CN110760060A - Composite metal oxide solid base catalyst, preparation method and application - Google Patents
Composite metal oxide solid base catalyst, preparation method and application Download PDFInfo
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- CN110760060A CN110760060A CN201910972126.8A CN201910972126A CN110760060A CN 110760060 A CN110760060 A CN 110760060A CN 201910972126 A CN201910972126 A CN 201910972126A CN 110760060 A CN110760060 A CN 110760060A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 83
- 239000007787 solid Substances 0.000 title claims abstract description 49
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 19
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 24
- 239000001301 oxygen Substances 0.000 claims abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000006104 solid solution Substances 0.000 claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 11
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims abstract description 5
- 239000004480 active ingredient Substances 0.000 claims abstract description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 38
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
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- 238000006243 chemical reaction Methods 0.000 claims description 14
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- 238000003786 synthesis reaction Methods 0.000 claims description 10
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 8
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- 238000005303 weighing Methods 0.000 claims description 7
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- 238000002791 soaking Methods 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 229910003130 ZrOCl2·8H2O Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 11
- -1 softener Substances 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 229910004625 Ce—Zr Inorganic materials 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 229910006213 ZrOCl2 Inorganic materials 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
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- 238000011069 regeneration method Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000002924 oxiranes Chemical class 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KOPBYBDAPCDYFK-UHFFFAOYSA-N Cs2O Inorganic materials [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001450 anions Chemical group 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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- 238000000354 decomposition reaction Methods 0.000 description 1
- AKUNKIJLSDQFLS-UHFFFAOYSA-M dicesium;hydroxide Chemical compound [OH-].[Cs+].[Cs+] AKUNKIJLSDQFLS-UHFFFAOYSA-M 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003974 emollient agent Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
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- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
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- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229910001953 rubidium(I) oxide Inorganic materials 0.000 description 1
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- 238000001179 sorption measurement Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
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- 239000002351 wastewater Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/269—Mixed catalyst systems, i.e. containing more than one reactive component or catalysts formed in-situ
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a composite metal oxide solid base catalyst, a preparation method and application thereof, wherein the solid base catalyst comprises t-ZrO serving as a carrier2And an active ingredient; the active component being present in ZrO2Alkali metal oxide K capable of providing Bronsted basic sites in octahedral vacancies2O and with ZrO2Composite solid solution Ce capable of providing oxygen vacancies2Zr2O7.04And (4) forming. The invention is in ZrO2Middle doped CeO2Can be reacted with ZrO2Forming solid solution and causing the formation of oxygen vacancy, thereby leading the solid solution to have excellent oxygen storage/release capacity, further forming O2-/O-/O2-on the surface of the catalyst to increase alkaline sites, enhance alkalinity and improve catalytic activity.
Description
Technical Field
The invention relates to a catalyst for synthesizing polypropylene glycol, in particular to a composite metal oxide solid base catalyst, a preparation method and application thereof.
Background
Polypropylene Glycol (PPG) is a colorless to yellowish viscous liquid, non-volatile, non-corrosive. The polypropylene glycol is mainly prepared by reacting glycerol as an initiator with epoxide (ethylene oxide or propylene oxide), and products with different molecular weights are produced by changing the conditions such as the feeding ratio of the initiator to the epoxide and the like. The polypropylene glycol has wide application and is an important raw material for synthesizing polyurethane; polypropylene glycol is used as emollient, softener, lubricant in cosmetics; in the industries of spices, resins, rubber, latex and the like, polypropylene glycol is used as a lubricant, an antistatic agent, a plasticizer, an antifoaming agent and a defoaming agent, and also can be used as a mold release agent and a solubilizer; it can also be used as intermediate for esterification, etherification and polycondensation reaction. At present, the preparation method of polypropylene glycol mainly adopts anion ring-opening polymerization, that is, alcohols are used as an initiator, H on an alcoholic hydroxyl group is stripped under the action of KOH, and a formed negative oxygen ion attacks a C-O bond in propylene oxide to generate ring opening, so that chain growth is generated to generate polypropylene glycol, and the specific reaction mechanism is shown in equations 1-5. The KOH used in the synthesis method has low cost and easily obtained raw materials, so the synthesis method is widely applied to the traditional industrial production. However, KOH is easy to corrode the device in the production process, the catalyst and the product are not easy to separate after the reaction is finished, and salt and alkaline wastewater generated by post-treatment are easy to cause serious pollution to the environment.
(1) Generation of negative oxygen ions:
R-OH+K+OH-→R-O-K++H2O (1)
(2) chain initiation process:
disclosure of Invention
The purpose of the invention is as follows: the invention provides a composite metal oxide solid base catalyst, which has a plurality of basic sites, strong alkalinity and can be repeatedly used. The second aspect of the invention provides a preparation method of the composite metal oxide solid base catalyst. In a third aspect, the invention provides the use of a solid base catalyst in the synthesis of polypropylene glycol. In a fourth aspect, the invention provides a method for synthesizing polypropylene glycol using a solid base catalyst.
The technical scheme is as follows: the invention provides a composite metal oxide solid base catalyst in a first aspect, wherein the catalyst is K2O/CeO2@ZrO2(KCZ) comprising a tetragonal phase of ZrO as a carrier2(t-ZrO2) And an active ingredient present in ZrO2Alkali metal oxide K capable of providing Bronsted basic sites in octahedral vacancies2O and with ZrO2Composite solid solution Ce capable of providing oxygen vacancies2Zr2O7.04And (4) forming.
Ce2Zr2O7.04Has a structure of Zr4+Into CeO2The unit cell of (a) forms a Ce-Zr oxide solid solution, Ce-Zr oxide solid solution2Zr2O7.04The excellent oxygen storage/release capacity is obtained by that crystal lattice defects caused by the difference of unit cell sizes can generate oxygen vacancies and further form O on the surface of the catalyst2-/O-/O2 -Further increasing the alkaline sites and enhancing the alkalinity.
Solid solution Ce2Zr2O7.04Is at ZrO2In which CeO is doped2Form and utilizeRadius less than Ce4+ Thus Zr4+Can enter CeO2The crystal cell of (a) generates an oxide solid solution of Ce-Zr, and accordingly, the crystal lattice defect can generate oxygen vacancy, thereby providing the Ce-Zr oxide solid solution with excellent oxygen storage/release capacity when used as a solid carrier of a catalyst.
Preferably, said K2The mass percentage of O in the solid base catalyst is 5%10% (wt.%) of Ce and Zr in a molar ratio of 0.04-0.06: 1, based on the molar number of the metal element, wherein the molar ratio of the element is determined by the raw material Ce (NO)3)3·6H2O,ZrOCl2·8H2The molar ratio of the corresponding elements in O.
The solid base catalyst is prepared by the following method:
weighing ZrOCl according to quantity2·8H2O and Ce (NO)3)3·6H2Dissolving O in water to prepare a mixed solution, adjusting the pH value to 10-11 to allow the mixed solution to react fully, and performing ultrasonic treatment, aging, drying and cleaning to obtain a precursor; preferably, the molar ratio of Ce to Zr is 0.04-0.06: 1 based on the mole number of the metal elements.
Putting the precursor in KNO at the temperature of 60-85 DEG C3Dipping in the solution, filtering, drying and roasting to obtain the solid base catalyst. Preferably, said KNO3The dipping concentration is 0.4-0.6 mol/L; the roasting temperature is 650-750 ℃, and the roasting time is 5-7 h.
The invention utilizes the characteristic that hydroxyl generated by water adsorbed on the surface of alkali metal oxide and negatively charged lattice oxygen can accept protons to generate Bronsted basic sites, thereby being used for catalyzing the synthesis of polypropylene glycol. Since the alkali strength of alkali metal oxides increases with increasing atomic number, the order is Na2O<K2O<Rb2O<Cs2O, where Rb and Cs are radioactive metal elements, and in industrial applications for the preparation of K2The raw material of O is easy to obtain, so that the invention adopts K with stronger alkalinity2And O is taken as one of the active components to prepare the polypropylene glycol. K2O is mainly obtained by roasting potassium salt (e.g. KNO)3) Preparation, but direct calcination of KNO3Is relatively high, so that it can be loaded on ZrO2In which K is+Can enter ZrO2Of octahedral vacancy defects, thereby weakening K+With NO3 -By binding of KNO3Can be decomposed at a lower temperature to form K2O。
The Bronsted basic sites of the KCZ solid base catalyst can deprive protons on-OH in glycerol, and the formed negative oxygen ions attack C-O bonds in propylene oxide to open rings, so that chain growth is carried out to generate polypropylene glycol. The solid base catalyst has the advantages of multiple basic sites, strong alkalinity, repeated use and the like.
The second aspect of the present invention provides a preparation method of the above composite metal oxide solid base catalyst, comprising the following steps:
(1) weighing ZrOCl2·8H2O and Ce (NO)3)3·6H2Preparing a mixed solution, adjusting the pH value to 10-11 at the temperature of 25-30 ℃ to fully react, and performing ultrasonic treatment, aging, drying and cleaning to obtain a precursor;
(2) placing the precursor in KNO3Dipping in the solution, filtering, drying and roasting to obtain the solid base catalyst.
Preferably, in the step (1), the molar ratio of Ce to Zr is 0.04-0.06: 1 based on the mol of the metal element.
Preferably, in the step (2), the KNO3The concentration of the solution is 0.4-0.6 mol/L.
Preferably, in the step (2), the precursor is placed in KNO under the water bath condition of 60-85 DEG C3And soaking in the solution for 8-13 h.
Preferably, in the step (2), the roasting temperature is 650-750 ℃, and the roasting time is 5-7 h.
The preparation method of the composite metal oxide solid base catalyst comprises the following steps:
the method for preparing the composite metal oxide solid base catalyst can be selected from the following specific operation modes:
first, CeO was prepared2-ZrO2Precursor of the carrier: ZrOCl is weighed according to the molar ratio of n (Ce) to n (Zr) of 0.04-0.06: 1 based on the mol of the metal elements2·8H2O and Ce (NO)3)3·6H2O, preparing a mixed solution in water, transferring the mixed solution into a three-neck flask, continuously stirring and slowly dropwise adding ammonia water under the condition of a water bath at 25-30 DEG CAdjusting the pH value to 10-11, continuously stirring for 7-9 h to fully react, performing ultrasonic treatment, aging, suction filtration and drying, and washing Cl with distilled water-And preparing a precursor.
Secondly, the precursor is placed in a water bath at the temperature of 60-85 ℃ under the condition of 0.4-0.6 mol/L KNO3Soaking the solution for 8-13 h, filtering, drying, and roasting at 650-750 ℃ for 5-7 h to obtain the solid base catalyst KCZ.
The third aspect of the invention provides the application of the solid base catalyst or the solid base catalyst obtained by the preparation method in the synthesis of polypropylene glycol.
The fourth aspect of the invention provides a preparation method of polypropylene glycol, which comprises the following steps: placing reactants of glycerol, propylene oxide and a solid base catalyst into a high-pressure reaction kettle, introducing enough nitrogen to replace air in the kettle before reaction, and carrying out reaction polymerization for 5-7 h under the conditions of initial pressure of 1.5-2.5 MPa, temperature of 170-190 ℃ and rotation speed of 300-400 r/min; the mass ratio of the glycerol to the propylene oxide is 0.075-0.125: 1, and the mass ratio of the solid base catalyst to the propylene oxide is 0.05-0.07: 1.
And after the reaction is finished, separating the product and the catalyst by suction filtration, and removing water in the product by rotary evaporation for 2-4 h under the conditions of 80-110 ℃ and-1.0 MPa.
Has the advantages that: (1) doped CeO of the invention2Can be reacted with ZrO2Form a solid solution and cause the formation of oxygen vacancies, thereby enabling CeO2@ZrO2The solid solution has excellent oxygen storage/release capacity, and further forms O on the surface of the catalyst2-/O-/O2 -The alkaline sites are increased, the alkalinity is enhanced, and the catalytic activity is further improved; (2) the invention utilizes the K which is easy to be prepared in industry2O is used as one of the alkaline components as a catalyst of polypropylene glycol; (3) the invention will prepare K2Starting materials for O, e.g. KNO3Loaded on ZrO2Upper, lower KNO3Decomposition temperature of (b) is favorable for the basic component K2Preparing O; (4) compared with the traditional homogeneous catalyst, the solid base catalyst has small corrosion to equipment, is easy to separate from the product, can be repeatedly used,acid neutralization treatment is not needed, and the pollution degree to the environment is reduced.
Drawings
FIG. 1 is a graph comparing catalytic performances of KCZ, KZ and Z catalysts;
FIG. 2 is a graph showing FT-IR comparison of polypropylene glycol standards and polypropylene glycol products obtained by experiments;
FIG. 3 is CO of KCZ, KZ and Z catalysts2-a TPD profile;
FIG. 4 is an XRD representation of three catalysts, KCZ, KZ and Z;
FIG. 5 is an HR-TEM image of KCZ, KZ and Z catalysts at a magnification of 8 ten thousand;
FIG. 6 is a graph of the number of regenerations of a KCZ catalyst.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following drawings and examples.
First, sample preparation
Example 1: solid base catalyst K2O/CeO2@ZrO2Preparation of (KCZ)
(1) The composite metal oxide solid base catalyst K2O/CeO2@ZrO2The preparation steps of (KCZ) are as follows:
a. weighing 12g of ZrOCl according to the molar ratio of n (Ce) to n (Zr) of 0.05:12·8H2O and 0.8gCe (NO)3)3·6H2And O, preparing a mixed solution in 100ml of water, transferring the mixed solution into a three-neck flask, continuously stirring and slowly dropwise adding ammonia water under the condition of a water bath at the temperature of 30 ℃, adjusting the pH value to 11, and continuously stirring for 8 hours to fully react. Ultrasonically treating, aging, vacuum filtering, drying, and washing Cl with distilled water-To prepare a precursor;
b. placing the prepared carrier precursor in KNO of 0.5mol/L under the condition of water bath at 75 DEG C3Soaking in the solution for 12h, filtering, drying, calcining at 700 deg.C for 6h to obtain solid base catalyst KCZ, and measuring K by ICP-AES2The loading of O was 5% (wt.%).
Comparative example 1: catalyst ZrO2(Z) preparation
Weighing 12g ZrOCl2·8H2Dissolving O in 100ml of water to prepare a mixed solution, transferring the mixed solution into a three-neck flask, continuously stirring and slowly dropwise adding ammonia water under the condition of a water bath at the temperature of 30 ℃, adjusting the pH value to 11, and continuously stirring for 8 hours to fully react. Ultrasonically treating, aging, vacuum filtering, drying, and washing Cl with distilled water-To prepare a precursor;
soaking the prepared carrier precursor in pure water at 75 deg.C for 12h, filtering, drying, and calcining at 700 deg.C for 6h to obtain solid base catalyst ZrO2(Z)。
Comparative example 2: catalyst K2O/ZrO2Preparation of (KZ)
Weighing 12g ZrOCl2·8H2Dissolving O in 100ml of water to prepare a mixed solution, transferring the mixed solution into a three-neck flask, continuously stirring and slowly dropwise adding ammonia water under the condition of a water bath at the temperature of 30 ℃, adjusting the pH value to 11, and continuously stirring for 8 hours to fully react. Ultrasonically treating, aging, vacuum filtering, drying, and washing Cl with distilled water-To prepare a precursor;
placing the prepared carrier precursor in KNO of 0.5mol/L under the condition of water bath at 75 DEG C3Soaking in the solution for 12h, filtering, drying, and roasting at 700 deg.C for 6h to obtain solid base catalyst K2O/ZrO2(KZ)。
Example 2: polypropylene glycol Synthesis
Putting reactants of glycerol, propylene oxide and a catalyst into a high-pressure reaction kettle, introducing enough nitrogen to replace air in the kettle before reaction, and carrying out reaction polymerization for 6 hours under the conditions of initial pressure of 2MPa, temperature of 180 ℃ and rotation speed of 350r/min, wherein the mass ratio of raw materials m (glycerol) to m (propylene oxide) is 0.1: the synthesis of polypropylene glycol was catalyzed by the catalysts prepared in example 1 and comparative examples 1 to 2, respectively, using m (catalyst): m (propylene oxide): 0.06: 1.
And (3) filtering: and taking out the reacted product from the kettle, and performing suction filtration and separation. Firstly, filtering by adopting double-layer medium-speed qualitative filter paper, wherein the aperture of the filter paper is 30-50 mu m; and in the second step, double layers of slow qualitative filter paper are adopted to further separate the product and the catalyst, wherein the aperture of the filter paper is 1-3 mu m.
And (3) rotary steaming: rotary steaming for 3h at 95 ℃ and-1.0 MPa to remove water in the product.
Second, detection method
Product detection: the hydroxyl value is calibrated by a phthalic anhydride method.
Third, the detection result of the sample
It can be seen from FIG. 1 that Z, KZ and KCZ catalytic activities are sequentially enhanced, wherein the hydroxyl value of polypropylene glycol prepared by using KCZ prepared in example 1 as a catalyst is 244.13, and the molecular weight is 689.38.
FIG. 2 is an infrared spectrum characterization chart of the final product, in which A is an infrared spectrum of a polypropylene glycol standard sample and B is an infrared spectrum of the polypropylene glycol product obtained in example 1, and comparison shows that the synthesized polypropylene glycol is consistent with the standard sample. 3458.0cm in infrared image-1The wide and strong absorption peak appeared in the process is the characteristic absorption peak of the stretching vibration of the hydroxyl (-OH) at the tail end of the polypropylene glycol, 2970.6cm-1When it is methyl (-CH)3) Has an antisymmetric telescopic vibration absorption peak of 2873.3cm-1Is methyl (-CH)3) 1457.7cm-1And 1375.1cm-1Is then-CH3And absorption peak of the symmetric deformation vibration of 1108.0cm-1The strong absorption peak appears at the left and right is the absorption peak of the antisymmetric stretching vibration characteristic of the ether bond (C-O-C) in the polypropylene glycol, and 943.3cm-1The absorption peaks appearing on both sides can be assigned to the symmetric stretching vibration absorption peaks of the ether bond.
The key point of the reaction between glycerol and propylene oxide is that negative oxygen ions attack C-O bonds in propylene oxide to open rings, and further chain growth occurs to generate polypropylene glycol. The Bronsted alkali can strip H in the alcoholic hydroxyl group to promote the generation of negative oxygen ions, wherein the number of basic sites and the strength of the alkalinity are key for catalyzing the formation of the negative oxygen ions. As can be seen from FIG. 3, Z, KZ and KCZ have sequentially enhanced alkalinity and sequentially increased alkaline sites, and KCZ has weakly alkaline sites (T) compared with Z, KZm,1) And a strong basic site (T)m,2) In addition, it also has strong alkaline sites (T)m,3) This is the main reason that the composite solid base catalyst KCZ has the best catalytic activityThus, the method is simple and easy to operate.
FIG. 4 is an XRD representation of KCZ, the predominant species present in the catalyst being tetragonal ZrO in comparison with standard card2(t-ZrO2),K2O and solid solution Ce2Zr2O7.04. Wherein K2Hydroxyl and negatively charged lattice oxygen generated by water adsorption on the surface of O are one of the reasons for generating the catalyst base center, Ce2Zr2O7.04Is mainly due to Zr4+ Radius less than Ce4+ Thus Zr4+Can enter CeO2To form a solid solution of an oxide of Ce-Zr. Accordingly, the lattice defects due to the difference in unit cell size can generate oxygen vacancies, thereby making Ce2Zr2O7.04Has excellent oxygen storage/release capacity, and further forms O on the surface of the catalyst2-/O-/O2 -Further increasing the alkaline sites and enhancing the alkalinity.
FIG. 5 is an HR-TEM image of KCZ, and it can be seen from the image that the catalyst is mainly in a cuboid shape, and the average particle size of the catalyst is 10-20 nm, so that the catalyst has a large specific surface area.
IV, solid base catalyst K2O/CeO2-ZrO2(KCZ) reproducibility test
The catalyst after the reaction in example 1 was regenerated by the following procedure:
taking out the catalyst after catalyzing the synthesis reaction of the polypropylene glycol, repeatedly pumping, filtering and washing by using industrial ethanol, washing out the polypropylene glycol adhered to the surface of the catalyst, drying for 1h at 100 ℃, roasting for 6h at 700 ℃, and burning off the carbon deposit on the surface of the catalyst.
Polypropylene glycol synthesis and determination: polypropylene glycol was synthesized and measured according to the procedure of example 2
The above steps are repeated for 5 times of catalyst regeneration, and the performance is measuredAs shown in FIG. 6, it can be seen that the performance of the catalyst was reduced after 5 regenerations, which was mainly caused by the surface-supported K2The gradual shedding of O reduces the alkalinity and the number of alkaline sites.
Five, K2O/CeO2@ZrO2Single-dimensional test of the molar ratio of Ce to Zr in (KCZ)
Catalyst KCZ was prepared and used for the synthesis reaction of polypropylene glycol with reference to example 1 (experimental conditions were according to the method provided in example 2), except that the molar ratio of Ce to Zr in the raw material was adjusted.
The results of the experiment are shown in table 1 below:
TABLE 1 PPG Performance indices
Six, K2O/CeO2@ZrO2KNO in (KCZ)3Single dimensional test of solution dip concentration
Catalyst KCZ was prepared and used for the synthesis of polypropylene glycol with reference to example 1, except that KNO was used3Solution impregnation concentration.
The results of the experiment are shown in table 2 below:
TABLE 2 PPG Performance indices
Claims (10)
1. A solid base catalyst of composite metal oxide, characterized in that it comprises t-ZrO as a carrier2And an active ingredient; the active component being present in ZrO2Alkali metal oxide K capable of providing Bronsted basic sites in octahedral vacancies2O and with ZrO2Composite solid solution Ce capable of providing oxygen vacancies2Zr2O7.04And (4) forming.
2. The composite metal oxide solid base catalyst of claim 1, wherein K is2The mass percentage of O in the solid base catalyst is 5-10%: the molar ratio of Ce to Zr is 0.04-0.06: 1 in terms of the mole number of the metal elements.
3. The composite metal oxide solid base catalyst of claim 1, wherein the solid base catalyst is prepared by a process comprising:
weighing ZrOCl according to quantity2·8H2O and Ce (NO)3)3·6H2Dissolving O in water to prepare a mixed solution, adjusting the pH value to 10-11 to fully react, and performing ultrasonic treatment, aging, drying and cleaning to obtain a precursor;
putting the precursor in KNO at the temperature of 60-85 DEG C3Dipping in the solution, filtering, drying and roasting to obtain the solid base catalyst.
4. A method for preparing the composite metal oxide solid base catalyst according to claim 1, comprising the steps of:
(1) weighing ZrOCl2·8H2O and Ce (NO)3)3·6H2Preparing a mixed solution, adjusting the pH value to 10-11 at the temperature of 25-30 ℃ to fully react, and performing ultrasonic treatment, aging, drying and cleaning to obtain a precursor;
(2) placing the precursor in KNO3Dipping in the solution, filtering, drying and roasting to obtain the solid base catalyst.
5. The method for preparing the composite metal oxide solid base catalyst according to claim 4, wherein in the step (1), the molar ratio of Ce to Zr is 0.04-0.06: 1 in terms of the molar number of the metal element.
6. According to the claimsThe method for producing a composite metal oxide solid base catalyst according to claim 4, wherein in the step (2), the KNO is used3The concentration of the solution is 0.4-0.6 mol/L.
7. The method for preparing the composite metal oxide solid base catalyst according to claim 4, wherein in the step (2), the precursor is placed in KNO under the condition of water bath at 60-85 ℃3And soaking in the solution for 8-13 h.
8. The method for preparing the composite metal oxide solid base catalyst according to claim 5, wherein in the step (2), the roasting temperature is 650-750 ℃ and the roasting time is 5-7 h.
9. Use of a solid base catalyst according to any one of claims 1 to 3 or obtained by a method according to any one of claims 4 to 8 for the synthesis of polypropylene glycol.
10. The preparation method of the polypropylene glycol is characterized by comprising the following steps: placing reactants of glycerol, propylene oxide and the solid base catalyst as described in any one of claims 1 to 3 or the solid base catalyst obtained by the preparation method as described in any one of claims 4 to 8 in a high-pressure reaction kettle, introducing enough nitrogen to replace air in the kettle before reaction, and carrying out reaction polymerization for 5 to 7 hours under the conditions that the initial pressure is 1.5 to 2.5MPa and the temperature is 170 to 190 ℃;
glycerol: the mass ratio of the propylene oxide is 0.075-0.125: 1, and the mass ratio of the solid base catalyst to the propylene oxide is 0.05-0.07: 1.
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