CN105315130B - A kind of method that 1,3 dihydric alcohols are prepared by Prins condensation reactions - Google Patents
A kind of method that 1,3 dihydric alcohols are prepared by Prins condensation reactions Download PDFInfo
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Abstract
The present invention relates to a kind of method that 1,3 dihydric alcohols are prepared by Prins condensation reactions.This method, as reaction substrate, under the catalytic action of acid metal composite oxide, directly prepares 1,3 dihydric alcohols using alkene and formalin.Its course of reaction is as follows：After formalin is mixed with catalyst, it is put into closed in pressure vessel, pours olefin gas, stirring, reaction temperature is higher than 80 DEG C, and the reaction time is longer than 2h, post catalyst reaction and reaction system are easily separated and can be recycled for multiple times, and the yield of 1,3 dihydric alcohol is up to 90%.
Description
Technical field
The present invention relates to the method that one kind prepares 1,3- dihydric alcohols by Prins condensation reactions, and in particular to formaldehyde
Condensation and hydrolysis with alkene prepare 1,3- dihydric alcohols.
Background technology
1,3- dihydric alcohol has important purposes in terms of medicine, chemical industry, fuel, is mainly used as the list of polyester and polyurethane
Body and solvent, antifreeze or protective agent etc., are also important medicine intermediate and organic synthesis intermediate.1,3- propane diols can
For synthetic paint, it can also synthesize 3- hydracrylic acids and malonic acid through air oxidation, with urea reaction synthesis of cyclic carbonic acid
Ester.1,3-BDO can be used as the raw material of polyester resin, alkyd resin, it is also possible to makees the synthesis of plasticizer, can also act as simultaneously
Wetting agent and softening agent.
The method for preparing 1,3- dihydric alcohols has been reported.CN87105645A is in acid medium, in the presence of rhodium and phosphine
Under, epoxides and synthesis gas reaction are prepared into 1,3- dihydric alcohols.CN1424993 uses Cu-contained catalyst, catalyst hydrogenation 3-
Hydroxy aldehyde prepares 1,3- dihydric alcohols.CN1215715 discloses one kind allylic epoxy alcohol and prepares 1,3- glycol with lewis acid
Method, yield 30%~100%.US013834 uses cobalt carbonyl catalyst, and 1 is prepared by epoxides hydroformylation,
3- dihydric alcohols and 3- hydroxy aldehydes.CN 1733667 is by carrier of molecular sieve, oxide or the two mixture, nickeliferous support type double
Component is catalyst, and the 3-HPA aqueous solution is converted into 1,3-PD by two-stage hydrogenation reaction.CN101139253 leads to
Cross two-step method and prepare 1,3- propane diols.First step 1,3- bromo-chloropropanes generate double with sodium acetate in the presence of alcohols catalyst
Ester, second step is that above-mentioned dibasic acid esters and methanol are generated into 1,3-PD, conversion ratio and purity in the presence of resinae catalyst
It is higher.CN1711228A discloses the mixtures of use ruthenium or ruthenium and other metals a kind of by 3- hydracrylic acids, 3- hydroxyls third
The method that the ester and other acid ester mixtures of acid are hydrogenated with to prepare 1,3- propane diols；CN101003462A discloses a kind of glycerine method
The method for preparing 1,3-PD, conversion ratio reaches more than 95%；US5345004 reports three-step approach and prepares 1,3-BDO,
The first step is that acetaldehyde prepares 2,6- dimethyl -1,3- dioxane -4- alcohol with alcohol condensation, and above-mentioned decomposition product is obtained two by second step
Hydroxyl butyraldehyde between poly-, finally hydrogenation obtains 1,3-BDO.Patent CN1016654409A disclose it is a kind of using acidic ion liquid as
The formaldehyde of catalyst prepares 1,3- dihydric alcohols or the method for its cyclic acetal with olefinic hydrocarbon condensate.
Have that route is long in the syntheti c route of current 1,3- dihydric alcohols, yield is low, catalyst preparation is complicated and is difficult to separate
And the problems such as catalyst easy in inactivation.Therefore, the technology path that a kind of high-efficiency and low-cost prepares 1,3- dihydric alcohols is developed, had
Important application prospect.
The content of the invention
Meaning of the present invention is to overcome prepares shortcoming present in 1,3- dihydric alcohol processes at present, in relatively mild bar
Under part, high-efficiency and low-cost prepares such compound, and catalyst preparation is simply easily separated with substrate and can be recycled for multiple times.
A kind of method that 1,3- dihydric alcohols are prepared by Prins condensation reactions, it is characterised in that：By formalin with urging
After agent mixing, it is put into closed in pressure vessel, pours olefin gas, stir, reaction temperature is higher than 80 DEG C, and the reaction time is longer than
2h, reaction product is 1,3- dihydric alcohols.Mass concentration of the formaldehyde in initial reaction system is 1wt%~60wt%, just
Beginning reaction system reclaimed water and the mol ratio of formaldehyde are more than or equal to 1；The alkene is：Ethene, trimethyl-ethylene, propylene, 1- fourths
It is more than one or both of alkene, isobutene, 1,3-butadiene；The catalyst is acid metal composite oxide, and acidity is multiple
Closing metal oxide is：Al2O3-SiO2、TiO2-SiO2、ZrO2-SiO2、TiO2-ZrO2、Al2O3-B2O3、Al2O3-ZnO、Al2O3-
TiO2、Al2O3-Fe3O4、SnO2-ZnO、CeO2-ZrO2、CeO2-La2O3、CeO2-Al2O3、CeO2-Eu2O3、Y2O3-ZrO2In one
Plant or two or more；Acid complex metal can be labeled as A-B, and A and B mol ratio is 1：1~20：1；It is described
The molar ratio value of formaldehyde and alkene is 0.01~100；The consumption of the catalyst is 0.01g (mmol formaldehyde)-1~
0.50g (mmol formaldehyde)-1；The reaction temperature is 80 DEG C~230 DEG C；The reaction time is 2h~100h.
Mass concentration of the formaldehyde in initial reaction system be 7wt%~38wt%, initial reaction system reclaimed water with
The mol ratio of formaldehyde is more than or equal to 10；The alkene is：It is more than one or both of propylene, isobutene, 1- butylene；It is described to urge
Agent is acid metal composite oxide, and the acid composite oxides are：TiO2-ZrO2、Al2O3-B2O3、Al2O3-TiO2、
Al2O3-Fe3O4、SnO2-ZnO、CeO2-ZrO2、CeO2-La2O3、CeO2-Eu2O3、Y2O3-ZrO2One or both of more than；
The molar ratio value of the formaldehyde and alkene is 0.1~50；The consumption of the catalyst is：0.05g·(mmol
Formaldehyde)-1~0.2g (mmol formaldehyde)-1；The reaction temperature is 120 DEG C~200 DEG C；
The reaction time is 8h~50h.
The catalyst is acid metal composite oxide, and the acid metal composite oxide is：TiO2-ZrO2、
Al2O3-B2O3、Al2O3-Fe3O4、SnO2-ZnO、CeO2-ZrO2、CeO2-La2O3、Y2O3-ZrO2One or both of more than；Institute
The molar ratio value for stating formaldehyde and alkene is 0.5~5；The consumption of the catalyst is：0.08g (mmol formaldehyde)-1~
0.1g (mmol formaldehyde)-1；The reaction temperature is 150 DEG C~180 DEG C；The reaction time is 10h~20h.
It is as follows using formaldehyde and end group alkene as the path that reaction substrate generates 1,3- dihydric alcohols：In the effect of acid catalyst
Under, H+With formaldehyde effect generation formaldehyde carbonium ion, then the C=C double bonds of formaldehyde carbonium ion attack alkene again obtain enol
Carbonium ion, in aqueous H2Electronic attack enol carbonium ion on O molecules, sloughs H+, generate 1,3- glycol.Other H+
The formaldehyde carbonium ion attack alkene generated with formaldehyde, forms enol carbonium ion, and enol carbonium ion continues to occur with formaldehyde
Annulation, generation 1,3- dioxane or derivatives thereof, hydrolysis, generation 1,3- occur in acidic aqueous solution for the product
Dihydric alcohol.
According to Thomas rules, valence mumber difference is added in metal oxide or other different oxides of ligancy will
The acid site of activation is produced, thus has a certain amount of defective bit can conduct as the acid metal composite oxide of carrier
Lewis acid acidic site catalytic reaction processes, and suitable acid strength, are to influence the key factor of catalytic efficiency.Acid strength compared with
Gao Shi, can not only protonate formaldehyde, can also protonate propylene, generate oxinane -4- alcohol (4- methyl isophthalic acids, 3- dioxies six
The isomer of ring), reduce the selectivity of 1,3-BDO, or 1,3- dihydric alcohol and 1,3- dioxane and its derivative
In the mutual conversion reaction of thing, the generation of dioxane is more beneficial for, so as to reduce the selectivity of dihydric alcohol；Meanwhile, hydrone
It will be completely dissociated after occurring strong absorption in the sour positions of Lewis, cause the sour position inactivations of Lewis；When acid weaker, catalyst activity is relatively low,
Reaction time extends, and conversion ratio and selectivity reduction even reaction can not be carried out.Therefore selecting the catalyst of suitable acid strength is
Improve the key of formamide yield.Acidic oxide is preferably in the reaction：TiO2-ZrO2、Al2O3-B2O3、Al2O3-
Fe3O4、SnO2-ZnO、CeO2-ZrO2、CeO2-La2O3、Y2O3-ZrO2One or both of more than.The consumption of catalyst is：
0.08g (mmol formaldehyde)-1~0.1g (mmol formaldehyde)-1；
Compared with the method for existing preparation 1,3- dihydric alcohols, the present invention has some following advantage：
1. catalyst activity is high, the conversion ratio of formaldehyde and the selectivity of 1,3- dihydric alcohol are higher, the receipts of 1,3- dihydric alcohol
Rate is up to 90%.
2. catalyst preparation is simple, preparing raw material is easy to get, and cost is relatively low, can by existing chemical engineering unit operation with it is anti-
Answer system to separate, and can be recycled for multiple times；
3. for most gaseous olefin, especially there is good catalyzed conversion to imitate to propylene, isobutene, 1- butylene
Really.
Embodiment：
In order to which the present invention will be described in further detail, several specific implementation cases are given below, but the present invention is not limited
In these embodiments.
Embodiment 1
CeO obtained by coprecipitation2-ZrO2Process is as follows：By the nitric hydrate ceriums of 17.4g six and 2.31g zirconyl nitrates (cerium with
The molar ratio of zirconium is 4：1) it is dissolved separately in 100mL water, the solution of gained two is mixed, the ammonia spirit (body of ammoniacal liquor and water
Product is than being 1：1) pH=11 is adjusted, 4h is stirred at room temperature, gained precipitation is separated by filtration, deionized water is washed three times, by filter cake
It is dried overnight in 100 DEG C of baking ovens, 500 DEG C of roasting 4h obtain metal composite oxide CeO2-ZrO2.Poly- the four of 250ml
In the reactor of fluorine lining, 60mmol38% formalin, 3g catalyst and 10ml water is separately added into, 0.9MPa is poured
Isobutene, the stirring reaction 2h at 150 DEG C, after reaction terminates, chromatogram detection product, 3- methyl isophthalic acids, 3- butanediol yields are shown in Table
1。
Embodiment 2
CeO obtained by coprecipitation2-ZrO2Process is as follows：By the nitric hydrate ceriums of 17.4g six and 2.31g zirconyl nitrates (cerium with
The molar ratio of zirconium is 4：1) it is dissolved separately in 100mL water, the solution of gained two is mixed, the ammonia spirit (body of ammoniacal liquor and water
Product is than being 1：1) pH=11 is adjusted, 4h is stirred at room temperature, gained precipitation is separated by filtration, deionized water is washed three times, by filter cake
It is dried overnight in 100 DEG C of baking ovens, 500 DEG C of roasting 4h obtain metal composite oxide CeO2-ZrO2.Poly- the four of 250ml
In the reactor of fluorine lining, 60mmol38% formalin, 3g catalyst and 10ml water is separately added into, 0.9Mpa is poured
Propylene, the stirring reaction 12h at 180 DEG C, after reaction terminates, chromatogram detection product, 1,3-BDO yield is shown in Table 1.
Embodiment 3
CeO obtained by coprecipitation2-ZrO2Process is as follows：By the nitric hydrate ceriums of 17.4g six and 2.31g zirconyl nitrates (cerium with
The molar ratio of zirconium is 4：1) it is dissolved separately in 100mL water, the solution of gained two is mixed, the ammonia spirit (body of ammoniacal liquor and water
Product is than being 1：1) pH=11 is adjusted, 4h is stirred at room temperature, gained precipitation is separated by filtration, deionized water is washed three times, by filter cake
It is dried overnight in 100 DEG C of baking ovens, 500 DEG C of roasting 4h obtain metal composite oxide CeO2-ZrO2.Poly- the four of 250ml
In the reactor of fluorine lining, 60mmol38% formalin, 3g catalyst and 10ml water is separately added into, 0.9Mpa is poured
Ethene, the stirring reaction 12h at 200 DEG C, after reaction terminates, chromatogram detection product, 1,3-PD yield is shown in Table 1.
Embodiment 4
CeO obtained by coprecipitation2-ZrO2Process is as follows：By the nitric hydrate ceriums of 21.7g six and 1.2g zirconyl nitrates (cerium and zirconium
Molar ratio be 10：1) it is dissolved separately in 100mL water, the solution of gained two is mixed, the ammonia spirit (volume of ammoniacal liquor and water
Than for 1：1) adjust pH=11,4h is stirred at room temperature, by gained precipitation be separated by filtration, deionized water wash three times, by filter cake in
It is dried overnight in 100 DEG C of baking ovens, 500 DEG C of roasting 4h obtain metal composite oxide CeO2-ZrO2.In 250ml polytetrafluoro
In the reactor of lining, 60mmol38% formalin, 3g catalyst and 10ml water is separately added into, 0.9Mpa tri- is poured
Ethylene methacrylic, the stirring reaction 2h at 150 DEG C, after reaction terminates, chromatogram detection product, trimethyl -1,3-PD yield is shown in
Table 1.
Embodiment 5
CeO obtained by coprecipitation2-ZrO2Process is as follows：By the nitric hydrate ceriums of 21.7g six and 1.2g zirconyl nitrates (cerium and zirconium
Molar ratio be 10：1) it is dissolved separately in 100mL water, the solution of gained two is mixed, the ammonia spirit (volume of ammoniacal liquor and water
Than for 1：1) adjust pH=11,4h is stirred at room temperature, by gained precipitation be separated by filtration, deionized water wash three times, by filter cake in
It is dried overnight in 100 DEG C of baking ovens, 500 DEG C of roasting 4h obtain metal composite oxide CeO2-ZrO2.In 250ml polytetrafluoro
In the reactor of lining, 60mmol38% formalin, 3g catalyst and 10ml water is separately added into, 0.9MPa1- is poured
Butylene, the stirring reaction 2h at 150 DEG C, after reaction terminates, chromatogram detection product, 1,3- pentanediol yield is shown in Table 1.
Embodiment 6
CeO obtained by sol-gel process2-La2O3Process is as follows：By the water cerous nitrates of 17.4g six and 4.33g lanthanum nitrate hexahydrates
(molar ratio of cerium and lanthanum is 4), is dissolved separately in 100mL water, two solution is mixed, add 30mL thickener second two
Alcohol, uses 1：1(v：V) ammoniacal liquor adjusts stirring dehydration at pH=10,140 DEG C and is allowed to form cellular xerogel, and gained is done into molten
Glue handles 4h at 400 DEG C in atmosphere, that is, obtains metal composite oxide CeO2-La2O3.250ml polytetrafluoro lining it is anti-
Answer in kettle, be separately added into 80mmol38% formalin and 0.15mol1- butylene, weigh 8g Amberlyst-15 and urge
Change the reaction, and add 15ml water, the stirring reaction 30h at 130 DEG C, after reaction terminates, chromatogram detection product, 1,3- pentanediol
Yield is shown in Table 1.
Embodiment 7
CeO obtained by sol-gel process2-La2O3Process is as follows：By the water cerous nitrates of 8.2g six and 0.43g lanthanum nitrate hexahydrate (ceriums
Molar ratio with lanthanum mixes two solution 19), to be dissolved separately in 100mL water, adds 30mL thickener ethylene glycol,
Use 1：1(v：V) ammoniacal liquor adjusts stirring dehydration at pH=10,140 DEG C and is allowed to form cellular xerogel, and the dry colloidal sol of gained is existed
4h is handled in air at 400 DEG C, that is, obtains metal composite oxide CeO2-La2O3.In the reactor of 250ml polytetrafluoro lining
In, 60mmol38% formalin and 90mmol isobutenes is separately added into, the 3g catalysts reactions is weighed, and add
Enter 10ml water, the stirring reaction 2h at 150 DEG C, after reaction terminates, chromatogram detection product, 3- methyl isophthalic acids, 3- butanediol yields are shown in
Table 1.
Embodiment 8
Coprecipitation prepares CeO2-La2O3Process is as follows：By the water cerous nitrates of 8.2g six and 0.43g lanthanum nitrate hexahydrates (cerium with
The molar ratio of lanthanum mixes two solution 19), to be dissolved separately in 100mL water, ammoniacal liquor regulation pH=11, stirs at room temperature
4h, gained precipitation is separated by filtration, deionized water is washed 3 times, and filter cake is dried overnight in 100 DEG C of baking ovens, 500 DEG C of roastings
4h, that is, obtain metal composite oxide CeO2-La2O3.In the reactor of 250ml polytetrafluoro lining, it is separately added into
80mmol38% formalin and 0.15mol1- butylene, weighs 8g Amberlyst-15 and is catalyzed the reaction, and add
15ml water, the stirring reaction 30h at 150 DEG C, after reaction terminates, chromatogram detection product, 1,3- pentanediol yield is shown in Table 1.
Embodiment 9
CeO obtained by coprecipitation2-Eu2O3Process is as follows：By the water cerous nitrates of 17.4g six and the water europium nitrates of 4.5g six (cerium with
Two solution are mixed 4), to be dissolved separately in 100mL water, use 1 by the molar ratio of europium：1(v：V) ammoniacal liquor regulation pH=10,
4h is stirred at room temperature, gained precipitation is separated by filtration, deionized water is washed three times, and filter cake is dried overnight in 100 DEG C of baking ovens,
500 DEG C of roasting 4h, that is, obtain metal composite oxide CeO2-Eu2O3.In the reactor of 250ml polytetrafluoro lining, respectively
80mmol38% formalin and 0.15mol1- butylene is added, the 3g catalysts reactions is weighed, and add 15ml
Water, the stirring reaction 30h at 130 DEG C, after reaction terminates, chromatogram detection product, 1,3- pentanediol yield is shown in Table 1.
Embodiment 10
SnO obtained by hydro-thermal method2- ZnO processes are as follows：By 13g stannic chlorides and 0.7g zinc chloride, (molar ratio of tin and zinc is
10) it is dissolved separately in 100mL water, after two solution are mixed, uses 1：1(v：V) ammoniacal liquor regulation pH=11, is stirred at room temperature
4h, gained precipitation is poured into Hydrothermal Synthesiss kettle with mother liquor, 48h is placed in 200 DEG C of baking oven, naturally cools to room temperature, mistake
Precipitation and separation is filtered, deionized water is washed three times, filter cake is dried overnight in 100 DEG C of baking ovens, that is, obtains metal composite oxide
SnO2-ZnO.In the reactor of 250ml polytetrafluoro lining, be separately added into 80mmol38% formalin and
0.15mol1- butylene, weighs the 2g catalysts reactions, and adds 15ml water, the stirring reaction 30h at 130 DEG C, reaction knot
Shu Hou, chromatogram detection product, 1,3- pentanediol yield is shown in Table 1.
Embodiment 11
Y obtained by hydro-thermal method2O3-ZrO2Process is as follows：By 3.9g yttrium chlorides and the 0.18g basic zirconium chlorides (mol ratio of yttrium and zirconium
Two solution are mixed 20), to be dissolved separately in 50mL water, use 1 by example：1(v：V) ammoniacal liquor regulation pH=11, is stirred at room temperature
It is transferred to after 4h in Hydrothermal Synthesiss kettle, 2h is handled in 200 DEG C of baking ovens.Naturally cool to after room temperature, be separated by filtration, deionized water
It is dried overnight at washing three times, 100 DEG C, that is, obtains metal composite oxide Y2O3-ZrO2.250ml polytetrafluoro lining it is anti-
Answer in kettle, be separately added into 0.2mol38% formalin and 0.4mol propylene, weigh 5g and be catalyzed the reaction, and add
30ml water, the stirring reaction 10h at 180 DEG C, after reaction terminates, chromatogram detection product, 1,3-BDO yield is shown in Table 1.
Embodiment 12
Y obtained by hydro-thermal method2O3-ZrO2Process is as follows：By 39.2g yttrium chlorides and the 3.6g basic zirconium chlorides (mol ratio of yttrium and zirconium
Two solution are mixed 10), to be dissolved separately in 100mL water, use 1 by example：1(v：V) ammoniacal liquor regulation pH=11, is stirred at room temperature
Mix and be transferred to after 4h in Hydrothermal Synthesiss kettle, 2h is handled in 200 DEG C of baking ovens.Naturally cool to after room temperature, be separated by filtration, deionization
It is dried overnight at water washing three times, 100 DEG C, that is, obtains metal composite oxide Y2O3-ZrO2.In 250ml polytetrafluoro lining
In reactor, 80mmol38% formalin and 0.15mol1- butylene is separately added into, weighing 2g catalysts, this is anti-
Should, and 15ml water is added, and the stirring reaction 20h at 180 DEG C, after reaction terminates, chromatogram detection product, 1,3- pentanediol yield is shown in
Table 1.
Embodiment 13
CeO obtained by coprecipitation2-Eu2O3Process is as follows：By the water cerous nitrates of 21.7g six and the water europium nitrates of 4.5g six (cerium with
Two solution are mixed 5), to be dissolved separately in 100mL water, use 1 by the molar ratio of europium：1(v：V) ammoniacal liquor regulation pH=10,
4h is stirred at room temperature, gained precipitation is separated by filtration, deionized water is washed three times, and filter cake is dried overnight in 100 DEG C of baking ovens,
500 DEG C of roasting 4h, that is, obtain metal composite oxide CeO2-Eu2O3.In the reactor of 250ml polytetrafluoro lining, respectively
0.1mol38% formalin and 0.3mol ethene is added, 5g catalysts reactions is weighed, and add 10ml
Water, the stirring reaction 18h at 180 DEG C, after reaction terminates, chromatogram detection product, 1,3-PD yield is shown in Table 1.
Embodiment 14
SnO obtained by hydro-thermal method2- ZnO processes are as follows：By 13.4g stannic chlorides and the 1.4g zinc chloride (molar ratio of tin and zinc
5), to be dissolved separately in 100mL water, after two solution are mixed, 1 is used：1(v：V) ammoniacal liquor regulation pH=11, is stirred at room temperature
4h, gained precipitation is poured into Hydrothermal Synthesiss kettle with mother liquor, 48h is placed in 200 DEG C of baking oven, naturally cools to room temperature, mistake
Precipitation and separation is filtered, deionized water is washed three times, filter cake is dried overnight in 100 DEG C of baking ovens, that is, obtains metal composite oxide
SnO2-ZnO.In the reactor of 250ml polytetrafluoro lining, be separately added into 60mmol38% formalin and
90mmol isobutenes, weigh the 3g catalysts reactions, and add 10mL water, the stirring reaction 10h at 120 DEG C, reaction knot
Shu Hou, chromatogram detection product, 3- methyl isophthalic acids, 3- butanediol yields are shown in Table 1.
Embodiment 15
CeO obtained by sol-gel process2-La2O3Process is as follows：By the water cerous nitrates of 8.2g six and 0.43g lanthanum nitrate hexahydrate (ceriums
Molar ratio with lanthanum mixes two solution 19), to be dissolved separately in 100mL water, adds 30mL thickener ethylene glycol,
Use 1：1(v：V) ammoniacal liquor adjusts stirring dehydration at pH=10,140 DEG C and is allowed to form cellular xerogel, and the dry colloidal sol of gained is existed
4h is handled in air at 400 DEG C, that is, obtains metal composite oxide CeO2-La2O3.In the reactor of 250ml polytetrafluoro lining
In, 60mmol38% formalin and 90mmol isobutenes is separately added into, the 3g catalysts reactions is weighed, and add
Enter 10ml water, the stirring reaction 24h at 150 DEG C, after reaction terminates, chromatogram detection product, 3- methyl isophthalic acids, 3- butanediol yields are shown in
Table 1.
Embodiment 16
CeO obtained by coprecipitation2-ZrO2Process is as follows：By the nitric hydrate ceriums of 17.4g six and 2.31g zirconyl nitrates (cerium with
The molar ratio of zirconium is 4：1) it is dissolved separately in 100mL water, the solution of gained two is mixed, the ammonia spirit (body of ammoniacal liquor and water
Product is than being 1：1) pH=11 is adjusted, 4h is stirred at room temperature, gained precipitation is separated by filtration, deionized water is washed three times, by filter cake
It is dried overnight in 100 DEG C of baking ovens, 500 DEG C of roasting 4h obtain metal composite oxide CeO2-ZrO2.Poly- the four of 250ml
In the reactor of fluorine lining, 60mmol38% formalin, 3g catalyst and 10ml water is separately added into, 0.9MPa is poured
Isobutene, the stirring reaction 24h at 150 DEG C, after reaction terminates, chromatogram detection product, 3- methyl isophthalic acids, 3- butanediol yields are shown in Table
1。
Comparative example 1：
In the reactor of 250ml polytetrafluoro lining, be separately added into 60mmol38% formalin and
90mmol isobutenes, weigh 3g CeO2The reaction is catalyzed, and adds 10ml water, the stirring reaction 2h at 150 DEG C, reaction terminates
Afterwards, chromatogram detection product, 3- methyl isophthalic acids, 3- butanediol yields are shown in Table 1.
Comparative example 2：
In the reactor of 250ml polytetrafluoro lining, be separately added into 0.1mol38% formalin and
0.3mol ethene, weighs 5g CeO2The reaction is catalyzed, and adds 10ml water, the stirring reaction 18h at 150 DEG C, reaction terminates
Afterwards, chromatogram detection product, 1,3-PD yield is shown in Table 1.
The alkene of table 1 directly prepares the reaction evaluating result of 1,3- dihydric alcohols
| Formaldehyde conversion/% | The selectivity of 1,3- dihydric 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, as reactant, under catalytic action, contracted using formalin and gaseous olefin by Prins
Close and hydrolysis prepares 1,3- dihydric alcohols.This method catalyst preparation is simple, and catalytic activity is high, and product yield can reach
90%, product and catalyst separation process are simple, and catalyst can be recycled for multiple times, and course of reaction controllability is high.
Claims (4)
1. a kind of method that 1,3- dihydric alcohols are prepared by Prins condensation reactions, it is characterised in that：
After water-containing acetal is mixed with catalyst, it is put into closed in pressure vessel, pours olefin gas, stir, reaction temperature is big
In equal to 80 DEG C, the reaction time is more than or equal to 2h, and reaction product is 1,3- dihydric alcohols；
The catalyst is acid metal composite oxide, and acid metal composite oxide is：Al2O3-SiO2、TiO2-SiO2、
ZrO2-SiO2、TiO2-ZrO2、Al2O3-B2O3、Al2O3-ZnO、Al2O3-TiO2、Al2O3-Fe3O4、SnO2-ZnO、CeO2-ZrO2、
CeO2-La2O3、CeO2-Al2O3、CeO2-Eu2O3、Y2O3-ZrO2One or both of more than；Acid metal composite oxide knot
Structure can be labeled as A-B, and A and B mol ratio is 1：1~20：1.
2. in accordance with the method for claim 1, it is characterised in that：
Mass concentration of the formaldehyde in initial reaction system is 1wt%~60wt%, initial reaction system reclaimed water and formaldehyde
Mol ratio be more than or equal to 1；
The alkene is：One or both of ethene, trimethyl-ethylene, propylene, 1- butylene, isobutene, 1,3-butadiene with
On；
The molar ratio value of the formaldehyde and alkene is 0.01~100；
The consumption of the catalyst is 0.01g (mmol formaldehyde)-1~0.50g (mmol formaldehyde)-1；
The reaction temperature is 80 DEG C~230 DEG C；
The reaction time is 2h~100h.
3. according to the method described in claim 1 or 2, it is characterised in that：
Mass concentration of the formaldehyde in initial reaction system is 7wt%~38wt%, initial reaction system reclaimed water and formaldehyde
Mol ratio be more than or equal to 10；
The alkene is：It is more than one or both of propylene, isobutene, 1- butylene；
The catalyst is acid metal composite oxide, and the acid metal composite oxide is：TiO2-ZrO2、Al2O3-
B2O3、Al2O3-TiO2、Al2O3-Fe3O4、SnO2-ZnO、CeO2-ZrO2、CeO2-La2O3、CeO2-Eu2O3、Y2O3-ZrO2In one
Plant or two or more；
The molar ratio value of the formaldehyde and alkene is 0.1~50；
The consumption of the catalyst is：0.05g (mmol formaldehyde)-1~0.2g (mmol formaldehyde)-1；
The reaction temperature is 120 DEG C~200 DEG C；
The reaction time is 8h~50h.
4. according to the method described in claim 1 or 2, it is characterised in that：
The catalyst is acid metal composite oxide, and the acid metal composite oxide is：TiO2-ZrO2、Al2O3-
B2O3、Al2O3-Fe3O4、SnO2-ZnO、CeO2-ZrO2、CeO2-La2O3、Y2O3-ZrO2One or both of more than；
The molar ratio value of the formaldehyde and alkene is 0.5~5；
The consumption of the catalyst is：0.08g (mmol formaldehyde)-1~0.1g (mmol formaldehyde)-1；
The reaction temperature is 150 DEG C~180 DEG C；
The reaction time 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 |
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| CN112645787B (en) * | 2019-10-11 | 2022-03-08 | 中国科学院大连化学物理研究所 | Method for preparing isoprene |
| 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 |
| 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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