CN107442154A - A kind of cryptomelane based composite metal element catalyst and its production and use - Google Patents
A kind of cryptomelane based composite metal element catalyst and its production and use Download PDFInfo
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- CN107442154A CN107442154A CN201710773753.XA CN201710773753A CN107442154A CN 107442154 A CN107442154 A CN 107442154A CN 201710773753 A CN201710773753 A CN 201710773753A CN 107442154 A CN107442154 A CN 107442154A
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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
- B01J29/00—Catalysts comprising molecular sieves
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- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
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Abstract
The invention provides a kind of cryptomelane based composite metal element catalyst and its production and use.The cryptomelane based composite metal element catalyst includes cryptomelane type manganese oxide molecular sieve and doped metallic elements, doped metallic elements enter cryptomelane type manganese oxide molecular sieve skeleton, and the mol ratio of manganese element and doped metallic elements in cryptomelane type manganese oxide molecular sieve is (100:1)~(10:1), wherein cryptomelane type manganese oxide molecular sieve reacts to obtain by septivalency manganese and bivalent manganese, and the mol ratio of septivalency manganese and bivalent manganese is (2:1)~(0.5:1).The cryptomelane based composite metal element catalyst catalytic activity of the present invention is high, the use of noble metal is not had to or reduces, significantly reduce the cost of catalyst, and catalyst activates without using hydrogen reducing, use condition is simple, can be widely applied to the stationary sources such as smeltery, oil plant, chemical plant and discharges the purified treatment containing benzene in waste gas.
Description
Technical field
The invention belongs to catalyst technical field, is related to a kind of cryptomelane based composite metal element catalyst and its preparation
Method and purposes.
Background technology
With the intensity increase of human industry's activity, substantial amounts of volatile organic matter (Volatile Organic
Compound, abbreviation VOCs) it is discharged into atmospheric environment, reacted by sequence of chemical and trigger environmental pollution.For example, some are active
Strong VOCs can be with another atmosphere pollution nitrogen oxides (NOx) photochemical reaction occurs, cause surface ozone concentration liter
Height, form photochemical pollution；The VOCs that some steam force down can also be formed by complex process nucleation and growth process secondary to be had
Machine aerosol, and secondary organic aerosol is exactly fine particle PM2.5 important component.It can be seen that VOCs is to form photochemistry
Pollution and the important precursor of Brownish haze.In addition, VOCs can also form grave danger to health in itself.Example
Such as, common VOCs such as formaldehyde, benzene, toluene etc. has carcinogenic, teratogenesis harm.Therefore, photochemical fog, reduction to be removed
Grain thing pollution, improves urban air-quality, protects the health of the common people, VOCs emission controls and removal are imperative.
VOCs wide material sources, mainly include oil, chemical industry, medicine, packaging, printing, application etc., using paint industry as
Example, nearly 7,000,000 tons/year of its VOCs discharge capacity, accounts for the 1/3 of VOCs total releases.Purification neck is eliminated in paint industry VOCs
Domain, west Main Developed Countries and Japan's starting are more early.Nineteen fifty-five the U.S. just promulgated《Air Pollution Control Board preparation method》, it is right
Air pollutant emission classification and total amount have done detailed regulation, promulgate again later《Pure air method》, and in 1970 and
Nineteen ninety has done revises twice；Technicality regulation has been formulated in VOCs discharges in 1966 also exclusively for paint industry, i.e. " 66 methods
Rule ".Law obligate the promotion with company interest under, difference eliminate VOCs technologies be developed and use.
China pays much attention to VOCs pollution problem at present, it is desirable to the year two thousand twenty, realize substantially VOCs from raw material to product,
From production to the overall process emission reduction of consumption.Therefore, VOCs emission-reduction technology has obtained extensive research and probe.
Benzene is the larger one kind of volatile organic matter Poisoning,《Code for indoor environmental pollution control of civil building engineering》
Strict limitation is carried out to its concentration in GB50325-2001, it is desirable to which it is less than 0.09mg/m3.Therefore to tail of the emission source containing benzene
Gas is handled very necessary.Catalysis burning benzene is current more efficient control technology, still, conventional powder catalyst at present
The shortcomings of in the presence of a large amount of noble metals such as palladium, platinum is needed to use, make the preparation cost height of catalyst, catalytic activity also has much room for improvement.
The content of the invention
In view of the shortcomings of the prior art, an object of the present invention is to provide a kind of cryptomelane based composite metal element
Catalyst, its catalytic activity is high, does not have to or reduces the use of noble metal, significantly reduce the cost of catalyst.
To use following technical scheme up to this purpose, the present invention：
A kind of cryptomelane based composite metal element catalyst, the active component of the catalyst include cryptomelane type oxygen
Change manganese molecular sieve and doped metallic elements, manganese element and doping metals member in the cryptomelane type manganese oxide molecular sieve
The mol ratio of element is (100:1)~(10:1), wherein the cryptomelane type manganese oxide molecular sieve passes through septivalency manganese and bivalent manganese
Reaction obtains, and the mol ratio of the septivalency manganese and the bivalent manganese is (2:1)~(0.5:1).
Cryptomelane type manganese oxide molecular sieve is a kind of new material similar to zeolite-type molecular sieve structure, is had than table
The advantages of area is big, isoelectric point is low, oxidability is strong, cation exchange capacity (CEC) is high, it has abundant pore structure, makes its display excellent
The characteristics such as different conduction, magnetic, ion exchange, selective absorption, catalysis.The present invention passes through in cryptomelane type manganese oxide point
Son sieves rare-earth metal doped, transition metal or a small amount of precious metal element, is not changing cryptomelane type manganese oxide molecular sieve crystalline substance
On the premise of type, the excellent catalyst of catalytic activity is made, its catalytic activity can compare favourably with noble metal catalyst, and without H2
Reduction activation.
The mol ratio of manganese element and the doped metallic elements in the cryptomelane type manganese oxide molecular sieve is (100:
1)~(10:1), such as the mol ratio of manganese element and the doped metallic elements is 100:1、90:1、80:1、70:1、60:1、
50:1、40:1、30:1、20:1、10:1, preferably 80:1, more preferably 40:1.
Preferably, the mol ratio of the septivalency manganese and the bivalent manganese is (2:1)~(0.5:, such as the septivalency manganese 1)
Mol ratio with the bivalent manganese is 2:1、1.5:1、1:1、0.8:1、0.5:1, it is preferably (1:1)~(0.5:1), more preferably
0.87:1。
The doped metallic elements are iron, copper, molybdenum, tungsten, cobalt, nickel, silver, palladium, platinum, iridium, niobium, one kind in cerium or at least two
The mixture of kind.
The second object of the present invention is to provide a kind of preparation side of above-mentioned cryptomelane based composite metal element catalyst
Method, this method is simple and easy, no H2Reduction activation step, the cost of material that uses is low, it is convenient easily realize, the preparation method bag
Include following steps：
1) liquor potassic permanganate is prepared：Potassium permanganate is dissolved in deionized water, liquor potassic permanganate is obtained after stirring；
2) the manganous salt mixed solution containing doped metallic elements is prepared：Manganous salt is dissolved in deionized water, stirred
Manganous salt solution is obtained after mixing；Salt containing doped metallic elements is dissolved in the manganous salt solution, acid is added after stirring,
Continue to stir, obtain the manganous salt mixed solution containing doped metallic elements；
3) the quantitative implantation step 2 of liquor potassic permanganate is made in step 1)) made from mixed solution, be transferred to after stirring anti-
Answer and hydro-thermal reaction is carried out in kettle；
4) the product filtration washing after step 3) hydro-thermal reaction is obtained into filter cake, roasting, tabletting after the filter cake is dried
After obtain the cryptomelane based composite metal element catalyst.
In step 1), the solid-to-liquid ratio of the potassium permanganate and the deionized water is (1:10)~(1:100) g/mL, such as
Solid-to-liquid ratio is 1:10g/mL、1:20g/mL、1:30g/mL、1:40g/mL、1:50g/mL、1:60g/mL、1:70g/mL、1:80g/
mL、1:90g/mL、1:100g/mL, preferably 1:20g/mL.
In step 2), the solid-to-liquid ratio of the manganous salt and the deionized water is (1:4)~(1:20) g/mL, for example, it is solid
Liquor ratio is 1:4g/mL、1:5g/mL、1:6g/mL、1:7g/mL、1:8g/mL、1:9g/mL、1:10g/mL、1:11g/mL、1:
12g/mL、1:13g/mL、1:14g/mL、1:15g/mL、1:16g/mL、1:17g/mL、1:18g/mL、1:19g/mL、1:20g/
ML, preferably 1:5g/mL.
Preferably, in step 2), the manganous salt be manganese nitrate, manganese sulfate, manganese acetate, carbonic acid Asia manganese, manganese sulfate,
One kind or at least two mixture in manganese chloride, phosphate dihydrogen manganese.
Preferably, in step 2), the mol ratio of the doped metallic elements and the divalence manganese element is (1:10)~(1:
100), such as the mol ratio of the doped metallic elements and the divalence manganese element is 1:10、1:20、1:30、1:40、1:50、
1:60、1:70、1:80、1:90、1:100, it is preferably (1:20)~(1:30).
Preferably, in step 2), the salt containing doped metallic elements be ferric nitrate, copper nitrate, nitric acid molybdenum, nitric acid tungsten,
One kind in cobalt nitrate, nickel nitrate, silver nitrate, palladium nitrate, platinum nitrate, ammonium chloroiridate, niobium chloride, cerous nitrate or at least two
Mixture；
Preferably, the particle diameter of catalyst is made to diminish in step 2), after pickling, beneficial to the activity for improving catalyst, wherein, institute
The mass ratio for stating manganese in the sour and manganous salt solution is (4:1)~(0.5:1) it is, such as described sour molten with the manganous salt
The mass ratio of manganese is 4 in liquid:1、3.5:1、3:1、2.5:1、2:1、1.5:1、1:10.5:1.
Preferably, in step 2), the acid is oxalic acid, one kind in glacial acetic acid, carbonic acid.
In step 3), the liquor potassic permanganate is quantitatively injected in the mixed solution by syringe pump, due to height
The solubility of potassium manganate solution is not high, and hydro-thermal reaction itself is with regard to slow, so the injection rate of liquor potassic permanganate will be controlled
System is appropriate, it is preferable that the flow velocity of the syringe pump is 1~100mL/min, such as 1mL/min, 10mL/min, 20mL/min,
30mL/min、40mL/min、50mL/min、60mL/min、70mL/min、80mL/min、90mL/min、100mL/min。
Preferably, in step 3), the temperature conditionss of the hydro-thermal reaction are：Room temperature rises to 80~200 DEG C, and constant temperature 12~
72h, Temperature fall.
Preferably, in step 3), the mol ratio of the potassium permanganate and the mixed solution is 0.87:1.
In step 4), it is described washing be deionized water wash to filtrate be neutrality.
Preferably, in step 4), the temperature of the drying is 100 DEG C, and the time of the drying is 12h.
In step 4), the roasting is carried out in Muffle furnace, and the condition of the roasting is：It is to slowly warm up to roasting temperature
Constant temperature after degree, the speed of the heating is 2~10 DEG C/min, and the sintering temperature is 450~600 DEG C, the time of the constant temperature
For 2~5h.
The third object of the present invention is to provide a kind of cryptomelane based composite metal element catalyst as described above
Purposes, the catalysis that the catalyst is used for volatile organic matter benzene are burnt, and can all be divided through the hypertoxic pollutant benzene of catalysis burning
Solve as nontoxic carbon dioxide and water, can be widely applied to the stationary sources such as smeltery, oil plant, chemical plant and discharge waste gas
In the purified treatment containing benzene.
Compared with prior art, beneficial effects of the present invention are：
(1) cryptomelane based composite metal element catalyst of the invention, does not have to or reduces the use of noble metal, significantly drop
The low cost of catalyst, catalytic activity is high, and during catalysis burning for benzene, when air speed is 90L/ (gh), reaction temperature exists
With regard to that can reach more than 90%, its catalytic activity can compare favourably the conversion ratio of benzene with noble metal catalyst at 250 DEG C.
(2) preparation method of cryptomelane based composite metal element catalyst of the invention is simple and easy, no H2Reduction is lived
Change step, the cost of material used is low, conveniently easily realizes.The cryptomelane based composite metal element catalyst of the present invention is through a step
Hydrothermal Synthesiss obtain, and without adding other active components in load, and catalyst keeps cryptomelane based molecular sieve basic structure
Constant, doped metallic elements can enter among framework of molecular sieve.
(3) cryptomelane based composite metal element catalyst of the invention is used for the catalysis burning of volatile organic matter benzene,
Can all be decomposed into nontoxic carbon dioxide and water through burn hypertoxic pollutant benzene of catalysis, can be widely applied to smeltery,
The stationary sources such as oil plant, chemical plant discharge the purified treatment containing benzene in waste gas.
Brief description of the drawings
Fig. 1 is that catalyst made from embodiments of the invention 1-7 burns for the catalysis of benzene, the contrast of the conversion ratio of benzene
Figure；
Fig. 2 is catalyst and Pd/Al made from embodiments of the invention 1,4,5,62O3Catalysis for benzene is burnt, benzene
The comparison diagram of conversion ratio；
Fig. 3 is catalyst and Pd/Al made from embodiments of the invention 52O3Catalysis for benzene is burnt, carbon dioxide production
The comparison diagram of rate；
Fig. 4 is that the XRD spectrum contrast of catalyst made from embodiments of the invention 1-7 and cryptomelane reference material is illustrated
Figure；
Fig. 5 is that the catalyst that embodiments of the invention 5,8,9,10 are made burns for the catalysis of benzene, pair of the conversion ratio of benzene
Than figure；
Fig. 6 is embodiments of the invention 5, catalyst made from 11-14 burns for the catalysis of benzene, pair of the conversion ratio of benzene
Than figure；
Fig. 7 is that catalyst made from embodiments of the invention 5,15,16 burns for the catalysis of benzene, pair of the conversion ratio of benzene
Than figure.
Embodiment
1-3 and technical scheme is further illustrated by embodiment below in conjunction with the accompanying drawings.
Embodiment 1
Configure solution 1：Potassium permanganate 10.27g is weighed, for solution in 400mL water, strong stirring is standby.
Configure solution 2：Manganese acetate 18.38g is weighed, is dissolved in 200mL water.The sealing of 12.5mL glacial acetic acid is added, magnetic force stirs
Mix.
Solution 1 is added dropwise in solution 2 with syringe pump, injection rate is：2.4 milliliters per minute.Solution 2 seals, together
When magnetic agitation.After injection, solution 1 and the mixed liquor of solution 2 are transferred in 1L hydrothermal reaction kettle.Reactor inserts baking
Case carries out hydro-thermal reaction.Hydrothermal condition is：150 DEG C of constant temperature 24h, Temperature fall.It is after being down to room temperature, crystallized product is washed
Filter, to filtered fluid in neutrality.Filter cake is dried, and is put into calcination process in Muffle furnace afterwards.Roasting condition is：5 DEG C of heating rate is every
Point, 500 DEG C are warming up to, constant temperature 3h.The catalyst of acquisition by tabletting be sieved into 40~60 mesh evaluation it is standby.
Evaluating catalyst condition：The composition of reaction mixture gas is：Benzene [C6H6]=1500ppm, [O2]=20%, N2Put down
Weigh gas, and total gas flow rate 300mL/min, air speed is 90L/ (gh), 150~400 DEG C of reaction temperature.Benzene, carbon dioxide, oxygen
The gas concentrations such as gas are determined using gas chromatograph (Agilent -7980B, FID and TCD).
Embodiment 2
In solution 2, third element is adulterated.Operating method is：After 12.7g manganese acetates are added, the water of 0.9326g bis- is added
Palladium nitrate, mix solution.Other specification such as embodiment 1 is constant.
Embodiment 3
In solution 2, third element is adulterated.The water cerous nitrates of 1.52g six are mixed, mix strong stirring.Other specification is strictly according to the facts
It is constant to apply example 1.
Embodiment 4
In solution 2, third element is adulterated.1.54g chloric acid iridium ammoniums are mixed, mix strong stirring.Other specification is as implemented
Example 1 is constant.
Embodiment 5
In solution 2, third element is adulterated.0.59g silver nitrates are mixed, mix strong stirring.Other specification such as embodiment 1
It is constant.
Embodiment 6
In solution 2, third element is adulterated.0.84g nitrate trihydrate copper is mixed, mixes strong stirring.Other specification is strictly according to the facts
It is constant to apply example 1.
Embodiment 7
In solution 2, third element is adulterated.The water ferric nitrates of 1.41g nine are mixed, mix strong stirring.Other specification is strictly according to the facts
It is constant to apply example 1.
Embodiment 8
In solution 2, third element is adulterated.0.59g silver nitrates are mixed, mix strong stirring.Not acid adding, other specification is such as
Embodiment 1 is constant.
Embodiment 9
Configure solution 1：Potassium permanganate 10.27g is weighed, for solution in 400mL water, strong stirring is standby.
Configure solution 2：Manganese acetate 7.96g is weighed, 0.59g silver nitrates is mixed, is dissolved in 200mL water.Add 20mL ice vinegar
Acid sealing, magnetic agitation；(Mn7+:Mn2+=2:1).
Embodiment 10
Configure solution 1：Potassium permanganate 10.27g is weighed, for solution in 400mL water, strong stirring is standby.
Configure solution 2：Manganese acetate 31.86g is weighed, 0.59g silver nitrates is mixed, is dissolved in 200mL water.Add 20mL ice vinegar
Acid sealing, magnetic agitation, (Mn7+:Mn2+=0.5:1).
Embodiment 11
In solution 2, third element is adulterated.2.38g silver nitrates are mixed, mix strong stirring.Other specification such as embodiment 1
It is constant.
Embodiment 12
In solution 2, third element is adulterated.1.19g silver nitrates are mixed, mix strong stirring.Other specification such as embodiment 1
It is constant.
Embodiment 13
In solution 2, third element is adulterated.0.39g silver nitrates are mixed, mix strong stirring.Other specification such as embodiment 1
It is constant.
Embodiment 14
In solution 2, third element is adulterated.0.29g silver nitrates are mixed, mix strong stirring.Other specification such as embodiment 1
It is constant.
Embodiment 15
The catalyst 5g in embodiment 1 is weighed, by 0.229g silver nitrates (Mn:Ag=40:1) it is dissolved in 100mL water, mixes
Catalyst is closed among solution, stirring.60 degree of rotary evaporation slurries.Obtain the 120 degree of drying of product baking oven overnight, catalyst warp
5 DEG C every point of heating rate is crossed, is warming up to 500 DEG C, constant temperature 3h.The catalyst of acquisition by tabletting be sieved into 40~60 mesh evaluation it is standby
With obtained infusion process MnAg catalyst.Evaluating catalyst condition：The composition of reaction mixture gas is：Benzene [C6H6]=1500ppm,
[O2]=20%, N2Make Balance Air, total gas flow rate 300mL/min, air speed is 90L/ (gh), reaction temperature 150~400
℃.The gas concentrations such as benzene, carbon dioxide, oxygen are determined using gas chromatograph (Agilent -7980B, FID and TCD).
Embodiment 16
24.01g manganese acetates and 0.407g silver nitrates are mixed and are dissolved in (Mn in 372mL deionized waters:Ag=40:1), add
64.3g urea, strong stirring.Warming-in-water is to 90 DEG C afterwards, and 12h, obtains being co-precipitated slurries overnight.By washing, filtering, doing
Co-precipitation MnAg catalyst is made in dry roasting.Evaluating catalyst condition：The composition of reaction mixture gas is：Benzene [C6H6]=
1500ppm, [O2]=20%, N2Make Balance Air, total gas flow rate 300mL/min, air speed is 90L/ (gh), reaction temperature
150~400 DEG C.The gas concentrations such as benzene, carbon dioxide, oxygen are surveyed using gas chromatograph (Agilent -7980B, FID and TCD)
It is fixed.
The catalysis that catalyst made from embodiment 1-7 is used for benzene is burnt, and contrast Activity Results are as shown in Figure 1.With routine
Noble metal catalyst Pd mass content be 1wt% Pd/Al2O3To contrast, by catalyst made from embodiment 1,4,5,6
With Pd/Al2O3Catalysis for benzene is burnt, and contrast Activity Results are as shown in Figure 2.The dioxy of example 5 and conventional noble metal catalyst
Change the contrast of carbon yield, as a result as shown in Figure 3.The crystalline structure of catalyst made from embodiment 1-7 is detected, experimental result
As shown in Figure 4.
To sum up test, as seen from Figure 4, the cryptomelane based composite metal element prepared by the preparation method of the present invention
Catalyst shows the basic crystalline structure of cryptomelane, i.e., obtained catalyst does not change hidden potassium manganese after doped metallic elements
The basic crystal formation of ore deposit, doped metallic elements are entered among the lattice framework of the cryptomelane molecular sieve.
As seen from Figure 1, relative to embodiment 1, after embodiment 2,3,4,5,6,7 adds doped metallic elements, it is made
Catalyst have large increase to the conversion ratio of benzene.With reference to Fig. 2, understood according to embodiment 3-7 activity contrast, wherein adulterating
A small amount of third element silver or the active highest of iridium, are preferable catalyst.The catalyst wherein prepared with the doping component of silver,
With Typical precious metal catalyst (1wt%Pd/Al2O3) activity contrast in understand, adulterate the cryptomelane catalyst of a small amount of silver
Activity can match in excellence or beauty with noble metal catalyst.As shown in figure 3, relative to business noble metal catalyst (1wt%Pd/Al2O3), it is hidden
Its poisonous benzene vapour of conversion of the catalyst (embodiment 5) of potassium manganese ore base composite silver is stronger for the ability of nontoxic carbon dioxide,
Performance is more superior.Do not add precious metal element it can be seen from embodiment 6, embodiment 7, but conventional copper and iron metallic element,
The activity of obtained catalyst remains unchanged higher.As shown in figure 5, in not acid adding and keeping silver-colored compound quantity constant, the two of manganese is adjusted
The ratio of kind presoma, obtained catalyst activity is poor, and therefore, the addition of acetic acid is necessary, optimal Mn7+:Mn2+
Mol ratio be 0.87.
Optimize the load capacity of silver, the catalysis that catalyst made from embodiment 5,11-14 is used for benzene is burnt, to specific activity knot
Fruit is as shown in Figure 6.Wherein Mn in embodiment 11:Ag=10:1 best performance, but the dosage of argent is excessive, it is corresponding
It is embodiment 5Mn:Ag=40:1, argent dosage is less, and catalytic performance is more excellent, is optimal proportioning.The amount of silver is reduced again
For Mn:Ag=60:1 and 80:1, catalyst activity reduction is more, without application value.
It (is Mn to contrast MnAg catalyst activities prepared by one step hydro thermal method, infusion process, coprecipitation:Ag=40:1),
It is that the catalysis that catalyst made from embodiment 5,15,16 is used for benzene is burnt, contrast Activity Results are as shown in Figure 7.As schemed
Show, one step hydro thermal method prepare catalyst, have cryptomelane base crystalline characteristics, silver-colored species be scattered in framework of molecular sieve it
In, embody optimal catalytic activity.Although the sample of infusion process also keeps cryptomelane crystal formation, silver-colored species are immersed in molecule
Outside sieve skeleton frame, its activity is poor.Illustrate the silver-colored species good catalysis efficiency of competence exertion only in framework of molecular sieve of activity.Altogether
The sample of the precipitation method is due to that cannot form favourable cryptomelane structure, and activity silver is also embedded in co-precipitation Mn oxide
In, so activity is worst.
The cryptomelane base composite transition metal catalyst activity of the present invention is high, does not have to or reduces making for noble metal
With, the cost of catalyst is significantly reduced, and catalyst activates without using hydrogen reducing, and use condition is simple, is used
Burnt in the catalysis of volatile organic matter benzene, nontoxic titanium dioxide can be all decomposed into through the hypertoxic pollutant benzene of catalysis burning
Carbon and water, it can be widely applied to the stationary sources such as smeltery, oil plant, chemical plant and discharge the purified treatment containing benzene in waste gas.
Above example is only used for the method detailed for illustrating the present invention, the invention is not limited in above-mentioned method detailed, i.e.,
Do not mean that the present invention has to rely on above-mentioned method detailed and could implemented.Person of ordinary skill in the field is it will be clearly understood that right
Any improvement of the present invention, addition, the selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention
Deng within the scope of all falling within protection scope of the present invention and disclosing.
Claims (10)
1. a kind of cryptomelane based composite metal element catalyst, it is characterised in that the active component of the catalyst includes hidden
Potassium manganese ore type manganese oxide molecular sieve and doped metallic elements, the doped metallic elements divide into the cryptomelane type manganese oxide
Sub- sieve skeleton frame, the mol ratio of manganese element and the doped metallic elements in the cryptomelane type manganese oxide molecular sieve are
(100:1)~(10:1) it is described, wherein the cryptomelane type manganese oxide molecular sieve reacts to obtain by septivalency manganese and bivalent manganese
The mol ratio of septivalency manganese and the bivalent manganese is (2:1)~(0.5:1).
2. cryptomelane based composite metal element catalyst according to claim 1, it is characterised in that the cryptomelane
The mol ratio of manganese element and the doped metallic elements in type manganese oxide molecular sieve is (80:1)~(10:1)；
Preferably, the mol ratio of the septivalency manganese and the bivalent manganese is (2:1)~(0.5:1).
3. cryptomelane based composite metal element catalyst according to claim 1 or 2, it is characterised in that the doping
Metallic element is iron, copper, molybdenum, tungsten, cobalt, nickel, silver, palladium, platinum, iridium, niobium, one kind in cerium or at least two mixture.
4. the preparation method of the cryptomelane based composite metal element catalyst according to one of claim 1-3, its feature
It is, comprises the following steps：
1) liquor potassic permanganate is prepared：Potassium permanganate is dissolved in deionized water, liquor potassic permanganate is obtained after stirring；
2) the manganous salt mixed solution containing doped metallic elements is prepared：Manganous salt is dissolved in deionized water, after stirring
Obtain manganous salt solution；Salt containing doped metallic elements is dissolved in the manganous salt solution, acid is added after stirring, is continued
Stirring, obtains the manganous salt mixed solution containing doped metallic elements；
3) the quantitative implantation step 2 of liquor potassic permanganate is made in step 1)) made from mixed solution, reactor is transferred to after stirring
Middle carry out hydro-thermal reaction；
4) the product filtration washing after step 3) hydro-thermal reaction is obtained into filter cake, after the filter cake is dried after roasting, tabletting
To the cryptomelane based composite metal element catalyst.
5. preparation method according to claim 4, it is characterised in that in step 1), the potassium permanganate with it is described go from
The solid-to-liquid ratio of sub- water is (1:10)~(1:100)g/mL.
6. the preparation method according to claim 4 or 5, it is characterised in that in step 2), the manganous salt is gone with described
The solid-to-liquid ratio of ionized water is (1:4)~(1:20)g/mL；
Preferably, the manganous salt is manganese nitrate, manganese sulfate, manganese acetate, carbonic acid Asia manganese, manganese sulfate, manganese chloride, di(2-ethylhexyl)phosphate
One kind or at least two mixture in hydrogen manganese；
Preferably, in step 2), the mol ratio of the doped metallic elements and the divalence manganese element is (1:10)~(1:
100) it is preferably, (1:20)~(1:30)；
Preferably, the salt containing doped metallic elements be ferric nitrate, copper nitrate, nitric acid molybdenum, nitric acid tungsten, cobalt nitrate, nickel nitrate,
One kind or at least two mixture in silver nitrate, palladium nitrate, platinum nitrate, ammonium chloroiridate, niobium chloride, cerous nitrate；
Preferably, in step 2), the mass ratio of manganese is (4 in the described sour and manganous salt solution:1)~(0.5:1)；
Preferably, the acid is one kind in oxalic acid, glacial acetic acid, carbonic acid.
7. according to the preparation method described in one of claim 4-6, it is characterised in that in step 3), the liquor potassic permanganate
It is quantitatively to be injected in the mixed solution by syringe pump, the flow velocity of the syringe pump is 1~100mL/min；
Preferably, in step 3), the temperature conditionss of the hydro-thermal reaction are：Room temperature rises to 80~200 DEG C, 12~72h of constant temperature, from
So cooling；
Preferably, the mol ratio of the potassium permanganate and the mixed solution is 0.87:1.
8. according to the preparation method described in one of claim 4-7, it is characterised in that in step 4), the washing is deionization
Water washing to filtrate is neutrality；
Preferably, in step 4), the temperature of the drying is 100 DEG C, and the time of the drying is 12h.
9. according to the preparation method described in one of claim 4-8, it is characterised in that in step 4), the roasting is in Muffle
Carried out in stove, the condition of the roasting is：Be to slowly warm up to constant temperature after sintering temperature, the speed of the heating for 2~10 DEG C/
Min, the sintering temperature are 450~600 DEG C, and the time of the constant temperature is 2~5h.
10. a kind of purposes of cryptomelane based composite metal element catalyst as described in one of claim 1-3, its feature exist
In the catalysis that the catalyst is used for volatile organic matter benzene is burnt.
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| CN108686650A (en) * | 2018-05-16 | 2018-10-23 | 中国科学院城市环境研究所 | A kind of cryptomelane type manganese dioxide, preparation method and use |
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