CN112827510B - Porous composite material for catalytic synthesis of propylene carbonate and preparation method thereof - Google Patents
Porous composite material for catalytic synthesis of propylene carbonate and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000007036 catalytic synthesis reaction Methods 0.000 title claims abstract description 13
- 239000013207 UiO-66 Substances 0.000 claims abstract description 36
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002262 Schiff base Substances 0.000 claims abstract description 16
- 150000003624 transition metals Chemical class 0.000 claims abstract description 16
- 150000004753 Schiff bases Chemical class 0.000 claims abstract description 15
- 230000003197 catalytic effect Effects 0.000 claims abstract description 15
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 15
- 238000006482 condensation reaction Methods 0.000 claims abstract description 3
- 239000002243 precursor Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 16
- 238000009210 therapy by ultrasound Methods 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 13
- 238000001291 vacuum drying Methods 0.000 claims description 13
- 229910007926 ZrCl Inorganic materials 0.000 claims description 12
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000012621 metal-organic framework Substances 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 230000000536 complexating effect Effects 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 20
- 230000002194 synthesizing effect Effects 0.000 abstract description 9
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 10
- -1 Schiff base metal complex Chemical class 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 230000004913 activation Effects 0.000 description 7
- 238000006352 cycloaddition reaction Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 229960000583 acetic acid Drugs 0.000 description 6
- 239000012362 glacial acetic acid Substances 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 5
- 239000002808 molecular sieve Substances 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 239000002841 Lewis acid Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- 150000002924 oxiranes Chemical class 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
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- B01J35/615—
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- B01J35/643—
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/64—Molybdenum
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a porous composite material for catalytic synthesis of propylene carbonate and a preparation method thereof, wherein NH is added2-UiO-66 is used as a precursor to carry out ammonia-aldehyde condensation reaction with salicylaldehyde to prepare Schiff base, and the obtained Schiff base is complexed with transition metal to prepare the porous composite material with the bimetallic active site. When the propylene carbonate is catalytically synthesized, the porous composite material can show extremely excellent catalytic activity at lower catalyst input and lower temperature and pressure, greatly reduces the equipment cost and the production cost required for synthesizing the propylene carbonate, overcomes the defects of low catalytic efficiency and poor catalyst recycling in the prior art, and is beneficial to industrial popularization and application.
Description
Technical Field
The invention belongs to the field of catalyst preparation, and particularly relates to a porous composite material for catalytic synthesis of propylene carbonate and a preparation method thereof.
Background
With the arrival of the large industrial age, more and more CO is generated2Is discharged into the atmosphere to cause great harm to the environment and the climate, so how to utilize CO in a resource way2Become a research hotspot. From a chemical point of view, CO2Is an excellent C1 resource, has wide source and low price, is successfully applied to synthesizing products such as methanol, formic acid and the like at present, but has lower economic added value of the products and needs to consume a large amount of energy for reaction, which becomes CO2The biggest obstacle on the way of industrial utilization. Therefore, it is urgently needed to find a product which not only has higher economic added value, but also has reaction condition of temperatureAnd CO of2Resource utilization route.
Propylene carbonate is widely used for synthesizing fine chemicals, lithium battery electrolytes, extracting metal compounds and the like, and is also a clean solvent with high boiling point and high polarity. Through the constant search of predecessors, the discovery is made of CO2The method for synthesizing the propylene carbonate is a recycling route with great application prospect, and has the advantages of high atom utilization rate (up to 100%), simple process, environmental friendliness and the like. However, this method also has the following problems: (1) the reaction conditions are severe. Albeit CO2The reaction with propylene oxide is exothermic and of reduced volume, so that lowering the temperature and raising the pressure favours the reaction in the forward direction, whereas temperatures too low are detrimental to the CO2The catalytic efficiency is reduced due to the activation of the propylene oxide and the catalytic components, so that only higher reaction temperature and pressure can be adopted for accelerating the reaction rate, the energy consumption is increased, higher requirements are provided for a reactor, and the investment of equipment is directly increased; (2) heterogeneous catalysts have poor catalytic effect. The catalysts generally applied to the route are homogeneous catalysts, and although extremely high product yield is obtained, the problem that the catalysts and products are difficult to separate exists.
In order to solve the above problems, scientists have improved the route mainly from the catalyst, for example, chinese patent (CN 105037317 a) discloses a method for synthesizing propylene carbonate by using an ionic liquid/molecular sieve catalyst, wherein an ionic liquid is loaded on an HY molecular sieve, a La/HY molecular sieve or an HZSM-5 molecular sieve, and when the input mass of the catalyst is 0.5-5% of the input mass of propylene oxide, CO is used to make the input mass of the catalyst be 0.5-5% of the input mass of propylene oxide2The reaction is carried out for 2 h with propylene oxide at 120 ℃ and 2 MPa, and the yield of the propylene carbonate can reach 89%. The catalyst can obtain extremely excellent catalytic effect in a short reaction time, but the reaction conditions are still harsh. Chinese patent (CN 108097309B) discloses a method for synthesizing propylene carbonate by using a catalyst with active carbon as a carrier and a nitrogen-containing polymer as an active center, wherein the space velocity is 1.5 h-1Under the reaction conditions of 120 ℃ and 2 MPa, the conversion rate reaches 97 percent, and the selectivityThe catalyst can reach 99%, but the method has the conditions that the preparation steps of the catalyst are complicated, and N element is lost in the reaction, thereby providing a challenge for subsequent separation. Chinese patent (CN 108164497B) discloses a method for catalyzing CO by using quaternary ammonium salt-polyethylene glycol (PEG) low eutectic agent as catalyst and reaction medium2And performing cycloaddition reaction with propylene oxide, wherein after 1.5 mmol of catalyst is added for reaction for 5 hours at 150 ℃ and 1.2 MPa, the conversion rate of the propylene oxide can reach 99.3 percent, and the yield of the propylene carbonate can reach 99.0 percent. The method has the advantages of simple preparation method and higher yield, but the reaction temperature is overhigh, and the energy consumption is increased.
In recent years, metal-organic framework Materials (MOFs) and Schiff bases have been widely used for CO2The cycloaddition reaction of (2), however, both are superior and inferior. MOFs have larger specific surface area and more Lewis acid sites, have very positive effect on the ring opening of epoxide, are heterogeneous catalysts and are very beneficial to subsequent product separation, but the MOFs have the effect on CO2The activation capacity is relatively weak, limiting its catalytic activity in this reaction. With continuous upgrade and optimization of a Schiff base metal complex catalytic system, the method not only greatly improves the CO content of Schiff base2The catalytic activity and the reaction conditions in the cycloaddition reaction are greatly optimized, but the catalytic efficiency of the Schiff base is greatly reduced due to the limitation of the number of Lewis acid sites of the Schiff base.
In view of this, how to combine MOFs with Schiff base metal complexes to obtain highly efficient CO2The cycloaddition reaction catalyst is recycled by a simple filtering or centrifuging method, and the technical problem to be solved by the invention is solved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a novel porous composite material for catalyzing and synthesizing propylene carbonate and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a porous composite material for catalytic synthesis of propylene carbonate, which is prepared from NH2-UiO-66 as a precursor and salicylaldehyde undergo an ammonia-aldehyde condensation reaction to prepare Schiff base, and the obtained Schiff base is complexed with a transition metal to prepare Salen (M) @ UiO-66 (wherein M = Fe, Co, Ni, Cu, Zn, Al and Mo).
The preparation method of the porous composite material comprises the following steps:
(1) metal-organic framework material NH2-synthesis of UiO-66: measuring a certain amount of N, N-Dimethylformamide (DMF) as a solvent, adding ZrCl into the solvent4Stirring until it is completely dissolved, adding a certain amount of 2-amino terephthalic acid (NH)2-BDC), sonicating until the solution is completely clear, and adding a certain amount of CH to the clear solution obtained3COOH, stirring and mixing uniformly, transferring the obtained solution into a hydrothermal kettle for high-temperature treatment, and after the reaction is finished, centrifuging, washing and vacuum activating to obtain NH2-UiO-66；
(2) Complexing with a transition metal: measuring a certain amount of absolute ethyl alcohol as a dispersing agent, and adding the NH prepared in the step (1) into the absolute ethyl alcohol2And (3) carrying out ultrasonic treatment on the-UiO-66 and a certain amount of transition metal complex to obtain turbid liquid without obvious solids, then quickly adding a certain amount of salicylaldehyde into the turbid liquid, refluxing the obtained mixed liquid for a period of time at a certain temperature, and then carrying out centrifugation, washing and vacuum drying to obtain Salen (M) @ UiO-66 loaded with transition metal.
Preferably, ZrCl used in step (1)4The molar ratio of the 2-amino terephthalic acid to the 2-amino terephthalic acid is (0.5-2): 1.
Preferably, ZrCl used in step (1)4And CH3The molar ratio of COOH was (0.001-0.1): 1.
Preferably, the temperature of the high-temperature treatment in the step (1) is 100-150 ℃, and the time is 12-24 h.
Preferably, NH is added in step (2)2The ratio of the mass of the-UiO-66 to the volume of the absolute ethanol is 1 (200-700) g/mL.
Preferably, step (2)) Transition metal complex and NH used in (1)2The molar ratio of the (E) -UiO-66 is 1 (0.5-2). The transition metal complex is one or more of iron acetate, cobalt acetate, nickel acetate, copper acetate, zinc acetate, aluminum acetate and molybdenum acetylacetonate.
Preferably, NH used in step (2)2The molar ratio of the-UiO-66 to the salicylaldehyde is (0.5-1): 1.
Preferably, the reflux temperature in step (2) is 60-80 ℃ and the time is 8-20 h.
The synthesized Salen (M) @ UiO-66 porous composite material has bimetallic active sites, can greatly improve the catalytic activity thereof, and can be used for catalytically synthesizing propylene carbonate. The temperature of the catalytic synthesis is 80 ℃, the time is 6h, and the dosage of the catalyst is 1.7 percent of the input mass of the propylene oxide.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the preparation method of the porous composite material is simple, and the composite material contains the Schiff base structure and can be complexed with transition metal atoms, so that bimetallic concerted catalysis of Zr and transition metal can be formed in the composite material, and the preparation method can greatly improve the application of the porous composite material in CO2Catalytic activity in cycloaddition reactions.
(2) The MOFs is innovatively used as a monomer for synthesizing the Schiff base, so that compared with the conventional MOFs, the synthesized porous composite material has more acidic sites in a unit catalyst, the capability of the material for epoxide ring opening is improved, and the input amount of the catalyst for catalyzing a unit reactant is reduced. Compared with the traditional Schiff base metal complex, the obtained porous composite material has larger specific surface area and increased active contact area. Especially when the transition metal is Mo, the resulting porous composite is directed to CO2The catalytic effect of the cycloaddition reaction is outstanding, and the reaction is convenient to recover.
Drawings
FIG. 1 is NH2-XRD contrast of UiO-66 with the composites obtained in examples 1 to 4;
FIG. 2 is a comparison graph of infrared spectra of the composite materials obtained in examples 1 to 4;
FIG. 3 is an XPS N1 s spectrum of the composite obtained in example 2;
FIG. 4 is a scanning electron micrograph of the composite obtained in example 2;
FIG. 5 shows N in the composite obtained in example 22Adsorption-desorption curves;
FIG. 6 is a graph showing the pore size distribution of the composite material obtained in example 2.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
EXAMPLE 1 preparation of Salen (Ni) @ UiO-66 porous composite
(1) 20.42 mL of DMF was weighed into a 50 mL beaker, and 46.7 mg (0.2 mmol) of ZrCl was added4And 36.3 mg (0.2 mmol) of 2-amino terephthalic acid, performing ultrasonic treatment to obtain a completely clear solution, adding 4.58 mL (0.08 mol) of glacial acetic acid into the clear solution, stirring for 10 minutes, transferring the solution into a 50 mL stainless steel reaction kettle with a polytetrafluoroethylene lining, crystallizing at 120 ℃ for 12 hours, centrifugally washing the obtained product, performing vacuum drying at 80 ℃ for 24 hours to obtain light yellow powder, and performing vacuum drying on the obtained light yellow powder at 150 DEG CActivating for 2 h in vacuum at the temperature of DEG C to finally obtain NH2-UiO-66；
(2) A50 mL round-bottom flask was charged with 100 mg (0.16 mmol) of NH obtained in step (1)2-UiO-66 and 49.6 mg (0.20 mmol) of nickel acetate, adding 35 mL of absolute ethyl alcohol as a dispersing agent, carrying out ultrasonic treatment until the solid is completely dispersed, quickly adding 2.85 mL (0.28 mmol) of salicylaldehyde into the mixture, carrying out reflux reaction on the obtained turbid liquid at 80 ℃ for 10 h, carrying out centrifugal washing separation, and carrying out vacuum drying at 80 ℃ for 24 h to obtain Salen (Ni) @ UiO-66.
Example 2 preparation of Salen (Mo) @ UiO-66 porous composite Material
(1) 40.84 mL of DMF was weighed into a 50 mL beaker, and 93.4 mg (0.4 mmol) of ZrCl was added4And 72.6 mg (0.2 mmol) of 2-amino-p-benzenePerforming ultrasonic treatment on dicarboxylic acid until the dicarboxylic acid is completely clarified, adding 9.16 mL (0.16 mol) of glacial acetic acid into the clarified solution, stirring for 10 minutes, transferring the mixture to a 50 mL stainless steel reaction kettle with a polytetrafluoroethylene lining, crystallizing at 140 ℃ for 24 hours, performing centrifugal washing on the obtained product, performing vacuum drying at 80 ℃ for 24 hours to obtain light yellow powder, performing vacuum activation at 150 ℃ for 2 hours to obtain NH (NH) finally2-UiO-66；
(2) A50 mL round-bottom flask was charged with 100 mg (0.16 mmol) of NH obtained in step (1)2-UiO-66 and 65.2 mg (0.20 mmol) of molybdenum acetylacetonate, 35 mL of absolute ethyl alcohol as a dispersing agent is added, after ultrasonic treatment is carried out until the solid is completely dispersed, 2.85 mL (0.28 mmol) of salicylaldehyde is rapidly added into the mixture, the obtained turbid liquid is refluxed and reacted for 10 hours at the temperature of 80 ℃, and after centrifugal washing and separation, the obtained turbid liquid is dried for 24 hours under vacuum at the temperature of 80 ℃ to obtain Salen (Mo) @ UiO-66.
EXAMPLE 3 preparation of Salen (Co) @ UiO-66 porous composite
(1) 30.63 mL of DMF was weighed into a 50 mL beaker, and 46.7 mg (0.2 mmol) of ZrCl was added first4And 45.875 mg (0.25 mmol) of 2-amino terephthalic acid, performing ultrasonic treatment to obtain a completely clear solution, adding 6.87 mL (0.12 mol) of glacial acetic acid into the clear solution, stirring for 10 minutes, transferring the solution into a 50 mL stainless steel reaction kettle with a polytetrafluoroethylene lining, crystallizing at 130 ℃ for 12 hours, centrifugally washing the obtained product, performing vacuum drying at 80 ℃ for 24 hours to obtain light yellow powder, and performing vacuum activation at 150 ℃ for 2 hours to obtain NH (NH)2-UiO-66；
(2) A50 mL round-bottom flask was charged with 100 mg (0.16 mmol) of NH obtained in step (1)2-UiO-66 and 35.4 mg (0.20 mmol) of cobalt acetate, adding 35 mL of absolute ethyl alcohol as a dispersing agent, carrying out ultrasonic treatment until the solid is completely dispersed, quickly adding 2.85 mL (0.28 mmol) of salicylaldehyde into the mixture, carrying out reflux reaction on the obtained turbid liquid at 80 ℃ for 10 h, carrying out centrifugal washing separation, and carrying out vacuum drying at 80 ℃ for 24 h to obtain Salen (Co) @ UiO-66.
EXAMPLE 4 preparation of Salen (Zn) @ UiO-666 porous composite
(1) 20.42 mL of DMF was weighed into a 50 mL beaker, and 46.7 mg (0.2 mmol) of ZrCl was added4And 36.3 mg (0.2 mmol) of 2-amino terephthalic acid, performing ultrasonic treatment to obtain a completely clarified solution, adding 4.58 mL (0.08 mol) of glacial acetic acid into the clarified solution, stirring for 10 minutes, transferring the solution into a 50 mL stainless steel reaction kettle with a polytetrafluoroethylene lining, crystallizing at 120 ℃ for 12 hours, centrifugally washing the obtained product, performing vacuum drying at 80 ℃ for 24 hours to obtain light yellow powder, and performing vacuum activation at 150 ℃ for 2 hours to obtain NH (NH)2-UiO-66；
(2) A50 mL round-bottom flask was charged with 100 mg (0.16 mmol) of NH obtained in step (1)2-UiO-66 and 36.6 mg (0.20 mmol) of zinc acetate, adding 35 mL of absolute ethyl alcohol as a dispersing agent, carrying out ultrasonic treatment until the solid is completely dispersed, quickly adding 2.85 mL (0.28 mmol) of salicylaldehyde into the mixture, carrying out reflux reaction on the obtained turbid liquid at 80 ℃ for 10 h, carrying out centrifugal washing separation, and carrying out vacuum drying at 80 ℃ for 24 h to obtain Salen (Zn) @ UiO-66.
EXAMPLE 5 preparation of Salen (Mo) @ UiO-66 (40% Mo) porous composite
(1) 20.42 mL of DMF was weighed into a 50 mL beaker, and 46.7 mg (0.2 mmol) of ZrCl was added4And 36.3 mg (0.2 mmol) of 2-amino terephthalic acid, performing ultrasonic treatment to obtain a completely clarified solution, adding 4.58 mL of glacial acetic acid (0.08 mol) into the clarified solution, stirring for 10 minutes, transferring the solution into a 50 mL stainless steel reaction kettle with a polytetrafluoroethylene lining, crystallizing at 120 ℃ for 12 hours, centrifugally washing the obtained product, performing vacuum drying at 80 ℃ for 24 hours to obtain light yellow powder, and performing vacuum activation at 150 ℃ for 2 hours to obtain NH (NH)2-UiO-66；
(2) A50 mL round-bottom flask was charged with 100 mg (0.16 mmol) of NH obtained in step (1)2-UiO-66 and 52.16 mg (0.16 mmol) of molybdenum acetylacetonate, 35 mL of absolute ethyl alcohol as a dispersing agent is added, after ultrasonic treatment is carried out until the solid is completely dispersed, 2.28 mL (0.22 mmol) of salicylaldehyde is rapidly added into the mixture, the obtained turbid liquid is refluxed and reacted for 8 hours at the temperature of 80 ℃, and after centrifugal washing and separation, the vacuum drying is carried out for 24 hours at the temperature of 80 ℃ to obtain Salen(Mo)@UiO-66（40% Mo）。
EXAMPLE 6 preparation of Salen (Mo) @ UiO-66 (60% Mo) porous composite
(1) 20.42 mL of DMF was weighed into a 50 mL beaker, and 46.7 mg (0.2 mmol) of ZrCl was added4And 36.3 mg (0.2 mmol) of 2-amino terephthalic acid, performing ultrasonic treatment to obtain a completely clarified solution, adding 4.58 mL (0.08 mol) of glacial acetic acid into the clarified solution, stirring for 10 minutes, transferring the solution into a 50 mL stainless steel reaction kettle with a polytetrafluoroethylene lining, crystallizing at 120 ℃ for 12 hours, centrifugally washing the obtained product, performing vacuum drying at 80 ℃ for 24 hours to obtain light yellow powder, and performing vacuum activation at 150 ℃ for 2 hours to obtain NH (NH)2-UiO-66；
(2) A50 mL round-bottom flask was charged with 100 mg (0.16 mmol) of NH obtained in step (1)2-UiO-66 and 97.8 mg (0.30 mmol) of molybdenum acetylacetonate, 35 mL of absolute ethyl alcohol as a dispersant are added, after ultrasonic treatment is carried out until the solid is completely dispersed, 4.28 mL (0.41 mmol) of salicylaldehyde is rapidly added into the mixture, the obtained turbid liquid is refluxed and reacted for 20 h at 80 ℃, and after centrifugal washing and separation, the obtained turbid liquid is dried for 24 h at 80 ℃ in vacuum, thus obtaining Salen (Mo) @ UiO-66 (60% Mo).
FIG. 1 is NH2-UiO-66 and XRD contrast of the composite material obtained in examples 1-4. As can be seen from the figure, the resulting composite material and NH as provided in the literature2The characteristic peaks of the-UiO-66 XRD are kept consistent, which shows that the synthesized composite material basically keeps NH2-structure of UiO-66.
FIG. 2 is a comparison graph of infrared spectra of the composite materials obtained in examples 1 to 4. Normally, the Schiff base is at 1650 cm-1Characteristic absorption peak of H-C = N appears at (C), but due to NH2The deprotonation of Zr ion in-UiO-66 by coordination with-COOH was at 1500-1700 cm-1An absorption peak was formed.
FIG. 3 is an XPS N1 s spectrum of the composite material obtained in example 2. The characteristic peak at 399.8 eV in the figure is formed by a group of-C = N-, so that the Schiff base structure in the synthesized composite material can be accurately proved, and the Schiff base/NH is successfully synthesized2-UiO-66 porous composite.
FIG. 4 is a scanning electron micrograph of the composite obtained in example 2. The resulting composite with NH is evident from the figure2the-UiO-66 also has a regular octahedral structure, which is also consistent with XRD results.
FIGS. 5 and 6 are respectively N values of the composite material obtained in example 22Adsorption-desorption curve and its aperture distribution diagram. As can be seen from FIG. 5, N of the resulting composite material2The adsorption-desorption curve is a typical I isotherm, which indicates that the synthesized Salen (Mo) @ UiO-66 is a microporous material and the BET specific surface area is 514.5 m2.g-1. As can be seen from FIG. 6, the pore size distribution of the resulting composite material is concentrated around 0.5 nm and 1.3nm, and the pore size distribution is relatively uniform.
2Cycloaddition reaction with propylene oxide:
50 mg of Salen (M) @ UiO-66 (catalyst) obtained in examples 1 to 6 and 0.693 g of tetrabutylammonium bromide (cocatalyst) were added to a 50 mL autoclave, 3 g of propylene oxide was added thereto, the mixture was vigorously stirred, and 1.2 MPa of CO was introduced thereinto2Reaction at 80 ℃ for 6h and using the NH obtained in example 22-UiO-66 (catalyst) for comparison; the resulting product was analyzed by GC-2014c gas chromatography (column: DB-1 capillary column, detector: hydrogen flame ion detector). Table 1 shows the results of measuring the specific surface area, pore size and catalytic performance of the composite materials obtained in examples 1 to 6.
TABLE 1
NH by comparison in Table 12The comparison of-UiO-66 shows that the complex is further complexed with transition metal, although the specific surface area of the obtained composite material is reduced, the pore change is not large, and the catalytic performance is obviously improved, which proves that the synergistic effect of bimetal exists.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (8)
1. A preparation method of a porous composite material for catalytic synthesis of propylene carbonate is characterized by comprising the following steps: by NH2-UiO-66 is taken as a precursor to carry out ammonia-aldehyde condensation reaction with salicylaldehyde to prepare Schiff base, and the obtained Schiff base is complexed with transition metal to prepare the porous composite material;
the method comprises the following steps:
(1) metal-organic framework material NH2-synthesis of UiO-66: measuring a certain amount of N, N-dimethylformamide as a solvent, and adding ZrCl into the solvent4Stirring until it is completely dissolved, adding a certain amount of 2-amino terephthalic acid, performing ultrasonic treatment until the solution is completely clarified, and adding a certain amount of CH into the clarified solution3COOH, stirring and mixing uniformly, transferring the obtained solution into a hydrothermal kettle for high-temperature treatment, and after the reaction is finished, centrifuging, washing and vacuum activating to obtain NH2-UiO-66；
(2) Complexing with a transition metal: measuring a certain amount of absolute ethyl alcohol as a dispersing agent, and adding the NH prepared in the step (1) into the absolute ethyl alcohol2-UiO-66 and a certain amount of transition metal complex, performing ultrasonic treatment to obtain turbid liquid without obvious solids, then quickly adding a certain amount of salicylaldehyde into the turbid liquid, refluxing the obtained mixed liquid at a certain temperature for a period of time, and performing centrifugation, washing and vacuum drying to obtain the porous composite material;
the transition metal complex is molybdenum acetylacetonate.
2. The process for the preparation of the porous composite material for the catalytic synthesis of propylene carbonate according to claim 1, characterized in that: ZrCl used in the step (1)4The molar ratio of the 2-amino terephthalic acid to the 2-amino terephthalic acid is (0.5-2): 1.
3. The method of claim 1 for catalytic synthesisThe preparation method of the porous composite material of propylene carbonate is characterized by comprising the following steps: ZrCl used in the step (1)4And CH3The molar ratio of COOH was (0.001-0.1): 1.
4. The process for the preparation of the porous composite material for the catalytic synthesis of propylene carbonate according to claim 1, characterized in that: the temperature of the high-temperature treatment in the step (1) is 100-150 ℃, and the time is 12-24 h.
5. The process for the preparation of a porous composite material for the catalytic synthesis of propylene carbonate according to claim 1, characterized in that NH is added in step (2)2The ratio of the mass of the-UiO-66 to the volume of the absolute ethanol is 1 (200-700) g/mL.
6. The process for the preparation of the porous composite material for the catalytic synthesis of propylene carbonate according to claim 1, characterized in that: the transition metal complex used in the step (2) and NH2The molar ratio of the (E) -UiO-66 is 1 (0.5-2).
7. The process for the preparation of the porous composite material for the catalytic synthesis of propylene carbonate according to claim 1, characterized in that: NH used in step (2)2The molar ratio of the-UiO-66 to the salicylaldehyde is (0.5-1): 1.
8. The process for the preparation of the porous composite material for the catalytic synthesis of propylene carbonate according to claim 1, characterized in that: the reflux temperature in the step (2) is 60-80 ℃, and the time is 8-20 h.
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