CN111992249B - Palladium/sulfonated (polymer-inorganic two-dimensional material) composite catalyst, preparation thereof and application thereof in catalyzing acetone hydrogenation - Google Patents
Palladium/sulfonated (polymer-inorganic two-dimensional material) composite catalyst, preparation thereof and application thereof in catalyzing acetone hydrogenation Download PDFInfo
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
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- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/643—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of R2C=O or R2C=NR (R= C, H)
Abstract
The invention belongs to the field of organic catalytic synthesis, and particularly discloses a palladium/sulfonated (polymer-inorganic two-dimensional material) composite catalyst, which comprises a sulfonated composite carrier and metal palladium loaded on the composite carrier; the composite carrier is an in-situ composite of a polymer and an inorganic two-dimensional material; the chain segment of the polymer is provided with aromatic groups. The invention also comprises a preparation method of the composite catalyst and application of the composite catalyst in preparation of methyl isobutyl ketone (MIBK) by catalyzing hydrogenation of acetone. The composite catalyst of the invention can fundamentally solve the problem of poor long-term stability of polymer catalysts.
Description
Technical Field
The invention relates to a high-stability catalyst for preparing methyl isobutyl ketone by acetone hydrogenation and a preparation method thereof.
Background
Methyl isobutyl ketone (MIBK for short) is an excellent intermediate-boiling-point organic solvent, has stable chemical properties and is widely applied to the field of chemical industry. At present, acetone and hydrogen are mainly mixed at home and abroad, and condensation (alkali or acid catalysis), dehydration (acid catalysis) and hydrogenation (metal catalysis) processes are completed under the action of a multifunctional catalyst to prepare MIBK, namely a one-pot process called in literature. The one-pot method gradually becomes the main stream of MIBK synthesis due to the advantages of short flow and low energy consumption. The multifunctional catalyst with acid (or acid-base) and metal components is the key to realize the synthesis of MIBK by one-pot method.
Currently, the one-pot catalyst used industrially is a palladium catalyst supported on a strongly acidic resin (denoted as Pd/resin). Such as patents CN200910008896.7, CN991220519.7, CN98111252.8, US3953517 and US 4269943. Although good activity and stability are achieved, the MIBK synthesized by acetone hydrogenation is a strong exothermic reaction, the heat effect is-120 kJ/mol, and the existing Pd/resin catalyst has the defects of poor long-term catalytic stability and short service life.
In order to solve the outstanding problem of poor stability of the Pd/resin catalyst, no good solution is available in the industry, and the problem of poor stability of the Pd/resin catalyst cannot be fundamentally solved only by proposing the use temperature of the resin catalyst to be below 120 ℃.
Disclosure of Invention
The first purpose of the present invention is to provide a palladium/sulfonated (polymer-inorganic two-dimensional material) composite catalyst with high stability.
The second purpose of the invention is to provide a preparation method of the palladium/sulfonated (polymer-inorganic two-dimensional material) composite catalyst.
The third objective of the invention is to provide an application method of the palladium/sulfonated (polymer-inorganic two-dimensional material) composite catalyst in the synthesis of MIBK by acetone hydrogenation catalysis (namely, a method for synthesizing MIBK by acetone hydrogenation catalysis).
The purpose of the invention is realized by the following scheme.
A palladium/sulfonated (polymer-inorganic two-dimensional material) composite catalyst comprises a composite carrier treated by sulfonation and metallic palladium supported on the composite carrier; the composite carrier is an in-situ composite of a polymer and an inorganic two-dimensional material; the chain segment of the polymer is provided with aromatic groups.
In the prior art, the idea for solving the stability of the Pd/polymer catalyst is mainly to reduce the temperature of a catalytic reaction system, and the idea cannot fundamentally solve the problems of long-term stability and short service life of the catalyst. Therefore, the invention provides a brand-new idea for solving the stability of the Pd/polymer catalyst, namely the idea of improving the thermal effect and the multiple synergistic effects such as Pd loading strength and the like by carrying out in-situ inorganic two-dimensional material and sulfonation modification on the polymer carrier is adopted, so that the problem of poor stability is fundamentally solved. Compared with the existing Pd/polymer catalyst, the composite catalyst has better catalytic stability.
The key of the composite catalyst is the mutual cooperation of the control of the polymer chain segment aromatic group, the innovative use of the inorganic two-dimensional material, the in-situ composite mode of the polymer and the inorganic two-dimensional material and the sulfonation modification means.
Preferably, the aromatic group on the chain segment of the polymer is at least one of phenyl, chlorphenyl and nitrobenzene.
Preferably, the polymer is polystyrene.
In the invention, the in-situ compounding mode of the polymer and the inorganic two-dimensional material is one of the keys for ensuring the good stability of the composite catalyst. The in-situ compounding mode can be understood as that the inorganic two-dimensional material is added into a raw material system for polymer polymerization and is highly dispersed in a polymer structure along with the polymerization process.
For example, the composite carrier is obtained by in-situ polymerization of a mixed raw material solution containing the inorganic two-dimensional material, the aromatic group-containing monomer and the polymerization assistant.
Preferably, the inorganic two-dimensional material is at least one of graphene oxide, graphene or boron nitride.
Preferably, the inorganic two-dimensional material has a particle size of 2000 to 2500 mesh.
Preferably, in the composite carrier, the mass content of the inorganic two-dimensional material is 0.4-4%; more preferably 1 to 3%. The research shows that the catalyst has better catalytic effect and higher stability when controlled in the preferable range.
Preferably, the particle size of the metal palladium is 1-10 nm, and more preferably 1-3 nm;
preferably, in the composite catalyst, the loading amount of metal palladium is 0.1-1.0 wt%; more preferably 0.1 to 0.7 wt%.
The invention also provides a preparation method of the palladium/sulfonated (polymer-inorganic two-dimensional material) composite catalyst, which comprises the following steps:
step (1): mixing the raw material for synthesizing the polymer and the inorganic two-dimensional material to obtain a raw material solution, and then carrying out in-situ polymerization to prepare the composite carrier for in-situ compounding the polymer and the inorganic two-dimensional material;
step (2): sulfonating the composite carrier;
and (3): and loading metal palladium on the surface of the composite carrier subjected to sulfonation treatment to prepare the composite catalyst.
The method can prepare the brand new composite catalyst which has better catalytic stability.
The raw materials for synthesizing the polymer comprise monomers and polymerization aids.
Preferably, the monomer is a monomer with an aromatic group; preferably at least one of styrene, divinylbenzene, chlorostyrene and nitrostyrene; more preferably at least one of styrene and divinylbenzene.
In the invention, the monomer is styrene and divinylbenzene, and the volume ratio of the amount of the divinylbenzene to the amount of the styrene is 1: 3-5, preferably 1: 4.
Preferably, the polymerization auxiliary agent comprises at least one of pore-forming agent, emulsifier and initiator; further preferably comprises a pore-forming agent, an emulsifier and an initiator.
Preferably, the pore-forming agent is at least one of toluene and liquid paraffin; further preferred are toluene and liquid paraffin; further preferably, the volume ratio of the liquid paraffin to the toluene is 1: 1-2, preferably 1: 1.5.
Preferably, the volume ratio of the monomer to the pore-forming agent is 1: 0.8-1.2; further preferably 1:1.
Preferably, the initiator is azobisisobutyronitrile, and the using amount of the initiator is 2-4% of the mass of the monomer, preferably 4%.
Preferably, the emulsifier is an amphoteric surfactant, and more preferably at least one of triton X-100, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and the like.
Preferably, the amount of emulsifier used is 2 to 10%, preferably 6%, of the volume of the monomer.
In the invention, the inorganic two-dimensional material is at least one of graphene oxide, graphene or boron nitride;
preferably, the mass content of the inorganic two-dimensional material in the composite carrier is 0.4-4%. More preferably, the content is 1 to 3%. The research of the invention finds that the control of the optimal addition amount is beneficial to successfully obtaining the in-situ composite carrier, and further beneficial to preparing the composite catalyst with good catalytic stability.
The inorganic two-dimensional material can be a commercial product purchased from outsourcing, or prepared by adopting the existing method.
Preferably, the in-situ polymerization in step (1) is carried out at 70 to 90 ℃.
After completion of the polymerization, an in situ polymer is obtained, followed by sulfonation.
In the invention, the sulfonating agent adopted in the sulfonation treatment is concentrated sulfuric acid, fuming sulfuric acid or chlorosulfonic acid.
The sulfonation process comprises the following steps: and (2) swelling the in-situ polymer in an organic solvent, adding a sulfonating agent for sulfonation, and then washing, filtering and drying to obtain the sulfonated composite carrier.
Preferably, the temperature in the sulfonation treatment process is 70-90 ℃; the sulfonation treatment time is 6-12 h.
Preferably, in the step (3), the metal palladium is loaded on the sulfonation-treated composite carrier by using an impregnation method or a precipitation method.
For example: the process of loading Pd is as follows: the composite carrier after sulfonation treatment is dipped in a solution of a palladium precursor and is prepared by a dipping method or a precipitation method.
Further preferably, the composite carrier after sulfonation treatment is placed in a solution of a palladium precursor, subjected to ultrasonic dispersion and drying, and then subjected to reduction, washing and drying to obtain the composite catalyst.
In the invention, the palladium precursor can be at least one of palladium acetylacetonate, chloropalladic acid, sodium chloropalladate, palladium tetraammine dichloride or palladium acetate.
The reducing agent is potassium borohydride.
The mass ratio of the palladium precursor to the reducing agent is 1: 0.7-3.5, and preferably 1: 0.7-1.4.
The invention provides a preparation method of a preferred palladium/sulfonated (polymer-inorganic two-dimensional material) composite catalyst, which comprises the following steps:
(1) mixing monomers (styrene and divinylbenzene), pore-forming agents (toluene and liquid paraffin), an emulsifier (triton X-100), an initiator (azodiisobutyronitrile), water and inorganic two-dimensional materials (graphene oxide, graphene and boron nitride), carrying out in-situ polymerization, removing unreacted raw materials and the pore-forming agents by using petroleum ether through a Soxhlet extractor, and drying to obtain the in-situ polymer (composite carrier).
(2) And (3) swelling the in-situ polymer in a solvent, adding a sulfonating agent for sulfonation, and then washing, filtering and drying to obtain the sulfonated composite carrier.
(3) And (3) soaking the obtained sulfonated composite carrier in a palladium precursor solution, performing ultrasonic dispersion and drying, and then performing reduction, washing and drying to obtain the composite catalyst.
The invention also provides an application of the palladium/sulfonated (polymer-inorganic two-dimensional material) composite catalyst, and the composite catalyst is used as a catalyst for preparing methyl isobutyl ketone by hydrogenating acetone. The composite catalyst is a whole, and has the advantages of good product selectivity, high adaptive temperature, good catalytic stability and the like when being used as a catalyst for preparing methyl isobutyl ketone by acetone hydrogenation.
The invention also provides a method for preparing methyl isobutyl ketone by acetone hydrogenation, which comprises the step of carrying out hydrogenation reaction on acetone and hydrogen under the catalysis of the palladium/sulfonation (polymer-inorganic two-dimensional material) composite catalyst to synthesize the methyl isobutyl ketone in one pot.
The temperature of the hydrogenation reaction is preferably 100-160 ℃; further preferably 120 to 130 ℃.
The principle is as follows:
the method is developed mainly aiming at the current situation that the industrial Pd/resin catalyst for preparing MIBK by an acetone hydrogenation one-step method is not high in stability. The prior art only reduces the use temperature of the catalyst to prolong the catalytic life to a certain extent, but the method cannot fundamentally solve the problem of poor stability of the Pd/resin catalyst at high temperature.
Based on the knowledge and the deficiency of the prior art, the primary innovation of the invention lies in the innovation of the technical knowledge and the inventive concept. The invention innovatively provides a method for improving the catalytic stability and solving the problem of low adaptive temperature by improving the heat effect of the catalyst and the synergistic action ideas such as Pd loading strength and the like; the problem of poor stability of the catalyst can be fundamentally solved.
According to the composite material, the inorganic two-dimensional material is added in the polymerization process of the polymer, and the thermal stability of an in-situ composite can be improved by utilizing the inorganic characteristics, the two-dimensional structure characteristics and the surface active group characteristics of the inorganic two-dimensional material and matching with the in-situ composite mode of the inorganic two-dimensional material and the polymer; moreover, by carrying out sulfonation treatment on the in-situ compound and loading palladium metal, the dual-solid-carrying strength of the sulfonic group and the palladium metal is improved, and good binding force between the sulfonic group and the palladium metal and a carrier is ensured, so that loss is reduced fundamentally.
In the technology of the invention, the inventor uses an in-situ emulsion polymerization method to prepare an inorganic two-dimensional material (preferably at least one of graphene oxide, graphene and boron nitride)/polymer in-situ composite with an aromatic ring. Through various instrumental analyses, we find that the first and the second inorganic two-dimensional materials and aromatic ring polymer such as benzene ring structure of polystyrene generate pi-pi interaction with each other; secondly, oxygen-containing and nitrogen-containing functional groups are arranged on the surface of the graphene oxide (or graphene and boron nitride), and a covalent bond is formed between the graphene oxide and polystyrene; the existence of the two bonding forces greatly improves the bonding force between the sulfonic acid group and the carrier and the bonding force between the palladium and the carrier, which can be seen from the attached drawings of the patent. And thirdly, the composite carrier has good thermal stability, and can avoid thermal decomposition of sulfonic acid groups and agglomeration and falling of palladium. The idea of the invention brings the improvement effect of the two-dimensional material on the catalyst to the utmost extent, and obtains multiple effects: the thermal stability of the carrier is obviously improved; the binding force of the sulfonic group and the palladium metal is greatly improved, so that the service life of the catalyst is obviously prolonged compared with that of an industrial Pd/resin catalyst.
Advantageous effects
The composite catalyst of the invention successfully performs the reaction for 500 hours at the temperature of 150 ℃, and the Pd/sulfonated (polystyrene-boron nitride) catalyst shows good stability in the reaction process. After 500h reaction, the catalyst still maintains higher activity. The acetone conversion rate is reduced from 60.64 percent to 54.20 percent, the MIBK selectivity is increased from 73.76 percent to 80.91 percent, and the MIBK yield is reduced from 44.73 percent to 43.85 percent without obvious change. After the Pd/sulfonation (polystyrene-graphene oxide) is reacted for 500 hours, the acetone conversion rate is reduced to 45.98% from 50.85%, the MIBK selectivity is reduced to 76.58% from 77.84%, and the corresponding MIBK yield is reduced to 35.21% from 39.58%. In contrast, after 500 hours of reaction of the Dow chemical Pd/resin industrial catalyst, the acetone conversion rate is reduced from 55.53 percent to 30.93 percent, the MIBK selectivity is reduced from 78.88 percent to 71.89 percent, and the corresponding MIBK yield is reduced from 43.80 percent to 22.24 percent. It is anticipated that the catalyst of the present invention will have a service life superior to existing commercial catalysts when operated under commercial conditions.
Description of the drawings:
FIG. 1 Transmission Electron Microscopy (TEM) image of polystyrene-graphene oxide
FIG. 2 ultraviolet-visible (UV-vis) spectrum of polystyrene-graphene oxide
FIG. 3 shows (a) XPS survey spectra, (b) S2p spectra and (c) Pd3d spectra of Pd/sulfonated (polystyrene-graphene oxide) and Dow Pd/resin catalysts.
Detailed Description
The invention is further illustrated by the following examples.
Example 1
Preparation of Pd/sulfonated (polystyrene-graphene oxide) catalyst
(1): preparation of polystyrene-graphene oxide composite
Adding 0.15g of commercially available graphite oxide into a beaker, adding 50mL of distilled water, performing ultrasonic treatment for 30min to obtain 3mg/mL of GO/water dispersion, respectively adding 4mL of styrene, 1mL of divinylbenzene, 2mL of liquid paraffin, 3mL of toluene, 0.2g of azobisisobutyronitrile and 0.3mL of triton X-100, and adding into a 150mL three-neck flask after performing ultrasonic treatment for 30 min. Stirring at 50 deg.C for 30min, heating to 60 deg.C, stirring for 30min, heating to 70 deg.C, reacting for 4h, heating to 90 deg.C, and maintaining for 1h to solidify the composite. And taking out the compound after the reaction is finished, washing and drying. The compound is put into a Soxhlet extractor and extracted for 12 hours at 95 ℃ by using 60 to 90 boiling petroleum ether, and unreacted monomers and pore-forming agent are removed. And washing and drying after extraction to obtain the polystyrene-graphene oxide compound. The TEM image is shown in FIG. 1. The ultraviolet-visible (UV-vis) spectrum is shown in FIG. 2. FIG. 1 is a transmission electron microscope image and a UV-vis image of a polystyrene-graphene oxide composite. It can be seen that the graphene oxide sheets have a number of polystyrene particles with diameters in the range of 5-30 nm. And the graph d can prove that the graphene oxide sheets and the polystyrene have pi-pi interaction. From the UV-vis spectrum, the characteristic peak of the benzene ring of pure polystyrene appears at 262.5nm, whereas after addition of graphene oxide, the peak position shifts 7nm high to 269.5nm, which 7nm shift is believed to be due to pi-pi stacking of the graphene oxide nanoplatelets with the benzene rings in polystyrene.
(2): sulfonation of polystyrene-graphene oxide composites
And putting 1.5g of polystyrene-graphene oxide compound into a three-neck flask, adding 15mL of dichloroethane, swelling at 70 ℃ for 30min, adding 2mL of concentrated sulfuric acid, reacting for 8h, filtering and washing a product, and drying in an oven to obtain the sulfonated (polystyrene-graphene oxide).
(3): palladium-carrying
Respectively putting 1g of sulfonated (polystyrene-graphene oxide) into 4 50mL crucibles, respectively adding 1mL, 3mL, 5mL and 7mL of palladium acetylacetonate/toluene solution with the concentration of 0.01mol/L and recording as No. (i), No. (ii), No. (iii) and No. (iv), performing ultrasonic treatment for 30min to ensure that the sulfonated (polystyrene-graphene oxide) fully absorbs the palladium acetylacetonate, sucking out supernate (toluene) by using a suction pipe, adding 8mL of ethanol/water solution with the volume ratio of 1:1 after drying, adding 2mg of No. (i), adding 6mg of No. (iii), adding 10mg of No. (iv), adding 14mg of potassium borohydride into No. (iv) for reduction reaction, washing for 2 times by using ethanol/water solution with the same ratio after 2 hours, and drying to obtain Pd/sulfonated (polystyrene-graphene oxide) catalysts of (i), (ii), (iii) and No. (iv).
Example 2
Preparation of Pd/sulfonation (polystyrene-graphene) catalyst
(1): preparation of polystyrene-graphene composite
0.02g of commercially available graphene is put into a beaker, 50mL of distilled water, 4mL of styrene, 1mL of divinylbenzene, 2mL of liquid paraffin, 3mL of toluene, 0.2g of azobisisobutyronitrile and 0.3mL of triton X-100 are respectively added, and the mixture is subjected to ultrasonic treatment for 30min and then added into a 150mL three-neck flask. Stirring at 50 deg.C for 30min, heating to 60 deg.C, stirring for 30min, heating to 70 deg.C, reacting for 4h, heating to 90 deg.C, and maintaining for 1h to solidify the composite. And taking out the compound after the reaction is finished, washing and drying. The compound is put into a Soxhlet extractor and extracted for 12 hours at 95 ℃ by using 60 to 90 boiling petroleum ether, and unreacted monomers and pore-forming agent are removed. And washing and drying after extraction to obtain the polystyrene-graphene compound.
(2): sulfonation of polystyrene-graphene composites
And putting 1.5g of polystyrene-graphene compound into a three-neck flask, adding 15mL of dichloroethane, swelling at 70 ℃ for 30min, adding 2mL of concentrated sulfuric acid, reacting for 8h, filtering and washing a product, and drying in an oven to obtain the sulfonated polystyrene-graphene.
(3): palladium-carrying
Putting 1g of sulfonated (polystyrene-graphene) into a 50mL crucible, adding 5mL of palladium acetylacetonate/toluene solution with the concentration of 0.01mol/L, carrying out ultrasonic treatment for 30min to enable the sulfonated (polystyrene-graphene) to fully absorb the palladium acetylacetonate, sucking out supernatant (toluene) by using a suction pipe, drying, adding 8mL of ethanol/water solution with the volume ratio of 1:1, adding 10mg of potassium borohydride to carry out reduction reaction, and washing for 2 times by using the ethanol/water solution with the same ratio after 2h to obtain the Pd/sulfonated (polystyrene-graphene) catalyst.
Example 3
Preparation of Pd/sulfonated (polystyrene-boron nitride) catalyst
(1): preparation of boron nitride nanosheet
0.4g of boric acid and 9.3g of urea were weighed into a beaker, and 30mL of deionized water was added to the beaker. Placing the beaker into an oil bath kettle with the set temperature of 80 ℃ and continuously stirring until recrystallization is achieved, thus obtaining white particles. And (3) placing the product in a vacuum oven at 50 ℃ for drying for 12h, then placing the product in a corundum ark, placing the product in a tube furnace, introducing ammonia gas at the flow rate of 60mL/min, heating to 800 ℃ at the speed of 5 ℃/min, roasting at constant temperature for 150min, cooling to room temperature, and taking down to obtain white powder, namely the hexagonal boron nitride nanosheet.
(2): preparation of polystyrene-boron nitride composite
0.1g of the prepared boron nitride is taken out of a beaker, 50mL of distilled water, 4mL of styrene, 1mL of divinylbenzene, 2mL of liquid paraffin, 3mL of toluene, 0.2g of azobisisobutyronitrile and 0.3mL of triton X-100 are respectively added, and the mixture is added into a 150mL three-neck flask after being subjected to ultrasonic treatment for 30 min. Stirring at 50 deg.C for 30min, heating to 60 deg.C, stirring for 30min, heating to 70 deg.C, reacting for 4h, heating to 90 deg.C, and maintaining for 1h to solidify the composite. And taking out the compound after the reaction is finished, washing and drying. The compound is put into a Soxhlet extractor and extracted for 12 hours at 95 ℃ by using 60 to 90 boiling petroleum ether, and unreacted monomers and pore-forming agent are removed. And washing and drying after extraction to obtain the polystyrene-boron nitride compound.
(2): sulfonation of polystyrene-boron nitride composites
And putting 1.5g of polystyrene-boron nitride compound into a three-neck flask, adding 15mL of dichloroethane, swelling at 70 ℃ for 30min, adding 2mL of concentrated sulfuric acid, reacting for 8h, filtering and washing a product, and drying in an oven to obtain the sulfonated (polystyrene-boron nitride).
(3): palladium-carrying
Putting 1g of sulfonated (polystyrene-boron nitride) into a 50mL crucible, adding 5mL of palladium acetylacetonate/toluene solution with the concentration of 0.01mol/L, carrying out ultrasonic treatment for 30min to enable the sulfonated (polystyrene-boron nitride) to fully absorb the palladium acetylacetonate, sucking out supernatant (toluene) by using a suction pipe, drying, adding 8mL of ethanol/water solution with the volume ratio of 1:1, adding 10mg of potassium borohydride to carry out reduction reaction, and washing for 2 times by using the ethanol/water solution with the same ratio after 2h to obtain the Pd/sulfonated (polystyrene-boron nitride) catalyst.
Example 4
Application of Pd/sulfonated (polystyrene-graphene oxide) catalyst in preparation of methyl isobutyl ketone by acetone hydrogenation
10mL of quartz sand is measured by a measuring cylinder and put in 4 identical reaction tubes, 1g of the catalysts of the first, second, third and fourth in the embodiment 1 are respectively added, the reaction tubes are arranged on the device, two ends of the reaction tubes are screwed, hydrogen is introduced, after no gas leakage is detected, the hydrogen is discharged, a PPS-100 explosion-proof metering pump is opened, and acetone is injected into the reaction tubes, wherein the flow rate is 0.2 mL/min. And (3) starting heating, opening a hydrogen valve after the temperature reaches 120 ℃, mixing acetone and hydrogen in a reaction tube, and reacting, wherein the hydrogen flow is 5mL/min, and the pressure in the reaction tube is 2 MPa. The product is refluxed and condensed by ethanol in a condensing tank, a valve is arranged below the condensing tank, and the reaction product can be collected by opening the valve. The valve was opened at intervals to collect the reaction products and the product composition was analyzed by Shimadzu GC-2010 gas chromatograph, model RTX-50 for the column and FID for the detector. The results are shown in Table 1.
TABLE 1 Pd/sulfonation (polystyrene-graphene oxide) catalyst applied to preparation of methyl isobutyl ketone by acetone hydrogenation
| Catalyst and process for preparing same | Acetone conversion (%) | MIBK Selectivity (%) | MIBK yield (%) |
| ① | 35.27 | 74.88 | 26.41 |
| ② | 35.56 | 82.56 | 29.36 |
| ③ | 36.30 | 87.52 | 31.77 |
| ④ | 37.88 | 92.87 | 35.18 |
As can be seen from Table 1, the acetone conversion and MIBK selectivity increased with the increase of the amount of palladium supported on the catalyst, which indicates that the increase of the amount of palladium supported is favorable for the reaction for preparing MIBK by hydrogenating acetone.
Example 5
Pd/sulfonated (polystyrene 1 graphene oxide) catalyst stability test
A heat-resistant Pd/sulfonation (polystyrene-graphene oxide) catalyst was prepared in the same manner as in example 1, wherein in example 1, (3) 1g of the sulfonation (polystyrene-graphene oxide), 5mL of a 0.01mol/L palladium acetylacetonate/toluene solution, and 10mg of potassium borohydride were used to prepare the Pd/sulfonation (polystyrene-graphene oxide) catalyst, and the supported amount of palladium was 0.5%.
Measuring 10mL of quartz sand by using a measuring cylinder, putting the quartz sand into a reaction tube, adding 1g of catalyst into the reaction tube, installing the reaction tube on a device, screwing two ends of the reaction tube tightly, introducing hydrogen, discharging the hydrogen after checking no gas leakage, opening a PPS-100 explosion-proof metering pump, and injecting acetone into the reaction tube at the flow rate of 0.2 mL/min. And (3) starting heating, opening a hydrogen valve after the temperature reaches 150 ℃, mixing acetone and hydrogen in a reaction tube, and reacting, wherein the hydrogen flow is 5mL/min, and the pressure in the reaction tube is 2 MPa. The product is refluxed and condensed by ethanol in a condensing tank, a valve is arranged below the condensing tank, and the reaction product can be collected by opening the valve. The valve was opened at intervals to collect the reaction products and the product composition was analyzed by Shimadzu GC-2010 gas chromatograph, model RTX-50 for the column and FID for the detector. The acetone conversion, MIBK selectivity and MIBK yield during the reaction are shown in fig. 1 and table 2.
TABLE 2 Pd/sulfonated (polystyrene-graphene oxide) catalyst stability test catalytic performance table for different periods of time
Example 6
Pd/sulfonated (polystyrene-boron nitride) catalyst stability test
10mL of quartz sand is measured by a measuring cylinder and put into a reaction tube, 1g of the Pd/sulfonation (polystyrene-boron nitride) catalyst in the embodiment 3 is added into the reaction tube, the reaction tube is arranged on a device, two ends of the reaction tube are screwed tightly, hydrogen is introduced, after no air leakage is detected, the hydrogen is discharged, a PPS-100 flame-proof metering pump is opened, and acetone is injected into the reaction tube, wherein the flow rate is 0.2 mL/min. And (3) starting heating, opening a hydrogen valve after the temperature reaches 150 ℃, mixing acetone and hydrogen in a reaction tube, and reacting, wherein the hydrogen flow is 5mL/min, and the pressure in the reaction tube is 2 MPa. The product is refluxed and condensed by ethanol in a condensing tank, a valve is arranged below the condensing tank, and the reaction product can be collected by opening the valve. The valve was opened at intervals to collect the reaction products and the product composition was analyzed by Shimadzu GC-2010 gas chromatograph, model RTX-50 for the column and FID for the detector. The acetone conversion, MIBK selectivity and MIBK yield during the reaction are shown in fig. 2 and table 3.
TABLE 3 Pd/sulfonated (polystyrene-boron nitride) catalyst stability test catalytic Performance Table for different periods of time
| t(h) | Acetone conversion (%) | MIBK Selectivity (%) | MIBK yield (%) |
| 10 | 60.64 | 73.76 | 44.73 |
| 100 | 58.03 | 75.85 | 44.02 |
| 200 | 55.77 | 78.07 | 43.54 |
| 300 | 57.12 | 79.53 | 45.43 |
| 400 | 56.95 | 78.36 | 44.63 |
| 500 | 54.20 | 80.91 | 43.85 |
Comparative example 1
Preparation of Pd/sulfonated (polystyrene-graphene oxide) catalyst (graphene oxide content is 10%)
(1): preparation of polystyrene-graphene oxide composite
Adding 0.5g of commercially available graphite oxide into a beaker, adding 50mL of distilled water, performing ultrasonic treatment for 30min to obtain 10mg/mL of GO/water dispersion, respectively adding 4mL of styrene, 1mL of divinylbenzene, 2mL of liquid paraffin, 3mL of toluene, 0.2g of azodiisobutyronitrile and 0.3mL of triton X-100, and adding into a 150mL three-neck flask after performing ultrasonic treatment for 30 min. Stirring at 50 deg.C for 30min, heating to 60 deg.C, stirring for 30min, heating to 70 deg.C, reacting for 4h, heating to 90 deg.C, and maintaining for 1h to solidify the composite. And taking out the compound after the reaction is finished, washing and drying. The compound is put into a Soxhlet extractor and extracted for 12 hours at 95 ℃ by using 60 to 90 boiling petroleum ether, and unreacted monomers and pore-forming agent are removed. And washing and drying after extraction to obtain the polystyrene-graphene oxide compound.
(2): sulfonation of polystyrene-graphene oxide composites
And putting 1.5g of polystyrene-graphene oxide compound into a three-neck flask, adding 15mL of dichloroethane, swelling at 70 ℃ for 30min, adding 2mL of concentrated sulfuric acid, reacting for 8h, filtering and washing a product, and drying in an oven to obtain the sulfonated (polystyrene-graphene oxide).
(3): palladium-carrying
Putting 1g of sulfonated (polystyrene-graphene oxide) in a 50mL crucible, adding 5mL of palladium acetylacetonate/toluene solution with the concentration of 0.01mol/L, performing ultrasonic treatment for 30min to enable the sulfonated (polystyrene-graphene oxide) to fully absorb the palladium acetylacetonate, sucking out supernatant (toluene) by using a suction pipe, drying, adding 8mL of ethanol/water solution with the volume ratio of 1:1, adding 10mg of potassium borohydride for reduction reaction, washing for 2 times by using the ethanol/water solution with the same ratio after 2 hours, and drying to obtain the Pd/sulfonated (polystyrene-graphene oxide) catalyst (the content of graphene oxide is 10%).
Comparative example 2
Preparation of Pd/sulfonated polystyrene catalyst (without addition of inorganic two-dimensional material)
(1): preparation of polystyrene
50mL of distilled water, 4mL of styrene, 1mL of divinylbenzene, 2mL of liquid paraffin, 3mL of toluene, 0.2g of azobisisobutyronitrile and 0.3mL of triton X-100 are respectively put in a beaker, and added into a 150mL three-neck flask after being subjected to ultrasonic treatment for 30 min. Stirring at 50 deg.C for 30min, heating to 60 deg.C, stirring for 30min, heating to 70 deg.C, reacting for 4h, heating to 90 deg.C, and maintaining for 1h to solidify the composite. And taking out the compound after the reaction is finished, washing and drying. The compound is put into a Soxhlet extractor and extracted for 12 hours at 95 ℃ by using 60 to 90 boiling petroleum ether, and unreacted monomers and pore-forming agent are removed. And washing and drying after extraction to obtain the polystyrene.
(2): sulfonation of polystyrene
And (3) putting 1.5g of polystyrene into a three-neck flask, adding 15mL of dichloroethane, swelling at 70 ℃ for 30min, adding 2mL of concentrated sulfuric acid, reacting for 8h, filtering and washing a product, and putting the product in an oven for drying to obtain the sulfonated polystyrene.
(3): palladium-carrying
Putting 1g of sulfonated polystyrene into a 50mL crucible, adding 5mL of palladium acetylacetonate/toluene solution with the concentration of 0.01mol/L, performing ultrasonic treatment for 30min to enable the sulfonated polystyrene to fully absorb the palladium acetylacetonate, sucking out supernatant (toluene) by using a suction pipe, drying, adding 8mL of ethanol/water solution with the volume ratio of 1:1, adding 10mg of potassium borohydride for reduction reaction, washing for 2 times by using the ethanol/water solution with the same ratio after 2 hours, and drying to obtain the Pd/sulfonated polystyrene catalyst.
Comparative example 3
Compared with the example 1, the difference is that the composite carrier is not sulfonated, and the specific difference is as follows:
putting 1g of the polystyrene-graphene oxide composite obtained in the example 1 and the step (1) into a 50mL crucible, adding 5mL of palladium acetylacetonate/toluene solution with the concentration of 0.01mol/L, performing ultrasonic treatment for 30min to enable the polystyrene-graphene oxide composite to fully absorb the palladium acetylacetonate, sucking out supernatant (toluene) by using a suction pipe, adding 8mL of ethanol/water solution with the volume ratio of 1:1 into 10mg of potassium borohydride after drying, performing reduction reaction, washing for 2 times by using the ethanol/water solution with the same ratio after 2 hours, and drying to obtain the Pd/polystyrene-graphene oxide catalyst.
Comparative example 4
The physical mixed composite carrier case is as follows:
(1): preparation of physical mixture of polystyrene and graphene oxide
And 2g of the polystyrene obtained in the comparative example 2 and the comparative example 1 is taken to be put in a ball milling tank, ball milling is carried out for 30min, then 100mL of graphene oxide/dichloroethane solution with the concentration of 3mg/mL and good dispersion is added, ultrasonic dispersion is carried out for 30min, then the mixture is put in an oil bath pot, heating is carried out at 100 ℃ to ensure that dichloroethane is completely evaporated, and then the mixture is put in a vacuum oven to be dried for 12 h.
(2): sulfonation of polystyrene-graphene oxide physical mixtures
And putting 1.5g of physical polystyrene-graphene oxide mixture into a three-neck flask, adding 15mL of dichloroethane, swelling at 70 ℃ for 30min, adding 2mL of concentrated sulfuric acid, reacting for 8h, filtering and washing a product, and drying in an oven to obtain the sulfonated polystyrene-graphene oxide physical mixture.
(3): palladium-carrying
Putting 1g of sulfonated (polystyrene-graphene oxide physical mixture) into a 50mL crucible, adding 5mL of palladium acetylacetonate/toluene solution with the concentration of 0.01mol/L, performing ultrasonic treatment for 30min to enable the sulfonated (polystyrene-graphene oxide physical mixture) to fully absorb the palladium acetylacetonate, sucking out supernatant (toluene) by using a suction pipe, drying, adding 8mL of ethanol/water solution with the volume ratio of 1:1, adding 10mg of potassium borohydride to perform reduction reaction, washing for 2 times by using the ethanol/water solution with the same ratio after 2h, and drying to obtain the Pd/sulfonated (polystyrene-graphene oxide physical mixture) catalyst (physical mixing).
Comparative example 5
10mL of quartz sand is respectively measured by a measuring cylinder and placed in 8 identical reaction tubes, 1g of the catalyst obtained in the third example 1, the second example 2, the third example 3, the third example 1, the third example 2, the third example 3, the third example 1, the fourth example 2, the third example 3 and the fourth example 4 and the catalyst obtained in the third example 4 are respectively added into the reaction tubes, the reaction tubes are arranged on a device, two ends of the reaction tubes are screwed tightly, hydrogen is introduced, after no gas leakage is detected, the hydrogen is discharged, a PPS-100 explosion-proof metering pump is opened, acetone is injected into the reaction tubes, and the flow rate is 0.2 mL/min. And (3) starting heating, opening a hydrogen valve after the temperature reaches 120 ℃, mixing acetone and hydrogen in a reaction tube, and reacting, wherein the hydrogen flow is 5mL/min, and the pressure in the reaction tube is 2 MPa. The product is refluxed and condensed by ethanol in a condensing tank, a valve is arranged below the condensing tank, and the reaction product can be collected by opening the valve. The valve was opened at intervals to collect the reaction products and the product composition was analyzed by Shimadzu GC-2010 gas chromatograph, model RTX-50 for the column and FID for the detector. The reaction results are shown in Table 4.
TABLE 4 Performance of different catalysts used in preparation of methyl isobutyl ketone by acetone hydrogenation
As can be seen from table 4, the acetone conversion rates of the catalysts prepared by adding the inorganic two-dimensional materials (graphene oxide, graphene, boron nitride) to the carrier prepared by the in-situ emulsion polymerization method are 36.30% (close to 40.04% of the dow resin catalyst), 43.06%, and 43.76% (greater than 40.04% of the dow resin catalyst), respectively, which indicates that the addition of the inorganic two-dimensional materials has a partial improvement effect on the catalytic performance of the catalysts. From comparative example 1, too much inorganic two-dimensional material cannot be added, otherwise too much inorganic two-dimensional material is occupied, resulting in difficulty in sulfonation and less acidic and Pd sites. From comparative example 4, the catalyst carrier prepared by the in-situ emulsion polymerization method has more site acids and Pd sites compared with the catalyst obtained by physical mixing, so the in-situ emulsion polymerization is also the key for improving the Pd/sulfonated (polystyrene-inorganic two-dimensional material) composite catalyst.
Comparative example 6
Stability testing of the Dow resin catalyst
Measuring 10mL of quartz sand by using a measuring cylinder, putting the quartz sand into a reaction tube, adding 1g of catalyst into the reaction tube, installing the reaction tube on a device, screwing two ends of the reaction tube tightly, introducing hydrogen, discharging the hydrogen after checking no gas leakage, opening a PPS-100 explosion-proof metering pump, and injecting acetone into the reaction tube at the flow rate of 0.2 mL/min. And (3) starting heating, opening a hydrogen valve after the temperature reaches 150 ℃, mixing acetone and hydrogen in a reaction tube, and reacting, wherein the hydrogen flow is 5mL/min, and the pressure in the reaction tube is 2 MPa. The product is refluxed and condensed by ethanol in a condensing tank, a valve is arranged below the condensing tank, and the reaction product can be collected by opening the valve. The valve was opened at intervals to collect the reaction products and the product composition was analyzed by Shimadzu GC-2010 gas chromatograph, model RTX-50 for the column and FID for the detector. The acetone conversion, MIBK selectivity and MIBK yield during the reaction are shown in fig. 3 and table 5.
TABLE 5 Tao's Pd/resin stability test catalysis Performance Table for different periods of time
FIG. 3 XPS survey spectra (a), S2p spectra (b) and Pd3d spectra (c) of Pd/sulfonate (polystyrene-graphene oxide) and Dow Pd/resin catalyst.
FIGS. 3a, b, c are XPS survey, S2p survey and Pd3d survey respectively of Pd/sulfonated (polystyrene-graphene oxide) and Dow Pd/resin catalyst. The presence of S and Pd is evident from fig. 3a, which demonstrates that polystyrene-graphene oxide was successfully sulfonated and palladium was successfully supported on the catalyst. From the two graphs of fig. 3b and c, the binding energy of the peaks of the Pd/sulfonation (polystyrene-graphene oxide) catalyst S2p and Pd3d is higher than that of the Pd/resin catalyst, which indicates that the valence states of the S and Pd elements are affected by the graphene oxide, and thus the Pd/resin catalyst has higher binding force. Thus, the catalyst shows excellent stability in long-time running tests.
Comparing tables 2, 3 and 5, it can be seen that the Pd/sulfonated (polystyrene-graphene oxide) catalyst ran stably for 1000h and also maintained higher activity.
Comparing the data from the three runs for 500h, it can be seen that the Pd/sulfonated (polystyrene-boron nitride) catalyst showed the best stability with the MIBK yield decreasing from 44.73% to 43.85% (acetone conversion decreasing from 60.64% to 54.20% and MIBK selectivity increasing from 73.76% to 80.91%) with no significant change. After 500h of reaction of Pd/sulfonation (polystyrene-graphene oxide), the yield of MIBK is reduced from 39.58% to 35.21% (the conversion rate of acetone is reduced from 50.85% to 45.98%, and the selectivity of MIBK is reduced from 77.84% to 76.58%). In contrast, after 500 hours of reaction of the DOW chemical Pd/resin industrial catalyst, the MIBK yield decreased from 43.80% to 22.24% (acetone conversion decreased from 55.53% to 30.93%, MIBK selectivity decreased from 78.88% to 71.89%). As can be seen by comparison, the Pd/sulfonated (polystyrene-graphene oxide) catalyst has the activity close to that of the Dow resin catalyst, and the stability is obviously superior to that of the Dow resin catalyst. The Pd/sulfonated (polystyrene-boron nitride) catalyst shows higher activity and stability than the Dow resin catalyst, and has strong industrial application potential.
Claims (14)
1. A palladium/sulfonated (polymer-inorganic two-dimensional material) composite catalyst, which is characterized by comprising a composite carrier treated by sulfonation and metallic palladium supported on the composite carrier; the composite carrier is an in-situ composite of a polymer and an inorganic two-dimensional material; the chain segment of the polymer is provided with aromatic groups;
the composite carrier is obtained by in-situ polymerization of a mixed raw material solution containing the inorganic two-dimensional material, the monomer containing the aromatic group and the polymerization auxiliary agent; the aromatic group on the chain segment of the polymer is at least one of phenyl, chlorphenyl and nitrobenzene;
the monomer is at least one of styrene, divinylbenzene, chlorostyrene and nitrostyrene;
the polymerization auxiliary agent comprises a pore-forming agent, an emulsifier and an initiator;
wherein the pore-forming agent is at least one of toluene and liquid paraffin; the volume ratio of the monomer to the pore-forming agent is 1: 0.8-1.2;
the emulsifier is an amphoteric surfactant; the using amount of the emulsifier is 2-10% of the volume of the monomer;
the using amount of the initiator is 2-4% of the mass of the monomer;
in the composite carrier, the inorganic two-dimensional material is at least one of graphene oxide, graphene or boron nitride; wherein the mass content of the inorganic two-dimensional material is 0.4-4%;
in the composite catalyst, the loading amount of metal palladium is 0.1-1.0 wt%.
2. The palladium/sulfonate (polymer-inorganic two-dimensional material) composite catalyst according to claim 1, wherein the mass content of the inorganic two-dimensional material in the composite carrier is 1 to 3%.
3. The palladium/sulfonate (polymer-inorganic two-dimensional material) composite catalyst according to claim 1, wherein said polymer is polystyrene.
4. The palladium/sulfonate (polymer-inorganic two-dimensional material) composite catalyst according to claim 1, wherein the particle size of the metallic palladium is 1 to 10 nm;
in the composite catalyst, the loading amount of metal palladium is 0.1-0.7 wt%.
5. A method for preparing a palladium/sulfonated (polymer-inorganic two-dimensional material) composite catalyst, comprising the steps of:
step (1): mixing the raw material for synthesizing the polymer and the inorganic two-dimensional material to obtain a raw material solution, and then carrying out in-situ polymerization to prepare the composite carrier for in-situ compounding the polymer and the inorganic two-dimensional material; the raw materials for synthesizing the polymer comprise monomers and a polymerization assistant;
the monomer is at least one of styrene, divinylbenzene, chlorostyrene and nitrostyrene;
the polymerization auxiliary agent comprises a pore-forming agent, an emulsifier and an initiator;
wherein the pore-forming agent is at least one of toluene and liquid paraffin; the volume ratio of the monomer to the pore-forming agent is 1: 0.8-1.2;
the emulsifier is an amphoteric surfactant; the using amount of the emulsifier is 2-10% of the volume of the monomer;
the using amount of the initiator is 2-4% of the mass of the monomer; the polymerization reaction temperature is 70-90 ℃;
the inorganic two-dimensional material is at least one of graphene oxide, graphene or boron nitride;
in the composite carrier, the mass content of the inorganic two-dimensional material is 0.4-4%;
step (2): sulfonating the composite carrier;
and (3): and loading metal palladium on the surface of the composite carrier subjected to sulfonation treatment to prepare the composite catalyst.
6. The method for preparing a palladium/sulfonated (polymer-inorganic two-dimensional material) composite catalyst according to claim 5, wherein the emulsifier is at least one of Triton X-100, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate.
7. The method of claim 5, wherein the initiator is azobisisobutyronitrile.
8. The method for preparing a palladium/sulfonated (polymer-inorganic two-dimensional material) composite catalyst according to claim 5, wherein the sulfonating agent used in the sulfonation is concentrated sulfuric acid, fuming sulfuric acid or chlorosulfonic acid.
9. The method for preparing the palladium/sulfonated (polymer-inorganic two-dimensional material) composite catalyst according to claim 5, wherein the temperature of the sulfonation process is 70 to 90 ℃; the sulfonation treatment time is 6-12 h.
10. The method for preparing a palladium/sulfonated (polymer-inorganic two-dimensional material) composite catalyst according to claim 5, wherein in the step (3), metallic palladium is supported on the sulfonated composite carrier by an impregnation method or a precipitation method.
11. The method for preparing a palladium/sulfonated (polymer-inorganic two-dimensional material) composite catalyst according to claim 10, wherein the sulfonated composite carrier is placed in a solution of a palladium precursor, ultrasonically dispersed, dried, reduced, washed, and dried to obtain the composite catalyst.
12. The method for preparing a palladium/sulfonated (polymer-inorganic two-dimensional material) composite catalyst according to claim 11, wherein the palladium precursor is at least one of palladium acetylacetonate, chloropalladic acid, sodium chloropalladate, palladium dichlorotetraamine or palladium acetate;
the reducing agent adopted in the reduction process is potassium borohydride;
the mass ratio of the palladium precursor to the reducing agent is 1: 0.7-3.5.
13. Use of the palladium/sulfonated (polymer-inorganic two-dimensional material) composite catalyst according to any one of claims 1 to 4 or the palladium/sulfonated (polymer-inorganic two-dimensional material) composite catalyst prepared by the preparation method according to any one of claims 5 to 12 as a catalyst for preparing methyl isobutyl ketone by hydrogenating acetone.
14. A method for preparing methyl isobutyl ketone by acetone hydrogenation is characterized in that acetone and hydrogen are subjected to hydrogenation reaction under the catalysis of the palladium/sulfonated (polymer-inorganic two-dimensional material) composite catalyst according to any one of claims 1 to 4 or the palladium/sulfonated (polymer-inorganic two-dimensional material) composite catalyst prepared by the preparation method according to any one of claims 5 to 12, and methyl isobutyl ketone is synthesized in one pot.
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| CN101474577A (en) * | 2009-02-12 | 2009-07-08 | 凯瑞化工有限责任公司 | Method for preparing strong-acid Pd-carrying cation exchange fibre catalyst |
| CN105130778A (en) * | 2015-08-31 | 2015-12-09 | 宁波镇洋化工发展有限公司 | Production process of methyl isobutyl ketone |
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| CN101474577A (en) * | 2009-02-12 | 2009-07-08 | 凯瑞化工有限责任公司 | Method for preparing strong-acid Pd-carrying cation exchange fibre catalyst |
| CN105130778A (en) * | 2015-08-31 | 2015-12-09 | 宁波镇洋化工发展有限公司 | Production process of methyl isobutyl ketone |
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| Title |
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