CN116060092A - Catalyst for preparing propylene carbonate from urea and propylene glycol, preparation method and application - Google Patents
Catalyst for preparing propylene carbonate from urea and propylene glycol, preparation method and application Download PDFInfo
- Publication number
- CN116060092A CN116060092A CN202211594914.6A CN202211594914A CN116060092A CN 116060092 A CN116060092 A CN 116060092A CN 202211594914 A CN202211594914 A CN 202211594914A CN 116060092 A CN116060092 A CN 116060092A
- Authority
- CN
- China
- Prior art keywords
- zinc
- catalyst
- molecular sieve
- sepiolite
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 title claims abstract description 49
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 title claims abstract description 28
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000004202 carbamide Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002808 molecular sieve Substances 0.000 claims abstract description 39
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000011701 zinc Substances 0.000 claims abstract description 36
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 34
- 239000011230 binding agent Substances 0.000 claims abstract description 13
- 239000004005 microsphere Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000004113 Sepiolite Substances 0.000 claims description 24
- 229910052624 sepiolite Inorganic materials 0.000 claims description 24
- 235000019355 sepiolite Nutrition 0.000 claims description 24
- 238000005342 ion exchange Methods 0.000 claims description 12
- 239000012266 salt solution Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 150000003751 zinc Chemical class 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical group [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 6
- 238000001694 spray drying Methods 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 6
- 229960004063 propylene glycol Drugs 0.000 description 13
- 239000000203 mixture Substances 0.000 description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011964 heteropoly acid Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910020218 Pb—Zn Inorganic materials 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/087—X-type faujasite
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/088—Y-type faujasite
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/7057—Zeolite Beta
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Abstract
The application discloses a catalyst for preparing propylene carbonate from urea and propylene glycol, a preparation method and application, wherein the catalyst is a microsphere catalyst consisting of a zinc-containing molecular sieve and a binder, the size is 10-100 microns, and the content of the zinc-containing molecular sieve is 0-40%; the content of the binder is 60-100%. The catalyst is used in propylene carbonate preparation, and has the characteristics of high selectivity, good wear resistance, simple preparation method, low cost and easy separation.
Description
Technical Field
The application relates to a catalyst for preparing propylene carbonate from urea and propylene glycol, a preparation method and application thereof, and belongs to the technical field of chemistry and chemical engineering.
Background
Propylene Carbonate (PC) is a solvent and an organic synthesis intermediate with excellent performance, has wide application in the fields of spinning, high polymer synthesis, gas separation, electrochemistry and the like, and can be subjected to transesterification with methanol to prepare dimethyl carbonate.
At present, propylene oxide and carbon dioxide are adopted to react at a certain temperature and pressure to prepare PC, but the catalyst and the reaction product are not easy to separate, the reaction condition is harsh, and the development of a catalytic system with mild reaction condition and easy separation still faces great challenges. The raw materials of propylene carbonate generated by the reaction of urea and 1, 2-propylene glycol are cheap and easy to obtain, and the byproduct ammonia gas can be recycled to a urea unit. Patent CN10145031a discloses a heteropolyacid catalyst prepared by the reaction of heteropolyacid and salts, and the PC yield reaches 78.71%. Patent CN 103721697a discloses a composite oxide catalyst consisting of active components zinc oxide and auxiliary oxides, the yield of PC can reach 98%. Patent CN105601609a discloses a method for preparing propylene carbonate by catalyzing urea and propylene glycol with an ionic liquid catalyst containing zinc-based metal oxide and zinc-based metal salt and quaternary ammonium salt. CN101979142A discloses a mixed carbonate catalyst of Pb-Zn, pb-Mg, pb-Cr, zn-Mg, zn-Cr or Mg-Cr and the like, and the PC yield reaches 98 percent. Although development of the catalyst has been advanced to some extent, the catalyst exists in a reaction system in a powder or liquid form during the reaction process, and separation and recovery of the catalyst are difficult.
Disclosure of Invention
The invention aims to produce and provide a catalyst for preparing propylene carbonate from urea and propylene glycol, a preparation method and application thereof, wherein a zinc-containing molecular sieve is adopted as a main active component, and sepiolite is adopted as a binder to prepare a microsphere catalyst, and particularly the zinc-exchanged sepiolite can be used as an active component and a binder at the same time, so that the catalyst is excellent in catalytic performance and wear resistance and easy to separate in reaction.
According to one aspect of the present invention, there is provided a catalyst comprising a zinc-containing molecular sieve in an amount of 0 to 40% and a binder in an amount of 60 to 100%;
the molecular sieve in the zinc-containing molecular sieve is at least one selected from X, Y, beta, MOR molecular sieves;
the zinc content in the zinc-containing molecular sieve is 2-20%.
Optionally, the catalyst is a microsphere of 10 to 100 microns.
Optionally, the molecular sieve has a silica to alumina ratio of: siO (SiO) 2 /Al 2 O 3 ＝2.0～100。
Optionally, the binder is sepiolite and/or zinc ion exchanged sepiolite.
Optionally, the zinc ion-exchanged sepiolite has a zinc content of 0-20%.
According to another aspect of the present invention, there is provided a method for preparing the catalyst described above, the method comprising the steps of:
(1) Ion exchange, washing, drying and roasting are carried out on the molecular sieve in a zinc salt solution to prepare a zinc-containing molecular sieve;
(2) Ion exchanging sepiolite in a zinc salt solution, washing, drying and roasting to prepare zinc ion exchanged sepiolite;
(3) Uniformly mixing a zinc-containing molecular sieve, sepiolite and water according to a proportion, and performing spray drying forming and roasting to obtain the catalyst.
Optionally, the zinc salt solution is selected from at least one of nitrate, sulfate, acetate and chloride salt containing zinc.
Optionally, the temperature of the ion exchange is 20-90 ℃, and the time of the ion exchange is 2-12 h.
Optionally, the roasting temperature is 300-800 ℃.
According to a further aspect of the invention, there is provided the use of the catalyst described above, the catalyst prepared by the preparation method described above, in propylene carbonate.
Optionally, a mixture containing propylene glycol, urea and a catalyst is reacted to obtain propylene carbonate.
Optionally, the reaction temperature is 100-200 ℃, the reaction pressure is 20-100 KPa, and the reaction time is 0.5-4.0 h.
Alternatively, the temperature of the reaction is selected from any value of 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃ or a range of values between any two points.
Optionally, the pressure of the reaction is selected from any value of 20KPa, 40KPa, 60KPa, 80KPa, 100KPa or a range of values between any two of the above.
Optionally, the reaction time is selected from any value of 0.5h, 1h, 2h, 3h and 4h or a range value between any two points.
As a specific implementation mode, the invention is realized by the following technical scheme:
the invention also provides a preparation method of the catalyst for preparing propylene carbonate from urea and propylene glycol, which comprises the following steps:
(1) Ion exchange, washing, drying and roasting are carried out on the molecular sieve in a zinc salt solution to prepare a zinc-containing molecular sieve;
(2) Ion exchanging sepiolite in a zinc salt solution, washing, drying and roasting to prepare zinc ion exchanged sepiolite;
(3) Uniformly mixing a zinc-containing molecular sieve, sepiolite and water according to a proportion, and performing spray drying forming and roasting to obtain the catalyst.
Optionally, the zinc salt solution is selected from at least one of nitrate, sulfate, acetate and chloride.
The invention also provides an application of the catalyst for preparing propylene carbonate, which comprises the following steps: propylene glycol, urea and catalyst are added into a reaction kettle according to a certain proportion, and after inert gas replacement, the temperature is raised for reaction, and the reaction temperature is 100-200 o C, the reaction pressure is 20-100 KPa (absolute pressure), and the reaction time is 0.5-4.0 h.
The beneficial effects that this application can produce include:
1) The microsphere catalyst is prepared by spray drying by using the zinc-containing molecular sieve and sepiolite as binders, and has high catalyst activity, good strength and easy separation.
2) The catalyst provided by the invention has the advantages of simple preparation method, convenient operation, low cost, repeated use and potential economic benefit.
3) The catalyst disclosed by the invention is used for preparing propylene carbonate, and has the characteristics of high selectivity, good wear resistance, simple preparation method, low cost and easiness in separation.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially.
The analytical methods, conversions, selectivities in the examples were calculated as follows:
the urea conversion is:
m 1 for the mass of urea in the reaction liquid, m 01 Is the mass of urea in the raw material
Propylene carbonate the yield is as follows:
m 2 the mass of propylene carbonate in the reaction liquid;
M 2 is propylene carbonate relative molecular mass;
m 01 the mass of urea in the raw materials;
M 1 is the relative molecular mass of urea.
The room temperature in the examples of the present invention is 25 ℃.
The invention adopts XRF to test the Zn content in the molecular sieve.
Example 1 preparation of Zinc-containing molecular sieves
200g of NaX molecular sieves (SiO 2 /Al 2 O 3 =2.30) after roasting at 550 ℃ for 5 hours, the mixture is placed in 2.0L of zinc nitrate with concentration of 2.0mol/LStirring the mixture in water solution at 80 ℃ for 8 hours, carrying out ion exchange, washing the mixture to be neutral by deionized water after the ion exchange, drying the mixture, roasting the mixture at 550 ℃ for 4 hours to obtain a zinc-exchanged molecular sieve, namely a zinc-containing molecular sieve, and testing the Zn content in the molecular sieve by XRF.
Examples 2-6 preparation of Zinc-containing molecular sieves
The procedure was as in example 1, and the types of molecular sieves and the exchange conditions were changed to prepare different zinc ion exchanged molecular sieves, and the exchange conditions are shown in Table 1.
TABLE 1 Zinc-containing molecular sieves preparation conditions
Examples 7-11 preparation of Zinc-exchanged sepiolite
200g sepiolite is roasted for 5 hours at 550 ℃, then placed in 2.0L of zinc nitrate water solution with certain concentration, stirred for a certain time at a specific temperature, subjected to ion exchange, washed to be neutral by deionized water after the ion exchange, dried, roasted for 4 hours at 550 ℃, and repeatedly operated for a plurality of times to obtain the zinc-exchanged sepiolite. The specific zinc nitrate aqueous solution concentration, stirring temperature, stirring time and exchange conditions are shown in Table 2.
TABLE 2 Zinc exchanged sepiolite preparation Condition Table
Note that: sep refers to sepiolite.
Example 12 catalyst preparation
50.0g of the zinc-containing molecular sieve prepared in example 1, 200.0g of the binder 15.32Zn/sep prepared in example 10 and 375.0g of deionized water are uniformly mixed and stirred, spray-dried and molded, the spray-drying inlet temperature is 320 ℃, the obtained solid is roasted for 4 hours at 550 ℃ to prepare the catalyst cat-01, and the test attrition index is 0.95.
Examples 13-20 catalyst preparation
The procedure was as in example 12, and the zinc-containing molecular sieve and the binder were uniformly mixed in the proportions shown in Table 3, wherein the total mass of the molecular sieve and the binder was 250.0g, 375.0g of water was added and stirred for 30 minutes, wherein the total mass of all solid materials was 40%, and then spray-dried and molded, the spray-drying inlet temperature was 320℃and the resulting solid was calcined at 550℃for 4 hours to obtain a catalyst. The names and preparation conditions of the catalyst are shown in Table 3.
TABLE 3 list of catalyst preparation conditions
Evaluation of reactivity of the catalysts of examples 23 to 36
The reaction of urea and 1, 2-propylene glycol was carried out in a three-necked flask, 15.0g of urea, 29.0g of propylene glycol and 0.44g of a catalyst were added into the three-necked flask, the molar ratio of propylene glycol to urea was 1.5, the mass ratio of the catalyst to the reactant was 1.0%, the reaction pressure was evacuated, then the temperature was raised to the reaction pressure for the reaction, the reaction was cooled to room temperature, an internal standard acetophenone was added, the sample analysis was carried out, and the evaluation results of the catalyst were shown in table 4.
TABLE 4 reaction results of the reaction of urea and propylene glycol to propylene carbonate
As can be seen from Table 4, the catalyst provided in each example of the present invention has excellent reaction performance in the reaction of preparing propylene carbonate from urea and propylene glycol, the conversion rate of urea can reach 100%, and the yield of propylene carbonate reaches more than 98%. When the sepiolite exchanged by zinc is directly used as a catalyst, the yield of propylene carbonate can also reach more than 95 percent.
The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.
Claims (7)
1. The catalyst for preparing propylene carbonate from urea and propylene glycol is characterized by comprising a zinc-containing molecular sieve and a binder, wherein the content of the zinc-containing molecular sieve is 0-40%, and the content of the binder is 60-100%;
the molecular sieve in the zinc-containing molecular sieve is at least one selected from X, Y, beta, MOR molecular sieves;
the zinc content in the zinc-containing molecular sieve is 2-20%; the binder is sepiolite and/or zinc ion-exchanged sepiolite.
2. The catalyst of claim 1, wherein the catalyst is a microsphere of 10 to 100 microns;
preferably, the molecular sieve has a silica to alumina ratio of: siO (SiO) 2 /Al 2 O 3 ＝2.0～100。
3. The catalyst of claim 1 wherein the zinc ion exchanged sepiolite has a zinc content of from 0.02 to 20%.
4. A process for the preparation of a catalyst as claimed in any one of claims 1 to 3, comprising the steps of:
(1) Ion exchange, washing, drying and roasting are carried out on the molecular sieve in a zinc salt solution to prepare a zinc-containing molecular sieve;
(2) Ion exchanging sepiolite in a zinc salt solution, washing, drying and roasting to prepare zinc ion exchanged sepiolite;
(3) Uniformly mixing a zinc-containing molecular sieve, sepiolite and water according to a proportion, and performing spray drying forming and roasting to obtain the catalyst.
5. The method according to claim 4, wherein the zinc salt solution is at least one selected from the group consisting of nitrate, sulfate, acetate and chloride.
6. The catalyst of any one of claims 1 to 3, the DD220848I-DL of any one of claims 4 to 5
The catalyst prepared by the preparation method is applied to the preparation of propylene carbonate.
7. The use according to claim 6, characterized in that it comprises the steps of: propylene glycol, urea and catalyst are added into a reaction kettle in proportion, the reaction temperature is raised to 100-200 ℃ after the replacement of inert gas, the reaction pressure is 20-100 KPa (absolute pressure), and the reaction time is 0.5-4.0 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211594914.6A CN116060092A (en) | 2022-12-13 | 2022-12-13 | Catalyst for preparing propylene carbonate from urea and propylene glycol, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211594914.6A CN116060092A (en) | 2022-12-13 | 2022-12-13 | Catalyst for preparing propylene carbonate from urea and propylene glycol, preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116060092A true CN116060092A (en) | 2023-05-05 |
Family
ID=86177842
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211594914.6A Pending CN116060092A (en) | 2022-12-13 | 2022-12-13 | Catalyst for preparing propylene carbonate from urea and propylene glycol, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116060092A (en) |
-
2022
- 2022-12-13 CN CN202211594914.6A patent/CN116060092A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| NZ210549A (en) | Modified copper- and zinc- containing catalyst and methanol production | |
| CN110280250B (en) | Preparation method and application of zeolite imidazole framework material derived metal oxide | |
| CN101966460B (en) | Supported catalyst for synthesis of dimethyl carbonate, preparation method and using method thereof | |
| CN113387908B (en) | Application of magnesium cobaltate catalyst in selective oxidation reaction of styrene | |
| CN112774726A (en) | Spherical titanium-silicon molecular sieve catalyst and preparation method thereof | |
| CN115646501B (en) | Cobalt monoatomic catalyst synthesized by molten salt method and application thereof | |
| CN103801327B (en) | A kind of composite oxides, its manufacture method and application thereof | |
| CN113751080B (en) | Modified alumina carrier and preparation method and application thereof | |
| CN113877560B (en) | Synthesis method of methyl acrylate and solid base catalyst thereof | |
| CN116060092A (en) | Catalyst for preparing propylene carbonate from urea and propylene glycol, preparation method and application | |
| CN110204444B (en) | Synthesis method of dimethyl carbonate | |
| CN115501881A (en) | Catalyst particles for preparing acrylonitrile by propylene ammoxidation, and preparation method and application thereof | |
| CN110433863B (en) | Preparation method of catalyst for synthesizing dimethyl carbonate | |
| CN116328752B (en) | Catalyst, preparation method and application of catalyst in preparation of propylene carbonate | |
| CN111974409B (en) | Flaky porous manganese-doped nickel oxide catalyst, preparation method and application thereof | |
| CN110252320B (en) | Catalyst for synthesizing dimethyl carbonate and preparation method thereof | |
| CN103521235A (en) | Catalyst for preparing acrylic acid through acrolein oxidation and preparation method thereof | |
| CN116371417B (en) | Catalyst for synthesizing 3, 4-dimethyl pyrrole and preparation method and application thereof | |
| CN111992209A (en) | Catalyst for synthesizing dimethyl oxalate and preparation method and application thereof | |
| CN112517021B (en) | Cobalt-doped modified tin dioxide catalyst, preparation method and application thereof | |
| CN116060121B (en) | O-cresol isomerization catalyst, preparation method thereof and o-cresol isomerization method | |
| CN115779883B (en) | Catalyst for directionally synthesizing alkyl carbonate from alkyl oxalate | |
| CN112439405B (en) | Catalyst for preparing dimethyl carbonate from methanol, carbon dioxide and 2-cyanopyridine and preparation method and application thereof | |
| CN115487803B (en) | Hollow porous perovskite-type cerium-manganese composite oxide and preparation and application thereof | |
| CN114433188B (en) | Methyl acetate catalyst, preparation method thereof and synthesis method of methyl acetate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |