CN105315130A - Method used for preparing 1,3-dihydric alcohol via Prins condensation reaction - Google Patents
Method used for preparing 1,3-dihydric alcohol via Prins condensation reaction Download PDFInfo
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Abstract
The invention relates to a method used for preparing a 1,3-dihydric alcohol via Prins condensation reaction. According to the method, an olefin and a formaldehyde aqueous solution are taken as reaction substrates, and direct preparation of the 1,3-dihydric alcohol is carried out under catalytic effect of an acidic composite metal oxide. The reaction process comprises following steps: the formaldehyde aqueous solution is mixed with a catalyst, and an obtained mixture is delivered into a pressure vessel for sealing; the olefin gas is added, stirring is carried out, and reaction is carried out for more than 2h at a temperature higher than 80 DEG C. After reaction, the catalyst is easily collected via separation from a reaction system, and can be recycled for a plurality of time, and the highest yield of the 1,3-dihydric alcohol is 90%.
Description
Technical field
The present invention relates to a kind of method being prepared 1,3-dibasic alcohol by Prins condensation reaction, the condensation and the hydrolysis reaction that are specifically related to formaldehyde and alkene prepare 1,3-dibasic alcohol.
Background technology
1,3-dibasic alcohol has important purposes in medicine, chemical industry, fuel etc., and main monomer and solvent, antifreezing agent or the protective material etc. being used as polyester and urethane are also important medicine intermediate and organic synthesis intermediate.1,3-PD can be used to synthetic paint, and it can also synthesize 3-hydroxy-propionic acid and propanedioic acid through atmospheric oxidation, with urea reaction synthesizing annular carbonate.1,3 butylene glycol can be used as the raw material of polyester resin, Synolac, also can be used as the synthesis of softening agent, can also be used as wetting agent and softening agent simultaneously.
The method of preparation 1,3-dibasic alcohol has been reported.Epoxide and synthesis gas reaction, in acidic medium, under the existence of rhodium and phosphine, are prepared 1,3-dibasic alcohol by CN87105645A.CN1424993 adopts copper containing catalyst, and catalyst hydrogenation 3-hydroxy aldehyde prepares 1,3-dibasic alcohol.CN1215715 discloses the method that 1,3-glycol prepared by one allylic epoxy alcohol and Lewis acid, yield 30% ~ 100%.US013834 adopts cobalt carbonyl catalyst, prepares 1,3-dibasic alcohol and 3-hydroxy aldehyde by epoxide hydroformylation.CN1733667 with molecular sieve, oxide compound or the two mixture be carrier, the two component of nickeliferous loading type for catalyzer, the 3-HPA aqueous solution is converted into 1,3-PD by two-stage hydrogenation reaction.CN101139253 prepares 1,3-PD by two-step approach.The first step 1,3-bromo-chloropropane and sodium acetate generate dibasic acid esters under the effect of alcohols catalyzer, and second step is that above-mentioned dibasic acid esters and methyl alcohol are generated 1,3-PD under the effect of resene catalyzer, and transformation efficiency and purity are all higher.CN1711228A discloses and a kind ofly adopts the mixture of ruthenium or ruthenium and other metals by the ester of 3-hydroxy-propionic acid, 3-hydroxy-propionic acid and other acid ester mixtures hydrogenation to prepare the method for 1,3-PD; CN101003462A discloses the method for a kind of glycerine legal system for 1,3-PD, and transformation efficiency reaches more than 95%; US5345004 reports three-step approach and prepares 1,3 butylene glycol, and the first step is that 2,6-dimethyl-1,3-diox-4-alcohol is prepared in acetaldehyde and alcohol condensation, and above-mentioned decomposition product is obtained paraldol by second step, and last hydrogenation obtains 1,3 butylene glycol.Patent CN1016654409A discloses a kind of method taking acidic ion liquid as the formaldehyde of catalyzer and olefinic hydrocarbon condensate and prepare 1,3-dibasic alcohol or its cyclic acetal.
There is route in the syntheti c route of current 1,3-dibasic alcohol long, yield is low, and catalyst preparing is complicated and be difficult to be separated and the problem such as catalyzer easy in inactivation.Therefore, develop the technological line that a kind of high-efficiency and low-cost prepares 1,3-dibasic alcohol, there is important application prospect.
Summary of the invention
Meaning of the present invention is to overcome the shortcoming prepared at present and exist in 1,3-dibasic alcohol process, and under relatively mild condition, high-efficiency and low-cost prepares this compounds, and catalyst preparing is simple and easy to be separated with substrate and can repeatedly recycle.
A kind of method being prepared 1,3-dibasic alcohol by Prins condensation reaction, be is characterized in that: after formalin and catalyst mix, put into pressurized vessel airtight, pour olefin gas, stir, temperature of reaction is higher than 80 DEG C, reaction times is longer than 2h, and reaction product is 1,3-dibasic alcohol.The mass concentration of described formaldehyde in initial reaction system is 1wt% ~ 60wt%, and in initial reaction system, the mol ratio of water and formaldehyde is for being more than or equal to 1; Described alkene is: one or more in ethene, trimethyl-ethylene, propylene, 1-butylene, iso-butylene, 1,3-butadiene; Described catalyzer is acid complex metal oxides, and acid complex metal oxides is: Al
2o
3-SiO
2, TiO
2-SiO
2, ZrO
2-SiO
2, TiO
2-ZrO
2, Al
2o
3-B
2o
3, Al
2o
3-ZnO, Al
2o
3-TiO
2, Al
2o
3-Fe
3o
4, SnO
2-ZnO, CeO
2-ZrO
2, CeO
2-La
2o
3, CeO
2-Al
2o
3, CeO
2-Eu
2o
3, Y
2o
3-ZrO
2in one or more; Acid complex metal can be labeled as A-B, and the mol ratio of A and B is 1:1 ~ 20:1; The molar ratio value of described formaldehyde and alkene is 0.01 ~ 100; The consumption of described catalyzer is 0.01g (mmol formaldehyde)
-1~ 0.50g (mmol formaldehyde)
-1; Described temperature of reaction is 80 DEG C ~ 230 DEG C; The described reaction times is 2h ~ 100h.
The mass concentration of described formaldehyde in initial reaction system is 7wt% ~ 38wt%, and in initial reaction system, the mol ratio of water and formaldehyde is more than or equal to 10; Described alkene is: one or more in propylene, iso-butylene, 1-butylene; Described catalyzer is acid complex metal oxides, and described acid composite oxides are: TiO
2-ZrO
2, Al
2o
3-B
2o
3, Al
2o
3-TiO
2, Al
2o
3-Fe
3o
4, SnO
2-ZnO, CeO
2-ZrO
2, CeO
2-La
2o
3, CeO
2-Eu
2o
3, Y
2o
3-ZrO
2in one or more;
The molar ratio value of described formaldehyde and alkene is 0.1 ~ 50; The consumption of described catalyzer is: 0.05g (mmol formaldehyde)
-1~ 0.2g (mmol formaldehyde)
-1; Described temperature of reaction is 120 DEG C ~ 200 DEG C;
The described reaction times is 8h ~ 50h.
Described catalyzer is acid complex metal oxides, and described acid complex metal oxides is: TiO
2-ZrO
2, Al
2o
3-B
2o
3, Al
2o
3-Fe
3o
4, SnO
2-ZnO, CeO
2-ZrO
2, CeO
2-La
2o
3, Y
2o
3-ZrO
2in one or more; The molar ratio value of described formaldehyde and alkene is 0.5 ~ 5; The consumption of described catalyzer is: 0.08g (mmol formaldehyde)
-1~ 0.1g (mmol formaldehyde)
-1; Described temperature of reaction is 150 DEG C ~ 180 DEG C; The described reaction times is 10h ~ 20h.
As follows with the path that formaldehyde and end group alkene generate 1,3-dibasic alcohol for reaction substrate: under the effect of acid catalyst, H
+generate formaldehyde carbonium ion with formaldehyde effect, then the C=C double bond of formaldehyde carbonium ion attack alkene again obtains enol carbonium ion, H in aqueous
2electronic attack enol carbonium ion on O molecule, sloughs H
+, generate 1,3-glycol.H in addition
+with the formaldehyde carbonium ion attack alkene that formaldehyde generates, form enol carbonium ion, enol carbonium ion continues and formaldehyde generation annulation, generate 1,3-dioxane or derivatives thereof, there is hydrolysis reaction in this product in acidic aqueous solution, generate 1,3-dibasic alcohol.
According to Thomas rule, add in metal oxide that valence mumber is different or other oxide compounds that ligancy is different will produce the acid site of activation, thus having a certain amount of defective bit as the acid complex metal oxides of carrier can as Lewis acid acidic site catalytic reaction process, and suitable strength of acid, be the important factor affecting catalytic efficiency.When strength of acid is higher, formaldehyde not only can be made protonated, propylene also can be made protonated, generate tetrahydropyrans-4-alcohol (4-methyl isophthalic acid, the isomers of 3-dioxane), reduce the selectivity of 1,3 butylene glycol, or 1,3-dibasic alcohol and 1, in the mutual conversion reaction of 3-dioxane and derivative thereof, be more conducive to the generation of dioxane, thus reduce the selectivity of dibasic alcohol; Meanwhile, water molecules dissociates completely after strong absorption occurs in Lewis acid position, causes Lewis acid position inactivation; When acidity is more weak, catalyst activity is lower, and the reaction times extends, and transformation efficiency and selectivity reduce even reaction and cannot carry out.Therefore the catalyzer of suitable strength of acid is selected to be the key improving methane amide yield.In this reaction, acidic oxide is preferably: TiO
2-ZrO
2, Al
2o
3-B
2o
3, Al
2o
3-Fe
3o
4, SnO
2-ZnO, CeO
2-ZrO
2, CeO
2-La
2o
3, Y
2o
3-ZrO
2in one or more.The consumption of catalyzer is: 0.08g (mmol formaldehyde)
-1~ 0.1g (mmol formaldehyde)
-1;
Compare with the method for existing preparation 1,3-dibasic alcohol, the present invention has some advantage following:
1. catalyst activity is high, the transformation efficiency of formaldehyde and the selectivity of 1,3-dibasic alcohol all higher, the yield of 1,3-dibasic alcohol is up to 90%.
2. catalyst preparing is simple, and raw materials is easy to get, and cost is lower, can be separated, and can repeatedly recycle by existing chemical engineering unit operation with reaction system;
3., for most gaseous olefin, especially to propylene, iso-butylene, 1-butylene, there is good catalyzed conversion effect.
Embodiment:
In order to be further elaborated to the present invention, provide several concrete case study on implementation below, but the invention is not restricted to these embodiments.
Embodiment 1
Coprecipitation method gained CeO
2-ZrO
2process is as follows: be dissolved in 100mL water respectively by 17.4g six nitric hydrate cerium and 2.31g Zircosol ZN (molar ratio of cerium and zirconium is 4:1), gained two solution is mixed, ammonia soln (volume ratio of ammoniacal liquor and water is 1:1) regulates pH=11, stirred at ambient temperature 4h, be separated by gained sedimentation and filtration, deionized water wash three times, by filter cake dried overnight in 100 DEG C of baking ovens, 500 DEG C of roasting 4h, namely obtain complex metal oxides CeO
2-ZrO
2.In the reactor of the polytetrafluoro lining of 250ml, add the formalin of 60mmol38%, 3g catalyzer and 10ml water respectively, pour 0.9MPa iso-butylene, stirring reaction 2h at 150 DEG C, after reaction terminates, chromatogram detects product, 3-methyl isophthalic acid, 3-butyleneglycol yield is in table 1.
Embodiment 2
Coprecipitation method gained CeO
2-ZrO
2process is as follows: be dissolved in 100mL water respectively by 17.4g six nitric hydrate cerium and 2.31g Zircosol ZN (molar ratio of cerium and zirconium is 4:1), gained two solution is mixed, ammonia soln (volume ratio of ammoniacal liquor and water is 1:1) regulates pH=11, stirred at ambient temperature 4h, be separated by gained sedimentation and filtration, deionized water wash three times, by filter cake dried overnight in 100 DEG C of baking ovens, 500 DEG C of roasting 4h, namely obtain complex metal oxides CeO
2-ZrO
2.In the reactor of the polytetrafluoro lining of 250ml, add the formalin of 60mmol38%, 3g catalyzer and 10ml water respectively, pour 0.9Mpa propylene, stirring reaction 12h at 180 DEG C, after reaction terminates, chromatogram detects product, 1,3 butylene glycol yield is in table 1.
Embodiment 3
Coprecipitation method gained CeO
2-ZrO
2process is as follows: be dissolved in 100mL water respectively by 17.4g six nitric hydrate cerium and 2.31g Zircosol ZN (molar ratio of cerium and zirconium is 4:1), gained two solution is mixed, ammonia soln (volume ratio of ammoniacal liquor and water is 1:1) regulates pH=11, stirred at ambient temperature 4h, be separated by gained sedimentation and filtration, deionized water wash three times, by filter cake dried overnight in 100 DEG C of baking ovens, 500 DEG C of roasting 4h, namely obtain complex metal oxides CeO
2-ZrO
2.In the reactor of the polytetrafluoro lining of 250ml, add the formalin of 60mmol38%, 3g catalyzer and 10ml water respectively, pour 0.9Mpa ethene, stirring reaction 12h at 200 DEG C, after reaction terminates, chromatogram detects product, 1,3-PD yield is in table 1.
Embodiment 4
Coprecipitation method gained CeO
2-ZrO
2process is as follows: be dissolved in 100mL water respectively by 21.7g six nitric hydrate cerium and 1.2g Zircosol ZN (molar ratio of cerium and zirconium is 10:1), gained two solution is mixed, ammonia soln (volume ratio of ammoniacal liquor and water is 1:1) regulates pH=11, stirred at ambient temperature 4h, be separated by gained sedimentation and filtration, deionized water wash three times, by filter cake dried overnight in 100 DEG C of baking ovens, 500 DEG C of roasting 4h, namely obtain complex metal oxides CeO
2-ZrO
2.In the reactor of the polytetrafluoro lining of 250ml, add the formalin of 60mmol38%, 3g catalyzer and 10ml water respectively, pour 0.9Mpa trimethyl-ethylene, stirring reaction 2h at 150 DEG C, after reaction terminates, chromatogram detects product, trimethylammonium-1,3-PD yield is in table 1.
Embodiment 5
Coprecipitation method gained CeO
2-ZrO
2process is as follows: be dissolved in 100mL water respectively by 21.7g six nitric hydrate cerium and 1.2g Zircosol ZN (molar ratio of cerium and zirconium is 10:1), gained two solution is mixed, ammonia soln (volume ratio of ammoniacal liquor and water is 1:1) regulates pH=11, stirred at ambient temperature 4h, be separated by gained sedimentation and filtration, deionized water wash three times, by filter cake dried overnight in 100 DEG C of baking ovens, 500 DEG C of roasting 4h, namely obtain complex metal oxides CeO
2-ZrO
2.In the reactor of the polytetrafluoro lining of 250ml, add the formalin of 60mmol38%, 3g catalyzer and 10ml water respectively, pour 0.9MPa1-butylene, stirring reaction 2h at 150 DEG C, after reaction terminates, chromatogram detects product, 1,3-pentanediol yield is in table 1.
Embodiment 6
Sol-gel method gained CeO
2-La
2o
3process is as follows: by 17.4g six water cerous nitrate and 4.33g lanthanum nitrate hexahydrate (molar ratio of cerium and lanthanum is 4), be dissolved in 100mL water respectively, by two solution mixing, add the thickening material ethylene glycol of 30mL, 1:1 (v:v) ammoniacal liquor is used to regulate pH=10, stir dehydration at 140 DEG C to make it to form vesicular xerogel, process 4h by dry for gained colloidal sol in atmosphere 400 DEG C, namely obtain complex metal oxides CeO
2-La
2o
3.In the reactor of the polytetrafluoro lining of 250ml, add formalin and the 0.15mol1-butylene of 80mmol38% respectively, take this reaction of 8gAmberlyst-15 catalysis, and add 15ml water, stirring reaction 30h at 130 DEG C, after reaction terminates, chromatogram detects product, 1,3-pentanediol yield is in table 1.
Embodiment 7
Sol-gel method gained CeO
2-La
2o
3process is as follows: by 8.2g six water cerous nitrate and 0.43g lanthanum nitrate hexahydrate (molar ratio of cerium and lanthanum is 19), be dissolved in 100mL water respectively, by two solution mixing, add the thickening material ethylene glycol of 30mL, 1:1 (v:v) ammoniacal liquor is used to regulate pH=10, stir dehydration at 140 DEG C to make it to form vesicular xerogel, process 4h by dry for gained colloidal sol in atmosphere 400 DEG C, namely obtain complex metal oxides CeO
2-La
2o
3.In the reactor of the polytetrafluoro lining of 250ml, add formalin and the 90mmol iso-butylene of 60mmol38% respectively, take this reaction of 3g catalyst, and add 10ml water, stirring reaction 2h at 150 DEG C, after reaction terminates, chromatogram detects product, 3-methyl isophthalic acid, 3-butyleneglycol yield is in table 1.
Embodiment 8
Coprecipitation method prepares CeO
2-La
2o
3process is as follows: by 8.2g six water cerous nitrate and 0.43g lanthanum nitrate hexahydrate (molar ratio of cerium and lanthanum is 19), be dissolved in 100mL water respectively, by two solution mixing, ammoniacal liquor regulates pH=11, stirred at ambient temperature 4h, is separated by gained sedimentation and filtration, deionized water wash 3 times, by filter cake dried overnight in 100 DEG C of baking ovens, 500 DEG C of roasting 4h, namely obtain complex metal oxides CeO
2-La
2o
3.In the reactor of the polytetrafluoro lining of 250ml, add formalin and the 0.15mol1-butylene of 80mmol38% respectively, take this reaction of 8gAmberlyst-15 catalysis, and add 15ml water, stirring reaction 30h at 150 DEG C, after reaction terminates, chromatogram detects product, 1,3-pentanediol yield is in table 1.
Embodiment 9
Coprecipitation method gained CeO
2-Eu
2o
3process is as follows: by 17.4g six water cerous nitrate and 4.5g six water europium nitrate (molar ratio of cerium and europium is 4), be dissolved in 100mL water respectively, by two solution mixing, use 1:1 (v:v) ammoniacal liquor to regulate pH=10, stirred at ambient temperature 4h, gained sedimentation and filtration is separated, deionized water wash three times, by filter cake dried overnight in 100 DEG C of baking ovens, 500 DEG C of roasting 4h, namely obtain complex metal oxides CeO
2-Eu
2o
3.In the reactor of the polytetrafluoro lining of 250ml, add formalin and the 0.15mol1-butylene of 80mmol38% respectively, take this reaction of 3g catalyst, and add 15ml water, stirring reaction 30h at 130 DEG C, after reaction terminates, chromatogram detects product, 1,3-pentanediol yield is in table 1.
Embodiment 10
Hydrothermal method gained SnO
2-ZnO process is as follows: be dissolved in 100mL water respectively by 13g tin chloride and 0.7g zinc chloride (molar ratio of tin and zinc is 10), after two solution mixing, 1:1 (v:v) ammoniacal liquor is used to regulate pH=11, stirred at ambient temperature 4h, gained precipitation is poured in Hydrothermal Synthesis still with mother liquor, 48h is placed in the baking oven of 200 DEG C, naturally cool to room temperature, filtering separation precipitates, deionized water wash three times, by filter cake dried overnight in 100 DEG C of baking ovens, namely obtain complex metal oxides SnO
2-ZnO.In the reactor of the polytetrafluoro lining of 250ml, add formalin and the 0.15mol1-butylene of 80mmol38% respectively, take this reaction of 2g catalyst, and add 15ml water, stirring reaction 30h at 130 DEG C, after reaction terminates, chromatogram detects product, 1,3-pentanediol yield is in table 1.
Embodiment 11
Hydrothermal method gained Y
2o
3-ZrO
2process is as follows: by 3.9g Yttrium trichloride and 0.18g basic zirconium chloride (molar ratio of yttrium and zirconium is 20), be dissolved in 50mL water respectively, by two solution mixing, 1:1 (v:v) ammoniacal liquor is used to regulate pH=11, be transferred in Hydrothermal Synthesis still after stirred at ambient temperature 4h, in 200 DEG C of baking ovens, process 2h.After naturally cooling to room temperature, filtering separation, deionized water wash three times, dried overnight at 100 DEG C, namely obtains complex metal oxides Y
2o
3-ZrO
2.In the reactor of the polytetrafluoro lining of 250ml, add formalin and the 0.4mol propylene of 0.2mol38% respectively, take this reaction of 5g catalysis, and add 30ml water, stirring reaction 10h at 180 DEG C, after reaction terminates, chromatogram detects product, and 1,3 butylene glycol yield is in table 1.
Embodiment 12
Hydrothermal method gained Y
2o
3-ZrO
2process is as follows: by 39.2g Yttrium trichloride and 3.6g basic zirconium chloride (molar ratio of yttrium and zirconium is 10), be dissolved in 100mL water respectively, by two solution mixing, 1:1 (v:v) ammoniacal liquor is used to regulate pH=11, be transferred in Hydrothermal Synthesis still after stirred at ambient temperature 4h, in 200 DEG C of baking ovens, process 2h.After naturally cooling to room temperature, filtering separation, deionized water wash three times, dried overnight at 100 DEG C, namely obtains complex metal oxides Y
2o
3-ZrO
2.In the reactor of the polytetrafluoro lining of 250ml, add formalin and the 0.15mol1-butylene of 80mmol38% respectively, take this reaction of 2g catalyst, and add 15ml water, stirring reaction 20h at 180 DEG C, after reaction terminates, chromatogram detects product, 1,3-pentanediol yield is in table 1.
Embodiment 13
Coprecipitation method gained CeO
2-Eu
2o
3process is as follows: by 21.7g six water cerous nitrate and 4.5g six water europium nitrate (molar ratio of cerium and europium is 5), be dissolved in 100mL water respectively, by two solution mixing, use 1:1 (v:v) ammoniacal liquor to regulate pH=10, stirred at ambient temperature 4h, gained sedimentation and filtration is separated, deionized water wash three times, by filter cake dried overnight in 100 DEG C of baking ovens, 500 DEG C of roasting 4h, namely obtain complex metal oxides CeO
2-Eu
2o
3.In the reactor of the polytetrafluoro lining of 250ml, add formalin and the 0.3mol ethene of 0.1mol38% respectively, take this reaction of this catalyst of 5g, and add 10ml water, stirring reaction 18h at 180 DEG C, after reaction terminates, chromatogram detects product, and 1,3-PD yield is in table 1.
Embodiment 14
Hydrothermal method gained SnO
2-ZnO process is as follows: by 13.4g tin chloride and 1.4g zinc chloride (molar ratio of tin and zinc is 5), be dissolved in 100mL water respectively, after two solution mixing, 1:1 (v:v) ammoniacal liquor is used to regulate pH=11, stirred at ambient temperature 4h, gained precipitation is poured in Hydrothermal Synthesis still with mother liquor, 48h is placed in the baking oven of 200 DEG C, naturally cool to room temperature, filtering separation precipitates, deionized water wash three times, by filter cake dried overnight in 100 DEG C of baking ovens, namely obtains complex metal oxides SnO
2-ZnO.In the reactor of the polytetrafluoro lining of 250ml, add formalin and the 90mmol iso-butylene of 60mmol38% respectively, take this reaction of 3g catalyst, and add 10mL water, stirring reaction 10h at 120 DEG C, after reaction terminates, chromatogram detects product, 3-methyl isophthalic acid, 3-butyleneglycol yield is in table 1.
Embodiment 15
Sol-gel method gained CeO
2-La
2o
3process is as follows: by 8.2g six water cerous nitrate and 0.43g lanthanum nitrate hexahydrate (molar ratio of cerium and lanthanum is 19), be dissolved in 100mL water respectively, by two solution mixing, add the thickening material ethylene glycol of 30mL, 1:1 (v:v) ammoniacal liquor is used to regulate pH=10, stir dehydration at 140 DEG C to make it to form vesicular xerogel, process 4h by dry for gained colloidal sol in atmosphere 400 DEG C, namely obtain complex metal oxides CeO
2-La
2o
3.In the reactor of the polytetrafluoro lining of 250ml, add formalin and the 90mmol iso-butylene of 60mmol38% respectively, take this reaction of 3g catalyst, and add 10ml water, stirring reaction 24h at 150 DEG C, after reaction terminates, chromatogram detects product, 3-methyl isophthalic acid, 3-butyleneglycol yield is in table 1.
Embodiment 16
Coprecipitation method gained CeO
2-ZrO
2process is as follows: be dissolved in 100mL water respectively by 17.4g six nitric hydrate cerium and 2.31g Zircosol ZN (molar ratio of cerium and zirconium is 4:1), gained two solution is mixed, ammonia soln (volume ratio of ammoniacal liquor and water is 1:1) regulates pH=11, stirred at ambient temperature 4h, be separated by gained sedimentation and filtration, deionized water wash three times, by filter cake dried overnight in 100 DEG C of baking ovens, 500 DEG C of roasting 4h, namely obtain complex metal oxides CeO
2-ZrO
2.In the reactor of the polytetrafluoro lining of 250ml, add the formalin of 60mmol38%, 3g catalyzer and 10ml water respectively, pour 0.9MPa iso-butylene, stirring reaction 24h at 150 DEG C, after reaction terminates, chromatogram detects product, 3-methyl isophthalic acid, 3-butyleneglycol yield is in table 1.
Comparative example 1:
In the reactor of the polytetrafluoro lining of 250ml, add formalin and the 90mmol iso-butylene of 60mmol38% respectively, take 3gCeO
2this reaction of catalysis, and add 10ml water, stirring reaction 2h at 150 DEG C, after reaction terminates, chromatogram detects product, and 3-methyl isophthalic acid, 3-butyleneglycol yield is in table 1.
Comparative example 2:
In the reactor of the polytetrafluoro lining of 250ml, add formalin and the 0.3mol ethene of 0.1mol38% respectively, take 5gCeO
2this reaction of catalysis, and add 10ml water, stirring reaction 18h at 150 DEG C, after reaction terminates, chromatogram detects product, and 1,3-PD yield is in table 1.
Table 1 alkene directly prepares the reaction evaluating result of 1,3-dibasic alcohol
| Formaldehyde conversion/% | The selectivity of 1,3-dibasic alcohol | |
| Embodiment 1 | 84 | 75 |
| Embodiment 2 | 45 | 89 |
| Embodiment 3 | 28 | 85 |
| Embodiment 4 | 70 | 80 |
| Embodiment 5 | 80 | 85 |
| Embodiment 6 | 75 | 97 |
| Embodiment 7 | 90 | 83 |
| Embodiment 8 | 85 | 99 |
| Embodiment 9 | 78 | 85 |
| Embodiment 10 | 87 | 92 |
| Embodiment 11 | 42 | 90 |
| Embodiment 12 | 78 | 99 |
| Embodiment 13 | 23 | 85 |
| Embodiment 14 | 83 | 99 |
| Embodiment 15 | 90 | 99 |
| Embodiment 16 | 85 | 99 |
| Comparative example 1 | 69 | 63 |
| Comparative example 2 | 12 | 85 |
The present invention relates to and adopt formalin and gaseous olefin as reactant, under katalysis, prepare 1,3-dibasic alcohol by Prins condensation and hydrolysis reaction.The method catalyst preparing is simple, and catalytic activity is high, and product yield can reach 90%, and simply, catalyzer can repeatedly recycle, and reaction process controllability is high for product and catalyst separating process.
Claims (4)
1. prepared the method for 1,3-dibasic alcohol by Prins condensation reaction for one kind, it is characterized in that:
After water-containing acetal and catalyst mix, put into pressurized vessel airtight, pour olefin gas, stir, temperature of reaction is more than or equal to 80 DEG C, and the reaction times is more than or equal to 2h, and reaction product is 1,3-dibasic alcohol.
2. in accordance with the method for claim 1, it is characterized in that:
The mass concentration of described formaldehyde in initial reaction system is 1wt% ~ 60wt%, and in initial reaction system, the mol ratio of water and formaldehyde is for being more than or equal to 1;
Described alkene is: one or more in ethene, trimethyl-ethylene, propylene, 1-butylene, iso-butylene, 1,3-butadiene;
Described catalyzer is acid complex metal oxides, and acid complex metal oxides is: Al
2o
3-SiO
2, TiO
2-SiO
2, ZrO
2-SiO
2, TiO
2-ZrO
2, Al
2o
3-B
2o
3, Al
2o
3-ZnO, Al
2o
3-TiO
2, Al
2o
3-Fe
3o
4, SnO
2-ZnO, CeO
2-ZrO
2, CeO
2-La
2o
3, CeO
2-Al
2o
3, CeO
2-Eu
2o
3, Y
2o
3-ZrO
2in one or more; Acid complex metal can be labeled as A-B, and the mol ratio of A and B is 1:1 ~ 20:1;
The molar ratio value of described formaldehyde and alkene is 0.01 ~ 100;
The consumption of described catalyzer is 0.01g (mmol formaldehyde)
-1~ 0.50g (mmol formaldehyde)
-1;
Described temperature of reaction is 80 DEG C ~ 230 DEG C;
The described reaction times is 2h ~ 100h.
3., according to the method described in claim 1 or 2, it is characterized in that:
The mass concentration of described formaldehyde in initial reaction system is 7wt% ~ 38wt%, and in initial reaction system, the mol ratio of water and formaldehyde is more than or equal to 10;
Described alkene is: one or more in propylene, iso-butylene, 1-butylene;
Described catalyzer is acid complex metal oxides, and described acid composite oxides are: TiO
2-ZrO
2, Al
2o
3-B
2o
3, Al
2o
3-TiO
2, Al
2o
3-Fe
3o
4, SnO
2-ZnO, CeO
2-ZrO
2, CeO
2-La
2o
3, CeO
2-Eu
2o
3, Y
2o
3-ZrO
2in one or more;
The molar ratio value of described formaldehyde and alkene is 0.1 ~ 50;
The consumption of described catalyzer is: 0.05g (mmol formaldehyde)
-1~ 0.2g (mmol formaldehyde)
-1;
Described temperature of reaction is 120 DEG C ~ 200 DEG C;
The described reaction times is 8h ~ 50h.
4., according to the method described in claim 1 or 2, it is characterized in that:
Described catalyzer is acid complex metal oxides, and described acid complex metal oxides is: TiO
2-ZrO
2, Al
2o
3-B
2o
3, Al
2o
3-Fe
3o
4, SnO
2-ZnO, CeO
2-ZrO
2, CeO
2-La
2o
3, Y
2o
3-ZrO
2in one or more;
The molar ratio value of described formaldehyde and alkene is 0.5 ~ 5;
The consumption of described catalyzer is: 0.08g (mmol formaldehyde)
-1~ 0.1g (mmol formaldehyde)
-1;
Described temperature of reaction is 150 DEG C ~ 180 DEG C;
The described reaction times is 10h ~ 20h.
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| CN108017513B (en) * | 2016-11-03 | 2021-06-01 | 中国科学院大连化学物理研究所 | Preparation method of 3-methyl-1, 3-butanediol |
| CN108586197A (en) * | 2018-05-03 | 2018-09-28 | 浙江新化化工股份有限公司 | A kind of production method of 1,3 butylene glycol |
| CN112645787A (en) * | 2019-10-11 | 2021-04-13 | 中国科学院大连化学物理研究所 | Method for preparing isoprene |
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| CN111908999B (en) * | 2020-08-21 | 2022-07-12 | 万华化学集团股份有限公司 | Method for preparing 1, 3-butanediol |
| CN113173832A (en) * | 2020-10-23 | 2021-07-27 | 源创核新(北京)新材料科技有限公司 | Method for synthesizing 1, 3-dihydric alcohol by using olefin and methanol as raw materials |
| CN113173832B (en) * | 2020-10-23 | 2022-05-17 | 源创核新(北京)新材料科技有限公司 | Method for synthesizing 1, 3-dihydric alcohol by using olefin and methanol as raw materials |
| CN113522265A (en) * | 2021-07-28 | 2021-10-22 | 中国科学院兰州化学物理研究所 | Metal oxide doped cerium oxide catalyst and preparation method and application thereof |
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