diameter＜100nm.
The dispersant that the present invention prepares the complex carrier process is a kind of in methyl alcohol, ethanol, the isobutanol.
(2) Preparation of catalysts
Get the nano composite powder of the above-mentioned requirement that makes, through kneaded and formed, again with the active transition metal-nitrate solutions of requirement dipping certain hour, drying activate needed catalyst.
Above-mentioned preparation method, it becomes glue pH value is 6.0～7.0,55～80 ℃ of reaction temperatures, reinforced timeliness 1.5～2.0h; Homogenizing pH value 7.0～7.5, time 40～60min; Aging pH value 8.0～8.5, temperature 50-65 ℃, time 60～90min.
Above-described catalyst contains naphthalene sulfonic salt and high NH at highly acid high concentration, high chroma, bio-refractory
4Application in the-N organic wastewater catalytic oxidation treatment is characterized in that: 60～90 ℃ of described catalytic oxidation temperature, pressure 0.05Mpa～0.15Mpa, liquid air speed 1.0～1.8h
-1, oxidant is O
2, ClO
2, H
2O
2, O
3In a kind of, the oxidation Decomposition conversion ratio of CODcr is greater than 95%, chroma removal rate is greater than 95%, the ammonia nitrogen conversion rate of oxidation is greater than 99%.
Catalyst of the present invention contains nanoscale sial titanium component 65～85% and 5～15%wt nano metal M (be selected among rare-earth elements La, Ce and Nd and the Nb one or both) oxide, it is mixed mixed the pinching of back adding adhesive, rolling agglomerating can mechanical-moulded granulation be strip, ring-type or different form and make carrier, carrying transition metal again, its aggregate metal oxide is 5～30wt%.
Specific surface area of catalyst 180～300m of the present invention
2/ g, pore volume 0.48～0.60ml/g comprises a kind of sial titanium rare earth oxide composite.In the related composite of catalyst of the present invention, SiO
2-Al
2O
3-TiO
2Content 65～85%, metal M (choosing) oxide M e from rare earth and Nb
2O
3Content 5～15wt%, composite is 380～500m as the carrier material specific area
2/ g, pore volume 0.9～1.4ml/g, infrared acidity 0.40～0.50mmol/g.
Catalyst provided by the invention comprises a kind of functional sial titanium rare earth element composite oxides component, it is provided for required internal surface area of supported active transition metal and acid centre, simultaneously provide the space, duct for oxidative cracking reaction again, that is: pore size distribution is generally at 8～15nm, more effective reaction spaces can be provided, be suitable as the condensed ring class or the reaction channel of branch subclass greatly.
In addition, the composite cooperative effect of the lattice defect in its composite has the auxiliary catalysis ability to make catalyst have and is equal to the high activity of precious metal oxidation catalyst, but is being better than noble metal catalyst again aspect the poison resistance (anti-S, N), thereby it is the reaction life-span is long, and cheap.
Mechanical forming method is adopted in the moulding of catalyst of the present invention, and as slivering, Cheng Huan, one-tenth honeycomb etc., forming method does not all constitute the present invention is limited.
For pore structure and the surface property that improves the composite nano materials carrier, the preparation employing of sial titanium rare earth element composite oxides involved in the present invention and stream is the PH grafting copolymerization process fixedly, course of reaction is easy to control, and composite has the more performance index, and the physicochemical characteristic of the related composite of catalyst of the present invention is: specific area 380～500m
2/ g, best 400～500m
2/ g, pore volume 0.9～1.4ml/g, best 1.1～1.4ml/g, infrared acidity 0.35～0.5mmol/g, best 0.35～0.45mmol/g.
PH value in the sial titanium rare earth element composite oxide carrier preparation involved in the present invention, temperature, charging rate, ageing time all is important control parameter, and generally being reacted into glue pH value is 6.0～7.0, best 6.0～6.5,55～85 ℃ of reaction temperatures, best 55～80 ℃, reinforced time 1.5～2.0hr, best 1.5～2.0h.Homogenizing general pH value 7.0～8.0, best 7.0～7.5, time 40～80min, best 40～60min.Ageing time general pH value 8.0～9.0, best 8.0～8.5, general 50～70 ℃ of temperature, best 50～65 ℃, time 60～100min, best 60～90min.
Because the preparation characteristic of the sial titanium rare earth element composite oxides that catalyst of the present invention is related, avoided the too fast trend of single species crystallization in the colloidal sol reaction, guarantee the three-dimensional homogenization lattice composition that embeds mutually that connects of synergy formation molecular structure between sial titanium rare earth element atom, form more lattice defect, thereby make composite carrier have more acid centre, and the macropore and the large pore volume of high-ratio surface and narrow distribution, promptly obtain to be used for preparing to contain catalyst carrier of the present invention and the catalyst thereof that naphthalene sulfonic salt organic wastewater with high concentration has high catalytic activity in oxidation processes.
The present invention compared with prior art has following positive effect except that above-mentioned distinguishing feature:
Catalyst of the present invention is to utilize sol-gel process and supercritical drying to develop the quaternary composite nano-powder to be carrier, and several components are that the oxidation catalyst of main catalytic is with O among transition-metal Fe, Co, Zn, Cu, Ni, W, the V
2, ClO
2, H
2O
2, O
3In the reaction system for oxidant.It contains naphthalene sulfonic salt and high dense NH to what discharge in the H acid production process
3The waste water of-N, that is: CODcr=10～30g/l, colourity (＞10000 times), high dense, high chroma, the catalytic oxidation treatment of poisonous waste water difficult for biological degradation is very effectively and make the oxidizing condition gentleness, 60～90 ℃ of average reaction temperature, reaction pressure is not more than 0.1～0.15Mpa, liquid air speed＞1.8h
-1, CODcr extrusion rate＞95%, ammonia nitrogen removal frank＞99%, decolouring degree＞95%, BOD/COD＞0.55 biodegradability is very strong, is getting final product qualified discharge after simple process, and the key of this catalyst is TiO
2-SiO
2-Al
2O
3The preparation of-rare earth element composite nano powder, the catalyst backbone of this composite granule preparation is a carrier, specific area is more than or equal to 480m
2/ g, surperficial B acid L acid coexistence, and total acidity is more than or equal to 0.30mmol/g.Compare with the existing technology of preparing of the used base metal oxidation catalyst of wastewater treatment, catalyst of the present invention adopts sol-gel process and supercritical drying combination technique, the TiO of the particle mean size＜100nm of preparation
2-SiO
2-Al
2O
3-Me
2O
3(a kind of among La, Nb, Nd, the Ce) composite oxide powder rolls and obtains carrier component through mediating; This composite possesses bigger serface, large pore volume, large aperture and equally distributed enough acid sites, needn't add in addition provides the faintly acid component macroporous aluminium oxide of macropore again, thereby makes the carrier inner surface effectively utilize the space more even, more abundant, make the main catalytic element/transition metal individual layer decentralization of load higher, Particle Cluster is littler, makes this catalyst not only have oxidation activity, but also has certain cracking performance.Finally make catalyst of the present invention that higher catalytic activity is arranged in oxidation reaction.
Catalyst of the present invention is compared with existing non-precious metal catalyst, has adopted TiO
2-SiO
2-Al
2O
3-Me
2O
3(a kind of among La, Nb, Nd, the Ce) quaternary graft copolymerization composite construction component is carrier, wherein TiO
2Semiconducting behavior more outstanding, and that rare earth oxide gets in the betatopic migration velocity is faster.Thereby make the ability of this catalyst mithridatism element S, N, Cl stronger, reactivity is higher.Use catalyst of the present invention, the best normal temperature of reaction temperature～80 ℃, the best 0.1～0.15Mpa of reaction pressure, reaction velocity 1.0～1.8h
1, oxidant is O
2, ClO
2, H
2O
2, O
3In the high dense CODcr=10～30g/l of catalytic oxidation treatment H acid production process discharging when a kind of, high chroma, the acid organic wastewater that high ammonia nitrogen contains naphthalene sulfonic salt component has high-efficiency catalytic activity, CODcr oxidative degradation rate＞95%, ammonia nitrogen conversion ratio＞99%, chroma removal rate＞95%, and actual cost is 1/20 of a burning method, use catalyst of the present invention because oxidation reaction condition is compared gentle greatly with existing conventional non-precious metal catalyst oxidation reaction condition, life-span is long, makes that the actual use of catalyst of the present invention is more economical.
The specific embodiment
Now the present invention is further described as follows in conjunction with the specific embodiment:
One, the preparation of carrier
Embodiment 1
Be the related SiO of catalyst of the present invention
2-Al
2O
3-TiO
2The preparation of-nanometer rare earth oxide composite granule.4000g solid sulphuric acid aluminium is joined 3.25L distilled water heat simultaneously and stir and be dissolved as aluminum sulfate solution (a) fully, with 500gH
2TiO
3(metatitanic acid) joins abundant reacted titanium sulfate solution (b) in the 900ml concentrated sulfuric acid, with 185g solid nitric acid cerium or lanthanum nitrate join fully dissolve in the 2L water cerous nitrate solution or lanthanum nitrate hexahydrate (c), concentrated ammonia liquor is added appropriate amount of deionized water be diluted to 10% weak aqua ammonia (d), 4.8L industry one-level modulus 3.0 concentrated sodium silicates are joined obtain rare water glass solution (e) in the 8L water, 10% isobutanol (or methyl alcohol or ethanol) 500ml (f), get one 20 liters of stainless steel reaction jars, have heating control system and double-deck dasher, adding 2L deionized water and stirring in jar (120～160 commentaries on classics/min), after being heated to 85 ± 5 ℃, open simultaneously and have aluminum sulfate, titanium sulfate, cerous nitrate, ammoniacal liquor, the valve of rare waterglass container, set a, b, c, during the flow of e makes and gelation time be 2 hours, and the valve flow of transferring d rapidly makes reaction system PH between 6.0～6.3,80～85 ℃ of hierarchy of control temperature, after institute's working solution that responds adds by 2 hours flows then, pH is transferred to about 7.5, stop to add ammoniacal liquor, make the mixed sols homogenizing 65min of generation, and then carry out ageing process, pH is transferred to about 8.0-8.8,65～70 ℃ of temperature, aging 80min, filtration colloidal solution gets wet cake and washes repeatedly 5 times with the 10L deionized water at every turn, use the 5L water slurryization then, add 10% isobutanol solution 150ml, the fluidisation attitude removes the process 6～10 hours of associated water in the supercritical reaction device, 375～400 ℃ of temperature, pressure 22.1～22.8Mpa gets nano composite powder.550 ℃ of activation of this powder specific area 495m after 2 hours
2/ g, pore volume 1.36ml/g, 8～15nm hole accounts for total hole 93.1%, infrared acidity 0.38mmol/g, bulk density 0.28～0.30g/ml, particle mean size 80～82nm, contents on dry basis about 83%.
Embodiment 2
Neodymium nitrate 95 gram, nitric acid niobium 90 grams are added in the 2L water fully dissolving respectively make mixed solution (c).Other steps and process conditions are all with embodiment 1.
Two, Preparation of catalysts
Embodiment 3
Be catalyst of the present invention related carrier A and catalyst KA.Take by weighing the example 1 nano composite powder 150g that obtains, add the about 111ml of 5% rare nitric acid and mediate 20min, be rolled into wet piece after, mechanical-moulded is ring-type, drying activate carrier A, contain V with 300ml again
2O
5The excessive dipping of wt%3-8% ammonium metavanadate immersion liquid 120g carrier A 4～6 hours, dry, activation contains MnO with 300ml again
2Mn (the NO of wt%8-17%
3)
2The excessive dipping of solution 120g carrier A 4～6 hours, drying activate catalyst KA of the present invention, the transient metal Mn of catalyst cupport-V total amount is in oxide about 20%.
Embodiment 4
For related carrier B of catalyst of the present invention and catalyst KB, take by weighing the example 1 nano composite powder 150g that obtains, add the about 100ml of 5% rare nitric acid, deionized water 11ml mediates 20min, be rolled into wet piece after, mechanical-moulded is ring-type, drying activate carrier B, contain V with 300ml again
2O
5The excessive dipping of wt%3-8% ammonium metavanadate immersion liquid 120g carrier A 4～6 hours, dry, activation contains MnO with 300ml again
2Mn (the NO of wt%8-17%
3)
2The excessive dipping of solution 120g carrier A 4～6 hours, drying activate catalyst KB of the present invention, the transient metal Mn of catalyst cupport-V total amount is in oxide about 23%.
Embodiment 5
Be the preparation of support C involved in the present invention and catalyst KC, used transition metal is Ni-V, the carrier that used carrier makes for embodiment 2, and other operating procedures and process conditions are all with example 3.The transition metal Ni-V total amount of catalyst cupport is in oxide about 14%.
Embodiment 6
Be the preparation of carrier D and catalyst KD involved in the present invention, used transition metal is Cu-Co, and used carrier is produced carrier for embodiment 1, and other operating process and process conditions are all with example 3.The transition metal C of catalyst cupport
t-C
0Total amount is in oxide about 30%.
Embodiment 7
Be the preparation of carrier E and catalyst KE involved in the present invention, used transition metal is Fe-Co-Zn, and used carrier is produced carrier for embodiment 2, and other operating process and process conditions are all with example 3.The transition-metal Fe of catalyst cupport-Co-Zn total amount is in oxide about 18%.
Comparative example 1
For reference carrier F and catalyst KF, take by weighing a kind of specific area 360m
2/ g, pore volume 0.86ml/g, SiO
2The sial 120g of content 30wt%, granularity 76um, anatase titanium dioxide TiO
2Powder 33g, specific area 110m
2/ g, pore volume 0.66ml/g, granularity 76um, CeO
2Powder 16g, specific area 80m
2/ g, pore volume 0.45ml/g, granularity 76um adds 200g is added the nitric acid peptization by the little porous aluminum oxide of pore volume＜0.38ml/g adhesive behind the mixing, mediate, be rolled into wet piece, mechanical-moulded is ring-type, drying activate support C, again with 300ml about 120g carrier of the excessive dipping of Mn-V co-impregnated solution, in drying, activate reference catalyst KF, activation rear catalyst KF load Mn-V total metal content is in oxide about 20%.
Find out from following table 1 carrier and catalyst materialization, comparative example carrier and catalyst pore volume, specific area is all lower, can influence decentralization and the reaction compartment of the carried metal Mn-V of institute undoubtedly, the catalyst of example 3,4,5,6,7 and comparison 1 is carried out reaction evaluating, find out catalyst involved in the present invention on the greater activity basis from evaluation result, it is longer to receive a mandate.
Table 1. carrier and catalyst physical and chemical performance
| Carrier and catalyst numbering | A | KA | B | KB | C | KC |
| Specific area m 2/g | 498 | 381 | 496 | 370 | 230 | 155 |
| Pore volume ml/g | 1.36 | 0.91 | 1.38 | 0.95 | 0.65 | 0.36 |
| 8-15nm pore size distribution % | 92.5 | - | 93.6 | - | 41.1 | - |
| Infrared acidity mmol/g | 0.41 | 0.39 | 0.39 |
The water quality of table 2.H acid producing waste water
| Detect index | H acid waste water * testing result |
| COdcr mg/l | 7.9×10 1 |
| Ammonia nitrogen mg/l | 6×10 1 |
| Colourity doubly | ＞10 4 |
| Salinity % | 19.87 |
| PH | ＜1 |
| SO 4 2- ％ | 14.67 |
This water is H acid mother liquor in the technology, T acid mother liquor, T acid washing water mixing water.
The catalytic oxidation condition:
Temperature: 80 ± 2 ℃, pressure: 0.1 ± 0.01Mpa, liquid air speed: 1.1～1.2h
-1
Oxidant [H
2O
2(35%wt)]/H
20 (V/V)=7.5 * 10
-2
Use loaded catalyst: 200ml
The evaluation result of table 3. catalyst in catalytic oxidation treatment H acid waste water
| Handle back water quality | Catalyst KA | Catalyst KB | Catalyst KC | KA catalyst KD | Catalyst KE | Reference catalyst KF |
| COD crmg/l | 0.312×10 4 | 0.297×10 4 | 0.341×10 4 | 0.208×10 4 | 0.183×10 | 4.5×10 4 |
| Colourity doubly | 130 | 130 | 130 | 130 | 130 | ＞5×10 3 |
| Ammonia nitrogen mg/l | 0.215×10 3 | 0.191×10 3 | 0.223×10 3 | 0.138×10 3 | 0.077×10 3 | 4.2×10 4 |
| PH | 3～4 | 3～4 | 3～4 | 3～4 | 3～4 | 1.5 |
| Total salt % | 18.21 | 18.21 | 18.21 | 18.21 | 18.21 | 19.76 |
| B/C | 0.30 | 0.38 | 0.46 | 0.51 | 0.55 | ＜＜0.1 |
Annotate: possess biochemical condition through catalyst oxidation processed waste water of the present invention, reach three grades of discharge standards of regulation in (GB8978-1996) through the SRB-BAC biochemical treatment.
Analyze common analytical methods such as adopting atomic absorption spectrography (AAS) in the catalyst preparation process of the present invention; CODcr analyzes and adopts GB GB11914-89 in the wastewater treatment; BOD
5Analyze and adopt GB GB7488-87; The ammonia nitrogen analytical method adopts GB GB11891-89; Other are common method.
Claims (8)
1, a kind of nano grade transition metal efficient oxidation catalyst is characterized in that: the oxide composite end with Ti, Si, Al and the metal M of particle mean size＜100nm makes specific area 380～500m
2/ g, pore volume 0.9～1.4ml/g, the complex carrier of infrared acidity 0.35～0.50mmol/g is by at least two kinds of active transition metallic elements of infusion process load; By weight, the catalyst that makes is 100 parts, wherein, and TiO
2-SiO
2-Al
2O
3Account for 65～85 parts, the metal M oxide accounts for 5～15 parts, and oxidation of interim metal accounts for 5～30 parts; In the carrier by weight, SiO
2Be 15～30%, TiO
2Be 15～30%, Al
2O
3Content 15～25%, the metal M oxide is 5～15%, each component sum is 100% in the carrier; Described metal M is selected from few a kind of among rare earth element and the Nb.
2, catalyst according to claim 1 is characterized in that: described carrier specific area 400～500m
2/ g, pore volume 1.1～1.4ml/g, infrared acidity 0.35～0.45mmol/g.
3, catalyst according to claim 1 is characterized in that: it is at least a among La, Ce, the Nd that carrier is formed the middle rare earth element.
4, catalyst according to claim 1 is characterized in that: described active transition metal is selected among Fe, Co, Zn, Cu, Ni, W, V, the Mn at least two kinds.
5, catalyst according to claim 1 is characterized in that: described specific surface area of catalyst is 180～300m
2/ g, pore volume 0.48～0.60ml/g, infrared acidity 0.35～0.40mmol/g.
6, as the arbitrary described Preparation of catalysts method of claim 1～6, it is characterized in that: this method is made up of following process:
(1) preparing carriers
1. with the acid aluminium salt of requirement, titanium salt, metal M for be selected among rare earth element and the Nb at least-kind nitrate and silicate and another kind of alkaline precipitating agent, add in the reactor that fills the deionized water that has dissolved certain density organic dispersing agent, pH=6～7,65～85 ℃ of temperature, form colloidal sol, neutralization reaction time 1.5～2.5h, then
2. homogenizing 40～80min under pH=7～8 conditions, then
3. in pH=8～9, temperature is aging 60～100min under 50～70 ℃ of conditions;
4. filter and spend deionised water 4～6 times, again
5. with the deionized water making beating, add the organic dispersing agent homogenizing of requirement, pH=7～8,50～70 ℃ of temperature;
6. will be 5. under super critical condition, in 375～400 ℃ of temperature, pressure 22.1～22.8Mpa takes off associated water 6～10h, and the nano composite powder that obtains in 550 ℃ of activation 2h, makes needed rerum natura butt powder again;
(2) Preparation of catalysts
Get the nano composite powder of the above-mentioned requirement that makes, through kneaded and formed, with the active transition metal-nitrate solutions dipping 4～6h of requirement, the drying activation obtains needed catalyst again.
7, preparation method according to claim 6 is characterized in that: becoming glue pH value is 6.0～7.0,55～80 ℃ of reaction temperatures, reinforced time 1.5～2.0h; Homogenizing pH value 7.0～7.5, time 40-60min; PH value 8.0～8.5 when aging, 50～65 ℃ of temperature, time 60～90min.
8, contain application in naphthalene sulfonic salt and the high ammonia-nitrogen organic wastewater catalytic oxidation treatment as the arbitrary described catalyst of claim 1～5 at highly acid high concentration, high chroma, bio-refractory, it is characterized in that: 60～90 ℃ of described catalytic oxidation temperature, pressure 0.05Mpa～0.15Mpa, liquid air speed 1.0～1.8h
-1, oxidant is O
2, ClO
2, H
2O
2, O
3In a kind of, the oxidation Decomposition conversion ratio of CODcr is greater than 95%, chroma removal rate is greater than 95%, the ammonia nitrogen conversion rate of oxidation is greater than 99%.
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| CN102773112B (en) * | 2012-08-10 | 2014-06-04 | 西安交通大学 | Method for preparing ternary complex carrier supported nickel phosphide catalyst |
| CN103386305B (en) * | 2013-07-31 | 2015-09-09 | 南京威安新材料科技有限公司 | For the preparation of hydrazine and ammonia nitrogen waste water process catalyst and technique for applying thereof and device |
| US9012349B1 (en) | 2013-11-01 | 2015-04-21 | Ut-Battelle Llc | Method of synthesizing bulk transition metal carbide, nitride and phosphide catalysts |
| CN105036292B (en) * | 2015-08-19 | 2017-04-26 | 河南师范大学 | Method for degrading rhodamine B dye wastewater by catalyzing Oxone with magnetic cobalt catalyst |
| CN106362751A (en) * | 2016-08-29 | 2017-02-01 | 江苏海普功能材料有限公司 | Heterogeneous catalyst, and preparation method and application method thereof |
| CN106693974A (en) * | 2016-11-11 | 2017-05-24 | 大连理工大学 | Preparation method and application of supported metal oxide catalyst for removing ammonia nitrogen in water through catalytic ozonation |
| CN107754789A (en) * | 2017-11-09 | 2018-03-06 | 湖南永清环保研究院有限责任公司 | Catalyst and micro-hole aerator for Ozonation processing organic wastewater |
| CN108079984B (en) * | 2017-12-11 | 2019-12-20 | 河南师范大学 | Preparation method of rounded cube type zinc hydroxystannate solar catalyst |
| CN110743531B (en) * | 2019-11-11 | 2022-08-30 | 南京工业大学 | Preparation method of biphase V-Ti efficient catalyst for naphthalene degradation |
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| CN1174175A (en) * | 1996-08-20 | 1998-02-25 | 中国科学院大连化学物理研究所 | Electric multiphase catalyzed reaction process disposing industrial waste water containing dinitrophenol |
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| CN1174175A (en) * | 1996-08-20 | 1998-02-25 | 中国科学院大连化学物理研究所 | Electric multiphase catalyzed reaction process disposing industrial waste water containing dinitrophenol |
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