CN113289666A - Simple preparation method of Co/CM ceramic catalytic membrane - Google Patents
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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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
- 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
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a simple preparation method of a Co/CM ceramic catalytic membrane, belonging to the technical field of membrane catalysis. The catalyst takes a ceramic membrane as a carrier, ZIF-67 is synthesized on the surface of the ceramic membrane and in the pore channel in situ, and the catalyst is prepared by adopting one-step pyrolysis in-situ reduction. The method has the advantages that the nano-scale Co particles are loaded on the ceramic membrane instead of noble metals, and meanwhile, the surfaces of the Co particles are wrapped by carbon and nitrogen, so that the loss of the Co particles in the reaction process is effectively inhibited; the obtained Co/CM ceramic membrane has excellent catalytic activity and stability, solves the problem that the traditional catalyst is difficult to separate from the product in the follow-up process, and can be widely applied to the hydrogenation reaction process.
Description
Technical Field
The invention relates to a preparation method of a novel Co/CM ceramic catalytic membrane, belonging to the technical field of membrane catalysis.
Background
Nitrophenols are persistent organic pollutants common in the plasticizer, pesticide, dye and pharmaceutical industries. The long-term contact with the waste water containing the p-nitrophenol can cause organ damage, blood disorder, endocrine system dysfunction and the like of human beings or animals. P-aminophenol has received a great deal of attention as a main reduction product of p-nitrophenol because of its industrial application, particularly as a basic intermediate in the pharmaceutical industry. Therefore, how to effectively reduce p-nitrophenol into p-aminophenol is of great significance from the viewpoints of industrial production and environmental protection. At present, methods such as photocatalytic degradation, electrochemical reactors, adsorption, biodegradation, heterogeneous catalysis and the like are widely applied to treatment of p-nitrophenol pollutants. However, in practical application, the methods have the problems of low catalytic efficiency, difficult product separation, high preparation cost, short service life and the like.
In order to solve the above problems, in recent years, researchers have proposed the application of membrane catalytic technology. The membrane catalysis technology is a technology combining catalytic reaction and product separation, namely, the membrane separation and the catalytic reaction are coupled to form a catalytic reactor. The membrane reactor is characterized by breaking the restriction of chemical equilibrium, simplifying the process steps, saving energy and improving the reaction conversion rate and the product selectivity. Patent (ZL 201010617062.9) reports a preparation method of a membrane catalyst, namely, firstly, a ceramic membrane carrier is subjected to amino modification, and then the ceramic membrane carrier is immersed in an anion solution of active component palladium, and then the membrane catalyst is prepared by chemical reduction, so that the catalytic activity of the catalyst is improved. This improves the catalytic activity and stability of the catalytic membrane to some extent, however, noble metals are easy to be lost in the reaction process, and the cost is high, which makes large-scale application difficult. Therefore, in addition to these noble metal-based catalysts, non-noble metal catalysts such as carbon-nitrogen composites are also used for catalytic reactions. In recent years, MOFs have attracted much attention as template materials for the preparation of high porosity carbonaceous materials. MOFs are a novel ordered nano-porous material assembled by metal ions and organic ligands, and have the characteristics of high specific surface area, ordered pore structure and pore adjustability. Direct carbonization of MOFs (without addition of a carbon source) has also been reported to produce MOFs-derived metal or metal oxide-carbon composites. However, the incorporation of MOFs with catalytic membranes remains a challenge.
Disclosure of Invention
Aiming at the problems of high cost and difficult recovery of multipurpose noble metal of a catalyst for preparing p-aminophenol by hydrogenation reduction of p-nitrophenol, the invention provides a novel membrane catalyst. In order to achieve the above purpose, the technical scheme of the invention is as follows:
MOFs is a novel ordered nano-porous material assembled by metal ions and organic ligands, and the MOFs derivative metal or metal oxide-carbon nitride composite material can be prepared by direct carbonization (without adding a carbon source). The invention effectively avoids the agglomeration of metal based on the carbonization of organic ligands in the MOFs thermal decomposition process, obtains metal nano-particles with uniform dispersion and small particle size by adjusting various parameters in the preparation process, and further applies MOFs to a catalytic membrane to synthesize a Co/CM ceramic catalytic membrane rich in active sites based on the principle that the nano-particles coated by carbon and nitrogen obtained by further carbonization can effectively inhibit the loss of active components in the reaction process.
The technical scheme of the invention is that
A preparation method of a novel Co/CM ceramic catalytic membrane comprises the following specific steps:
the method comprises the following steps: dissolving 2-methylimidazole in methanol, and stirring until the solution is clear and transparent to obtain a solution I;
step two: dissolving cobalt nitrate hexahydrate in methanol, and stirring until the solution is clear and transparent to obtain a solution II;
step three: rapidly adding the solution II into the solution I under a stirring state to obtain a mixed solution, and then soaking the ceramic membrane into the mixed solution to perform in-situ soaking on the surface and the inside of the pore channel to synthesize ZIF-67;
step four: taking out the immersed ceramic membrane, washing the ceramic membrane for a plurality of times by using methanol, and drying to obtain a ZIF-67/CM ceramic membrane;
step five: and calcining the ZIF-67/CM ceramic membrane to obtain the Co/CM ceramic catalytic membrane.
Preferably, the concentration of the 2-methylimidazole in the solution I prepared in the first step is 0.8-6.4 mol/L.
Preferably, the concentration of the cobalt nitrate hexahydrate in the solution II prepared in the step two is 0.1-0.8 mol/L.
Preferably, the in-situ impregnation process in the third step is finished by water bath heat preservation and rotor stirring; the stirring speed is 20-40r/min, and the water bath temperature is 20-40oAnd C, the dipping time is 12-36 h.
Preferably, the washing times in the fourth step are 2-4 times, and the drying temperature is 50-70oAnd C, drying for 12-36 h.
Preferably, the temperature of the calcination in the step five is in the range of 800-1000-oC, the calcining atmosphere is argon, and the heating rate is 2-10oC/min, raising the temperature to the target temperature and keeping the temperature for 4-6 h.
The catalytic performance of the prepared catalyst is evaluated by using the model reaction of preparing p-aminophenol by selective hydrogenation of p-nitrophenol. The specific process is as follows:
the reaction is carried out in a flow-through membrane reactor and employs 50oC water bath to keep the reaction temperature constant. 0.25 g of p-nitrophenol was added to a mixed solvent composed of ethanol and deionized water (60 mL, volume ratio of ethanol to deionized water =1: 5), and stirred for 20 min, and 0.4 mL of the reaction solution was taken as an initial sample. Then 0.65 g of NaBH was added4Stirring for 10 min, adding into a storage tank of a flow-through membrane reactor, timing when the reaction solution flows back to the storage tank through a peristaltic pump, periodically taking 0.4 mL of the reaction solution, and detecting the product composition by high performance liquid chromatography (HPLC, Agilent 1200). The conversion and selectivity of the reaction were then calculated from the standard curve.
The invention takes a catalytic membrane compounded by ZIF-67 and a ceramic membrane substrate as a research object, and prepares a novel Co/CM ceramic membrane through high-temperature one-step pyrolysis. The evidence proves that the ZIF-67 does not contain oxygen atoms, so that a large amount of C and N atoms are reserved in the inert gas calcination process, a nitrogen-rich catalytic film is obtained, the transmission of electrons is facilitated, the loss of active components can be effectively inhibited, and the excellent catalytic performance is shown in the reaction of preparing p-aminophenol by hydrogenating p-nitrophenol.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the ZIF-67 derived metal or metal oxide-carbon composite material is effectively prepared by regulating and controlling the calcination temperature and the impregnation concentration. Research shows that Co is generated in the calcining process2+Will be reduced to Co by the reducing gas of the ZIF-67 calcination process and act as a catalytically active center. In addition, with the increase of the calcining temperature, the proportion of mesopores is gradually increased, which is beneficial to the contact between a reaction substrate and an active component, shortens the mass transfer path and further enhances the reaction activity. The results show that the calcination temperature is 800-oAnd C, when the impregnation concentration of the cobalt nitrate hexahydrate is 0.5-0.7mol/L, the prepared catalytic performance is excellent. In particular, the carbonization of the organic ligand in the MOFs thermal decomposition process effectively avoids the agglomeration of metal, gradually generates pyrrole nitrogen in the pyrolysis process, and is beneficial to the conversion of reactants. Meanwhile, the Co/CM ceramic catalytic membrane has good stability, the catalytic membrane can still maintain good catalytic activity after 5 times of recovery and repeated reaction, and the content of active components in the catalytic membrane obtained by 5 times of reaction is not different from that of a fresh catalyst, so that the catalytic membrane prepared by the invention breaks through the problems of serious loss, difficult separation and poor stability of the traditional fine-particle heavy metal catalyst, and has good industrial application prospect.
Drawings
FIG. 1 shows the Co 2p peak of the Co/CM ceramic catalyst film of example 1.
FIG. 2 is a reaction mechanism diagram of the Co/CM ceramic catalytic membrane of example 1.
FIG. 3 shows the stability test results of the Co/CM ceramic catalyst film of example 4.
Detailed Description
The method and the effect of the catalytic membrane of the present invention will be specifically described below by way of examples, which are only for illustrating the present invention and are not intended to limit the scope of the present invention.
Example 1
This example provides a specific process for the preparation of Co/CM ceramic catalytic membranes.
(1) Preparation of ZIF-67/CM
In a 50 mL beaker, ZIF-67 was synthesized in situ on the surface of the ceramic membrane and inside the pore channels under the stirring of a rotor: respectively preparing 4.8M, 25 mL dimethyl imidazole methanol solution, 0.6M, 25 mL cobalt nitrate hexahydrate methanol solution, respectively stirring until the solution is clear and transparent (stirring speed is not limited), placing the cobalt nitrate hexahydrate methanol solution into a water bath kettle, and controlling the water bath temperature to be 30 DEGoC, quickly adding the dimethyl imidazole methanol solution into the cobalt nitrate hexahydrate methanol solution, and stirring at the speed of 30 r/min to 30oC, using a polytetrafluoroethylene support to support and fix a ceramic membrane (commercially available, aluminum oxide, the pore diameter is about 3 mu m, the diameter is 3.2cm, and the thickness is 1.7 mm), vertically putting the ceramic membrane into a mixed solution for dipping, fixing the position of the ceramic membrane in the middle of a beaker in the dipping process, completely immersing the ceramic membrane, taking out the dipped ceramic membrane to wash the immersed ceramic membrane for 3 times by using methanol after dipping for 24 hours, and then putting the immersed ceramic membrane into a container 60 timesoAnd drying in an oven C for 24 hours, and marking the obtained sample as ZIF-67/CM-0.6.
(2) Preparation of Co/CM catalyst
The treated ZIF-67/CM-0.6 was placed in a tube furnace and calcined to 900 deg.C at the initial temperature (room temperature)oC, keeping the temperature for 5 hours at the target temperature, wherein the temperature rise rate is 5oC/min, the calcining atmosphere is argon, and the obtained sample is marked as Co/CM-0.6-900.
FIG. 1 shows the N1s peak of Co/CM ceramic catalytic membrane, and it can be seen from FIG. 1 that Co is CoN at lower calcination temperaturexAnd Co2+Is present, with a gradual increase in the calcination temperature, CoN is foundxAnd Co2+Can be reduced to Co by the reducing gas. Co serving as a catalytic active site can efficiently catalyze p-nitrophenol to prepare p-aminophenol by hydrogenation, and a simple in-situ reduction process is realized.
Table 1 shows that, in the powdered catalyst obtained by performing the impregnation reaction in the same manner as in example 1, and then centrifuging, washing and drying the mother solution, the active particles on the surface of the catalytic membrane have a mesoporous structure as the temperature gradually increases, and the proportion of mesopores to the total pores gradually increases as the calcination temperature gradually increases, as shown in table 1.
Note: in the table, Co-0.6-X, X represents the calcination temperature
The catalytic membrane Co/CM is applied to an experiment for preparing p-aminophenol by hydrogenating p-nitrophenol, the catalytic performance of the catalytic membrane is tested by a flow-through membrane reactor, the molar ratio of p-nitrophenol to sodium borohydride is 1: 9.6, the concentration of p-nitrophenol is 31.3 mM, and the reaction temperature is 50 DEGoUnder the condition of C, the conversion rate is 100 percent and the selectivity is 100 percent after 20 min of reaction.
Table 2 shows the conversion frequency values (TOF) of the Co/CM catalytic membranes and the catalysts reported in the literature in recent years. At the expense of a small amount of NaBH4Under the conditions, the Co/CM ceramic catalytic membrane obtained in example 1 still has a high TOF value (13.36 s)-1) The Co/CM catalytic membrane has excellent catalytic performance and good application prospect.
TABLE 2 conversion frequency values (TOF) for Co/CM catalytic membranes and catalysts reported in the literature of recent years
a: TOF is calculated as the amount of p-nitrophenol reduced per mole of active ingredient per hour.
FIG. 2 shows a possible reaction mechanism of Co/CM catalytic membrane, p-nitrophenol and NaBH in the initial stage of reaction4Respectively adsorbed on the catalyst, then the B-H bond of Co nano particles at the active center is broken, so that the active H and electrons are accelerated to be separated from NaBH4Transfer to p-nitrophenol, which in turn produces p-aminophenol. The content of active components for activating H has great influence on the reduction of p-nitrophenol, the higher the content of Co,the conversion is also relatively high. Due to the appropriate mesoporous structure, the Co/CM catalytic membrane is beneficial to the diffusion and transmission of reactants, so that the Co/CM catalytic membrane has good conversion rate in the p-nitrophenol hydrogenation reaction. In addition, the Co/CM catalyzed membranes have good reproducibility.
Example 2
This example provides a specific process for preparing Co/CM ceramic catalyst membranes, and is not specifically described and is consistent with example 1.
(1) Preparation of ZIF-67/CM
ZIF-67 was synthesized in situ on the ceramic membrane surface and inside the channels in a 50 mL beaker with agitation by a rotor. The dimethyl imidazole methanol solution (0.8M, 25 mL) is rapidly added into the cobalt nitrate hexahydrate methanol solution (0.1M, 25 mL), the stirring speed is 10 r/min, and the water bath temperature is 20oC. After 12 h of immersion, the membrane was washed 2 times with methanol and subsequently placed at 50oAnd drying in an oven C for 12 hours, and marking the obtained sample as ZIF-67/CM-0.1.
(2) Preparation of Co/CM catalyst
The treated ZIF-67/CM was placed in a tube furnace and calcined to an initial temperature of 800 deg.CoC, keeping the temperature for 4 hours at the target temperature, wherein the temperature rise rate is 2oC/min, the calcining atmosphere is argon, and the obtained sample is marked as Co/CM-0.1-800.
The catalytic membrane Co/CM is applied to an experiment for preparing p-aminophenol by hydrogenating p-nitrophenol, the conversion rate is 90.1 percent after the reaction is carried out for 20 min, and the selectivity is 100 percent.
Example 3
This example provides a specific process for preparing Co/CM ceramic catalyst membranes, and is not specifically described and is consistent with example 1.
(1) Preparation of ZIF-67/CM
ZIF-67 was synthesized in situ on the ceramic membrane surface and inside the channels in a 50 mL beaker with agitation by a rotor. The dimethyl imidazole methanol solution (6.4M, 25 mL) is rapidly added into the cobalt nitrate hexahydrate methanol solution (0.8M, 25 mL), the stirring speed is 40r/min, and the water bath temperature is 40oC. After immersion for 36 h, the membrane is washed 4 times with methanol and subsequently placed at 70oAnd C, drying in an oven for 36 h, and marking the obtained sample as ZIF-67/CM-0.8.
(2) Preparation of Co/CM catalyst
The treated ZIF-67/CM was placed in a tube furnace and calcined to an initial temperature of 1000 deg.CoC, keeping the temperature for 6 hours at the target temperature, wherein the temperature rise rate is 10oC/min, the calcining atmosphere is argon, and the obtained sample is marked as Co/CM-0.8-1000.
The catalytic membrane Co/CM is applied to an experiment for preparing p-aminophenol by hydrogenating p-nitrophenol, the conversion rate is 92.0 percent after the reaction is carried out for 20 min, and the selectivity is 100 percent.
Example 4
This example was tested for catalytic stability using the Co/CM prepared in example 1.
The catalytic membrane Co/CM is applied to an experiment for mechanically applying p-aminophenol to p-nitrophenol hydrogenation, after the reaction is finished, the ceramic membrane is not taken out, the solution left after the reaction is poured out from the opening of the material storage tank, fresh reaction liquid is prepared and added from the opening, and the next reaction is carried out. After the catalyst is used for five times, the catalytic membrane still can keep higher activity and has no obvious inactivation, and the result is shown in figure 3.
The above description is only a preferred embodiment of the present invention, and not intended to limit the present invention in other forms, and any person skilled in the art may apply the above modifications or changes to the equivalent embodiments with equivalent changes, without departing from the technical spirit of the present invention, and any simple modification, equivalent change and change made to the above embodiments according to the technical spirit of the present invention still belong to the protection scope of the technical spirit of the present invention.
Claims (6)
1. A preparation method of a novel Co/CM ceramic catalytic membrane comprises the following specific steps:
the method comprises the following steps: dissolving 2-methylimidazole in methanol to obtain a solution I;
step two: dissolving cobalt nitrate hexahydrate in methanol to obtain a solution II;
step three: rapidly adding the solution II into the solution I under a stirring state to obtain a mixed solution, and then soaking the ceramic membrane into the mixed solution to perform in-situ soaking on the surface and the inside of the pore channel to synthesize ZIF-67;
step four: taking out the immersed ceramic membrane, washing the ceramic membrane for a plurality of times by using methanol, and drying to obtain a ZIF-67/CM ceramic membrane;
step five: and calcining the ZIF-67/CM ceramic membrane to obtain the Co/CM ceramic catalytic membrane.
2. The method for preparing a novel Co/CM ceramic catalytic membrane according to claim 1, wherein 2-methylimidazole and cobalt nitrate hexahydrate are dissolved in methanol and then stirred until the solution is clear and transparent, and the concentration of 2-methylimidazole in the solution I prepared in the first step is 0.8-6.4 mol/L.
3. The method for preparing a novel Co/CM ceramic catalytic membrane, according to claim 1, wherein the concentration of cobalt nitrate hexahydrate in the solution II prepared in step two is 0.1-0.8 mol/L.
4. The method for preparing the novel Co/CM ceramic catalytic membrane as claimed in claim 1, wherein in step three, the ceramic membrane is used for vertical in-situ synthesis of ZIF-67, the stirring speed is 20-40r/min, and the dipping temperature is 20-40oAnd C, the dipping time is 12-36 h.
5. The method for preparing a novel Co/CM ceramic catalytic membrane according to claim 1, wherein the number of washing times in the fourth step is 2-4, and the drying temperature is 50-70oAnd C, drying for 12-36 h.
6. The method for preparing a novel Co/CM ceramic catalytic membrane as claimed in claim 1, wherein in step five, the ZIF-67/CM ceramic membrane is calcined in a tube furnace at a calcination temperature of 800-oC, the calcining atmosphere is argon, and the heating rate is 2-10oC/min, raising the temperature to the target temperature, and then preserving the heat for 4-6 h.
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