LI, Hongchao (Yuqiao Road 1978-25-601, Pudong, Shanghai 4, 20120, CN)
WANG, Junwei (27 South Taoyuan Road, Taiyuan, Shanxi 1, 03000, CN)
KANG, Maoqing (27 South Taoyuan Road, Taiyuan, Shanxi 1, 03000, CN)
NEFZGER, Hartmut (Zu den Fußfällen 24, Pulheim, 50259, DE)
FRIEDERICHS, Wolfgang (Am Ackerrain 16, Köln, 50933, DE)
WANG, Xingkui (27 South Taoyuan Road, Taiyuan, Shanxi 1, 03000, CN)
LI, Hongchao (Yuqiao Road 1978-25-601, Pudong, Shanghai 4, 20120, CN)
WANG, Junwei (27 South Taoyuan Road, Taiyuan, Shanxi 1, 03000, CN)
KANG, Maoqing (27 South Taoyuan Road, Taiyuan, Shanxi 1, 03000, CN)
NEFZGER, Hartmut (Zu den Fußfällen 24, Pulheim, 50259, DE)
FRIEDERICHS, Wolfgang (Am Ackerrain 16, Köln, 50933, DE)
| Claims 1 . A catalyst for preparing cyclic carbonates, comprising catalytically active component and a catalyst support, wherein, the catalytically active component comprises a heteropoly acid; the catalyst support comprises a metal oxide of a first transition metal, wherein the first transition metal oxide is selected from the group consisting of zirconium oxide, titanium dioxide, zinc oxide, silicon oxide, alumina, vanadium pentoxide, magnesium oxide, calcium oxide, tin oxide, barium oxide, cerium oxide and lanthanum oxide; and the catalytically active component further comprises a second transition metal or a metal compound of a second transition metal, wherein the second transition metal is selected from the grou p consisting of palladium, nickel, iron, manganese, ruthenium, rhodium, silver, osmium, iridium, platinum and gold. 2. The catalyst as claimed in Claim 1 , wherein the second transition metal is palladium and/or platinum. 3. The catalyst as claimed in Claim 1 , wherein the heteropoly acid is a Keggin type heteropoly acid. 4. The catalyst as claimed in Claim 3, wherein the Keggin type heteropoly acid is selected from the group consisting of H3PW1204oTil-l20, H3P M012O40T1 H2O, and H4SiMoi204o-nH20. 5. The catalyst as claimed in Claim 1 , wherein the load of the catalytically active component is 1 -30 wt.%, based on 100 wt.% of the catalyst support. 6. The catalyst as claimed in Claim 1 , wherein the load of the second transition metal or the metal compound of the second transition metal is 0.1 -5 wt.%, based on 100 wt.% of the catalyst support. 7. A method for preparing the catalyst as claimed in Claim 1 , comprising the steps of Impregnating a catalyst support using a first solution and a second solution respectively or co-impregnating a catalyst support into a mixed solution of a first solution and a second solution to obtain a catalyst precursor; and calcinating the catalyst precursor to obtain a catalyst; wherein, the components of the catalyst support comprises a metal oxide of a first transition metal, wherein the first transition metal oxide is selected from the group consisting of zirconium oxide, titanium dioxide, zinc oxide, silicon oxide, alumina, vanadium pentoxide, magnesium oxide, calcium oxide, tin oxide, barium oxide, cerium oxide and lanthanum oxide; the solute of the first solution comprises one or more heteropoly acids; the solute of the second solution comprises one or more second transition metal salt, wherein the second transition metal is selected from the group consisting of palladium, nickel, iron, manganese, ruthenium, rhodium, silver, osmium, iridium, platinum and gold; the temperature of the calcinating process is 150-700 °C. 8. The method as claimed in Claim 7, wherein the second transition metal is palladium and/or platinum. 9. The method as claimed in Claim 7, wherein the heteropoly acid is a Keggin type heteropoly acid. 10. The method as claimed in Claim 9, wherein the Keggin type heteropoly acid is selected from the group consisting of H3PW1204oTi l-l20, H3P M012O40T1 H2O, H4SiWi204o-nH20 and H4SiMoi204o-nH20. 1 1 . The method as claimed in Claim 7 or 8, wherein the method further comprises a drying step after the impregnating step and before the calcination step, wherein the temperature of the drying step is 100-120°C, the time of the drying step is less than or equal to 12 hours, and the atmosphere of the drying step is selected from the group consisting of air, oxygen and nitrogen. 12. A method for preparing a cyclic carbonate by reacting epoxide with carbon dioxide, in the presence of the catalyst as claimed in Claim 1 -6. 13. The method as claimed in Claim 12, wherein the functionality of the epoxide is equal to or more than 1 .5. 14. The method as claimed in Claim 13, wherein the epoxide is epoxidized soybean oil. 15. The method as claimed in Claim 12, wherein the amount of the catalyst is less than or equal to 20 wt.%, based on 100 wt.% of the epoxide. 16. The method as claimed in Claim 12, wherein the reaction temperature is 100-200 °C, the pressure of carbon dioxide during the reaction is less than or equal to 4 MPa, the reaction time is less than or equal to 50 hours. 17. The method as claimed in Claim 12, wherein the reaction is carried out in a polar solvent, the polar solvent is selected from the group consisting of Ν,Ν-dimethyl fomamide (DMF), dimethyl sulphoxide (DMSO), tetrahydrofuran (TH F), methylethyl ketone (MEK), 1 - butanol, 2-butanol and tert-butanol. 18. The method as claimed in Claim 12, wherein the reaction is carried out in a non-polar solvent, the non-polar solvent is selected from the group consisting of benzene, toluene and dimethylbenzene. 19. A method for recovering the catalyst as claimed in Claim 1 , comprising the steps of treatment of the inactivated or partially inactivated catalyst at the temperatures from 200 to 600 °C for at least 1 hour. |
The present invention relates to a synthesis of cyclic carbonates, especially to a catalyst for preparing cyclic carbonates, the method for preparing the same and the use thereof.
An important use of cyclic carbonates is their reaction with primary amine in order to obtain polyurethanes (J. Polym. Sci. Part A 2000, 28, P2375-2380, Steblyanko et al). The polyurethanes prepared through this non-isocyanate route possess some special features, such as low permeability and high chemical resistance.
In the prior art, cyclic carbonates have been prepared by carbonation reaction of epoxy resins or epoxidized unsaturated oils (J. Appl. Polym. Sci. 2004, 91 , p. 3513, and Green Chem, 2005, 7, p. 849-854). However, the raw materials coming from petroleum chemical industry are not environment friendly.
For the purpose of reducing the dependence of raw materials from petroleum and to protect the environment, US 7,045,577 disclosed a method for preparing cyclic soybean oil carbonates (CSBO) by reacting renewable vegetable oils and the derivatives thereof, such as epoxidized soybean oil (ESBO), with carbon dioxide. The obtained CSBO can be converted with diamines to prepare NIPUs. Catalysts, such as the homogeneous phase catalyst n-tetra butyl ammonium bromide
(TBABr) were introduced in such reactions for preparing CSBO (J. Appl. Polym. Sci. 2004, 92, p.883-891 Wilkes et al.). Nevertheless, such kind of homogeneous phase catalysts were difficult to recover. Furthermore, the reaction time was too long, the reported catalysts are less attractive for scale-up test and commercial application.
Doll disclosed a method to reduce one third of the reaction time by using super-critical carbon dioxide as a reaction medium (Green Chem. 2005, 7, p.849-854). However, this method required a high reaction pressure, which wou ld significantly increase both the energy consumption and the safety costs.
In addition, Farzuchowski disclosed a method for preparing CSBO by using of Kl and 18- crown-6 catalyst system (J. Appl. Polym. Sci. 2006, 102, p.2904-2914). Nevertheless, the catalyst used in this method is expensive, and the reaction times are also too long, and the catalysts are also not useful for scale-up test and commercial application.
The objective of the present invention is to provide a catalyst for preparing cyclic carbonates. Accord i n g to a n example of this invention, the catalyst comprises a catalytically active component and a catalyst support, wherein,
the catalyst active component comprises a heteropoly acid;
the component of the catalyst support comprises a metal oxide of a first transition metal , wherein the first transition metal oxide is selected from the group consisting of zirconium oxide, titanium dioxide, zinc oxide, silicon oxide, alumina, vanadium pentoxide, magnesium oxide, calcium oxide, tin oxide, barium oxide, cerium oxide and lanthanum oxide; and
the catalyst support further comprises a second transition metal or a metal compound of a second transition metal , wherein the second transition metal is selected from the group consisting of palladium, nickel, iron, manganese, ruthenium, rhodium, silver, osmium, iridium, platinum and gold.
Preferably, the heteropoly acid is a Keggin type heteropoly acid.
Preferably, the Keggin type heteropoly acid is selected from the group consisting of H 3 PW 12 04o-nH20, Η 3 Ρ Μθΐ2θ4ο-ηΗ 2 0,
Preferably, the first transition metal oxide is selected from the group consisting of zirconium oxide, titanium dioxide, silicon oxide and alumina. Preferably, the second transition metal is selected from the group consisting of palladium, nickel and platinum.
Preferably, the load of the catalytically active component is 1 -30 wt.%, based on 100 wt.% of the catalyst support.
Preferably, the load of the second transition metal or the metal compound of second transition metal is 0.1 -5 wt.%, based on 100 wt.% of the catalyst support.
Preferably, the average diameter of the catalyst support is 0.1 - 4 mm, the pore volume of the catalyst support is 0.01 -10 ml/g, and the BET specific surface area less than or equal to 300 Another objective of the present invention is to provide a method for preparing the catalyst. According to an example of this invention, the method comprises the steps of
Impregnating a catalyst support using a first solution and a second solution respectively or co-impregnating a catalyst support with a mixed solution of a first solution and a second solution to obtain a catalyst precursor; and
calcinating the catalyst precursor to obtain a catalyst;
wherein,
the components of the catalyst support comprises a metal oxide of a first transition metal, wherein the first transition metal is selected from the group consisting of zirconium oxide, titanium dioxide, zinc oxide, silicon oxide, alumina, vanadium pentoxide, magnesium oxide, calcium oxide, tin oxide, barium oxide, cerium oxide and lanthanum oxide;
the solute of the first solution comprises one or more heteropoly acids;
the solute of the first solution comprises one or more second transition metal salt, wherein the second transition metal is selected from the group consisting of palladium , nickel, iron, manganese, ruthenium, rhodium, silver, osmium, iridium, platinum and gold; the temperature of the calcinating process is 150-700 °C.
The solvent of the first solution and/or the second solution is aqueous solvent or nonaqueous solvent. Preferably, the non-aqueous solvent is selected from the group consisting of methanol, ethanol, propyl alcohol, butyl alcohol, acetone, butanone, acetonitrile, dimethyl sulfone, dimethyl sulfoxide and dimethyl formamide.
Preferably, the method further comprises a drying step before the calcination step, wherein the temperature of the drying step is 100-120°C, the time of the drying step is less than or equal to 12 hours, the atmosphere of the drying step is selected from the group consisting of air, oxygen and nitrogen.
Another objective of the present invention is to provide a method for preparing a cyclic carbonate by reacting an epoxide with carbon dioxide, in the presence of the catalyst.
Preferably, the amount of the catalyst is less than or equal to 20 wt.%, based on 100 wt.% of the epoxide.
Preferably, the reaction temperature of the reaction for preparing the cyclic carbonate is more than or equal to 100 °C, the pressure of carbon dioxide during the reaction is less than or equal to 4 MPa, the reaction time is less than or equal to 50 hours. Preferably, the functionality of the epoxide is equal to or more than 1 .5.
Another objective of the present invention is to provide a method for recovering the catalyst provided in the present invention, comprising the step of treatment wherein the inactivated or partially inactivated catalyst is exposed to a temperature of 200-600 °C for at least 1 hour.
The catalyst provided in this invention can be used to catalyze the reaction between epoxides and carbon dioxide in order to efficiently obtain cyclic carbonates. The reaction conditions of the reaction is relative mild, the activity and the selectivity of the catalyst is high, the reaction time is relatively shorter, furthermore, the catalyst provided in this invention can be conveniently separated from the reaction system and recycled, therefore, this approach can be used to facilitate the further scale-up test and commercial application.
The present invention provides a catalyst for preparing cyclic carbonates, the method for preparing the catalyst and the use thereof.
The catalyst provided in the present invention can be used to catalyze the reaction of epoxides and carbon dioxide to obtain cyclic carbonates efficiently. In addition to the first catalytically active compound, the catalyst further comprises a second transition metal or a metal compound of a second transition metal, which can accelerate the reactivation of the catalyst by faster thermal decomposition of the macromolecule produced in side reactions; This catalyst can be conveniently separated from the reaction system and easily recycled.
Catalyst
The objective of the present invention is to provide a catalyst for preparing cyclic carbonates. Accord i n g to a n exa m pl e of th i s i n ven ti o n , th e cata lyst com p ri ses a catalytically active component and a catalyst support, wherein,
the catalytically active component comprises a heteropoly acid;
the component of the catalyst support comprises a metal oxide of a first transition metal , wherein the first transition metal oxide is selected from the group consisting of zirconium oxide, titanium dioxide, zinc oxide, silicon oxide, alumina, vanadium pentoxide, magnesium oxide, calcium oxide, tin oxide, barium oxide, cerium oxide and lanthanum oxide; and
the catalytically active component further comprises a second transition metal or a metal compou nd of a second transition metal , wherein the second transition metal is selected from the group consisting of pallad ium , n ickel , iron, manganese, ruthenium , rhodium, silver, osmium, iridium, platinum and gold. The heteropoly acid can be selected from, but is not limited to, Keggin type heteropoly acid.
The Keggin type heteropoly acid can be selected from, but is not limited to, tungstophoric a ci d ( H 3 PW 12 0 4 o nH 2 0), molybdophosphoric acid (H 3 PM012O4 0 1H2O), tungstosilicic acid (HUSiW-^C nl-^O), molybdosilicic acid (HUSiMo-^C nl-^O), or the mixtures thereof, more preferably, tungstophosphoric acid (HsPW^C nl- O), molybdophosphoric acid (Η 3 ΡΜθ ΐ 2θ4ο ηΗ 2 0), or the mixtures thereof.
The first transition metal oxide can be selected from, but is not limited to, zirconium oxide, titanium dioxide, silicon oxide, alumina, or the mixtures thereof, preferably zirconium oxide.
The second transition metal can be selected from, but is not limited to, palladium, nickel, iron, manganese, ruthenium, rhodium, silver, osmium, iridium , platinum, gold, preferably platinum, palladium, nickel, iron, manganese, more preferably platinum, palladium, nickel, most preferably platinum, palladium. The metal compound of the second transition metal can be selected from, but is not limited to, the chlorides, nitrates, acetates, ammonium salts, and chloroplatinic acid.
The second transition metal or the metal compound of the second transition metal can be carried on the catalyst carrier by either deposition or adsorption.
The average diameter of the catalyst support can be selected from, but is not limited to, 0.1 - 4 mm, more preferably 0.5-3 mm, most preferably 1 -2 mm. The pore volume of the catalyst support can be selected from, but is not limited to, 0.1 -1 ml/g, more preferably 0.2-0.8 ml/g, most preferably 0.4-0.6 ml/g.
The BET specific surface area of the catalyst support can be selected from, but is not limited to, less than or equal to 300 m 2 /g, preferably 1 -250 m 2 /g, more preferably 5-1 00 m 2 /g, most preferably 10-60 m 2 /g.
There is no specific limit with regard to the shape of the catalyst carrier, for example, the shape can be globular, columnar or eroded. The load of the catalyst active component is 1 -30 wt.%, more preferably 1 -20 wt.%,, most preferably 1 -10 wt.%, based on 100 wt.% of the catalyst support.
The load of the second transition metal or the metal compound of second transition metal is 0.1 -5 wt.%, more preferably 0.1 -3 wt.%, most preferably 0.1 -2 wt.%, based on 100 wt.% of the catalyst support.
Method for preparing the catalyst
In the present invention, the method for preparing the catalyst comprises the steps of impregnation and calcination, etc. The steps can further include a step of drying the catalyst precursor after the impregnating step and before the calcination step.
In the present invention, the method for preparing the catalyst comprises the steps of impregnating a catalyst support using a first solution and a second solution respectively or co- impregnating a catalyst support into a mixed solution of a first solution and a second solution to obtain a catalyst precursor, preferably co-impregnating a catalyst support using co-impregnation by a mixed solution of a first solution and a second solution to obtain a catalyst precursor to obtain a catalyst precursor.
The first solution is a solution comprising one or more heteropoly acid.
The heteropoly acid can be selected from, but is not limited to Keggin type heteropoly acid.
The Keggin type heteropoly acid can be selected from, but is not limited to, tungstophoric acid (H 3 PW 12 0 4 o nH 2 0), molybdophosphoric acid (H 3 PM012O4 0 1H2O), tungstosilicic acid (hUSiW-^C nl-^O), molybdosilicic acid (HUSiMo-^C nl-^O), or the mixtures thereof, more preferably, tungstophosphoric acid (HsPW^C nl- O), molybdophosphoric acid (H 3 PM012O4 0 nH 2 0), or the mixtures thereof.
The solvent of the first solution is aqueous solvent or non-aqueous solvent. The nonaqueous solvent can be selected from, but is not limited to, ethers, alcohols, ketones, nitriles or amides, preferably diethyl ether, methanol, ethanol, propanol-1 , propanol-2, butanol-1 , butanol-2, acetone, butanone, acetonitrile, dimethyl sulfone, dimethyl sulfoxide and dimethyl formamide.
The solute of the second solution comprises one or more second transition metal salt, wherein the second transition metal is selected from the group consisting of palladium , nickel, iron, manganese, ruthenium, rhodium, silver, osmium, iridium, platinum and gold, preferably platinu m , pallad ium , n ickel , iron, manganese, more preferably platinum, palladiu m , nickel , most preferably platinu m , palladiu m . The metal salt of the secon d transition metal can be selected from, but is not limited to, the chlorides, nitrates, acetates, ammonium salts, chloroplatinic acid. The solvent of the second solution is either an aqueous solvent or a non-aqueous solvent. The non-aqueous solvent can be selected from, but is not limited to, alcohol, ketone, nitrile or amide, preferably methanol , ethanol , propyl alcohol , butyl alcohol , acetone, butanone, acetonitrile, dimethyl sulfone, dimethyl sulfoxide and dimethyl formamide.
The catalyst support can be impregnated by the first solution or the second solution separately, to obtain the catalyst precursor. There is no special sequence requirement with regard to whether the catalyst support shall be impregnated by the first solution or by the second solution firstly. The catalyst support can be impregnated by the first solution, and impregnated with the second sol ution thereafter. The catalyst support can also be impregnated by the second solution, and impregnated by the first solution thereafter.
The catalyst support can also be co-impregnated by a mixture of a first solution and a second solution to obtain a catalyst precursor. When the catalyst support is co-impregnated by a mixture of a first solution and a second solution, the first solution solvent and the second solution solvent shall be miscible and shall not react with each other.
There is no specific limit with regard to the temperature of the impregnating step, preferably room temperature. The time of the impregnating step is less than or equal to 20 hours, preferably1 -4 hours.
In the calcination step, the calcination temperature shall be high enough to result in the transformation of the catalyst precursor to the catalyst. The calcination temperature can be selected from, but is not limited to, 150-700 °C, more preferably 200-600 °C, most preferably 250-600 °C. There is no specific limit with regard to the calcination time, preferably 1 -20 hours, more preferably 2-10 hours.
The calcination step can be carried out in an oxid izing atmosphere. The oxidizing atmosphere can be selected from, but is not limited to, oxygen or an oxygen containing gas, more preferably an oxygen containing gas, most preferably air. A mixture of air and nitrogen can be applied as well.
The temperature of the drying step can be selected from, but is not limited to, 100-120 °C. The time needed for the drying step can be selected from, but is not limited to, less than or equal to 24 hours, more preferably less than or equal to 15 hours, most preferably 5-12 hours. There is no specific limit with regard to the pressure maintained during the drying step, preferably 1 atm. The atmosphere of the drying step can be selected from, but is not limited to, air, oxygen and nitrogen, most preferably air.
Method for preparing cyclic carbonate
The catalyst provided in the present invention can be used to catalyze the reaction between epoxides and carbon dioxide in order to obtain a cyclic carbonate. The catalyst further comprises a second transition metal or a metal compound of a second transition metal, which can be used to accelerate the thermal decomposition of the macromolecule produced in the reaction, significantly reduce the macromolecule by-product deposited on the surface of the catalyst, increase the reaction rate, recover the activity of the catalyst and realize the use of the catalyst.
The functionality of the epoxide is equal to or more than 1 .5.
The term "functionality of the epoxide" used henceforth is a number average functionality and whereby the functionality represents the number of oxirane-groups (oxacyclopropane-groups) per molecule. The functionality of the epoxide may be determined in a 2-step procedure, consisting of
a. ) determination of epoxy content, or the equivalent weight, e.g., using "ASTM D1652 - 04 Standard Test Method for Epoxy Content of Epoxy Resins" and
b. ) dividing the molecular weight of the starting material, which the epoxy resin is based on, by the equivalent weight a.)
Numbers other than integers for the functionality of the epoxy resin can originate from a. ) incomplete epoxidation of the natural oil, and/or
b. ) the number of epoxidizable double bonds per molecule of the natural oil which the epoxy resin is based on.
The epoxide can be selected from, but is not limited to, epoxidized soybean oil. The epoxidized soybean oil and the carbon dioxide can be obtained by commercial ways. In this reaction, the viscosity of the reaction mixture is relatively high, therefore, the reaction can be carried out in a solvent in order to provide a better dispersion. The solvent can be selected from, but is not limited to, Ν,Ν-dimethyl formamide (DMF), dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), methyl ethyl ketone (MEK), butanol, benzene, toluene, dimethylbenzene, more preferably Ν,Ν-dimethyl formamide (DMF), dimethyl sulfoxide (DMSO), tetrahydrofuran (TH F), most preferably Ν,Ν-dimethyl formamide (DMF), dimethyl sulfoxide (DMSO).
I n this reaction, there is no specific limit with regard to the amount of the catalyst, but enough to accelerate the reaction rate as the reaction requires. The amount of the catalyst can be selected from, but is not limited to, less than or equal to 20 weight parts, preferably 0.1 -15 weight parts, more preferably 1 -10 weight parts, most preferably 3-8 weight parts, based on 100 weight parts of the epoxidized soybean oil.
The reaction temperature can be selected from, but is not limited to, more than or equal to 100 °C, preferably 100-200 °C, more preferably 120-180 °C, most preferably 140-160 °C. If the reaction temperature is too low, the reaction rate might be reduced too much. If the reaction temperature is too high, the risk of undesired side reactions increases, and thus the yield and/or selectivity will be significantly reduced. The reaction time depends on many reaction conditions and can be determined in orienting experiments. The reaction time can be selected from, but is not limited to, less than or equal to 50 hours, more preferably less than or equal to 40 hours; furthermore preferably less than or equal to 30 hours. In the reaction, a relative high pressure of the carbon dioxide will push the reaction to the side of reaction product (cyclic carbonate). However, higher pressure of the carbon dioxide leads to higher equipment requirement and higher costs. From a cost perspective, the pressure of the carbon dioxide can be selected from, but is not limited to, less than or equal to 4.0 MPa, more preferably less than or equal to 3.0 MPa, most preferably less than or equal to 2.0 MPa.
In the present invention, the catalyst can be employed in fixed bed, fluidized bed or slurry reactor.
The reaction can be carried out continuously, semi-continuously or batch-wise. The order of the addition of the raw materials and/or the catalyst to the reactor is not critical, and the best way and/or most advantageous order to add the material and catalyst can be determined in orienting experiments. Furthermore, the cyclic carbonate formed during the reaction can be removed from the reactor by appropriate means continuously or intermittently in order to push the reaction equilibrium to the product side.
Appropriate reactors can be selected from preferably, but are is not limited to, stirred reactors and tubular reactors. The tubular reactors can be selected from preferably, but are is not limited to, tubular reactors with or without inserts, tubular reactors with or without mixing elements, tubular reactors with or without redispersing elements, tubular reactors with a combination of two or more members of the group including inserts, mixing elements and redispersing elements. I n the reaction process, the starting materials, the intermediates, the solvents or the catalysts can be recovered or recycled to any appropriate step of the reaction process.
After the reaction is finished, the reaction product can be removed from the reactor. The process of work-up and/or product isolation can be achieved by means of any appropriate technique/means/process step. The appropriate technique/means/process step can be selected from, but is not limited to, distillation, crystallization, filtration, sedimentation, decantation, centrifugation, extraction, membrane separation, or other means, or a combination of two or more of the aforesaid techniques/means.
In the process of the reaction or after the reaction is finished, the catalyst can be recovered and recycled by means of any appropriate technique/means/process step. The appropriate technique/means/process step can be selected from preferably, but is not limited to, distillation, crystallization, filtration, sedimentation, decantation, centrifugation, extraction, membrane separation, o r oth er m ea n s or by a combination of two or more of the aforesaid techniques/means. For example, the catalyst can be washed by a solvent and recovered by drying it for 12 hours at a temperature of 100 °C, for instance. The recovered catalyst can be treated by an oxidation process in order to renew its activity for subsequent uses. The oxidizing atmosphere of the oxidation process can be selected from, but is not limited to, air or oxygen, preferably air. The temperature of the oxidation process can be selected from, but is not limited to, 200-600 °C more preferably 200-500 °C, most preferably 200-400 °C. The duration of the oxidation process can be selected from, but is not limited to, more than or equal to 1 hour.
Examples
The examples and the methods disclosed in the present invention is illustrative and non- restrictive.
The description of the material
EDENOL® D81 Epoxidized soybean oil, with an average molecular weight of 935g/mol, the ethylene oxide content of 6.3-7.0%, available from Cognis.
C0 2 Carbon dioxide with a purity of 99.999%, available from Air Products.
E-55 Bisphenol bis-glycidyl ether with an epoxy value of 0.55-0.56, available from Shanghai Resin.
CER-170 Alicyclic ester epoxy resin, with an epoxy value of 0.40-0.60, available from Shanghai Resin.
The synthetis of cyclic carbonates was carried out in a stainless steel high pressure reactor with a volume of 500 cm 3 .
The epoxidized soybean oil, the solvent, and the catalyst were introduced into the reactor, heated to the temperature required . In the reaction process, the reaction mixture was pressurized with C0 2 . After the reaction was finished, the excess C0 2 was discharged.
After a filtration step and a washing step, the catalyst could be separated from the reaction product. The separated catalyst could be recovered after being dried for 4 hours under the condition of 100°C.
The conversion of th e epoxidized soybean oil could be monitored by a standard titration method according to the procedure reported in J. Appl. Polym. Sci. 2006, 1 02, p.2904-2914. Example E1
According to the co-impregnation method, the zirconium oxide was impregnated by a mixtu re of, a n aq ueou s sol ution of H 3 PW 12 04o containing 5 wt.% H 3 PW 12 04o and an aqueous solution of H 2 PtCI 6 contain ing 0.3 wt.% Pt, for 4 h ou rs to obtain a catalyst precursor.
The obtained catalyst precursor was dried for 12 hours at a temperature of 120 °C, and was calcinated for 4 hours at a temperature of 300 °C, to obtain a catalyst F-i .
50g Edenol D81 (epoxid ized soybean oil), 25 g Ν , Ν-dimethyl formamide a n d 5g catalyst F-i were charged into the reactor. The reactor was heated to 1 50 °C, and the C0 2 was introduced into the reactor. After being reacted for 30 hours under a reaction pressure of 1 .0 MPa, the soybean oil cyclic carbonate was obtained. The conversion of the epoxidized soybean oil was 92.0%.
Example E2
The catalyst F-i (see example E1 ), was recovered, washed, and dried for 4 hours at a temperature of 100 °C. After being treated in air atmosphere for 4 hours at a temperature of 300 °C, the activity of the catalyst was renewed. The renewed catalyst could be re-used for the reaction of the epoxidized soybean oil and carbon dioxide for preparing the soybean oil based cyclic carbonate.
This process was repeated for 3 times, the conversion of the epoxidized soybean oil was 88.2%, 82.4% and 78.3%, respectively. The results of E1 and E2 were listed in the Table 1 . Table 1 Preparation of the cyclic carbonate by using the catalyst F-i
Recycle numbers of catalyst Reaction C0 2 Conversion of temperature pressure ESBO
(°C) (MPa) (%)
1 First time 150 1 .0 92.0
2 Second time 150 1 .0 88.2
3 Third time 150 1 .0 82.4
4 Fourth time 150 1 .0 78.3
Reaction time: 30 hours
Example E3
According to the co-impregnation method, the silicon oxide was impregnated by a mixture of an aqueous solution of H 3 PW 12 04o containing 5 wt.% H 3 PW 12 04o and an aqueous solution of H 2 PtCI 6 containing 0.3 wt.% Pt, for 4 hours to obtain the catalyst precursor.
The obtained catalyst precursor was dried for 12 hours at a temperature of 120 °C, and was calcinated for 4 hours at a temperature of 300 °C, to obtain a catalyst F 2 .
50g Edenol D81 (epoxidized soybean oil), 25g Ν,Ν-dimethyl formamide and 5g catalyst F 2 were charged into the reactor. The reactor was heated to 1 50 °C, and the C0 2 was introduced into the reactor. After a reaction time of 30 hours at a reaction pressure of 1 .0 MPa, the soybean oil cyclic carbonate was obtained. The conversion of the epoxidized soybean oil was 78.4%.
Example E4
Accord i ng to the co-impregnation method, zirconium oxide was impregnated i n a mixture, which comprises a n a q u eo u s s o l u ti o n of H 3 PW 12 0 4 o containing 15 wt.% H 3 PW 12 0 4 o and an aqueous solution of H 2 PtCI 6 containing 0.3 wt.% Pt, for 4 hours to obtain a catalyst precursor.
The obtained catalyst precursor was dried for 12 hours at a temperature of 120 °C, and was calcinated for 4 hours at a temperature of 300 °C to obtain the catalyst F 3 .
50g Edenol D81 (epoxidized soybean oil), 25g Ν,Ν-dimethyl formamide and 5g catalyst F 3 were charged into the reactor. The reactor was heated to 150 °C, and the C0 2 was introduced into the reactor. After a reaction time of 30 hours under a reaction pressure of 1 .0 MPa, the soybean oil based cyclic carbonate was obtained. The conversion of the epoxidized soybean oil was 81 .3%.
Comparative Example C1
The zirconium oxide was impregnated by a mixture, which comprises an aqueous solution of H 3 PW 12 04o containing 5 wt.% H 3 PW 12 04o , for 4 h ou rs to obtai n a catalyst precursor.
The obtained catalyst precursor was dried for 12 hours at 120 °C, and was calcinated for 4 hours at 300 °C, to obtain the catalyst F 4 .
50g Edenol D81 (epoxidized soybean oil), 25g Ν,Ν-dimethyl formamide and 5g catalyst F 4 were charged into the reactor. The reactor was heated to 1 50 °C, and the C0 2 was introduced into the reactor. After a reaction time of 30 hours under a reaction pressure of 1 .0 MPa, the soybean oil based cyclic carbonate was obtained. The conversion of the epoxidized soybean oil was 91 .6%.
Comparative Example C2
The catalyst F 4 (see Example C1 ) was recovered , washed , and dried for 4 hours at temperature of 1 00 °C. The obtained catalyst was re-used for the reaction of epoxidized soybean oi l and ca rbon d ioxide for preparing the soybean oil cyclic carbonate, the conversion of the epoxidized soybean oil was 44.5%.
Comparative Example C3
The catalyst F 4 , which was obtained after the reaction for preparing the soybean oil cyclic carbonate in the Example C1 , was recovered , washed , and dried for 4 hours at a temperature of 100 °C. After being treated in the air atmosphere for 4 hours at temperature of 300 °C, the obtained catalyst was re-used for the reaction of epoxidized soybean oil and the carbon dioxide for preparing the soybean oil cyclic carbonate, the conversion of the epoxidized soybean oil was 52.7%. Comparative Example C4
The catalyst F 4 , which was obtained after the reaction for preparing the soybean oil cyclic carbonate in the Example C1 , was recovered, washed, and dried for 4 hours at a temperature of 100 °C. After bei n g treated in the air atmosphere for 4 h ou rs at a temperature of 500 °C, the obtained catalyst was re-used for the reaction of epoxidized soybean oil and carbon dioxide for preparing the soybean oil cyclic carbonate, the conversion of the epoxidized soybean oil was 55.4%. Table 2 Preparation of the cyclic carbonate by using the catalyst F 4
Recycle numbers of the catalyst Reaction C0 2 Conversion of temperature pressure the ESBO
(°C) (MPa) (%)
C1 First time 150 1 .0 91 .6
C2 Second time after being wahing 150 1 .0 44.5
C3 Second time after being oxidated 150 1 .0 52.7
under a condition of 300 °C
C4 Second time after being oxidated 150 1 .0 55.4
under a condition of 500 °C
Reaction time: 30 hours
Accord ing to the Examples E1 -E4 a nd th e Com parative Exam ples C1 -4, in the presence of the catalyst provided in the present invention , the epoxidized soybean oil could be reacted with the carbon dioxide to obtain the cyclic carbonate efficiently. The reaction conditions of the reaction was relatively mild, the activity and the selectivity of the catalyst was high, the reaction time was relatively short, furthermore, the catalyst provided in this invention could be conveniently separated from the reaction system. In addition, the catalyst further comprised a second transition metal or a metal compound of a second transition metal, which can be used to accelerate the thermal decomposition of the byproduct adsorbed on the catalyst to recover the activity of the catalyst and realize the recycle of the catalyst. Example E5
55g E-55 and 5g catalyst F1 were charged into the reactor. The reactor was heated to 100 °C, and the C02 was introd uced into the reactor. After being reacted for 30 hours under a reaction pressure of 1 .0 MPa, the cyclic carbonate was obtained. The conversion of the E-55 was 91 .6%.
Example E6
50g CER-170 and 5g catalyst F-i were charged into the reactor. The reactor was heated to 1 00 °C, and the C0 2 was introduced into the reactor. After being reacted for 30 hou rs u nder a reaction pressu re of 1 .0 MPa, the cyclic carbonate was obtained . The conversion of the CER-170 was 95.8%.
According to the Example E5 and E6, in the presence of the catalyst provided in the present invention, the epoxy resin could be reacted with the carbon dioxide to obtain the cyclic carbonate efficiently, under a condition of relative low temperature (100 °C). In addition, comparing with the high viscosity epoxidized soybean oil, the low viscosity terminal group epoxy compound could be reacted with the carbon dioxide without additional solvent, wherein the viscosity of the product was also relative low, the catalyst could be reused directly.
Although the present invention is illustrated by Examples, it is not limited by these Examples in any way. Without departing from the spirit and scope of this invention, those skilled in the art can make any modifications and alternatives. And the protection of this invention is based on the scope defined by the claims of this application.
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