CN106111200A - Many metal corsslinkings for uns-dimethylhydrazine degraded coordinate catalyst and its preparation method and application - Google Patents
Many metal corsslinkings for uns-dimethylhydrazine degraded coordinate catalyst and its preparation method and application Download PDFInfo
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- CN106111200A CN106111200A CN201610453282.XA CN201610453282A CN106111200A CN 106111200 A CN106111200 A CN 106111200A CN 201610453282 A CN201610453282 A CN 201610453282A CN 106111200 A CN106111200 A CN 106111200A
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- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- 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
- C02F1/722—Oxidation by peroxides
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- 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
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- 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
- C02F2101/38—Organic compounds containing nitrogen
Abstract
The present invention discloses a kind of many metal corsslinkings for uns-dimethylhydrazine degraded and coordinates catalyst and its preparation method and application, these many metal corsslinkings coordinate catalyst formula M N to represent, wherein, M is at least two metal in transition metal and/or rare earth metal, N is modification of chitosan carrier, and the total mole number of M and the weight ratio of N are 0.5～5:100.Its preparation method is: take in transition metal and/or rare earth metal at least two metal as active component according to aforementioned proportion, loaded on modification of chitosan carrier after regulation temperature, wash, be dried, grind, sieve, obtain many metal corsslinkings and coordinate catalyst.Many metal corsslinkings that the present invention prepares coordinate catalyst, there is imitative enzymatic activity intimate with enzyme, at normal temperatures uns-dimethylhydrazine waste water can be degraded, its catalysis activity is high, reusable, especially for high concentration uns-dimethylhydrazine waste water, it is not necessary to dilute, regulate initial pH and carry out pretreated waste water.
Description
Technical field
The present invention relates to a kind of catalyst and its preparation method and application, particularly to a kind of for uns-dimethylhydrazine degraded
Many metal corsslinkings coordinate catalyst and its preparation method and application.
Background technology
Uns-dimethylhydrazine (Unsymmetric Dimethylhydrazine is called for short UDMH), as power fuel, has heat steady
Qualitative good, the excellent performance such as the combustion heat is big, specific impulse is high.Along with constantly exploration and the national defense industry of space one are needed by the mankind
The continuous lifting asked, uns-dimethylhydrazine, as a kind of high specific impulse liquid propellant, has obtained increasingly being widely applied, including defending
Star, guided missile, unmanned plane etc..But, the high toxicity that uns-dimethylhydrazine itself has gives high the wanting that the work of its liquid waste processing brings
Ask.Uns-dimethylhydrazine in the gas phase with the reaction of oxygen, reaction rate is very fast, half-life only 16h, can be toxic extremely strong in reaction
N-Nitrosodimethylamine produces, and the process of nitrosodimethylamine is the most difficult.After uns-dimethylhydrazine sewage enters environment, waste water
In do not contain only uns-dimethylhydrazine, also oxidation Decomposition can produce inclined hydrazone, the tetramethyl tetrazene, dimethylamine, formaldehyde, cyanide and N-
Nitrosodimethylamines etc., the ratio uns-dimethylhydrazine that these product toxicity have is bigger, if not processing directly discharge, is good for environment and the mankind
Health has the biggest harm.
At present, the treatment technology to high concentration, organic wastewater with difficult degradation thereby mainly has burning method, catalytic oxidation, wet type oxygen
Change method, photocatalytic oxidation, supercritical water oxidation method etc..But the equal Shortcomings of these biodegrading process, the gas that burning method produces
Environment is caused secondary pollution；The Threshold retention of photocatalytic method is on the low side；Supercritical water oxidation method is due to severe reaction conditions
It is difficult to obtain actual application；Conventional Fenton reagent method has the effect preferably processing Organic substance in water, but deposits in system
At substantial amounts of Fe2+So that H2O2Utilization rate be not the highest, organic matter degradation is also incomplete, and subsequent treatment produces big
Amount iron containing sludge.Additionally, the process of uns-dimethylhydrazine degraded and mechanism are extremely complex, there is intermediate product and continue decomposition, centre
Reaction between product.Therefore, when selecting the biodegrading process of uns-dimethylhydrazine, not only it is also contemplated that the degraded of uns-dimethylhydrazine self
Situation, is further noted that the degraded situation of intermediate product simultaneously.
Based on above-mentioned situation, explore a kind of green, catalysis activity is higher, the degraded of low cost, uns-dimethylhydrazine oxidoreduction
Catalyst be of great practical significance.
Chitosan (chitosan is called for short CTS) is a kind of by the product after chitin deacetylase base.Chitin, chemical name
For 2-deoxidation-2-acetamido-B-(1-4) glucosan, being the only naturally alkalescence macromolecule polysaccharide found so far, chitin is wide
In the general cell wall being distributed in nature Crustaceans shrimp, Eriocheir sinensis and the shell of insecticide and mushroom and rudimentary plant, its year biological
Yield is up to 10,000,000,000 tons, is only second to cellulose.Concentrated base processes free OH, the NH in the chitosan molecule structure of chitin gained2
There is good coordination ability, coordination compound can be formed with transition and rare earth ion.
Biological species macromolecule carrier forms composition catalyst with inorganic metal ion, changes active center metal ion kind
Class, changes the functional group of part and sterically hindered, has imitative enzymatic activity intimate with enzyme.This kind of catalyst is lived
Property center and carrier by chemical bonding, because of its high activity, high selectivity, high stable, be readily synthesized and structure be adjustable etc.
Advantage, is widely used in the catalyst of redox reaction.Present invention aim at providing a kind of for reproducibility uns-dimethylhydrazine
Many metal corsslinkings of degraded coordinate preparation and the application process of catalyst.
Summary of the invention
Goal of the invention: the first object of the present invention is to provide and a kind of is catalyzed that activity is strong, stability is high, the use of repeatable utilization
Many metal corsslinkings in uns-dimethylhydrazine degraded coordinate catalyst, and the second object of the present invention is to provide the preparation side of this catalyst
Method, the third object of the present invention is to provide a kind of method utilizing these many metal corsslinkings to coordinate catalyst degradation uns-dimethylhydrazine.
Technical scheme: the many metal corsslinkings for uns-dimethylhydrazine degraded of the present invention coordinate catalyst, with formula M-N
Represent, wherein, M is at least two metal in transition metal and/or rare earth metal, and N is modification of chitosan carrier, M mole
Number is 0.5～5:100 with the weight ratio of N.
Preferably, the molal quantity of M is 4～5:100 with the weight ratio of N.
Concrete, modification of chitosan carrier is chitosan-SiO2Complex carrier, wherein, chitosan and SiO2Weight ratio is 1:
0.5～2.
Preferably, chitosan and SiO2Weight ratio be 1:1～2.
The preparation method of above-mentioned modification of chitosan carrier comprises the steps: to dissolve chitosan in acid solution, adds
Enter the SiO through high-temperature calcination2, control chitosan and SiO2Weight ratio be 1:0.5～2, stirring, be subsequently adding NaOH, formed solidifying
Glue, is centrifuged, washs, dries, grinds to sieve and obtain modification of chitosan carrier.
Preferably, M is copper zinc cobalt, copper nickel zirconium, ferrum molybdenum, copper cerium or cobalt neodymium.
Many metal corsslinkings for uns-dimethylhydrazine degraded of the present invention coordinate the preparation method of catalyst, including as follows
Step: make active component with at least two metal in transition metal and/or rare earth metal, takes corresponding dissolving metal salts, adjusts
Loaded to, on modification of chitosan carrier, wash, be dried, grind, sieve after joint temperature, obtain many metal corsslinkings and coordinate catalysis
Agent；Wherein, the total mole number of slaine is 0.5～5:100 with the weight ratio of modification of chitosan carrier.
In above-mentioned preparation method, regulating described temperature is 40～70 DEG C.
The method utilizing many metal corsslinkings to coordinate catalyst degradation uns-dimethylhydrazine of the present invention, comprises the steps:
Adding hydrogen peroxide in the waste water containing uns-dimethylhydrazine, be subsequently adding many metal corsslinkings and coordinate catalyst, controlling reaction temperature is 40
～70 DEG C, flow velocity is 120～150L/ hour.
Further, controlling reaction temperature is 60～70 DEG C.
Beneficial effect: compared with prior art, the remarkable advantage of the present invention is: many metal corsslinkings of (1) present invention are joined
Close catalyst and improve the stability of catalyst by forming coordination compound between modification biological class carrier and metal, solve conventional physical and bear
Supported catalyst holds caducous problem, can repeatedly use；By design, catalyst active center forms and proportioning, changes
The electronic structure of change catalyzer and surface nature improve catalyst activity；The most active high catalytic action of this catalyst, holds concurrently again
Has traditional adsorption, before more common chitosan metal complexes has more preferable commercial Application with modified monometallic coordination compound
Scape；(2) many metal corsslinkings of the present invention coordinate the preparation process of catalyst to carry out under low-temperature atmosphere-pressure, it is not necessary to high-temperature calcination；
And without the introducing of poisonous and harmful substance, do not produce secondary pollution, environmental protection；Meanwhile, preparation process is simple to operate, catalyst
Easy-formation, low cost；(3) present invention uses heterogeneous catalysis high-level oxidation technology, coordinates catalyst to urge by many metal corsslinkings
Change decomposing hydrogen dioxide solution and produce hydroxyl radical free radical OH, and then fracture uns-dimethylhydrazine C N, N N chemical bond, effective mineralising organic waste
Water, safe and efficient, secondary pollution is little；Especially for high concentration uns-dimethylhydrazine waste water, it is not necessary to dilute, regulate initial pH in advance
Process waste water, solve the by-product that the treating capacity that this kind of organic wastewater faces at present is little, traditional method mineralising the most thoroughly causes dirty
The multiple difficult problems such as dye is big, long processing period.
Detailed description of the invention
Below technical scheme is described further.
The present invention for uns-dimethylhydrazine degraded many metal corsslinkings coordinate catalyst, represent by formula M N, M mole
Number is 0.5～5:100 with the weight ratio of N；Wherein, M represents at least two metal in transition metal and/or rare earth metal,
Such as copper zinc cobalt, copper nickel zirconium, ferrum molybdenum, copper cerium or cobalt neodymium；N represents modification of chitosan carrier: chitosan-SiO2Complex carrier, compound
In carrier, chitosan and SiO2Weight ratio be 1:0.5～2.
The preparation method of modification of chitosan carrier includes: dissolve chitosan in acid solution, such as acetic acid solution, adds
SiO through high-temperature calcination2, control chitosan and SiO2Weight ratio be 1:0.5～2, stirring, as in ultrasonic lower stirring at normal temperature, made
Both mix homogeneously, are subsequently adding NaOH, form gel, be centrifuged, wash, dry, grind and sieve, such as repeatable centrifugal, washing
To alkalescence, dry under infrared lamp, then grind, sieve, obtain modification of chitosan carrier.
Many metal corsslinkings for uns-dimethylhydrazine degraded coordinate the preparation method of catalyst to include: with transition metal and/or
At least two metal in rare earth metal makees active component, such as Cu, Ni and Co, copper nickel zirconium, ferrum molybdenum, copper cerium or cobalt neodymium, takes corresponding gold
Belonging to salt to dissolve, be dissolved in ethanol as taken corresponding metal chloride, metal chloride and ethanol form MClX-EtOH, x are 2-4；Adjust
Joint temperature, as temperature controlled at 40～70 DEG C, then load on modification of chitosan carrier, scrubbed, dry, grinding, mistake
Sieve, as first used 70% washing with alcohol, then using 95% washing with alcohol, use absolute ethanol washing again, dry under infrared lamp
Dry, grind, then cross 60 eye mesh screens, prepare many metal corsslinkings and coordinate catalyst.Wherein, the molal quantity of slaine is controlled with modified
The weight ratio of chitin carrier is 0.5～5:100.
Then in prepared catalyst fines, add γ-Al2O3With sesbania powder dilute nitric acid dissolution, use after mix homogeneously
Banded extruder molding, dries in an oven, standby.Take a certain amount of catalyst prepared and put in reaction bed, by hydrogen peroxide according to
Certain proportion joins in the waste water of uns-dimethylhydrazine, then according to waste water stream is added by certain flow rate enters the reaction equipped with catalyst
In Chuan.Wherein, controlling reaction temperature is 40～70 DEG C, flow velocity 120～150L/ hour, it is not necessary to presetting initial pH.Waste water is through urging
After changing degraded, use high performance liquid chromatography detection uns-dimethylhydrazine and nitrosodimethylamine concentration, use acetylacetone,2,4-pentanedione light splitting light
Degree method measures concentration of formaldehyde, uses the concentration of Na's reagent detection ammonia nitrogen.
Embodiment 1 pure chitosan bio-carrier and the Performance comparision of modification of chitosan bio-carrier
Using metallic copper nickel as catalyst active center, with pure chitosan or modification of chitosan as catalyst carrier, respectively
Preparation Cu2+/Ni2+-CTS catalyst and Cu2+/Ni2+-CTS-SiO2Catalyst.
Cu2+/Ni2+-CTS catalyst preparation process is as follows: weighs 2.0g Chitosan powder, joins containing 0.008mol
CuCl2·2H2O and 0.002mol NiCl2·6H2In the acid solution of O, at 65 DEG C, constant temperature stirring makes it adsorb, and inhales after 6h
Attached balance, adds dehydrated alcohol sucking filtration, with 70% washing with alcohol 2 times more colourless to wash solution for several times with absolute ethanol washing, dry
Dry aeruginous catalyst Cu2+/Ni2+-CTS。
Cu2+/Ni2+-CTS-SiO2Catalyst preparation process is as follows: chitosan and 1.5% acetic acid are mixed, the lower stirring of heating
It is allowed to dissolve, is subsequently adding the SiO of high-temperature calcination in Muffle furnace2, chitosan and SiO2Weight ratio be 1:2, ultrasonic lower often
Temperature stirs, and drips 4mol L-1NaOH slowly forms gel, and repeated centrifugation is washed under alkalescence, infrared lamp dry, grind
Honed sieve obtains SiO2-CS carrier；Control metal ion total mole number with the weight ratio of modified natural polymer carrier is
0.5:100, takes the CuCl of respective quality2·2H2O and NiCl2·6H2O is dissolved in ethanol, and at 70 DEG C, constant temperature stirring loads to
SiO2On-CS carrier, be washed out, be dried under infrared lamp, ground sieve series obtains aeruginous catalyst Cu2+/Ni2+-CTS-SiO2。
Two kinds of each 40g of catalyst, the degraded uns-dimethylhydrazine containing 500mg/L it is separately added in catalysis advanced oxidation reaction bed
Waste water, initial COD is 998.1mg/L, reaction temperature: 70 DEG C, flow velocity 120L/ hour, response time 25min.Use COD quick
COD numerical value before and after analyzer detection catalytic degradation, uses high performance liquid chromatography detection uns-dimethylhydrazine and nitrosodimethylamine dense
Degree, uses the concentration of Na's reagent detection ammonia nitrogen.Experimental result is shown in Table 1.
Table 1 pure chitosan carrier and the Performance comparision of modification of chitosan carried catalyst
Table 1 result shows, compared with pure chitosan carried catalyst, after being modified the degraded of chitin carrier catalyst
COD degradation rate, the degradation rate of uns-dimethylhydrazine in waste water significantly improve, nitrosodimethylamine concentration, NH4+Concentration is relatively low, and
And solve pure chitosan carried catalyst in degradation reaction, occur that ion comes off the problem of chroma pollution.Visible, the present invention
The degradation effect of modification of chitosan carried catalyst excellent, be better than pure chitosan carried catalyst.
The impact on degradation effect of the embodiment 2 modification of chitosan carrier different ratio
Using metallic copper nickel as catalyst active center, do five groups of parallel laboratory tests, prepare Cu2+/Ni2+-CTS-SiO2Catalysis
Agent, preparation method is as follows:
First group: chitosan and 1.5% acetic acid are mixed, the lower stirring of heating is allowed to dissolve, and is subsequently adding in Muffle furnace
The SiO of high-temperature calcination2, chitosan and SiO2Weight ratio be 1:5, ultrasonic lower stirring at normal temperature is uniform, drips 4mol L- 1NaOH slowly forms gel, and repeated centrifugation is washed under alkalescence, infrared lamp to dry, grind to sieve and obtain SiO2-CS carrier；Control
Metal ion total mole number processed is 1:100 with the weight ratio of modified natural polymer carrier, takes the Cu that mol ratio is 1:1
(NO3)2·2H2O and Ni (NO3)2·6H2O is dissolved in ethanol, and at 40 DEG C, constant temperature stirring loads to SiO2On-CS carrier, then wash
Wash, be dried under infrared lamp, ground sieve series obtains aeruginous catalyst Cu2+/Ni2+-CTS-SiO2。
Second group: with reference to the method for first group, difference is, chitosan and SiO2Weight ratio be 1:2；
3rd group: with reference to the method for first group, difference is, chitosan and SiO2Weight ratio be 1:1；
4th group: with reference to the method for first group, difference is, chitosan and SiO2Weight ratio be 2:1；
5th group: with reference to the method for first group, difference is, chitosan and SiO2Weight ratio be 5:1.
Being separately added into each 40g of catalyst that three groups of experiments prepare in catalysis advanced oxidation reaction bed, degraded is containing 500mg/L
Uns-dimethylhydrazine waste water, initial COD is 1000mg/L, and reaction temperature: 50 DEG C does not regulate pH, and flow velocity 150L/ hour, during reaction
Between 25min.Use COD numerical value before and after COD Quick testing instrument detection catalytic degradation, use high performance liquid chromatography to detect inclined diformazan
Hydrazine and nitrosodimethylamine concentration, use the concentration of Na's reagent detection ammonia nitrogen.Experimental result is shown in Table 2.
The comparison of the modification of chitosan supported catalyst activity of table 2 different ratio
Table 2 result shows, as chitosan and SiO2Weight ratio when being 1:0.5～2, use the modified shell of different ratio to gather
Sugar carrier catalyst is degraded, and the degradation rate of COD all reaches more than 85%, and the degradation rate of uns-dimethylhydrazine is all more than 99.8%；
Wherein, chitosan and SiO2Weight ratio when being 1:2, prepared catalyst activity is the highest, and the degradation rate of COD exceedes
90%, the degradation rate of uns-dimethylhydrazine is more than nitrosodimethylamine concentration, NH in 99.9%, and waste water4+Concentration is minimum；Work as chitosan
With SiO2Weight ratio be less than 1:2 or more than 2:1 time, the catalysis activity of prepared catalyst decreases.
The impact on degradation reaction of the embodiment 3 catalyst active center composition
Chitosan with weight ratio as 1:2 and SiO2Modification of chitosan be carrier, choose different active center respectively,
Carrying out five groups of parallel laboratory tests, prepare many metal corsslinkings and coordinate catalyst agent, preparation method is as follows:
First group: chitosan and 1.5% acetic acid are mixed, the lower stirring of heating is allowed to dissolve, and is subsequently adding in Muffle furnace
The SiO of high-temperature calcination2, chitosan and SiO2Weight ratio be 1:2, ultrasonic lower stirring at normal temperature is uniform, drips 4mol L- 1NaOH slowly forms gel, and repeated centrifugation is washed under alkalescence, infrared lamp to dry, grind to sieve and obtain SiO2-CS carrier；With
Metallic copper zinc cobalt as catalyst active center, control metal ion total mole number and modified natural polymer carrier weight it
Ratio is 5:100, wherein, Cu2+、Zn2+、Co2Mol ratio be 3:1:1, the metal chloride taking respective quality is dissolved in ethanol, 60 DEG C
The stirring of lower constant temperature loads to SiO2On-CS carrier, be washed out, be dried under infrared lamp, ground sieve series obtains aeruginous catalyst
Cu2+/Ni2+-CTS-SiO2。
Second group: with reference to the method for first group, difference is, the Cu with mol ratio as 3:1:12+、Ni2+、Zr2+As urging
Agent active center；
3rd group: with reference to the method for first group, difference is, the Fe with mol ratio as 4:13+、Mo3+Live as catalyst
Property center；
4th group: with reference to the method for first group, difference is, the Cu with mol ratio as 4:12+、Ce3+Live as catalyst
Property center；
5th group: with reference to the method for first group, difference is, the Co with mol ratio as 4:12+、Nd3+Live as catalyst
Property center.
Being separately added into each 40g of catalyst that five groups of experiments prepare in catalysis advanced oxidation reaction bed, degraded is containing 500mg/L
Uns-dimethylhydrazine waste water, initial COD is 1000mg/L, reaction temperature: 60 DEG C, flow velocity 140L/ hour, response time 25min.Adopt
With COD numerical value before and after COD Quick testing instrument detection catalytic degradation, use high performance liquid chromatography detection uns-dimethylhydrazine and nitroso-group
Dimethylamine concentration, uses the concentration of Na's reagent detection ammonia nitrogen.Experimental result is shown in Table 3.
Table 3 different activities center is with the comparison of composition and ratio catalyst activity
Table 3 result shows, the catalyst of five kinds of different activities centers composition is used for degrading after uns-dimethylhydrazine waste water, COD's
Clearance is all higher than 90%, and the degradation rate of uns-dimethylhydrazine is all higher than 99%.Five kinds of active components are different, and the result of reaction is also
Variant, but be all effective active component.From nitrosodimethylamine concentration it can also be seen that the different ions degraded to by-product
Efficiency is different, thus can select applicable compounding ion.
The impact on degradation reaction of the embodiment 4 catalyst active center composition and ratio
With reference to embodiment 1, using metallic copper nickel as active center, with chitosan and SiO2The modification that mass ratio is 1:2
Chitosan, as carrier, changes the weight ratio of metal ion total mole number and modification of chitosan carrier, prepares in identical activity
The Cu of heart different ratio2+/Ni2+-CTS-SiO2Catalyst, and the uns-dimethylhydrazine of the 500mg/L that is used for prepared catalyst degrading
Waste water, initial COD is 1000mg/L, reaction temperature: 70 DEG C, flow velocity 130L/ hour, response time 25min.Experimental result is shown in Table
4。
Table 4 is with the comparison of active center difference composition and ratio catalyst activity
Table 4 result shows, after using the different catalyst degraded uns-dimethylhydrazine waste water of four kinds of active composition and ratios,
The clearance of COD is all higher than 90%, and the degradation rate of uns-dimethylhydrazine is all higher than 99%.And when metal ion total mole number and modified shell
When the weight ratio of polysaccharide carrier is 4～5:100, prepared catalyst activity activity is higher, and its catalytic effect all meets
Missile propellant pollution discharge standard (GB14374-93, COD are less than 150mg/L, and uns-dimethylhydrazine content is less than 0.5mg/L,
N-Nitrosodimethylamine content is less than 0.1mg/L, and ammonia-nitrogen content is less than 25mg/L, and content of formaldehyde is less than 2mg/L).
As can be seen here, catalyst provided by the present invention, to the degradation effect of uns-dimethylhydrazine waste water along with active component Cu2 +, Ni2+The change of molal quantity and change, its reason is the ion concentration impact on load capacity, and ion concentration low-load amount is not
Height, ion concentration height easily causes the waste of raw material；When total ion concentration is about 4%, catalyst can get maximally effective profit
With.
The impact on catalyst activity of embodiment 5 temperature
With reference to embodiment 1, with chitosan and SiO2The modification of chitosan that mass ratio is 1:2 as carrier, with metallic copper
Nickel is as active center, and the weight ratio controlling metal ion total mole number and modified natural polymer carrier is 4:100, its
In, Cu2+And Ni2+Mol ratio be 3:1, prepare Cu2+/Ni2+-CTS-SiO2Catalyst；It is used for degrading by prepared catalyst
The uns-dimethylhydrazine waste water of 500mg/L, initial COD is 1000mg/L, chooses different reaction temperatures, flow velocity 120L/ hour, reaction
Time 25min.
When temperature is about 80 DEG C, uns-dimethylhydrazine can be with water generation azeotropic, and drain evaporation, to catalyst effect
Judge to produce interference, therefore, select to test within the temperature range of 30～70 DEG C herein.Experimental result is shown in Table 5.Work as reaction temperature
When being 30 DEG C, response time 2～3h uns-dimethylhydrazine waste water is still without significant change, so place is only the temperature range pair of 40～70 DEG C
Catalyst activity compares.
The different initial reaction temperature impact on catalyst activity of table 5
Table 5 result shows, the catalysis activity of the catalyst prepared under condition of different temperatures is different, along with the liter of reaction temperature
Height, the clearance of COD, the clearance of uns-dimethylhydrazine constantly increase；Nitrosodimethylamine content, ammonia-nitrogen content constantly reduce.Instead
Answering temperature is that at 60～70 DEG C, the effect of catalytic reaction meets missile propellant pollution discharge standard (GB14374-93, COD
Less than 150mg/L, uns-dimethylhydrazine content is less than 0.5mg/L, and N-Nitrosodimethylamine content is less than 1.mg/L, and ammonia-nitrogen content is less than
25mg/L, content of formaldehyde is less than 2mg/L).
The impact on catalyst activity of embodiment 6pH
Carry out the preprocessing process of acid adding before treatment in view of the uns-dimethylhydrazine waste water having, changed catalysis for pH
Following experiment has been done in the impact of agent catalysis activity.
With reference to embodiment 1, with chitosan and SiO2The modification of chitosan that mass ratio is 1:2 as carrier, with metallic copper
Nickel is as active center, and the weight ratio controlling metal ion total mole number and modified natural polymer carrier is 4:100, its
In, Cu2+And Ni2+Mol ratio be 3:1, prepare Cu2+/Ni2+-CTS-SiO2Catalyst；Take the catalyst use that 100g prepares respectively
In the uns-dimethylhydrazine waste water of degraded initial concentration 500mg/L, initial COD is 1000mg/L, and controlling reaction temperature is 70 DEG C, respectively
The initial pH of regulation is 6,7,8,9, is contrast experiment with the matched group not regulating pH.Understand after tested, do not regulate the matched group of pH
Its initial pH is about 9.5.
Experimental result: after degradation reaction 30min, the initial pH of regulation is 6,7,8,9, and does not regulate the right of pH (≈ 9.5)
COD value according to group is respectively as follows: 77.43mg/L, 73.65mg/L, 70.37mg/L, 66.77mg/L, 67.32mg/L.
Experiment shows: change little at pH=6～9.5 degradation reaction catalytic efficiencies, the biodegrading process of this explanation present invention
Not limiting the initial pH of uns-dimethylhydrazine waste water, degradation reaction, without presetting pH, saves presetting pH compared to prior art
This operation.
Embodiment 7 catalyst degradation capability to the uns-dimethylhydrazine waste water of different initial concentrations
With reference to embodiment 1, with chitosan and SiO2The modification of chitosan that mass ratio is 1:2 as carrier, with metallic copper
Nickel is as active center, and the weight ratio controlling metal ion total mole number and modified natural polymer carrier is 4:100, its
In, Cu2+And Ni2+Mol ratio be 3:1, prepare Cu2+/Ni2+-CTS-SiO2Catalyst；Take the catalyst use that 100g prepares respectively
In the uns-dimethylhydrazine waste water of the different initial concentration of degraded, controlling reaction temperature is 70 DEG C, flow velocity 120L/ hour, the response time
25min.Experimental result is shown in Table 6.
Table 6 same catalyst initiates the comparison of COD wastewater degradation effect to difference
Table 6 result shows, along with the increase of uns-dimethylhydrazine initial concentration, the COD in waste water after process, uns-dimethylhydrazine are dense
Degree has risen, i.e. COD, the clearance of uns-dimethylhydrazine decline with the increase of uns-dimethylhydrazine initial concentration.But, for difference
The uns-dimethylhydrazine waste water of initial concentration, after using the catalyst degraded of the present invention, COD clearance is above 90%, inclined two
Methylhydrazine degradation rate is all higher than 99%, and the catalyst of this explanation present invention is for the fall of the higher uns-dimethylhydrazine waste water of initial concentration
Solve, the most efficiently.
The impact on catalysis activity of the embodiment 8 catalyst access times
With reference to embodiment 1, with chitosan and SiO2The modification of chitosan that mass ratio is 1:2 as carrier, with metallic copper
Nickel is as active center, and the weight ratio controlling metal ion total mole number and modified natural polymer carrier is 4:100, its
In, Cu2+And Ni2+Mol ratio be 3:1, prepare Cu2+/Ni2+-CTS-SiO2Catalyst.
Add the catalyst 300g of above-mentioned preparation at catalysis advanced oxidation reaction bed, catalyst is repeatedly applied to degraded
The uns-dimethylhydrazine waste water of 500mg/L, initial COD is 1000mg/L, reaction temperature: 65 DEG C, flow velocity 150L/ hour, the response time
For 25min.Experimental result is shown in Table 7.
Table 7 catalyst recycles the number of times impact on uns-dimethylhydrazine degradation effect
Table 7 result shows, the catalyst that the present invention prepares for degrade uns-dimethylhydrazine waste water time, catalyst is used for multiple times
After, in the waste water after process, COD, uns-dimethylhydrazine, ammonia nitrogen, the concentration of methylene dimethylamine still conform to missile propellant water and pollute
Thing discharge standard (GB14374-93), it can be seen that, the catalyst that the present invention prepares can be recycled for multiple times, and uses the present invention's
Catalyst degradation uns-dimethylhydrazine waste water, technique and plant running cost are relatively low.
Claims (10)
1. one kind coordinates catalyst for many metal corsslinkings of uns-dimethylhydrazine degraded, it is characterised in that described many metal corsslinkings are joined
Closing catalyst formula M-N to represent, wherein, M is at least two metal in transition metal and/or rare earth metal, and N is modified shell
Polysaccharide carrier, the molal quantity of M and the weight ratio of N are 0.5～5:100.
Many metal corsslinkings for uns-dimethylhydrazine degraded the most according to claim 1 coordinate catalyst, it is characterised in that institute
The weight ratio of the molal quantity and N of stating M is 4～5:100.
Many metal corsslinkings for uns-dimethylhydrazine degraded the most according to claim 1 coordinate catalyst, it is characterised in that institute
Stating modification of chitosan carrier is chitosan-SiO2Complex carrier, wherein, chitosan and SiO2Weight ratio is 1:0.5～2.
Many metal corsslinkings for uns-dimethylhydrazine degraded the most according to claim 3 coordinate catalyst, it is characterised in that institute
State chitosan and SiO2Weight ratio be 1:1～2.
Many metal corsslinkings for uns-dimethylhydrazine degraded the most according to claim 3 coordinate catalyst, it is characterised in that institute
The preparation method stating modification of chitosan carrier comprises the steps: to dissolve chitosan in acid solution, adds and forges through high temperature
The SiO burnt2, control chitosan and SiO2Weight ratio be 1:0.5～2, stirring, be subsequently adding NaOH, formed gel, be centrifuged, wash
Wash, dry, grind to sieve and obtain modification of chitosan carrier.
6. coordinate catalyst according to the many metal corsslinkings for uns-dimethylhydrazine degraded described in claim 1, it is characterised in that
Described M is copper zinc cobalt, copper nickel zirconium, ferrum molybdenum, copper cerium or cobalt neodymium.
Many metal corsslinkings for uns-dimethylhydrazine degraded the most according to claim 1 coordinate the preparation method of catalyst, its
It is characterised by, comprises the steps: to make active component with at least two metal in transition metal and/or rare earth metal, take phase
The dissolving metal salts answered, is loaded to, on modification of chitosan carrier, wash, be dried, grind, sieve, obtain after regulation temperature
Many metal corsslinkings coordinate catalyst；Wherein, the total mole number of described slaine is 0.5 with the weight ratio of modification of chitosan carrier
～5:100.
Many metal corsslinkings for uns-dimethylhydrazine degraded the most according to claim 7 coordinate the preparation method of catalyst, its
Being characterised by, regulating described temperature is 40～70 DEG C.
9. utilizing the method that the many metal corsslinkings described in claim 1 coordinate catalyst degradation uns-dimethylhydrazine, its feature exists
In, comprise the steps: to add hydrogen peroxide in the waste water containing uns-dimethylhydrazine, be subsequently adding many metal corsslinkings and coordinate catalyst,
Controlling reaction temperature is 40～70 DEG C, and flow velocity is 120～150L/ hour.
The method utilizing many metal corsslinkings to coordinate catalyst degradation uns-dimethylhydrazine the most according to claim 9, its feature exists
In, controlling reaction temperature is 60～70 DEG C.
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| CN111704229A (en) * | 2020-06-22 | 2020-09-25 | 东南大学 | Preparation method of nano low-dimensional catalyst for degrading acrylic fiber wastewater and degradation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109999781A (en) * | 2019-03-27 | 2019-07-12 | 江苏金环环保设备有限公司 | A kind of boracic rare earth oxide composite material and its processing method handling uns-dimethylhydrazine waste water |
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| CN111704229A (en) * | 2020-06-22 | 2020-09-25 | 东南大学 | Preparation method of nano low-dimensional catalyst for degrading acrylic fiber wastewater and degradation method |
| CN111704229B (en) * | 2020-06-22 | 2022-03-04 | 东南大学 | Preparation method of nano low-dimensional catalyst for degrading acrylic fiber wastewater and degradation method |
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