CN109553516A - A kind of method of glycerol indirect oxidation synthesis C3H6O3 - Google Patents
A kind of method of glycerol indirect oxidation synthesis C3H6O3 Download PDFInfo
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- CN109553516A CN109553516A CN201710878349.9A CN201710878349A CN109553516A CN 109553516 A CN109553516 A CN 109553516A CN 201710878349 A CN201710878349 A CN 201710878349A CN 109553516 A CN109553516 A CN 109553516A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
- C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings
Abstract
The present invention relates to a kind of glycerol indirect oxidation synthesis 1, the method of 3- dihydroxyacetone (DHA), method is as follows: acetalation: using organic solvent as water entrainer, aldolisation occurs under the action of solid acid catalyst and obtains 2- phenyl -5- hydroxyl -1,3- dioxane (HPD) for glycerol and benzaldehyde；Oxidation reaction: in organic solvent, 2- phenyl -5- hydroxyl -1,3- dioxane (HPD) is oxidized agent and is oxidized to 2- phenyl -5- carbonyl -1,3- dioxane (PDO) under the action of liquid catalyst and auxiliary agent sodium bromide；Hydrolysis: under the action of liquid acid catalyst hydrolysis occurs for 2- phenyl -5- carbonyl -1,3- dioxane (PDO), obtains target product.For synthesis route of the invention using glycerol as raw material, selectivity and yield are higher than direct oxidation method, and target product separation is simple, and product purity is up to 99%, is convenient for industrialized production.
Description
Technical field
The present invention relates to technical field of organic synthesis, and in particular to a kind of glycerol indirect oxidation synthesis 1,3-Dihydroxyacetone
Method.
Background technique
In recent years, being continuously increased with the increasingly depleted and demand of petroleum resources, the whole world all suffers from energy shortage
Crisis.Consider for national energy security, renewable energy is sought competitively to alleviate petroleum anxiety problem in countries in the world.It is raw
Object diesel oil has the characteristics that combustibility is superior, non-corrosive, cleanliness without any pollution, is a kind of non-as a kind of renewable energy
Often promising energy substitution product.
During preparing biodiesel, 10 tons of biodiesel of every production will about 1 ton of glycerol of by-product, this is a kind of pole
Attractive, reproducible green chemical industry basic material.A large amount of biodiesel be produced as chemical industry provide enrich it is honest and clean
The glycerol of valence.C3H6O3 (DHA) is one kind important medicine intermediate, industrial chemicals and food additives, makeup
The ingredient of product self-tanning agent.Furthermore, it may also be used in pig feed additive, reduce 12~15% of fat content in pork.Supplement
DHA can be improved organism metabolism rate and fatty acid oxidation, and body fat can potentially be effectively reduced and delay weight gain (weight-reducing work
With), and the disease incidence of related disease is reduced, the aerobic endurance achievement of sportsman can be improved in long-term supplement.
Currently, the industrialized process for preparing of DHA comparative maturity is microbe transformation method, i.e., with glycerol dehydrogenase by glycerol oxygen
Turn to DHA.Glycerol fermented by 60~80 hours oxygen consumptions, and fermentation liquid is through isolating and purifying to obtain DHA.However due in fermentation liquid
The content of DHA is low, is 50~80g/L, and the crystallization of impurity composition complex effects DHA is needed by cumbersome separation process
Impurity can be removed, the aqueous solution of DHA is obtained.Entire production process is many and diverse, time consumption and energy consumption, and production cost is high.
Chemical transformation can be divided into direct translation method and indirect reformer method.The conversion ratio of direct translation method glycerol is higher by (70
~96%), DHA
Selectivity it is lower (12.4~88.9%), and catalyst contains heavy metal or noble metal mostly, unfriendly to environment.China
Patent (application number 200710034730.3) is using silica, aluminium oxide, amorphous aluminium, magnesia, titanium oxide, zirconium oxide or divides
Son sieve is carrier, loads the combination partner being made of IB, group vib element and light rare earth elements, is used for the selective oxidation of gas phase glycerol
DHA is synthesized, the selectivity that glycerol conversion yield is up to 99.89%, DHA reaches 89.74%, however, there is no realize from sweet at present
Oily catalytic gas phase oxidation produces the industrialization report of DHA, mainly since catalyst easily inactivates, the unstable institute of catalytic performance
It causes.It can be seen that being only difficult the disadvantage for overcoming DHA selectively low by improving catalyst for glycerol direct oxidation method.
Since DHA has extensive purposes, and market capacity is big, and biodiesel also provides resource for the production of DHA
Abundant, cheap glycerol, therefore the new method for studying the glycerol selective oxidation synthesis DHA of high yield, purification simplicity has
Highly important meaning.
Summary of the invention
The purpose of the present invention is in view of the deficiencies of the prior art, solve glycerol direct oxidation to produce 1,3-Dihydroxyacetone
(DHA) target product DHA selectively low process difficulties during.The present invention can significantly improve DHA by indirect oxidation method
Selectivity, and preparation method glycerol conversion yield is high, and product 1,3-Dihydroxyacetone (DHA) separating-purifying is easy.
To achieve the above object, the present invention provides a kind of glycerol indirect oxidation synthesis 1,3-Dihydroxyacetone (DHA)
Method, comprising the following steps:
(1) aldolisation: glycerol, benzaldehyde, solid acid catalyst A are added in reaction vessel, and organic solvent is added
As water entrainer, oil bath heats up under vigorous stirring, isolates the water that reaction generates, is heated to reflux, reaction solution is cooled to room temperature
A period of time is stood, product 2- phenyl -5- hydroxyl -1,3- dioxane (HPD) and 2- phenyl -4- methylol -1,3- bis- are obtained
Oxygen five rings (HMPD), wherein HPD:HMPD is about 6:4, and for reaction solution after isolating and purifying, low temperature crystallization obtains -5 hydroxyl of 2- phenyl -
1,3- dioxane (HPD)；
(2) oxidation reaction: 2- phenyl -5- hydroxyl -1,3- dioxane (HPD) is added to containing liquid catalyst B and
In the organic solvent of auxiliary agent sodium bromide, 0.1~2h is reacted with the oxidant C in aqueous solution at room temperature, reaction solution passes through separation
Purifying obtains 2- phenyl -5- carbonyl -1,3- dioxane (PDO)；
(3) 2- phenyl -5- carbonyl -1,3- dioxane (PDO) and deionized water hydrolysis: are sequentially added into three mouthfuls of burnings
Bottle in and stirring and dissolving under the conditions of oil bath, hydrolysis occurs under the action of liquid acid catalyst D, obtains target product 1,
3- dihydroxyacetone (DHA) ((DHA))；After reaction, with sodium hydrate aqueous solution neutralising fluid acid catalyst D, dichloro is then added
Methane dissolves the benzaldehyde that hydrolysis generates, and by layering, mutually benzaldehyde is isolated in distillation to oil, is recycled；Water phase is added
Anhydrous ether, azeotropic distillation remove moisture, and dehydrated alcohol is added in remaining liq and mixes, crystallizes under cryogenic, gained
After solid is rinsed with anhydrous ether, vacuum drying obtains 1,3-Dihydroxyacetone (DHA) dimer.
Further, organic solvent is chloroform, toluene, dimethylbenzene, methylene chloride, hexamethylene in step (1) aldolisation
One of alkane or petroleum ether or several combinations.
Further, the solid acid catalyst A is Amberlyst-35, Amberlyst-36, Nafion-H NR-50, H-
Beta, montmorillonite K-10, SAPO-34 or H4[Si(W3O10)4]·XH2One of O/MCM-41 or several combinations.
Further, organic solvent is methylene chloride, chloroform, hexamethylene or N, N- diformazan in step (2) oxidation reaction
The combination of one or more of base formamide.
Further, liquid catalyst B is that 2,2,6,6- tetramethyl piperidine -1- oxygen are free in step (2) oxidation reaction
Base, oxidant C are sodium hypochlorite.
Further, liquid acid catalyst D is one of hydrochloric acid, phosphoric acid, sulfuric acid or several in step (3) hydrolysis
The combination of kind.
Further, the molar ratio of the benzaldehyde and glycerol is 0.8~1.3:1, solid acid catalyst A and glycerin weight ratio
For 0.005~0.15:1.
Further, the molar ratio of the liquid catalyst B and glycerol is 0.0005~0.05:1, oxidant C and 2- phenyl-
The molar ratio of 5- hydroxyl -1,3- dioxane is 1~3:1.
Further, the reaction condition of step (1) aldolisation are as follows: the oil bath temperature is 30~150 DEG C, is heated back
The stream time is 2~20h, and reaction solution time of repose is 10~30h, and crystallization temperature is -25 DEG C.
Further, the reaction condition of step (3) hydrolysis are as follows: the oil bath temperature is 60~80 DEG C, liquid acid
It is 1~4h that hydrolysis time occurs under the action of catalyst D, and for azeotropic distillation temperature less than 40 DEG C, low temperature crystallization temperature is -10
~0 DEG C, vacuum drying temperature is 40~50 DEG C.
The invention has the advantages that
Compared with the prior art, the present invention has following several advantages: (1) present invention passes through glycerol indirect oxidation method, DHA's
Selectivity and yield are higher than direct method, and DHA separation process is simple, and product purity is up to 99%；(2) present invention uses solid
Acid catalyst facilitates the separation of product and catalyst, avoids pollution the production of product, while also can be recycled.(3) this technique
Conversion of the HMPD to HPD is promoted in implementation process, is improved reaction efficiency, is convenient for industrialized production.
Detailed description of the invention
Fig. 1 is the nuclear magnetic resonance of C3H6O3 (DHA) in the present invention13C spectrum.
Specific embodiment
The present invention is described further combined with specific embodiments below, but protection scope of the present invention is not by embodiment
Limitation, if the person skilled in the art in the field makes some nonessential improvement to the present invention according to aforementioned present invention content
And adjustment, still fall within protection scope of the present invention.
Embodiment 1
(1): 152 grams of glycerol, 15 grams of H being added in 1 liter of four-hole boiling flask4[Si(W3O10)4]·XH2O/MCM-41,
100mL methylene chloride is passed through nitrogen as protection gas, 160 grams of benzaldehydes is added, keeping oil bath temperature is 45 as water entrainer
DEG C, the water that reaction generates is isolated, is heated to reflux 20 hours, reaction terminates.Reaction solution stands 16 hours, filters out catalyst H4
[Si(W3O10)4]·XH2After O/MCM-41,500mL anhydrous ether and filtrate is added and is sufficiently mixed, then -25 DEG C of low temperature into
Row crystallization obtains about 76 grams of white needle-like crystals, and HPD yield is 28%, and mother liquor is used for circulation crystallization.
(2): in 1 liter of three-necked flask, sequentially adding HPD (27 grams, 0.15mol), the CH of TEMPO2Cl2Solution (0.06
Mol/L, 50 milliliters), 400mL CH2Cl2With sodium bromide (0.5 mol/L, 30 milliliters), after stirring and dissolving, hypochlorous acid is added dropwise
The mixed solution of sodium solution (1.4 mol/Ls, 150 milliliters) and sodium bicarbonate (0.1 mol/L, 200 milliliters) buffer solution, room
Temperature stirring 1 hour, reaction was completed.After reaction, separation water phase and oily phase (dichloromethane solution).With 400 milli of methylene chloride
Aqueous phase extracted in two times is risen, liquid separation is carried out.It is dry with 50 grams of anhydrous sodium sulfates after two parts dichloromethane solution merges, distillation
Condensing recovery methylene chloride obtains about 25 grams of white crystals.White crystal is dried in vacuo after being recrystallized with anhydrous ether, and weight is
24 grams, PDO yield is 89%.
(3): in 1 liter of three-necked flask, sequentially adding PDO (54 grams, 0.3mol), deionized water (500 milliliters), 80
Stirring and dissolving under the conditions of DEG C oil bath after being passed through nitrogen, is added hydrochloric acid (2 mol/Ls, 6 milliliters), hydrolysis 2 hours.Reaction knot
Shu Hou is added sodium hydrate aqueous solution (2 mol/Ls, 6 milliliters) and separates fuel-displaced phase (benzaldehyde) after mixing.Water phase adds
Enter the benzaldehyde that 100 milliliters of methylene chloride extraction reactions generate, by layering, 500 milliliters of anhydrous ethers are added in water phase, and azeotropic steams
Unreacted water is removed in distillation, obtains 28 grams of sticky liquid, and 30 milliliters of dehydrated alcohols are added, after mixing, at -10 DEG C of low temperature
It is crystallized, after gained crystal is rinsed with ice anhydrous ether, is dried in vacuo at 40 DEG C, obtains 26 grams of white crystals, be DHA dimerization
Body, yield 96%, wherein product 1,3-Dihydroxyacetone (DHA) structure is as shown in Figure 1.
Embodiment 2
(1): 152 grams of glycerol, 1.5 grams of Amberlyst-36,100 milliliters of chloroform conducts being added in 1 liter of four-hole boiling flask
Water entrainer is passed through nitrogen as protection gas, 160 grams of benzaldehydes is added, and keeping oil bath temperature is 75 DEG C, isolates what reaction generated
Water is heated to reflux 4 hours, and reaction terminates.Reaction solution stands 20 hours, after filtering out catalyst Amberlyst-36, is added 500
Milliliter anhydrous ether and filtrate are sufficiently mixed, and are then crystallized at -25 DEG C of low temperature, obtain about 90 grams of white needle-like crystals, HPD
Yield is 33%.Mother liquor is used for circulation crystallization.
(2): in 1 liter of three-necked flask, sequentially adding HPD (27 grams, 0.15mol), the CH of TEMPO2Cl2Solution (0.06
Mol/L, 25 milliliters), CH2Cl2After stirring and dissolving, time chlorine is added dropwise in (400 milliliters) and sodium bromide (0.5 mol/L, 30 milliliters)
The mixed solution of acid sodium solution (1.4 mol/Ls, 130 milliliters) and sodium bicarbonate (0.1 mol/L, 200 milliliters) buffer solution,
It is stirred at room temperature 1 hour, reaction was completed.After reaction, separation water phase and oily phase (dichloromethane solution).With methylene chloride 400
Milliliter aqueous phase extracted in two times, carries out liquid separation.It is dry with 50 grams of anhydrous sodium sulfates after two parts dichloromethane solution merges, it steams
Condensing recovery methylene chloride is evaporated, about 26 grams of white crystals are obtained.White crystal is dried in vacuo after being recrystallized with anhydrous ether, weight
It is 25 grams, PDO yield is 92%.
(3): in 1 liter of three-necked flask, sequentially adding PDO (54 grams, 0.3mol), deionized water (500 milliliters), 80
DEG C oil bath stirring and dissolving after being passed through nitrogen, is added hydrochloric acid (2 mol/Ls, 3 milliliters), hydrolysis 2 hours.After reaction,
Sodium hydrate aqueous solution (2 mol/Ls, 3 milliliters) are added and separate fuel-displaced phase (benzaldehyde) after mixing.Dichloro is added in water phase
The benzaldehyde that 100 milliliters of methane extraction reactions generate, by layering, 500 milliliters of anhydrous ethers are added in water phase, and azeotropic distillation removes
Unreacted water obtains 29 grams of sticky liquid, and 30 milliliters of dehydrated alcohols are added, and after mixing, is tied at -10 DEG C of low temperature
Crystalline substance after gained crystal is rinsed with ice anhydrous ether, is dried in vacuo at 40 DEG C, obtains 26 grams of white crystals, is DHA dimer, receives
Rate is 96%, and wherein product 1,3-Dihydroxyacetone (DHA) structure is as shown in Figure 1.
Embodiment 3
(1): 152 grams of glycerol, 1.5 grams of Nafion-H NR-50 being added in 1 liter of four-hole boiling flask, 100 milliliters of toluene are made
For water entrainer, nitrogen being passed through as protection gas, 160 grams of benzaldehydes are added, keeping oil bath temperature is 125 DEG C, isolates reaction and produces
Raw water is heated to reflux 2 hours, and reaction terminates.Reaction solution stands 20 hours, after filtering out catalyst n afion-H NR-50,
500 milliliters of anhydrous ethers are added and filtrate is sufficiently mixed, are then crystallized at -25 DEG C of low temperature, about 90 grams of white needles are obtained
Crystal, HPD yield are 33%.Mother liquor is used for circulation crystallization.
(2): in 1 liter of three-necked flask, sequentially adding HPD (27 grams, 0.15mol), the CH of TEMPO2Cl2Solution (0.06
Mol/L, 100 milliliters), CH2Cl2(400 milliliters) and sodium bromide (0.5 mol/L, 30 milliliters) after stirring and dissolving, are added dropwise time
The mixing of sodium chlorate solution's (1.4 mol/Ls, 200 milliliters) and sodium bicarbonate (0.1 mol/L, 280 milliliters) buffer solution is molten
Liquid is stirred at room temperature 1 hour, and reaction was completed.After reaction, separation water phase and oily phase (dichloromethane solution).Use methylene chloride
400 milliliters of aqueous phase extracteds in two times carry out liquid separation.It is dry with 50 grams of anhydrous sodium sulfates after two parts dichloromethane solution merges,
Condensing recovery methylene chloride is distilled, about 25 grams of white crystals are obtained.White crystal is dried in vacuo after being recrystallized with anhydrous ether, weight
Amount is 24 grams, and PDO yield is 89%.
(3): in 1 liter of three-necked flask, sequentially adding PDO (54 grams, 0.3mol), deionized water (400 milliliters), 80
DEG C oil bath stirring and dissolving after being passed through nitrogen, is added sulfuric acid (2 mol/Ls, 3 milliliters), hydrolysis 2 hours.After reaction,
Sodium hydrate aqueous solution (2 mol/Ls, 6 milliliters) are added and separate fuel-displaced phase (benzaldehyde) after mixing.Dichloro is added in water phase
The benzaldehyde that 100 milliliters of methane extraction reactions generate, by layering, 500 milliliters of anhydrous ethers are added in water phase, and azeotropic distillation removes
Unreacted water obtains 27 grams of sticky liquid, and 30 milliliters of dehydrated alcohols are added, and after mixing, is tied at -10 DEG C of low temperature
Crystalline substance after gained crystal is rinsed with ice anhydrous ether, is dried in vacuo at 40 DEG C, obtains 25 grams of white crystals, is DHA dimer, receives
Rate is 92%, and wherein product 1,3-Dihydroxyacetone (DHA) structure is as shown in Figure 1.
Embodiment 4
(1): 152 grams of glycerol, 15 grams of H-Beta being added in 1 liter of four-hole boiling flask, 100 milliliters of hexamethylenes are used as band water
Agent is passed through nitrogen as protection gas, 160 grams of benzaldehydes is added, and keeping oil bath temperature is 95 DEG C, isolates the water that reaction generates,
It is heated to reflux 12 hours, reaction terminates.Reaction solution stands 20 hours, and after filtering out catalyst H-Beta, 500 milliliters of addition is anhydrous
Ether and filtrate are sufficiently mixed, and are then crystallized at -25 DEG C of low temperature, and about 89 grams of white needle-like crystals are obtained, and HPD yield is
33%.Mother liquor is used for circulation crystallization.
(2): in 1 liter of three-necked flask, sequentially adding HPD (27 grams, 0.15mol), the CH of TEMPO2Cl2Solution (0.06
Mol/L, 75 milliliters), CH2Cl2After stirring and dissolving, time chlorine is added dropwise in (400 milliliters) and sodium bromide (0.5 mol/L, 40 milliliters)
The mixed solution of acid sodium solution (1.4 mol/Ls, 150 milliliters) and sodium bicarbonate (0.1 mol/L, 230 milliliters) buffer solution,
It is stirred at room temperature 1 hour, reaction was completed.After reaction, separation water phase and oily phase (dichloromethane solution).With methylene chloride 400
Milliliter aqueous phase extracted in two times, carries out liquid separation.It is dry with 50 grams of anhydrous sodium sulfates after two parts dichloromethane solution merges, it steams
Condensing recovery methylene chloride is evaporated, about 26 grams of white crystals are obtained.White crystal is dried in vacuo after being recrystallized with anhydrous ether, weight
It is 25 grams, PDO yield is 92%.
(3): in 1 liter of three-necked flask, sequentially adding PDO (54 grams, 0.3mol), deionized water (400 milliliters), 80
DEG C oil bath stirring and dissolving after being passed through nitrogen, is added phosphoric acid (2 mol/Ls, 3 milliliters), hydrolysis 2 hours.After reaction,
Sodium hydrate aqueous solution (2 mol/Ls, 7 milliliters) are added and separate fuel-displaced phase (benzaldehyde) after mixing.Dichloro is added in water phase
The benzaldehyde that 100 milliliters of methane extraction reactions generate, by layering, 500 milliliters of anhydrous ethers are added in water phase, and azeotropic distillation removes
Unreacted water obtains 28 grams of sticky liquid, and 30 milliliters of dehydrated alcohols are added, and after mixing, is tied at -10 DEG C of low temperature
Crystalline substance after gained crystal is rinsed with ice anhydrous ether, is dried in vacuo at 40 DEG C, obtains 26 grams of white crystals, is DHA dimer, receives
Rate is 96%, and wherein product 1,3-Dihydroxyacetone (DHA) structure is as shown in Figure 1.
Claims (10)
1. a kind of method of glycerol indirect oxidation synthesis 1,3-Dihydroxyacetone, it is characterised in that method includes the following steps:
(1) aldolisation: glycerol, benzaldehyde, solid acid catalyst A are added in reaction vessel, and organic solvent conduct is added
Water entrainer, oil bath heats up under vigorous stirring, isolates the water that reaction generates, is heated to reflux, reaction solution is cooled to room temperature standing
For a period of time, for reaction solution after isolating and purifying, low temperature crystallization obtains -5 hydroxyl -1,3- dioxane of 2- phenyl；
(2) oxidation reaction: 2- phenyl -5- hydroxyl -1,3- dioxane is added to containing liquid catalyst B and auxiliary agent sodium bromide
Organic solvent in, react 0.1~2h with the oxidant C in aqueous solution at room temperature, reaction solution is by isolating and purifying to obtain 2-
Phenyl -5- carbonyl -1,3- dioxane；
(3) hydrolysis: by 2- phenyl -5- carbonyl -1,3- dioxane and deionized water sequentially add in three-necked flask and
Under the action of liquid acid catalyst D hydrolysis occurs for stirring and dissolving under the conditions of oil bath, obtains target product 1,3- dihydroxy
Acetone；After reaction, with sodium hydrate aqueous solution neutralising fluid acid catalyst D, it is anti-that methylene chloride dissolution hydrolysis is then added
The benzaldehyde that should be generated, by layering, mutually benzaldehyde is isolated in distillation to oil, is recycled；Anhydrous ether is added in water phase, and azeotropic steams
Moisture is removed in distillation, and dehydrated alcohol is added in remaining liq and mixes, crystallizes under cryogenic, obtained solid is rushed with anhydrous ether
After washing, vacuum drying obtains 1,3-Dihydroxyacetone (DHA) dimer.
2. the method for glycerol indirect oxidation synthesis 1,3-Dihydroxyacetone according to claim 1, it is characterised in that: described
In step (1) aldolisation organic solvent be one of chloroform, toluene, dimethylbenzene, methylene chloride, hexamethylene or petroleum ether or
Several combination of person.
3. the method for glycerol indirect oxidation synthesis 1,3-Dihydroxyacetone according to claim 1, it is characterised in that: described
Solid acid catalyst A is Amberlyst-35, Amberlyst-36, Nafion-H NR-50, H- in step (1) aldolisation
Beta, montmorillonite K-10, SAPO-34 or H4[Si(W3O10)4]·XH2One of O/MCM-41 or several combinations.
4. the method for glycerol indirect oxidation synthesis 1,3-Dihydroxyacetone according to claim 1, it is characterised in that: described
Organic solvent is one of methylene chloride, chloroform, hexamethylene or N,N-dimethylformamide or several in step (2) oxidation reaction
The combination of kind.
5. the method for glycerol indirect oxidation synthesis 1,3-Dihydroxyacetone according to claim 1, it is characterised in that: described
Liquid catalyst B is 2,2,6,6- tetramethyl piperidine -1- oxygen radicals in step (2) oxidation reaction, and oxidant C is hypochlorous acid
Sodium.
6. the method for glycerol indirect oxidation synthesis 1,3-Dihydroxyacetone according to claim 1, it is characterised in that: described
Liquid acid catalyst D is the combination of one or more of hydrochloric acid, phosphoric acid, sulfuric acid in step (3) hydrolysis.
7. the method for glycerol indirect oxidation synthesis 1,3-Dihydroxyacetone according to claim 1, it is characterised in that: described
The molar ratio of benzaldehyde and glycerol is 0.8~1.3:1 in step (1), solid acid catalyst A and glycerin weight ratio be 0.005~
0.15:1.
8. the method for glycerol indirect oxidation synthesis 1,3-Dihydroxyacetone according to claim 1, it is characterised in that: described
The molar ratio of liquid catalyst B and glycerol is hydroxyl -1 0.0005~0.05:1, oxidant C and 2- phenyl -5- in step (2),
The molar ratio of 3- dioxane is 1~3:1.
9. the method for glycerol indirect oxidation synthesis 1,3-Dihydroxyacetone according to claim 1, it is characterised in that: described
The reaction condition of step (1) aldolisation are as follows: the oil bath temperature is 30~150 DEG C, and being heated to reflux the time is 2~20h, reaction
Liquid time of repose is 10~30h, and crystallization temperature is -25 DEG C.
10. the method for glycerol indirect oxidation synthesis 1,3-Dihydroxyacetone according to claim 1, it is characterised in that: institute
State the reaction condition of step (3) hydrolysis are as follows: the oil bath temperature is 60~80 DEG C, is sent out under the action of liquid acid catalyst D
Raw hydrolysis time is 1~4h, and for azeotropic distillation temperature less than 40 DEG C, low temperature crystallization temperature is -10~0 DEG C, vacuum drying temperature
Degree is 40~50 DEG C.
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| CN114213230A (en) * | 2021-11-17 | 2022-03-22 | 山东师范大学 | Method for preparing 1, 3-dihydroxyacetone |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101412706A (en) * | 2008-12-01 | 2009-04-22 | 浙江工业大学 | Novel method for preparing 1,3-dihydroxy acetone from glycerol |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101412706A (en) * | 2008-12-01 | 2009-04-22 | 浙江工业大学 | Novel method for preparing 1,3-dihydroxy acetone from glycerol |
Non-Patent Citations (1)
| Title |
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| 向华明: "生物柴油副产物甘油间接法合成1，3 － 二羟基丙酮", 《现代化工》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114213230A (en) * | 2021-11-17 | 2022-03-22 | 山东师范大学 | Method for preparing 1, 3-dihydroxyacetone |
| CN114213230B (en) * | 2021-11-17 | 2024-03-01 | 山东师范大学 | Method for preparing 1, 3-dihydroxyacetone |
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