CN108067230A - A kind of preparation method of non-precious metal catalyst - Google Patents
A kind of preparation method of non-precious metal catalyst Download PDFInfo
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Abstract
The present invention discloses a kind of preparation method of non-precious metal catalyst, including following content：At least one of Mn, Fe, Co, Ni, Cu, Zn, Ce metal salt are denoted as at least one of A and Mg, Ca, Ti, Zr, Al metal salt and are denoted as B, complexant, solvent mixing acquisition solution C；Solution C is subjected to crystallization；Material is washed after crystallization, be molded, be dry, catalyst is made after roasting；This method, complexant and ternary solvent are introduced in preparation process, by coordination, buffer action, not only avoids the loss of active component, but also active component being uniformly distributed from inside to outside on a catalyst has been greatly facilitated, effectively improve the reactivity worth of catalyst.
Description
Technical field
The present invention relates to a kind of method for preparing catalyst, relate in particular to a kind of preparation side of non-precious metal catalyst
Method.
Background technology
China is coal production big country, every year because coal production will a large amount of various concentrations of output coal bed gas, exploitation
The direct discharge of effective gas utilization technology, reduction methane is that China builds energy saving and environment friendly mode of sustainable development, beats
Make a component of low-carbon economy system.Raising with reference to energy-saving and emission-reduction and to environmental requirement, conscientiously rational exploitation
This low-grade energy of coal bed gas, and available resource is translated into well, expand use scope and the rule of coal bed gas
Mould improves the utilization ratio of coal bed gas, has energy saving and environmentally friendly double meaning, meets planning of the country to energy policy, symbol
Control of the International Environmental Protection tissue to greenhouse effects is closed, more meets the support energetically that China uses low-grade energy exploitation, promotes
Fast development of the country to coal gas industry.
The key that cbm development utilizes is to remove oxygen therein, and existing coal bed gas deoxidation technology mainly has transformation
Adsorption method of separation, coke combustion method, catalytic deoxidation method etc..Chinese patent ZL85103557 discloses a kind of using pressure-variable adsorption
The method of method separation and concentration methane from coal bed gas.Under normal circumstances, methane discharges the oxygen of exhaust gas in purification process is concentrated and contains
Amount is also concentrated raising, due to inevitably containing 5 ~ 15% methane in exhaust gas, the exhaust gas of discharge is caused to be in the quick-fried of methane
Fried limit range, there are explosion dangers, this causes the application of the technology to be restricted.
Coke combustion method deoxidation（ZL02113627.0、200610021720.1）It is under the high temperature conditions, rich in methane gas
Oxygen and coke gasification reaction in body, while portion of methane reacts to reach deoxidation purpose with oxygen.The advantage is that about 70% oxygen with
Coke gasification reaction, 30% oxygen and methane reaction, therefore methane losses are smaller.But shortcoming is to consume valuable coke resource, burnt
Charcoal consuming cost accounts for 50% or so of whole service expense.In addition, coke deoxidization method labor intensity when adding coke, slagging tap is big, ring
Border dust is big, it is difficult to realize automatic operation and large-scale production, and with variform sulfide in coke, after causing deoxygenation
Sulfur content increases in gas.
The essence of catalytic deoxidation process is the catalysis burning of methane under fuel-rich oxygen-lean atmosphere, under appropriate catalyst action,
By CH4Oxidation is converted into CO2And H2O, oxygen content in coal bed gas can be dropped to less than 0.5% by this process, and completely eliminate operation
The security risk of process.Technological operation simultaneously is easy, and convenient for automatically controlling and expanding on a large scale, equipment is simple, from economy angle
For degree, which also has preferable commercial value.Catalytic deoxidation can be divided into precious metal catalyst according to catalyst activity component
Two major class of agent and non-precious metal catalyst.
The technology of research loaded noble metal catalyst is more mature both at home and abroad.The catalyst as where Chinese Academy of Sciences's Dalian materialization
Addition has the function of the cerium component for storing oxygen in system, prepares novel supported palladium noble metal catalyst, can be by first
Alkane concentration is 39.15%, and after the coal bed gas deoxidation processing that oxygen concentration is 12.6%, oxygen concentration is within 0.1% in aerogenesis, oxygen
Gas high conversion rate is in 96%.Since noble metal catalyst is expensive and resource is limited, application range is restricted.Rather than your gold
It is cheap and easy to get thus of great interest to belong to oxide catalyst raw material.But base metal receptor 1 activity is limited, it is necessary to higher
Temperature reacted, energy consumption is larger.
The content of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of preparation method of non-precious metal catalyst, preparing
Complexant and ternary solvent are introduced in journey, by coordination, buffer action, not only avoids the loss of active component, but also pole
It is big to promote active component being uniformly distributed from inside to outside on a catalyst, effectively improve the reactivity worth of catalyst.
A kind of preparation method of non-precious metal catalyst, including following content：
At least one of Mn, Fe, Co, Ni, Cu, Zn, Ce metal salt are denoted as at least one of A and Mg, Ca, Ti, Zr, Al
Metal salt is denoted as B, complexant, solvent mixing acquisition solution C；
Solution C is subjected to crystallization；
Material is washed after crystallization, be molded, be dry, catalyst is made after roasting；
The solvent is water, the ternary solvent of ethyl alcohol, n,N-Dimethylformamide composition, in terms of the weight of solvent：Water for 0.1~
10wt%, ethyl alcohol are 1~50wt% of second, and surplus is n,N-Dimethylformamide；It is preferred that water is 1~5wt%, 10~30wt% of ethyl alcohol,
Surplus is n,N-Dimethylformamide, mass fractions of the metal salt A in solution C be 1~10wt%, preferably 1~5wt%,
Mass fractions of the metal salt B in solution C be 20~70wt%, preferably 25~40wt%, mass fraction of the complexant in solution C
For 1~20wt%, preferably 3~10wt%.
In the above method, preferably by least one of at least one of Mn, Fe, Cu, Ce metal salt and Zr, Al metal
Salt, complexant, solvent mixing obtain solution C.
One or more of in the above method, the metal salt is nitrate, sulfate, acetate or chloride, it is excellent
Elect nitrate as.
In the above method, the complexant for oxalic acid, succinic acid, tartaric acid, phthalic acid, M-phthalic acid, to benzene
One or more of dioctyl phthalate, 2,5- dihydroxy-terephthalic acid (TPA), 1,3,5- benzene tricarbonic acids, pentamethylene tetrabasic carboxylic acid are preferably
2,5- dihydroxy-terephthalic acid (TPA), 1,3,5- benzenetricarboxylic acids.
In the above method, preferred mixed process is as follows：By at least one of Mn, Fe, Co, Ni, Cu, Zn, Ce metal
At least one of salt and Mg, Ca, Ti, Zr, Al metal salt are added in solvent, are adjusted after solution ph is 5~7 and are added in coordination
Agent.
In the above method, the crystallization temperature is 60 ~ 200 DEG C, is preferably 80 ~ 150 DEG C, and the crystallization time is 1 ~ 48
Hour, when being preferably 8 ~ 24 small.
In the above method, crystallization resulting material is washed 5 ~ 10 times, after filtering repeatedly with volatile organic solvent, by gained
Filter cake is placed in oven and dried after carrying out forming processes；Then dried formed body is put into Muffle furnace to roast at high temperature,
Finally obtain catalyst.The volatile organic solvent is methanol, ethyl alcohol, acetone, dichloromethane, one kind in chloroform or several
Kind, it is preferably ethyl alcohol, acetone.
In the above method, the drying temperature is 60 ~ 200 DEG C, is preferably 80 ~ 120 DEG C；The drying time is small for 2 ~ 24
When, when being preferably 8 ~ 24 small.
In the above method, the calcination temperature is 300 ~ 800 DEG C, is preferably 300 ~ 500 DEG C；The roasting time is 4 ~ 24
Hour, when being preferably 6 ~ 12 small.
A kind of non-precious metal catalyst preparation method provided by the invention, it is advantageous that：
（1）The method of the present invention utilizes the synergistic effect of Composite Coordination Agents and ternary solvent, and metal ion is anchored on complexant,
It is made to form macromolecule complex by coordination with metal ion；By the buffer action of complex, metal is prevented to carry
Assemble on body, effectively avoid occurring free species on catalyst, the losing issue for solving active component, it is therefore prevented that the wave of raw material
Take, improve the utilization rate of resource to greatest extent；By Composite Coordination Agents play coordination, isolation, pore-creating the effects that, greatly promote
Into being uniformly distributed for active component.TPR table is levied the results show that surface species and body phase species content are substantially close to showing this
Activity over catalysts species prepared by invention are distributed extremely uniformly from inside to outside；
（2）The catalyst prepared using the method for the present invention, cannot be only used in coal bed gas deoxidation, to methyl hydride combustion, natural gas vapour
Tail gas purification, VOCs, CO and H2Wait fuel gas that also there is higher catalytic combustion activity.
Description of the drawings
Fig. 1 is catalyst TPR spectrograms prepared by the embodiment of the present invention 5.
Fig. 2 is reference agent TPR spectrograms prepared by comparative example 1 of the present invention.
Fig. 3 is catalyst SEM spectrograms prepared by the embodiment of the present invention 5.
Fig. 4 is reference agent SEM spectrograms prepared by comparative example 1 of the present invention.
Specific embodiment
The technology contents and effect further illustrated the present invention with reference to embodiment, but do not limit the present invention.The present invention
Active specy on middle catalyst uses temperature programmed reduction（TPR）It is characterized, peak-fit processing is carried out to TPR spectrograms, is obtained
Represent the consumption hydrogen peak of different activities species.Active specy can be respectively attributed to by the position according to hydrogen peak is consumed in TPR spectrograms：It is free
Species（Near 170 DEG C）, surface species（198~202℃）, body phase species（208~212℃）.Wherein, the content of each active specy
Computational methods are：The consumption hydrogen peak area of active specy content %=100* species/total consumption hydrogen peak area.
Embodiment 1
By bis- hydroxyterephthalic acid's first acid ︰ ternary solvents of nitre acid copper ︰ nitre acid magnesium ︰ grass acid ︰ 2,5-（9.5wt% water -45.6wt% ethyl alcohol -
44.9wt%N, dinethylformamide）Molar ratio for 0.008 ︰, 0.317 ︰, 0.034 ︰, 0.106 ︰ 1, weigh first copper nitrate and
Magnesium nitrate is added in ternary solvent, and after stirring is allowed to be completely dissolved at 45 DEG C, it is 6 to adjust solution ph；Then, by oxalic acid and
2,5-Dihydroxyterephthalic acid is added in as Composite Coordination Agents in solution, and rapid stirring is allowed to after mixing, by the solution
It is transferred in the stainless steel cauldron of inner liner polytetrafluoroethylene, the crystallization 8h at 90 DEG C.Crystallization product is washed 5 times with ethyl alcohol, is filtered
Resulting material is first molded afterwards, the dry 12h at 110 DEG C.Finally, resulting material is roasted into 10h at 300 DEG C, catalysis is made
Agent 1#.
Catalyst performance is evaluated by probe reaction of coal bed gas deoxidation, unstripped gas composition is：CH420 vol%, O2 3
Vol%, surplus N2.Reaction temperature is 460 DEG C, and volume space velocity is 10000 h-1, after stable reaction, on-line chromatograph detection is anti-
Answer O in the tail gas of device outlet2Concentration is 0.69%.
Embodiment 2
By bis- hydroxyterephthalic acid's first acid ︰ ternary solvents of nitre acid manganese ︰ nitre acid calcium ︰ amber amber acid ︰ 2,5-（7.8wt% water -10.5wt% second
Alcohol -81.7wt%N, dinethylformamide）Molar ratio for 0.029 ︰, 0.229 ︰, 0.032 ︰, 0.076 ︰ 1, weigh manganese nitrate first
It is added in calcium nitrate in ternary solvent, after stirring is allowed to be completely dissolved at 45 DEG C, it is 6 to adjust solution ph；Then, by amber
Acid and 2,5-Dihydroxyterephthalic acid are added in as Composite Coordination Agents in solution, and rapid stirring is allowed to after mixing, by this
Solution is transferred in the stainless steel cauldron of inner liner polytetrafluoroethylene, the crystallization 12h at 100 DEG C.Crystallization product washs 5 with acetone
Secondary, resulting material is first molded after suction filtration, the dry 12h at 110 DEG C.Finally, resulting material is roasted into 8h at 300 DEG C, made
Obtain catalyst 2#.
Catalyst performance evaluation is with embodiment 1, the difference is that reaction temperature is 450 DEG C, the tail gas of reactor outlet
Middle O2Concentration is 0.73%.
Embodiment 3
By bis- hydroxyterephthalic acid's first acid ︰ ternary solvents of nitre acid iron ︰ nitre acid aluminium ︰ wine stone acid ︰ 2,5-（6.2wt% water -35.5wt% second
Alcohol -58.3wt%N, dinethylformamide）Molar ratio for 0.028 ︰, 0.195 ︰, 0.032 ︰, 0.065 ︰ 1, weigh ferric nitrate first
It is added in aluminum nitrate in ternary solvent, after stirring is allowed to be completely dissolved at 45 DEG C, it is 6 to adjust solution ph；Then, by winestone
Acid and 2,5-Dihydroxyterephthalic acid are added in as Composite Coordination Agents in solution, and rapid stirring is allowed to after mixing, by this
Solution is transferred in the stainless steel cauldron of inner liner polytetrafluoroethylene, the crystallization 16h at 110 DEG C.Crystallization product washs 5 with ethyl alcohol
Secondary, resulting material is first molded after suction filtration, the dry 12h at 110 DEG C.Finally, resulting material is roasted into 16h at 300 DEG C, made
Obtain catalyst 3#.
Catalyst performance evaluation is with embodiment 1, the difference is that reaction temperature is 440 DEG C, the tail gas of reactor outlet
Middle O2Concentration is 0.81%.
Embodiment 4
By nitre acid cerium ︰ nitre acid zirconium ︰ to two first acid ︰ 2,5- of benzene, bis- hydroxyterephthalic acid's first acid ︰ ternary solvents（1.2wt% water -40.2wt%
Ethyl alcohol -58.6wt%N, dinethylformamide）Molar ratio for 0.039 ︰, 0.189 ︰, 0.032 ︰, 0.063 ︰ 1, weigh nitric acid first
Cerium and zirconium nitrate are added in ternary solvent, and after stirring is allowed to be completely dissolved at 45 DEG C, it is 6 to adjust solution ph；It then, will be right
Phthalic acid and 2,5-Dihydroxyterephthalic acid are added in as Composite Coordination Agents in solution, and rapid stirring is allowed to uniformly mixed
Afterwards, which is transferred in the stainless steel cauldron of inner liner polytetrafluoroethylene, the crystallization 20h at 120 DEG C.Crystallization product ethyl alcohol
Washing 5 times, resulting material is first molded after suction filtration, the dry 12h at 110 DEG C.Finally, resulting material is roasted at 300 DEG C
Catalyst 4# is made in 12h.
Catalyst performance evaluation is with embodiment 1, the difference is that reaction temperature is 430 DEG C, the tail gas of reactor outlet
Middle O2Concentration is 0.58%.
Embodiment 5
By three carboxylic acid ︰ 2,5- of nitre acid copper ︰ nitre acid aluminium ︰ 1,3,5- benzene, bis- hydroxyterephthalic acid's first acid ︰ ternary solvents（5.4wt% water-
26.7wt% ethyl alcohol -67.9wt%N, dinethylformamide）Molar ratio for 0.016 ︰, 0.121 ︰, 0.015 ︰, 0.033 ︰ 1, first
It weighs copper nitrate and aluminum nitrate is added in ternary solvent, after stirring is allowed to be completely dissolved at 45 DEG C, it is 6 to adjust solution ph；
Then, 1,3,5- benzene tricarbonic acid and 2,5-Dihydroxyterephthalic acid are added in as Composite Coordination Agents in solution, it is rapid to stir
It is allowed to that after mixing, which is transferred in the stainless steel cauldron of inner liner polytetrafluoroethylene, the crystallization 12h at 120 DEG C.It is brilliant
Change product to be washed 5 times with ethyl alcohol, resulting material is first molded after suction filtration, the dry 12h at 110 DEG C.Finally, by resulting material in
10h is roasted at 300 DEG C, catalyst 5# is made.TPR table is levied the results show that surface copper content on the catalyst is 53%, body phase
Copper content is 47%.
Catalyst performance evaluation is with embodiment 1, the difference is that reaction temperature is 420 DEG C, chromatography the result shows that
O in the tail gas of reactor outlet2Concentration is 0, O2It converts completely.
Embodiment 6
By four carboxylic acid ︰ 2,5- of chlorine copper ︰ nitre acid aluminium ︰ pentamethylene, bis- hydroxyterephthalic acid's first acid ︰ ternary solvents（3.5wt% water-
20.9wt% ethyl alcohol -75.6wt%N, dinethylformamide）Molar ratio for 0.011 ︰, 0.098 ︰, 0.015 ︰, 0.033 ︰ 1, first
It weighs copper chloride and aluminum nitrate is added in ternary solvent, after stirring is allowed to be completely dissolved at 45 DEG C, it is 6 to adjust solution ph；
Then, pentamethylene tetrabasic carboxylic acid and 2,5-Dihydroxyterephthalic acid are added in as Composite Coordination Agents in solution, rapid stirring makes
After mixing, which is transferred in the stainless steel cauldron of inner liner polytetrafluoroethylene, the crystallization 16h at 100 DEG C.Crystallization
Product is washed 5 times with ethyl alcohol, and resulting material is first molded after suction filtration, the dry 12h at 110 DEG C.Finally, by resulting material in
8h is roasted at 300 DEG C, catalyst 6# is made.TPR table is levied the results show that surface copper content on the catalyst is 46%, body phase copper
Content is 54%.
Catalyst performance evaluation is with embodiment 1, the difference is that reaction temperature is 410 DEG C, the tail gas of reactor outlet
Middle O2Concentration is 0.26%.
Embodiment 7
By two first acid ︰ 2,5- of vinegar acid copper ︰ nitre acid aluminium ︰ neighbour benzene, bis- hydroxyterephthalic acid's first acid ︰ ternary solvents（5.1wt% water -16.1wt%
Ethyl alcohol -78.8wt%N, dinethylformamide）Molar ratio for 0.013 ︰, 0.087 ︰, 0.027 ︰, 0.029 ︰ 1, weigh acetic acid first
Copper and aluminum nitrate are added in ternary solvent, and after stirring is allowed to be completely dissolved at 45 DEG C, it is 6 to adjust solution ph；Then, by neighbour
Phthalic acid and 2,5-Dihydroxyterephthalic acid are added in as Composite Coordination Agents in solution, and rapid stirring is allowed to uniformly mixed
Afterwards, which is transferred in the stainless steel cauldron of inner liner polytetrafluoroethylene, the crystallization 12h at 110 DEG C.Crystallization product ethyl alcohol
Washing 5 times, resulting material is first molded after suction filtration, the dry 12h at 110 DEG C.Finally, resulting material is roasted at 300 DEG C
Catalyst 7# is made in 16h.TPR table is levied the results show that the surface copper content on the catalyst is 57%, and body phase copper content is 43%.
Catalyst performance evaluation is with embodiment 6, O in the tail gas of reactor outlet2Concentration is 0.42%.
Embodiment 8
By two first acid ︰ 2,5- of benzene, bis- hydroxyterephthalic acid's first acid ︰ ternary solvents between sulphur acid copper ︰ nitre acid aluminium ︰（2.2wt% water -30.5wt%
Ethyl alcohol -67.3wt%N, dinethylformamide）Molar ratio for 0.011 ︰, 0.075 ︰, 0.024 ︰, 0.025 ︰ 1, weigh sulfuric acid first
Copper and aluminum nitrate are added in ternary solvent, and after stirring is allowed to be completely dissolved at 45 DEG C, it is 6 to adjust solution ph；Then, by between
Phthalic acid and 2,5-Dihydroxyterephthalic acid are added in as Composite Coordination Agents in solution, and rapid stirring is allowed to uniformly mixed
Afterwards, which is transferred in the stainless steel cauldron of inner liner polytetrafluoroethylene, the crystallization 12h at 110 DEG C.Crystallization product ethyl alcohol
Washing 5 times, resulting material is first molded after suction filtration, the dry 12h at 110 DEG C.Finally, resulting material is roasted at 300 DEG C
Catalyst 8# is made in 12h.TPR table is levied the results show that the surface copper content on the catalyst is 39%, and body phase copper content is 61%.
Catalyst performance evaluation is with embodiment 6, O in the tail gas of reactor outlet2Concentration is 0.35%.
Embodiment 9
Method for preparing catalyst is with embodiment 5, the difference is that calcination temperature is 400 DEG C, catalyst 9# is made.TPR table is levied
The results show that the surface copper content on the catalyst is 54%, body phase copper content is 46%.
Catalyst performance evaluation is with embodiment 5, and chromatography is the result shows that O in the tail gas of reactor outlet2Concentration is 0, O2
It converts completely.
Embodiment 10
Method for preparing catalyst is with embodiment 5, the difference is that calcination temperature is 450 DEG C, catalyst 10# is made.TPR table is levied
The results show that the surface copper content on the catalyst is 51%, body phase copper content is 49%.
Catalyst performance evaluation is with embodiment 5, and chromatography is the result shows that O in the tail gas of reactor outlet2Concentration is 0, O2
It converts completely.
Embodiment 11
Method for preparing catalyst is with embodiment 5, the difference is that calcination temperature is 500 DEG C, catalyst 11# is made.TPR table is levied
The results show that the surface copper content on the catalyst is 48%, body phase copper content is 52%.
Catalyst performance evaluation is with embodiment 5, and chromatography is the result shows that O in the tail gas of reactor outlet2Concentration is 0, O2
It converts completely.
Embodiment 12
Method for preparing catalyst is with embodiment 5, the difference is that calcination temperature is 550 DEG C, catalyst 12# is made.TPR table is levied
The results show that the surface copper content on the catalyst is 29%, body phase copper content is 71%.
Catalyst performance evaluation is with embodiment 5, and chromatography is the result shows that O in the tail gas of reactor outlet2Concentration is 0, O2
It converts completely.
Comparative example 1
Supported copper oxide catalyst is prepared using conventional impregnation method, concrete operations are：Copper nitrate 100g is weighed, it is soluble in water,
Alumina support 160g is added in, carries out incipient impregnation.After standing 8h at room temperature, it is put into baking oven and 12h is handled at 120 DEG C, so
10h is roasted at 500 DEG C afterwards, reference agent is made.TPR table is levied the results show that free copper content in reference agent is 34%, surface
Copper content is 41%, and body phase copper content is 25%.
Catalyst performance evaluation is with embodiment 5, O in the tail gas of reactor outlet2Concentration is 1.52%.
The reference agent comparing result that catalyst 5# prepared by embodiment 5 is prepared with comparative example 1 shows to prepare using conventional impregnation method
Supported copper oxide catalyst, containing free copper, surface copper, wherein body phase copper three classes species, free copper during the reaction
It is easy to come off, content is 34% in reference agent, this shows to have 1/3rd copper species to be wasted.And use present invention side
Catalyst prepared by method only has two class species of surface copper and body phase copper in TPR spectrograms, this illustrates that this method can have copper species
Effect retains in the catalyst, avoids waste.It at the same time, can also from the content approximately equal of surface copper and body phase copper
Go out, copper species are uniformly distributed from inside to outside on the catalyst.The specific surface area of the catalyst（240 m2/g）Also it is far above reference
Agent（190 m2/g）, this pore passage structure illustrated on catalyst is also more flourishing than reference agent, can more effectively utilize copper species.Cause
This, has higher activity and stability.
Claims (12)
1. a kind of preparation method of non-precious metal catalyst, it is characterised in that：Including following content：
At least one of Mn, Fe, Co, Ni, Cu, Zn, Ce metal salt are denoted as at least one of A and Mg, Ca, Ti, Zr, Al
Metal salt is denoted as B, complexant, solvent mixing acquisition solution C；
Solution C is subjected to crystallization；
Material is washed after crystallization, be molded, be dry, catalyst is made after roasting；
The solvent is water, the ternary solvent of ethyl alcohol, n,N-Dimethylformamide composition, in terms of the weight of solvent：Water for 0.1~
10wt%, ethyl alcohol are 1~50wt% of second；Mass fractions of the metal salt A in solution C is 1~10wt%, and metal salt B is in solution
Mass fraction in C is 20~70wt%, and mass fraction of the complexant in solution C is 1~20wt%.
2. according to the method described in claim 1, it is characterized in that：In terms of the weight of solvent：Water be 1~5wt%, ethyl alcohol 10~
The mass fraction of 30wt%, the metal salt A in solution C is 1~10wt%, and mass fractions of the metal salt B in solution C is 25
~40wt%, mass fraction of the complexant in solution C are 3~10wt%.
3. according to the method described in claim 1, it is characterized in that：By at least one of Mn, Fe, Cu, Ce metal salt and Zr,
At least one of Al metal salts, complexant, solvent mixing obtain solution C.
4. according to the method described in claim 1, it is characterized in that：The metal salt is nitrate, sulfate, acetate or chlorine
One or more of compound.
5. according to the method described in claim 1, it is characterized in that：The complexant is oxalic acid, succinic acid, tartaric acid, adjacent benzene
Dioctyl phthalate, M-phthalic acid, terephthalic acid (TPA), 2,5- dihydroxy-terephthalic acid (TPA), 1,3,5- benzene tricarbonic acids, pentamethylene tetracarboxylic acid
One or more of acid.
6. according to the method described in claim 5, it is characterized in that：The complexant for 2,5- dihydroxy-terephthalic acid (TPA) or
The mixing of one or both of 1,3,5- benzenetricarboxylic acids.
7. according to the method described in claim 1, it is characterized in that：Mixed process is as follows：By Mn, Fe, Co, Ni, Cu, Zn, Ce
At least one of at least one of metal salt and Mg, Ca, Ti, Zr, Al metal salt, add in solvent in, adjust solution ph
To add in complexant after 5~7.
8. according to the method described in claim 1, it is characterized in that：The crystallization temperature is 60 ~ 200 DEG C, the crystallization time
For 1 ~ 48 it is small when.
9. according to the method described in claim 1, it is characterized in that：Crystallization resulting material is washed 5 ~ 10 repeatedly with organic solvent
It is secondary, after filtering, it is placed in oven and dried after gained filter cake is carried out forming processes；Then dried formed body is put into Muffle
Stove roasts at high temperature, finally obtains catalyst.
10. according to the method described in claim 9, it is characterized in that：The volatile organic solvent for methanol, ethyl alcohol, acetone,
One or more of dichloromethane, chloroform.
11. according to the method described in claim 1, it is characterized in that：The drying temperature is 60 ~ 200 DEG C, the drying time
For 2 ~ 24 it is small when.
12. according to the method described in claim 1, it is characterized in that：The calcination temperature is 300 ~ 800 DEG C, during the roasting
Between for 4 ~ 24 it is small when.
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| CN109772322A (en) * | 2017-11-14 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of coal gas layer dehydrogenation catalyst and preparation method thereof |
| CN110917872A (en) * | 2019-11-05 | 2020-03-27 | 河北科技大学 | A method for liquid alloy absorption and catalytic oxidation of halogenated hydrocarbons |
| CN111992253A (en) * | 2020-03-17 | 2020-11-27 | 武汉纺织大学 | Organic-metal framework catalyst for catalytic degradation of antibiotics and preparation method thereof |
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