CN110760060B - 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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- 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
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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
- C08G65/2603—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
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:
(3) and (3) chain growth 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 gold in octahedral vacancies capable of providing Bronsted basic sitesMetal oxide K2O 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 catalyst 2-/O-/O2 -Thereby further increasing the alkaline sites and enhancing the alkalinity.
Solid solution Ce2Zr2O7.04Is at ZrO2In which CeO is doped2Is formed by using
Radius 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.%), the molar ratio of Ce to Zr is 0.04-0.06: 1 in terms of the mole number of metal elements, and the molar ratio of the elements is respectively determined by 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)3·6H2O is dissolved inPreparing a mixed solution in water, adjusting the pH value to 10-11, fully reacting, 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 KNO 3The 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 elements 2·8H2O and Ce (NO)3)3·6H2O in water to prepare a mixed solution, transferring the mixed solution into a three-neck flask, continuously stirring and slowly dripping ammonia water under the condition of a water bath at 25-30 ℃, adjusting the pH value to 10-11, continuously stirring for 7-9 h to fully react, performing ultrasonic treatment, aging, performing suction filtration and drying, and then 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 present invention provides an application of the solid base catalyst or the solid base catalyst obtained by the preparation method in polypropylene glycol synthesis.
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 a product, can be repeatedly used for many times, does not need acid neutralization treatment, and reduces the pollution degree to the environment.
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 catalysts 2-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 12gZrOCl2·8H2Dissolving O in 100ml of water to prepare a mixed solution, transferring the mixed solution into a three-neck flask, continuously stirring and slowly dripping 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. After ultrasonic treatment, aging, suction filtration and drying, Cl is cleaned by distilled water-To prepare a precursor;
soaking the carrier precursor in pure water at 75 deg.C for 12 hr, filtering, drying, and heating at 700 deg.CRoasting for 6 hours 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
Z, KZ shows and KCZ catalytic activities are sequentially enhanced as shown in FIG. 1, 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) Antisymmetric telescopic vibration absorption peak of 2873.3cm-1Is methyl (-CH)3) 1457.7cm -1And 1375.1cm-1Is then-CH3And absorption peak of the asymmetric deformation vibration and 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 why the composite solid base catalyst KCZ possesses the best catalytic activity.
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, Ce 2Zr2O7.04Is 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 performance test result of the catalyst regenerated 5 times by repeating the above steps is shown in FIG. 6, and it can be seen from the figure that the performance of the catalyst is reduced after 5 times of regeneration, and the main reason is surface loaded K 2The 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 (6)
1. The application of the composite metal oxide solid base catalyst in the synthesis of polypropylene glycol is characterized in that the solid base catalyst comprises t-ZrO as a carrier2And an active ingredient; the active component consists of2Alkali metal oxide K capable of providing Bronsted basic sites in octahedral vacancies2O and with ZrO2Composite solid solution Ce capable of providing oxygen vacancies2Zr2O7.04Composition is carried out; said K2The 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 based on the mole number of the metal elements.
2. Use according to claim 1, wherein the solid base catalyst is prepared by a process comprising:
(1) 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;
(2) placing 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.
3. Use according to claim 2, wherein in step (2), said KNO3The concentration of the solution is 0.4-0.6 mol/L.
4. The method as claimed in claim 2, wherein in 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.
5. The application of claim 2, wherein in the step (2), the roasting temperature is 650-750 ℃ and the roasting time is 5-7 h.
6. 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 claim 1 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 that the initial pressure is 1.5-2.5 MPa and the temperature is 170-190 ℃;
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.
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