CN106111200B - More metal corsslinkings cooperation catalyst and its preparation method and application for uns-dimethylhydrazine degradation - Google Patents
More metal corsslinkings cooperation catalyst and its preparation method and application for uns-dimethylhydrazine degradation Download PDFInfo
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The present invention discloses a kind of more metal corsslinkings cooperation catalyst and its preparation method and application for uns-dimethylhydrazine degradation, more metal corsslinking cooperation catalyst are indicated with formula M-N, wherein, M is at least two metals 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.Preparation method are as follows: take in transition metal and/or rare earth metal at least two metals as active constituent according to aforementioned proportion, it is loaded on modification of chitosan carrier after adjusting temperature, washing, is ground up, sieved drying, obtains more metal corsslinkings cooperation catalyst.More metal corsslinkings produced by the present invention cooperate catalyst, with with the intimate imitative enzymatic activity of biological enzyme, it can degrade at normal temperature to uns-dimethylhydrazine waste water, its catalytic activity is high, reusable, especially for high concentration uns-dimethylhydrazine waste water, dilution is not needed, adjusting starting pH carrys out pretreated waste water.
Description
Technical field
The present invention relates to a kind of catalyst and its preparation method and application, in particular to it is a kind of for uns-dimethylhydrazine degradation
More metal corsslinking cooperation catalyst and its preparation method and application.
Background technique
Uns-dimethylhydrazine (Unsymmetric Dimethylhydrazine, abbreviation UDMH) is used as power fuel, has heat steady
Qualitative good, the excellent performance such as the combustion heat is big, specific impulse is high.As the mankind need the continuous exploration and national defense industry of space one
The continuous promotion asked, uns-dimethylhydrazine are more and more widely used, including defend as a kind of high specific impulse liquid propellant
Star, guided missile, unmanned plane etc..But the high toxicity that has of uns-dimethylhydrazine itself is to the work of its liquid waste processing that bring is high wants
It asks.Uns-dimethylhydrazine is reacted with oxygen in the gas phase, and reaction rate is very fast, half-life period only 16h, can be toxic extremely strong in reaction
N-Nitrosodimethylamine generates, and the processing of nitrosodimethylamine is then more difficult.After uns-dimethylhydrazine sewage is discharged into environment, waste water
In not only contain uns-dimethylhydrazine, can also oxygenolysis generate inclined hydrazone, the tetramethyl tetrazene, dimethylamine, formaldehyde, cyanide and N-
Nitrosodimethylamine etc., the ratio uns-dimethylhydrazine that these product toxicity have is bigger, strong to environment and the mankind if not handling direct emission
Health has very big harm.
Currently, mainly having incineration method, catalytic oxidation, wet type oxygen to the processing technique of high concentration, organic wastewater with difficult degradation thereby
Change method, photocatalytic oxidation, supercritical water oxidation method etc..But the equal Shortcomings of these biodegrading process, the gas that incineration method generates
Secondary pollution is caused to environment；The Threshold retention of photocatalytic method is relatively low；Supercritical water oxidation method is due to severe reaction conditions
It is difficult to obtain practical application；Common Fenton reagent method has the effect of preferably handling Organic substance in water, but deposits in system
In a large amount of Fe2+, so that H2O2Utilization rate be not it is very high, organic matter degradation is also incomplete, and subsequent processing generate it is big
Measure iron containing sludge.In addition, the process and mechanism of uns-dimethylhydrazine degradation are extremely complex, there is intermediate products to continue decomposition, centre
Reaction between product.Therefore, when selecting the biodegrading process of uns-dimethylhydrazine, it should not only consider the degradation of uns-dimethylhydrazine itself
Situation, while being further noted that the degradation situation of intermediate product.
Based on the above situation, explore that a kind of green, catalytic activity be higher, at low cost, uns-dimethylhydrazine redox degradation
Catalyst be of great practical significance.
Chitosan (chitosan abbreviation CTS) is the product after a kind of deacetylation by chitin.Chitin, chemical name
It is the unique natural alkaline macromolecule polysaccharide found so far for 2- deoxidation -2- acetamido-B- (1-4) glucan, chitin is wide
In the general shell and mushroom for being distributed in nature Crustaceans shrimp, crab and insect and the cell wall of rudimentary plant, year biology
Yield is up to 10,000,000,000 tons, is only second to cellulose.Concentrated base handles free OH, NH in the resulting chitosan molecule structure of chitin2
With good coordination ability, complex can be formed with transition and rare earth ion.
Biological species macromolecule carrier and inorganic metal ion form composition catalyst, change activated centre metal ion kind
Class changes functional group and the steric hindrance of ligand, has and the intimate imitative enzymatic activity of biological enzyme.This kind of catalyst is living
Property center and carrier by chemical bonding, because of its high activity, highly selective, high stable, be readily synthesized and structure be adjustable etc.
Advantage is widely used in the catalyst of redox reaction.It is an object of that present invention to provide one kind to be used for reproducibility uns-dimethylhydrazine
The preparation of more metal corsslinkings cooperation catalyst of degradation and application method.
Summary of the invention
Goal of the invention: the first object of the present invention is to provide the use that a kind of catalytic activity is strong, stability is high, reusable
Cooperate catalyst in more metal corsslinkings of uns-dimethylhydrazine degradation, the second object of the present invention is to provide the preparation side of the catalyst
Method, the third object of the present invention are to provide a kind of method using more metal corsslinking cooperation catalyst degradation uns-dimethylhydrazines.
Technical solution: more metal corsslinkings of the present invention for uns-dimethylhydrazine degradation cooperate catalyst, with formula M-N
It indicates, wherein M is at least two metals in transition metal and/or rare earth metal, and N is modification of chitosan carrier, mole of M
Several weight ratios with N are 0.5~5:100.
Preferably, the weight ratio of the molal quantity of M and N are 4~5:100.
Specifically, 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 includes the following 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 then added NaOH, formed it is solidifying
Glue is centrifuged, washs, drying, being ground up, sieved to obtain modification of chitosan carrier.
Preferably, M is copper zinc cobalt, cupro-nickel zirconium, iron molybdenum, copper cerium or cobalt neodymium.
The preparation method of more metal corsslinkings cooperation catalyst of the present invention for uns-dimethylhydrazine degradation, including it is as follows
Step: making active constituent at least two metals in transition metal and/or rare earth metal, take corresponding dissolving metal salts, adjusts
It is loaded on modification of chitosan carrier after section temperature, washing, is ground up, sieved drying, obtains more metal corsslinkings cooperation catalysis
Agent；Wherein, the weight ratio of the total mole number of metal salt and modification of chitosan carrier is 0.5~5:100.
In above-mentioned preparation method, adjusting the temperature is 40~70 DEG C.
Method of the present invention using more metal corsslinkings cooperation catalyst degradation uns-dimethylhydrazine, includes the following steps:
Hydrogen peroxide is added in the waste water containing uns-dimethylhydrazine, more metal corsslinking cooperation catalyst are then added, control reaction temperature is 40
~70 DEG C, flow velocity is 120~150L/ hours.
Further, control reaction temperature is 60~70 DEG C.
The utility model has the advantages that compared with prior art, remarkable advantage of the invention is: (1) more metal corsslinkings of the invention are matched
The stability that catalyst improves catalyst by forming complex between modification biological class carrier and metal is closed, it is negative to solve conventional physical
The problem of supported catalyst is easy to fall off can repeatedly use；By design catalyst active center composition and proportion, change
The electronic structure and surface nature of change catalyzer improve catalyst activity；The catalyst not only active high catalytic action, but it is simultaneous
Has traditional suction-operated, before more common chitosan metal complexes and modified monometallic complex have better industrial application
Scape；(2) preparation process of more metal corsslinkings of the invention cooperation catalyst carries out under low-temperature atmosphere-pressure, does not need high-temperature calcination；
And the introducing without poisonous and harmful substance, secondary pollution is not generated, it is environmentally protective；Meanwhile preparation process is easy to operate, catalyst
It is easily molded, at low cost；(3) present invention uses heterogeneous catalysis high-level oxidation technology, cooperates catalyst to urge by more metal corsslinkings
Change decomposing hydrogen dioxide solution and generate hydroxyl radical free radical OH, and then is broken uns-dimethylhydrazine C-N, N-N chemical bond, effective mineralising organic waste
Water, safe and efficient, secondary pollution is small；Especially for high concentration uns-dimethylhydrazine waste water, dilution is not needed, adjusting starting pH comes in advance
Waste water is handled, it is dirty to solve by-product caused by the treating capacity that this kind of organic wastewater faces at present is small, conventional method mineralising is not thorough
A variety of problems such as the big, long processing period of dye.
Specific embodiment
Technical solution of the present invention is described further below.
More metal corsslinkings for uns-dimethylhydrazine degradation of the invention cooperate catalyst, are indicated with formula M-N, mole of M
Several weight ratios with N are 0.5~5:100；Wherein, M represents at least two metals in transition metal and/or rare earth metal,
Such as copper zinc cobalt, cupro-nickel zirconium, iron molybdenum, copper cerium or cobalt neodymium；N represents modification of chitosan carrier: chitosan-SiO2Complex carrier, it is compound
In carrier, chitosan and SiO2Weight ratio be 1:0.5~2.
The preparation method of modification of chitosan carrier includes: to dissolve chitosan in acid solution, such as acetic acid solution, is added
SiO through high-temperature calcination2, control chitosan and SiO2Weight ratio be 1:0.5~2, stirring, such as under ultrasound stirring at normal temperature, make
The two is uniformly mixed, and NaOH is then added, forms gel, is centrifuged, washs, dries, is ground up, sieved, such as repeatable centrifugation, washing
To alkalescent, dries under infrared lamp, is then ground up, sieved, obtain modification of chitosan carrier.
The preparation method of more metal corsslinkings cooperation catalyst for uns-dimethylhydrazine degradation include: with transition metal and/or
At least two metals in rare earth metal make active constituent, such as Cu, Ni and Co, cupro-nickel zirconium, iron molybdenum, copper cerium or cobalt neodymium, take corresponding gold
Belong to salt dissolution, corresponding metal chloride is such as taken to be dissolved in ethyl alcohol, metal chloride and ethyl alcohol form MClX- EtOH, x 2-4；It adjusts
Temperature is saved, such as temperature is controlled at 40~70 DEG C, is then loaded on modification of chitosan carrier, washed, dry, grinding, mistake
Sieve is such as first washed using 70% ethanol washing, then using 95% ethanol washing, again using dehydrated alcohol, is done under infrared lamp
Dry, then 60 mesh screens are crossed in grinding, and more metal corsslinking cooperation catalyst are made.Wherein, molal quantity and the modification of metal salt are controlled
The weight ratio of chitin carrier is 0.5~5:100.
Then γ-Al is added in catalyst fines obtained2O3With sesbania powder dilute nitric acid dissolution, use after mixing
Banded extruder molding, is dried in an oven, spare.Take a certain amount of catalyst prepared to be put into reaction bed, by hydrogen peroxide according to
Certain proportion is added in the waste water of uns-dimethylhydrazine, then adds waste water stream into the reaction equipped with catalyst according to certain flow rate
In bed.Wherein, control reaction temperature is 40~70 DEG C, flow velocity 120~150L/ hours, is not necessarily to presetting starting pH.Waste water is by urging
After changing degradation, uns-dimethylhydrazine and nitrosodimethylamine concentration are detected using high performance liquid chromatography, light is divided using acetylacetone,2,4-pentanedione
Degree method measures concentration of formaldehyde, using the concentration of Na's reagent detection ammonia nitrogen.
The performance of 1 pure chitosan bio-carrier of embodiment and modification of chitosan bio-carrier compares
Using metal cupro-nickel as catalyst active center, using pure chitosan or modification of chitosan as catalyst carrier, respectively
Prepare Cu2+/Ni2+- CTS catalyst and Cu2+/Ni2+-CTS-SiO2Catalyst.
Cu2+/Ni2+- CTS catalyst preparation process is as follows: weighing 2.0g Chitosan powder, is added to containing 0.008mol
CuCl2·2H2O and 0.002mol NiCl2·6H2In the acid solution of O, constant temperature stirring makes its absorption at 65 DEG C, inhales after 6h
Attached balance, adds dehydrated alcohol to filter, with 70% ethanol washing 2 times, then it is colourless to wash solution for several times with dehydrated alcohol washing, it does
It is dry to obtain blue-green catalyst Cu2+/Ni2+-CTS。
Cu2+/Ni2+-CTS-SiO2Catalyst preparation process is as follows: chitosan being mixed with 1.5% acetic acid, heats lower stirring
It is allowed to dissolve, then be added in the burnt SiO of Muffle furnace high temperature2, chitosan and SiO2Weight ratio be 1:2, ultrasound under it is normal
Temperature stirs evenly, and 4molL is added dropwise-1NaOH slowly forms gel, and repeated centrifugation is washed to alkalescent, dries, grinds under infrared lamp
Honed sieve obtains SiO2- CS carrier；Control metal ion total mole number and the weight ratio of modified natural polymer carrier are
0.5:100 takes the CuCl of corrresponding quality2·2H2O and NiCl2·6H2O is dissolved in ethyl alcohol, and constant temperature stirring loads at 70 DEG C
SiO2It on-CS carrier, is washed out, is dried under infrared lamp, is ground up, sieved obtained blue-green catalyst Cu2+/Ni2+-CTS-SiO2。
Two kinds of each 40g of catalyst are separately added into catalysis advanced oxidation reaction bed, the uns-dimethylhydrazine containing 500mg/L of degrading
Waste water, starting COD be 998.1mg/L, reaction temperature: 70 DEG C, flow velocity 120L/ hours, reaction time 25min.It is quick using COD
Analyzer detects COD numerical value before and after catalytic degradation, detects uns-dimethylhydrazine using high performance liquid chromatography and nitrosodimethylamine is dense
Degree, using the concentration of Na's reagent detection ammonia nitrogen.Experimental result is shown in Table 1.
The performance of 1 pure chitosan carrier of table and modification of chitosan carried catalyst compares
Table 1 the result shows that, compared with pure chitosan carried catalyst, after the degradation of modified chitin carrier catalyst
The degradation rate of COD degradation rate, uns-dimethylhydrazine in waste water significantly improves, nitrosodimethylamine concentration, NH4+Concentration is relatively low, and
And solve the problems, such as that pure chitosan carried catalyst occurs ion in degradation reaction and falls off chroma pollution.As it can be seen that of the invention
Modification of chitosan carried catalyst degradation effect it is excellent, be better than pure chitosan carried catalyst.
Influence of the 2 modification of chitosan carrier different ratio of embodiment to degradation effect
Using metal cupro-nickel as catalyst active center, five groups of parallel laboratory tests are done, prepare Cu2+/Ni2+-CTS-SiO2Catalysis
Agent, the preparation method is as follows:
First group: chitosan being mixed with 1.5% acetic acid, lower stirring is heated and is allowed to dissolve, be then added in Muffle furnace
The SiO of high-temperature calcination2, chitosan and SiO2Weight ratio be 1:5, the lower stirring at normal temperature of ultrasound is uniform, and 4molL is added dropwise- 1NaOH slowly forms gel, and repeated centrifugation is washed to alkalescent, dries under infrared lamp, is ground up, sieved to obtain SiO2- CS carrier；Control
The weight ratio of metal ion total mole number processed and modified natural polymer carrier is 1:100, and taking molar ratio is the Cu of 1:1
(NO3)2·2H2O and Ni (NO3)2·6H2O is dissolved in ethyl alcohol, and constant temperature stirring loads to SiO at 40 DEG C2On-CS carrier, then wash
It washs, is dried under infrared lamp, is ground up, sieved obtained blue-green catalyst Cu2+/Ni2+-CTS-SiO2。
Second group: referring to first group of method, difference is, chitosan and SiO2Weight ratio be 1:2；
Third group: referring to first group of method, difference is, chitosan and SiO2Weight ratio be 1:1；
4th group: referring to first group of method, difference is, chitosan and SiO2Weight ratio be 2:1；
5th group: referring to first group of method, difference is, chitosan and SiO2Weight ratio be 5:1.
Each 40g of catalyst made from three groups of experiments is separately added into catalysis advanced oxidation reaction bed, degradation contains 500mg/L
Uns-dimethylhydrazine waste water, starting COD is 1000mg/L, and reaction temperature:, not adjusting pH by 50 DEG C, flow velocity 150L/ hours, when reaction
Between 25min.Using COD numerical value before and after COD Quick testing instrument detection catalytic degradation, inclined diformazan is detected using high performance liquid chromatography
Hydrazine and nitrosodimethylamine concentration, using 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 2 different ratio of table
Table 2 the result shows that, when chitosan and SiO2Weight ratio when being 1:0.5~2, it is poly- using the modification shell of different ratio
The degradation of sugar carrier catalyst, the degradation rate of COD reach 85% or more, and the degradation rate of uns-dimethylhydrazine is more than 99.8%；
Wherein, chitosan and SiO2Weight ratio when being 1:2, catalyst activity highest obtained, the degradation rate of COD is more than
90%, the degradation rate of uns-dimethylhydrazine is more than 99.9%, and nitrosodimethylamine concentration, NH in waste water4+Concentration is minimum；Work as chitosan
With SiO2Weight ratio be less than 1:2 or be greater than 2:1 when, the catalytic activity of catalyst obtained decreases.
The influence of the 3 pairs of degradation reaction of catalyst active center's group of embodiment
It is the chitosan and SiO of 1:2 with weight ratio2Modification of chitosan be carrier, choose different activated centres respectively,
Five groups of parallel laboratory tests are carried out, more metal corsslinking cooperation catalyst agent are prepared, the preparation method is as follows:
First group: chitosan being mixed with 1.5% acetic acid, lower stirring is heated and is allowed to dissolve, be then added in Muffle furnace
The SiO of high-temperature calcination2, chitosan and SiO2Weight ratio be 1:2, the lower stirring at normal temperature of ultrasound is uniform, and 4molL is added dropwise- 1NaOH slowly forms gel, and repeated centrifugation is washed to alkalescent, dries under infrared lamp, is ground up, sieved to 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
Than for 5:100, wherein Cu2+、Zn2+、Co2Molar ratio be 3:1:1, take the metal chloride of corrresponding quality to be dissolved in ethyl alcohol, 60 DEG C
Lower constant temperature stirring loads to SiO2It on-CS carrier, is washed out, is dried under infrared lamp, is ground up, sieved obtained blue-green catalyst
Cu2+/Ni2+-CTS-SiO2。
Second group: referring to first group of method, it is the Cu of 3:1:1 with molar ratio that difference, which is,2+、Ni2+、Zr2+As urging
Agent activated centre；
Third group: referring to first group of method, it is the Fe of 4:1 with molar ratio that difference, which is,3+、Mo3+It is living as catalyst
Property center；
4th group: referring to first group of method, it is the Cu of 4:1 with molar ratio that difference, which is,2+、Ce3+It is living as catalyst
Property center；
5th group: referring to first group of method, it is the Co of 4:1 with molar ratio that difference, which is,2+、Nd3+It is living as catalyst
Property center.
Each 40g of catalyst made from five groups of experiments is separately added into catalysis advanced oxidation reaction bed, degradation contains 500mg/L
Uns-dimethylhydrazine waste water, starting COD be 1000mg/L, reaction temperature: 60 DEG C, flow velocity 140L/ hours, reaction time 25min.It adopts
With COD numerical value before and after COD Quick testing instrument detection catalytic degradation, uns-dimethylhydrazine and nitroso are detected using high performance liquid chromatography
Dimethylamine concentration, using the concentration of Na's reagent detection ammonia nitrogen.Experimental result is shown in Table 3.
Comparison of the 3 different activities center of table with composition and ratio catalyst activity
Table 3 the result shows that, the catalyst of five kinds of different activities centers composition for degrading after uns-dimethylhydrazine waste water, COD's
Removal rate is all larger than 90%, and the degradation rate of uns-dimethylhydrazine is all larger than 99%.Five kinds of active components are different, the result of reaction
It is variant, but be all effective active component.From nitrosodimethylamine concentration it can also be seen that degradation of the different ions to by-product
Efficiency is different, it is possible thereby to select suitable compounding ion.
Influence of the 4 catalyst active center's composition and ratio of embodiment to degradation reaction
Referring to embodiment 1, using metal cupro-nickel as activated centre, with chitosan and SiO2Mass ratio be 1:2 modification
Chitosan changes the weight ratio of metal ion total mole number and modification of chitosan carrier as carrier, prepares in identical activity
The Cu of heart different ratio2+/Ni2+-CTS-SiO2Catalyst, and catalyst obtained is used to degrade the uns-dimethylhydrazine of 500mg/L
Waste water, starting COD be 1000mg/L, reaction temperature: 70 DEG C, flow velocity 130L/ hours, reaction time 25min.Experimental result is shown in Table
4。
Comparison of the table 4 with activated centre difference composition and ratio catalyst activity
Table 4 the result shows that, after the different catalysts degradation uns-dimethylhydrazine waste water of four kinds of active composition and ratios,
The removal rate of COD is all larger than 90%, and the degradation rate of uns-dimethylhydrazine is all larger than 99%.And when metal ion total mole number and modified shell
When the weight ratio of glycan carrier is 4~5:100, catalyst activity activity obtained is higher, and catalytic effect 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 lower than 0.1mg/L, and ammonia-nitrogen content is less than 25mg/L, and content of formaldehyde is less than 2mg/L).
It can be seen that catalyst provided by the present invention, to the degradation effect of uns-dimethylhydrazine waste water with active component Cu2 +, Ni2+The variation of molal quantity and change, reason is influence of the ion concentration to load capacity, and ion concentration low-load amount is not
Height, ion concentration height easily cause the waste of raw material；When total ion concentration is 4% or so, most effective benefit is can be obtained in catalyst
With.
Influence of 5 temperature of embodiment to catalyst activity
Referring to embodiment 1, with chitosan and SiO2Mass ratio be 1:2 modification of chitosan as carrier, with metallic copper
For nickel as activated centre, the weight ratio for controlling metal ion total mole number and modified natural polymer carrier is 4:100,
In, Cu2+And Ni2+Molar ratio be 3:1, prepare Cu2+/Ni2+-CTS-SiO2Catalyst；Catalyst obtained is used to degrade
The uns-dimethylhydrazine waste water of 500mg/L, starting COD are 1000mg/L, choose different reaction temperatures, flow velocity 120L/ hours, react
Time 25min.
When temperature is 80 DEG C or so, with water azeotropic, drain evaporation, to catalyst effect can occur for uns-dimethylhydrazine
Determine to generate interference, therefore, selects 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, 2~3h of reaction time uns-dimethylhydrazine waste water is still without significant change, therefore herein only in 40~70 DEG C of temperature range pair
Catalyst activity is compared.
Influence of the different initial reaction temperatures of table 5 to catalyst activity
Table 5 the result shows that, the catalytic activity of catalyst obtained is different under condition of different temperatures, with the liter of reaction temperature
Height, the removal rate of COD, the removal rate of uns-dimethylhydrazine constantly increase；Nitrosodimethylamine content, ammonia-nitrogen content are constantly reduced.Instead
Answering temperature is to be catalyzed the effect of reaction at 60~70 DEG C to meet 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 lower than 1.mg/L, and ammonia-nitrogen content is less than
25mg/L, content of formaldehyde are less than 2mg/L).
Influence of the embodiment 6pH to catalyst activity
In view of the uns-dimethylhydrazine waste water having has carried out the preprocessing process of acid adding before treatment, change for pH to catalysis
Following experiment has been done in the influence of agent catalytic activity.
Referring to embodiment 1, with chitosan and SiO2Mass ratio be 1:2 modification of chitosan as carrier, with metallic copper
For nickel as activated centre, the weight ratio for controlling metal ion total mole number and modified natural polymer carrier is 4:100,
In, Cu2+And Ni2+Molar ratio be 3:1, prepare Cu2+/Ni2+-CTS-SiO2Catalyst；Catalyst made from 100g is taken to use respectively
In the uns-dimethylhydrazine waste water of degradation initial concentration 500mg/L, starting COD is 1000mg/L, and control reaction temperature is 70 DEG C, respectively
Adjusting starting pH is 6,7,8,9, does comparative experiments with the control group for not adjusting pH.After tested it is found that not adjusting the control group of pH
It is about 9.5 that it, which originates pH,.
Experimental result: after degradation reaction 30min, adjusting starting pH is 6,7,8,9, and does not adjust pair of pH (≈ 9.5)
It is respectively as follows: 77.43mg/L, 73.65mg/L, 70.37mg/L, 66.77mg/L, 67.32mg/L according to the COD value of group.
Experiment shows: little in the variation of the degradation reaction catalytic efficiency of pH=6~9.5, this illustrates biodegrading process of the invention
To the starting pH of uns-dimethylhydrazine waste water, there is no limit degradation reaction is not necessarily to presetting pH, saves presetting pH compared to the prior art
This process.
Degradation capability of 7 catalyst of embodiment to the uns-dimethylhydrazine waste water of different initial concentrations
Referring to embodiment 1, with chitosan and SiO2Mass ratio be 1:2 modification of chitosan as carrier, with metallic copper
For nickel as activated centre, the weight ratio for controlling metal ion total mole number and modified natural polymer carrier is 4:100,
In, Cu2+And Ni2+Molar ratio be 3:1, prepare Cu2+/Ni2+-CTS-SiO2Catalyst；Catalyst made from 100g is taken to use respectively
In the uns-dimethylhydrazine waste water for the different initial concentrations of degrading, control reaction temperature is 70 DEG C, flow velocity 120L/ hours, the reaction time
25min.Experimental result is shown in Table 6.
Comparison of 6 same catalyst of table to different starting COD wastewater degradation effects
Table 6 the result shows that, with the increase of uns-dimethylhydrazine initial concentration, the COD, uns-dimethylhydrazine in treated waste water are dense
Degree risen, i.e. COD, uns-dimethylhydrazine removal rate decline with the increase of uns-dimethylhydrazine initial concentration.But for difference
The uns-dimethylhydrazine waste water of initial concentration, after catalyst degradation of the invention, COD removal rate is above 90%, inclined two
Methylhydrazine degradation rate is all larger than 99%, this illustrates the drop of catalyst of the invention uns-dimethylhydrazine waste water higher for initial concentration
Solution, still efficiently.
Influence of the 8 catalyst access times of embodiment to catalytic activity
Referring to embodiment 1, with chitosan and SiO2Mass ratio be 1:2 modification of chitosan as carrier, with metallic copper
For nickel as activated centre, the weight ratio for controlling metal ion total mole number and modified natural polymer carrier is 4:100,
In, Cu2+And Ni2+Molar ratio be 3:1, prepare Cu2+/Ni2+-CTS-SiO2Catalyst.
The catalyst 300g of above-mentioned preparation is added in catalysis advanced oxidation reaction bed, catalyst is repeatedly applied to degrade
The uns-dimethylhydrazine waste water of 500mg/L, starting COD be 1000mg/L, reaction temperature: 65 DEG C, flow velocity 150L/ hours, the reaction time
For 25min.Experimental result is shown in Table 7.
Influence of the 7 catalyst circulation access times of table to uns-dimethylhydrazine degradation effect
Table 7 the result shows that, catalyst produced by the present invention for degrade uns-dimethylhydrazine waste water when, catalyst is used for multiple times
Afterwards, COD in treated waste water, uns-dimethylhydrazine, ammonia nitrogen, methylene dimethylamine concentration still conform to missile propellant water pollution
Object discharge standard (GB14374-93), it can be seen that, catalyst produced by the present invention can be recycled for multiple times, using of the invention
Catalyst degradation uns-dimethylhydrazine waste water, technique and device operating cost are lower.
Claims (9)
1. a kind of more metal corsslinkings for uns-dimethylhydrazine degradation cooperate catalyst, which is characterized in that more metal corsslinkings are matched
Close catalyst is indicated with formula M-N, wherein M is at least two metals in transition metal and/or rare earth metal, and N is modified shell
Glycan carrier, the modification of chitosan carrier are chitosan-SiO2Complex carrier, chitosan and SiO2Weight ratio is 1:0.5~2,
The molal quantity of M and the weight ratio of N are 0.5~5:100.
2. more metal corsslinkings according to claim 1 for uns-dimethylhydrazine degradation cooperate catalyst, which is characterized in that institute
The weight ratio of the molal quantity and N of stating M is 4~5:100.
3. more metal corsslinkings according to claim 1 for uns-dimethylhydrazine degradation cooperate catalyst, which is characterized in that institute
State chitosan and SiO2Weight ratio be 1:1~2.
4. more metal corsslinkings according to claim 1 for uns-dimethylhydrazine degradation cooperate catalyst, which is characterized in that institute
The preparation method for stating modification of chitosan carrier includes the following steps: to dissolve chitosan in acid solution, and addition is forged through high temperature
The SiO of burning2, control chitosan and SiO2Weight ratio be 1:0.5~2, stirring, then be added NaOH, formed gel, be centrifuged, wash
It washs, dry, being ground up, sieved to obtain modification of chitosan carrier.
5. more metal corsslinkings according to claim 1 for uns-dimethylhydrazine degradation cooperate catalyst, which is characterized in that
The M is copper zinc cobalt, cupro-nickel zirconium, iron molybdenum, copper cerium or cobalt neodymium.
6. the preparation method of more metal corsslinkings cooperation catalyst according to claim 1 for uns-dimethylhydrazine degradation,
It is characterized in that, includes the following steps: to make active constituent at least two metals in transition metal and/or rare earth metal, take phase
The dissolving metal salts answered are loaded on modification of chitosan carrier after adjusting temperature, and washing, is ground up, sieved drying, are obtained
More metal corsslinkings cooperate catalyst；Wherein, the weight ratio of the total mole number of the metal salt and modification of chitosan carrier is 0.5
~5:100.
7. the preparation method of more metal corsslinkings cooperation catalyst according to claim 6 for uns-dimethylhydrazine degradation,
It is characterized in that, adjusting the temperature is 40~70 DEG C.
8. a kind of method using more metal corsslinkings cooperation catalyst degradation uns-dimethylhydrazine described in claim 1, feature exist
In, include the following steps: that hydrogen peroxide is added in the waste water containing uns-dimethylhydrazine, more metal corsslinking cooperation catalyst be then added,
Controlling reaction temperature is 40~70 DEG C, and flow velocity is 120~150L/ hours.
9. the method according to claim 8 using more metal corsslinkings cooperation catalyst degradation uns-dimethylhydrazine, feature exist
In control reaction temperature is 60~70 DEG C.
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| CN104014360A (en) * | 2014-06-12 | 2014-09-03 | 东南大学 | Multi-metal oxygen-group catalyst for unsymmetrical dimethylhydrazine degradation and preparation method and application thereof |
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| WO2004056479A1 (en) * | 2002-12-20 | 2004-07-08 | Sasol Technology (Pty) Ltd | Tetramerization of olefins |
| CN104014360A (en) * | 2014-06-12 | 2014-09-03 | 东南大学 | Multi-metal oxygen-group catalyst for unsymmetrical dimethylhydrazine degradation and preparation method and application thereof |
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Application publication date: 20161116 Assignee: JIANGSU TAIYUAN ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. Assignor: SOUTHEAST University Contract record no.: X2023320000120 Denomination of invention: Multimetal cross-linked coordination catalyst for degradation of unsymmetrical dimethylhydrazine and its preparation method and application Granted publication date: 20190312 License type: Common License Record date: 20230323 |