CN107442158A - A kind of catalyst of cobalt doped MCM 48 - Google Patents
A kind of catalyst of cobalt doped MCM 48 Download PDFInfo
- Publication number
- CN107442158A CN107442158A CN201710762377.4A CN201710762377A CN107442158A CN 107442158 A CN107442158 A CN 107442158A CN 201710762377 A CN201710762377 A CN 201710762377A CN 107442158 A CN107442158 A CN 107442158A
- Authority
- CN
- China
- Prior art keywords
- mcm
- catalyst
- cobalt
- cobalt doped
- doped mcm
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 40
- 239000010941 cobalt Substances 0.000 title claims abstract description 40
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011777 magnesium Substances 0.000 claims abstract description 10
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 8
- 230000023556 desulfurization Effects 0.000 claims abstract description 8
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 7
- 150000003624 transition metals Chemical class 0.000 claims abstract description 7
- 239000007790 solid phase Substances 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 239000010703 silicon Substances 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 229910001868 water Inorganic materials 0.000 claims description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 239000002808 molecular sieve Substances 0.000 claims description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000002242 deionisation method Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 abstract description 9
- 238000007254 oxidation reaction Methods 0.000 abstract description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract description 4
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 abstract description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000395 magnesium oxide Substances 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 description 11
- JESHZQPNPCJVNG-UHFFFAOYSA-L magnesium;sulfite Chemical compound [Mg+2].[O-]S([O-])=O JESHZQPNPCJVNG-UHFFFAOYSA-L 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- AIOWANYIHSOXQY-UHFFFAOYSA-N cobalt silicon Chemical compound [Si].[Co] AIOWANYIHSOXQY-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 102220500397 Neutral and basic amino acid transport protein rBAT_M41T_mutation Human genes 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001988 small-angle X-ray diffraction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002463 transducing effect Effects 0.000 description 1
Classifications
-
- 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
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0333—Iron group metals or copper
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/618—Surface area more than 1000 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/643—Pore diameter less than 2 nm
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of cobalt doped MCM 48 catalyst, and it is solid-phase catalyst, and being incorporated in MCM 48 skeleton has transition metals cobalt, and wherein the ratio between cobalt and silicon are 0.025 0.075:0.9‑1.The present invention also disclosed a kind of preparation method of the catalyst.Transition metals cobalt is introduced the skeletons of MCM 48 in a manner of incorporating and is applied to the oxidation of magnesium processes desulfurization sulfite magnesia and ammonium method desulfurization sulfite ammonium by the cobalt doped MCM 48 of present invention catalyst.
Description
Technical field
The present invention relates to a kind of cobalt doped MCM-48 catalyst and preparation method thereof, the catalyst is used for magnesium processes and ammonium method takes off
Sulphur.
Background technology
From 1992 successfully synthesize M41S series mesoporous materials since, the fields such as catalysis, absorption, energy storage research
Important breakthrough is achieved, wherein the MCM-48 for possessing Emission in Cubic has two separate three-dimensional open-frameworks and minute surface pair
Claim, the conveying of guest molecule in being advantageous to be catalyzed and separate, and MCM-48 has that mesopore molecular sieve aperture is homogeneous, hole again in itself
Road rule, the advantages of specific surface area is big, but because pure silicon M41s molecular sieves have, neutral skeleton structure, defect be few, ion is handed over
Transducing power is small, acid content and acid strength are low, reactivity is low, therefore, limits them in catalysis, absorption, separation and environmental protection etc.
The application of aspect.
Magnesium processes and ammonium method in wet type desulfurizing technology have wide development and application space.The oxidation of sulphite is magnesium processes
With the committed step in ammonium method sulfur removal technology, transition metal has important catalytic action to the process.But that is studied at present urges
Agent is added with ionic state mostly, and the catalyst added can not be reclaimed effectively, it is necessary to carry out regular replenishment to it, so as to
Operating cost is added, while catalyst can be stranded in mother liquor and product, will also trigger the secondary pollution etc. of water body and product
Problem.
The content of the invention
In order to solve the above-mentioned technical problem, the invention provides a kind of cobalt doped MCM-48 catalyst, by transition metals cobalt
MCM-48 skeletons are incorporated into a manner of involvement and applied to sulfurous in magnesium processes desulfurization sulfite magnesia and ammonium method desulfurization
The oxidation of sour ammonium.Its it is a kind of efficiently, stably, economic, recyclable, low-residual new solid-phase catalyst.
In order to solve the above technical problems, the present invention adopts the following technical scheme that：
A kind of preparation method of cobalt doped MCM-48 catalyst, it is solid-phase catalyst, and being incorporated in MCM-48 skeleton has
Transition metals cobalt, wherein the ratio between cobalt and silicon are 0.025-0.075:0.9-1.
Present invention also offers a kind of preparation method of cobalt doped MCM-48 catalyst, comprise the following steps：By hydrogen-oxygen
Change sodium to be dissolved in deionized water, then CTAB is added in above-mentioned sodium hydroxide solution, and enter simultaneously under 40 DEG C of water baths
Row magnetic agitation, after stirring, tetraethyl orthosilicate and cobalt nitrate solution, reaction time is sequentially added dropwise
2h；Product is poured into autoclave, and thermostatic crystallization three days under 100 DEG C of environment after the completion of reaction, treated certainly after completing crystallization
So cooling, then washed 5 times by deionization, ethanol is washed 1 time, is filtered, and 24h is dried under the conditions of 90 DEG C, finally again through 550 DEG C of height
Temperature roasting 6 hours, you can obtain cobalt doped MCM-48 mesopore molecular sieves.
Preferably, the amount ratio for reacting the material of total material is Co (NO3)2：TEOS：CTAB：NAOH：H2O=0.025-
0.075：0.9-1：0.45：0.48：61.
It is furthermore preferred that Co (the NO3)2Amount ratio with TEOS material is 0.05:0.95.
The present invention also proposes the application that a kind of cobalt doped MCM-48 catalyst described above is used for magnesium processes and ammonium method desulfurization.
Compared with prior art, advantageous effects of the invention：
For solid-phase catalyst, and can be applied to the oxidation of magnesium processes and ammonium method desulfurization sulfite salt, catalytic effect with it is non-
Catalysis is contrasted, and can improve 7-7.4 times or so of catalytic rate, catalytic rate, and active metal is greatly improved
It is the skeleton for entering MCM-48 in a manner of involvement, active metal is connected more firm with carrier, and it is residual to have prevented active metal
Stay in secondary pollution caused by mother liquor and the pollution of product；In addition, the involvement amount of active metal cobalt is relatively in the catalyst
It is low, largely reduce the production cost of catalyst.
Brief description of the drawings
The invention will be further described for explanation below in conjunction with the accompanying drawings.
Fig. 1 is the magnesium processes catalytic efficiency schematic diagram of cobalt doped MCM-48 catalyst of the present invention；
Fig. 2 is the ammonium method catalytic efficiency schematic diagram of cobalt doped MCM-48 catalyst of the present invention；
Fig. 3 is the adsorption isothermal curve figure of cobalt doped MCM-48 catalyst of the present invention；
Fig. 4 is the small angle XRD of cobalt doped MCM-48 catalyst of the present invention；
Fig. 5 is the wide-angle XRD of cobalt doped MCM-48 catalyst of the present invention；
The TEM that Fig. 6 is pure MCM-48 schemes；
Fig. 7 is Co:The TEM figures of MCM-48 during Si=0.05.
Embodiment
A kind of cobalt doped MCM-48 catalyst, it is solid-phase catalyst, and being incorporated in MCM-48 skeleton has transition metals cobalt,
Wherein the ratio between cobalt and silicon are 0.025-0.075:0.9-1, preferably 0.05:0.95.
Its preparation method comprises the following steps：
Sodium hydroxide is dissolved in deionized water, then CTAB is added in above-mentioned sodium hydroxide solution, and simultaneously 40
Magnetic agitation is carried out under DEG C water bath, after stirring, tetraethyl orthosilicate and cobalt nitrate is sequentially added dropwise
Solution, reaction time 2h；Product is poured into autoclave, and thermostatic crystallization three days under 100 DEG C of environment after the completion of reaction, it is complete
Natural cooling is treated after into crystallization, then is washed 5 times by deionization, ethanol is washed 1 time, is filtered, and 24h is dried under the conditions of 90 DEG C, most
Afterwards again through 550 DEG C of high-temperature roastings 6 hours, you can obtain cobalt doped MCM-48 mesoporous molecular sieve catalysts.
The amount ratio for wherein reacting the material of total material is Co (NO3)2：TEOS：CTAB：NAOH：H2O=0.05：0.95：
0.45：0.48：61.
Cobalt doped MCM-48 catalyst is used for magnesium processes and ammonium method desulfurization, greatly improves catalytic efficiency.
As shown in figure 1, different cobalt silicon than MCM-48 types catalyst it is as shown in Figure 1 to the catalytic rate of magnesium sulfite.It is sub-
Magnesium sulfate experiment condition is：The initial concentration that adds of magnesium sulfite is 50g/L, overall solution volume 0.2L, pH=8.0, temperature
45 DEG C, catalyst quality concentration is 0.5g/L, and partial pressure of oxygen is respectively 0.2atm, air mass flow 60L/h.
From Fig. 1 we have observed that under the conditions of compared to on-catalytic, add pure MCM-48 and magnesium sulfite oxidation rate is had no
It is obviously promoted effect.But after the MCM-48 for incorporating cobalt is added, the oxidation rate of magnesium sulfite is greatly improved, therefore
Illustrate that cobalt plays vital effect in catalytic oxidation.When cobalt silicon ratio is 0.05, magnesium sulfite oxidation rate reaches
Up to 0.074mmol/ (Ls) but when exceed this involvement amount rear oxidation speed have by a small margin decline cause the reason for such can
Can be that a large amount of involvements of cobalt cause certain side effect to agent structure.
As shown in Fig. 2 cobalt silicon ratio is 0.05:MCM-48 types catalyst when 0.95 is to the catalytic rate of ammonium sulfite as schemed
Shown in 2.Ammonium sulfite experiment condition is：To add concentration be 0.2mol/L, overall solution volume 0.2L, pH for magnesium sulfite initial
=7.0, temperature 45 C, catalyst quality concentration is 0.5g/L, and partial pressure of oxygen is respectively 0.2atm, air mass flow 60L/h.
It was found from entering in 2, its catalytic efficiency is improved significantly, and about lifts 7.3 times.
The physical property of the catalyst of preparation is as shown in table 1 below：
Table 1
Work as Co as shown in figure 3, being observed from figure:Si=0.2 adsorption isothermal curves have occurred and that significant change, and explanation is urged
There is certain change in the physical property of agent, and this is also confirmed in upper table 1, from the data in table 1, due to
The difference of metal proportion, there are Different Effects to the specific surface area of sample, pore volume and aperture.Relative to pure MCM-48, doping
There is different degrees of reduction in the surface area of MCM-48 after metal, wherein working as Co:Pore volume, varying aperture be not during Si≤0.1
Substantially, 1cm3g-1 and 2.6nm are concentrated on respectively, and it is regular single to show that the sample in the range of above-mentioned doping ratio still has
Duct.Wherein Co:During Si=0.2, all there is urgency and fallen, compare surface in either specific surface area or pore volume aperture
Product is only 1/5th of pure MCM48.Cause this drastic change reason be due to Co intervention amount it is excessive, cause skeleton structure not
It is stable, so as to cause caving in for overall skeleton.
As shown in figure 4, explanation Co:Si=0.05 maintains the skeleton structure of MCM-48 under the conditions of pure Si substantially.
As shown in figure 5, in explanation catalyst there is the skeleton that it is the skeleton for incorporating MCM-48 in Co in unbodied method
It is interior.
As shown in Figures 6 and 7, the presence of cobalt does not have much affect to MCM-48 body construction, and cobalt is to incorporate MCM-48
Inside skeleton, rather than as infusion process is carried on its surface.
Embodiment described above is only that the preferred embodiment of the present invention is described, and not the scope of the present invention is carried out
Limit, on the premise of design spirit of the present invention is not departed from, those of ordinary skill in the art make to technical scheme
Various modifications and improvement, all should fall into claims of the present invention determination protection domain in.
Claims (5)
- A kind of 1. cobalt doped MCM-48 catalyst, it is characterised in that:It is solid-phase catalyst, and being incorporated in MCM-48 skeleton has Transition metals cobalt, wherein the ratio between cobalt and silicon are 0.025-0.075:0.9-1.
- 2. a kind of preparation method of cobalt doped MCM-48 catalyst, it is characterised in that comprise the following steps：Sodium hydroxide is molten It is added in deionized water, then by CTAB in above-mentioned sodium hydroxide solution, and carries out magnetic force under 40 DEG C of water baths simultaneously Stirring, after stirring, is sequentially added dropwise tetraethyl orthosilicate and cobalt nitrate solution, reaction time 2h；Reaction After the completion of product poured into autoclave, and thermostatic crystallization three days under 100 DEG C of environment, treat natural cooling after completing crystallization, Washed 5 times by deionization again, ethanol is washed 1 time, is filtered, and 24h is dried under the conditions of 90 DEG C, finally again through 550 DEG C of high-temperature roastings 6 Hour, you can obtain cobalt doped MCM-48 mesopore molecular sieves.
- 3. the preparation method and applications of cobalt doped MCM-48 catalyst according to claim 2, it is characterised in that：Reaction The amount ratio of the material of total material is Co (NO3)2：TEOS：CTAB：NAOH：H2O=0.025-0.075：0.9-1：0.45：0.48： 61。
- 4. the preparation method and applications of cobalt doped MCM-48 catalyst according to claim 3, it is characterised in that：It is described Co(NO3)2Amount ratio with TEOS material is 0.05:0.95.
- 5. a kind of cobalt doped MCM-48 catalyst as claimed in claim 1 or 2 is used for the application of magnesium processes and ammonium method desulfurization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710762377.4A CN107442158A (en) | 2017-08-30 | 2017-08-30 | A kind of catalyst of cobalt doped MCM 48 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710762377.4A CN107442158A (en) | 2017-08-30 | 2017-08-30 | A kind of catalyst of cobalt doped MCM 48 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107442158A true CN107442158A (en) | 2017-12-08 |
Family
ID=60493503
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710762377.4A Pending CN107442158A (en) | 2017-08-30 | 2017-08-30 | A kind of catalyst of cobalt doped MCM 48 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107442158A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110201710A (en) * | 2019-07-09 | 2019-09-06 | 华北电力大学（保定） | A kind of cobalt-based mesoporous material Co-TUD-1 catalyst and its preparation method and application |
| CN113634224A (en) * | 2020-12-30 | 2021-11-12 | 华北电力大学（保定） | Functional material for synchronously controlling magnesium sulfite and heavy metal ions and desulfurization method |
| CN116078154A (en) * | 2023-01-17 | 2023-05-09 | 昆明理工大学 | Method for improving oxidation rate of magnesium sulfite |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105384181A (en) * | 2015-11-06 | 2016-03-09 | 中国科学院山西煤炭化学研究所 | Method for synthesizing aluminum-containing MCM-48 mesoporous molecular sieve with co-template agent |
-
2017
- 2017-08-30 CN CN201710762377.4A patent/CN107442158A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105384181A (en) * | 2015-11-06 | 2016-03-09 | 中国科学院山西煤炭化学研究所 | Method for synthesizing aluminum-containing MCM-48 mesoporous molecular sieve with co-template agent |
Non-Patent Citations (2)
| Title |
|---|
| LIDONG WANG ET AL: ""A green and robust solid catalyst facilitating the magnesium sulfite oxidation in the magnesia desulfurization process"", 《J. MATER. CHEM. A》 * |
| 蔡强 等: ""一种过渡金属(Ti, Zr, Mn, Cu, Mo, Cr, Co)离子掺杂的MCM-48的合成、表征与催化性能研究"", 《高等学校化学学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110201710A (en) * | 2019-07-09 | 2019-09-06 | 华北电力大学（保定） | A kind of cobalt-based mesoporous material Co-TUD-1 catalyst and its preparation method and application |
| CN113634224A (en) * | 2020-12-30 | 2021-11-12 | 华北电力大学（保定） | Functional material for synchronously controlling magnesium sulfite and heavy metal ions and desulfurization method |
| CN113634224B (en) * | 2020-12-30 | 2023-07-28 | 华北电力大学（保定） | Functional material for synchronously controlling magnesium sulfite and heavy metal ions and desulfurization method |
| CN116078154A (en) * | 2023-01-17 | 2023-05-09 | 昆明理工大学 | Method for improving oxidation rate of magnesium sulfite |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105417586B (en) | Preparation method for manganic manganous oxide | |
| CN107442158A (en) | A kind of catalyst of cobalt doped MCM 48 | |
| CN103359794B (en) | A kind of spherical cobaltic-cobaltous oxide and preparation method thereof | |
| CN107488789B (en) | A method of the co-desorption gold thiosulfate anion complex ion from strong-base anion-exchange resin | |
| CN105056719A (en) | Preparation method of FeOOH low-temperature desulfurizer and desulfurizer prepared through same | |
| CN102553436B (en) | Method for removing sulfur dioxide from iron-based ionic liquid | |
| CN106179360A (en) | A kind of CuZnAl catalyst and preparation method thereof | |
| CN113620334B (en) | Dendritic ordered mesoporous copper oxide nano material and preparation method and application thereof | |
| CN110474123A (en) | Positive material of waste lithium iron phosphate comprehensive recovering process | |
| CN101007285A (en) | Organic-inorganic hybrid hydrotalcite-like heteropoly acid-supported catalyst | |
| CN107812450A (en) | A kind of method of alkaline nonaqueous phase wet method catalysis oxidation hydrogen sulfide | |
| CN104741071A (en) | Preparation method of attapulgite-based nano compound desulfurizer | |
| CN112723330B (en) | Preparation method and application of iso-phospho-ferromanganese iron phosphate | |
| CN107557598A (en) | The method for preparing V electrolyte | |
| CN110898794A (en) | Preparation method of lithium ion sieve | |
| CN109182791A (en) | A kind of method that organic acid complexing-solid phase adsorption removes aluminium from rare-earth liquid | |
| CN109395710A (en) | A kind of preparation method of cerium, carbon co-doped zinc oxide | |
| CN106622143B (en) | A kind of hydridization organic framework material and the preparation method and application thereof | |
| CN104944462B (en) | Preparation method for feed grade zinc oxide | |
| CN109943733A (en) | A kind of crude cobalt/nickel salt raw material efficiently separates cobalt/nickel magnesium manganese method | |
| CN107090546B (en) | A kind of method of the arsenic removal from nickel sulfate solution | |
| CN104399485B (en) | A kind of methane vapor low-temperature reformate catalyst and preparation method thereof | |
| CN112619399B (en) | Tail gas treatment method in nitrosyl sulfuric acid preparation process | |
| CN105217696A (en) | A kind of preparation method of nickel acid magnesium nanometer sheet of three-dimensional super-structure | |
| CN109266871A (en) | The preparation method of submicron order scandium oxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20171208 |
|
| RJ01 | Rejection of invention patent application after publication |