CN107200686A - A kind of method that utilization phenyl phosphate class bionic catalyst continuously produces acetoglyceride - Google Patents
A kind of method that utilization phenyl phosphate class bionic catalyst continuously produces acetoglyceride Download PDFInfo
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- CN107200686A CN107200686A CN201710285929.7A CN201710285929A CN107200686A CN 107200686 A CN107200686 A CN 107200686A CN 201710285929 A CN201710285929 A CN 201710285929A CN 107200686 A CN107200686 A CN 107200686A
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- phenyl phosphate
- acetoglyceride
- phosphate class
- reaction
- utilization
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- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical class OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 title claims abstract description 31
- KMZHZAAOEWVPSE-UHFFFAOYSA-N 2,3-dihydroxypropyl acetate Chemical compound CC(=O)OCC(O)CO KMZHZAAOEWVPSE-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000011664 nicotinic acid Substances 0.000 title abstract description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 68
- 238000006243 chemical reaction Methods 0.000 claims abstract description 66
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 53
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000005917 acylation reaction Methods 0.000 claims abstract description 22
- 235000011187 glycerol Nutrition 0.000 claims abstract description 22
- 230000032050 esterification Effects 0.000 claims abstract description 17
- 238000005886 esterification reaction Methods 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- ASMQGLCHMVWBQR-UHFFFAOYSA-N Diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(O)OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-N 0.000 claims description 6
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical group C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 claims description 6
- 239000004305 biphenyl Substances 0.000 claims description 5
- 235000010290 biphenyl Nutrition 0.000 claims description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- -1 trifluoromethanesulfonic acid amine diphenyl ester Chemical class 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 abstract description 26
- 239000007788 liquid Substances 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 229960000583 acetic acid Drugs 0.000 description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 101100298225 Caenorhabditis elegans pot-2 gene Proteins 0.000 description 8
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 8
- 229940005657 pyrophosphoric acid Drugs 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 7
- 239000003377 acid catalyst Substances 0.000 description 7
- 150000002148 esters Chemical group 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 5
- QYRVPBBOQIPGGV-UHFFFAOYSA-N benzene propane-1,2,3-triol Chemical compound OCC(O)CO.c1ccccc1 QYRVPBBOQIPGGV-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 101100298222 Caenorhabditis elegans pot-1 gene Proteins 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000003225 biodiesel Substances 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MCWXGJITAZMZEV-UHFFFAOYSA-N dimethoate Chemical compound CNC(=O)CSP(=S)(OC)OC MCWXGJITAZMZEV-UHFFFAOYSA-N 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 235000013773 glyceryl triacetate Nutrition 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 2
- 229960002622 triacetin Drugs 0.000 description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical compound [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 1
- GJMMXPXHXFHBPK-UHFFFAOYSA-N [P].[Cl] Chemical compound [P].[Cl] GJMMXPXHXFHBPK-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- HXBZCHYDLURWIZ-UHFFFAOYSA-N diphenyl hydrogen phosphate;hydrochloride Chemical class Cl.C=1C=CC=CC=1OP(=O)(O)OC1=CC=CC=C1 HXBZCHYDLURWIZ-UHFFFAOYSA-N 0.000 description 1
- DWNAQMUDCDVSLT-UHFFFAOYSA-N diphenyl phthalate Chemical compound C=1C=CC=C(C(=O)OC=2C=CC=CC=2)C=1C(=O)OC1=CC=CC=C1 DWNAQMUDCDVSLT-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000834 fixative Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 239000001087 glyceryl triacetate Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0271—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a kind of method that utilization phenyl phosphate class catalyst continuously produces acetoglyceride; belong to chemical products synthesis field; glycerine, acetic acid, catalyst, solvent pump are entered in micro passage reaction; occurs esterification under phenyl phosphate class catalyst; acylation reaction is occurred into for obtained product and acetic anhydride, acetoglyceride is obtained.The present invention uses phenyl phosphate class bionic catalyst, compared with liquid acid, it is acid smaller, it is smaller to equipment corrosion, and phenyl phosphate class catalyst is difunctional micromolecule catalyst, catalytic efficiency is higher under hydrogen bond action, and glycerol conversion yield reaches 100%, and the yield of triacetyl glycerine reaches more than 95%.
Description
Technical field
The invention belongs to chemical products synthesis field, and in particular to one kind using microchannel reaction unit continuously production and
The method of bionic catalyst phenyl phosphate micromolecular catalysis.
Background technology
Acetoglyceride (glyceryl triacetate, Glycerol Triacetate) is a kind of colourless odorless oily liquids,
It is nontoxic nonirritant.Acetoglyceride dissolves in alcohol, benzene, ethers, the organic solvent such as castor oil, can dissolve nitrocellulose, third
Olefin(e) acid resin, polyvinyl acetate etc..Acetoglyceride has good gelatification and physiological inertia, is widely used as cigarette
Filter tip cellulose acetate plasticising curing agent, food additives, perfume fixative, cosmetics fixastive and lubricating substance etc..Vinegar
Acid glyceride is widely used in tobacco, food, metallurgy industry as a kind of plasticizer of safety non-toxic.
The synthetic method of traditional triacetyl glycerine be using the liquid acid such as the concentrated sulfuric acid as catalyst glycerine with
Glacial acetic acid is esterified and is made.The reaction is poor due to esterification effect, and what is largely obtained is that an acetoglyceride and two acetic acid are sweet
Grease, and liquid acid is more serious to equipment corrosion.After follow-up improve, production triacetyl glycerine is frequently with two-step method at present
Be made, occur esterification under acid catalyst catalysis using glycerine and acetic acid first, then by obtained acetoglyceride with
Acylation reaction occurs for acetic anhydride, and the triacetyl glycerine of high-purity is made.
The A of the patent CN 105087087 and A of CN 103159622 propose a kind of new method for preparing acetoglyceride,
Under alkali ionic liquid effect ester exchange reaction is occurred into for biodiesel (animals and plants glyceride fat) and short chain alcohol, three are made
Acetoglyceride, this method is the method that another prepares triacetyl glycerine, but because biodiesel fuel component is complex,
After ester exchange reaction terminates, product component is more, and triacetyl glycerine content is less, and purity is not high.Patent CN
102675095 A improve method before, and substitute liquid acid using acidic ion liquid ties as catalyst, but reaction
Shu Hou, the more difficult separation of product, and ionic liquid cost is higher, reaction temperature is also higher in addition.
The content of the invention
The technical problem to be solved in the present invention is to find a kind of efficient bionic catalyst catalytic esterification, and is provided
A kind of suitable microchannel reaction condition catalytic esterification.
In order to solve the above technical problems, the present invention is adopted the following technical scheme that：
A kind of method that utilization phenyl phosphate class catalyst continuously produces acetoglyceride, by glycerine, acetic acid, catalyst,
Solvent pump enters in micro passage reaction, occurs esterification under phenyl phosphate class catalyst, by obtained product and second
Acylation reaction occurs for acid anhydrides, obtains acetoglyceride.
Wherein, the solvent is benzene.
Wherein, the phenyl phosphate class catalyst is diphenyl phosphate, diphenylphosphoric acid, phosphinylidyne trifluoromethanesulfonic acid amine hexichol
One or more of mixtures in ester, pyrophosphoric acid (IDPA), preferably pyrophosphoric acid (IDPA).
Wherein, phenyl phosphate class catalyst, glycerine, acetic acid and mol ratio ratio be 1: (8~10): (30-50).
Specific operating method is as follows：Glycerine is mixed with benzene, material I is obtained, by acetic acid, phenyl phosphate class catalyst with
Benzene is mixed, and obtains material II, and the flow velocity that material I is pumped into micro passage reaction is 0.5~2mL/min, preferably 1mL/min, material 2
The flow velocity for being pumped into micro passage reaction is 0.5~2.4mL/min, preferably 1.2mL/min.
Wherein, material 1 is 1 according to velocity ratio with material 2: (1~1.2) is pumped into micro passage reaction.
Preferably, in micro passage reaction, the temperature of esterification is 60~80 DEG C, preferably 80 DEG C；Reaction time
For 20~40min, preferably 30min.
Wherein, during acylation reaction, the mol ratio of acetic anhydride and glycerine in esterification is (3~5): 1, preferably 5: 1.
Wherein, the temperature of acylation reaction is 100~150 DEG C, preferably 150 DEG C；Reaction time is 2~3h, preferably 2h.
Preferably, acylation reaction adds water after terminating, remaining acetic anhydride is set to be hydrolyzed to acetic acid.
Wherein, described microchannel reaction unit includes：Microstucture mixer, micro passage reaction, described micro-structural
Blender is connected with micro passage reaction, a diameter of 1.5mm of the micro passage reaction, and volume is 150ml.
Separation and recovery method after reaction terminates：
Acylation reaction terminates to add water in backward reactor, acetic anhydride unnecessary in reaction is hydrolyzed to acetic acid, stands, makes
Reaction liquid layer, separation lower floor's aqueous phase and upper organic phase, lower floor's aqueous phase take 70 DEG C of removing moisture that are concentrated under reduced pressure, and reclaim catalysis
Agent and acetic acid, upper organic phase take 80 DEG C of removing benzene that are concentrated under reduced pressure, and obtain triacetyl glycerine.
Beneficial effect：
Compared with prior art, main advantage of the invention has：
The present invention uses phenyl phosphate class bionic catalyst, compared with liquid acid, acid smaller, smaller to equipment corrosion,
And phenyl phosphate class catalyst is difunctional micromolecule catalyst, catalytic efficiency is higher under hydrogen bond action, and glycerol conversion yield reaches
To 100%.Other esterification of the present invention is carried out in micro passage reaction, and micro passage reaction has preferable mass-and heat-transfer
Effect, greatly reduces reaction temperature and reaction time, and tubular reactor has taken away the water of esterification generation in addition, suppresses
Back reaction progress so that yield is higher.After acylation reaction terminates, add water hydrolysis acetic anhydride, and the acetic acid of generation is dissolved in water, remaining
Benzene liquid can be divided to obtain as organic phase with triacetyl glycerine, separation method is more simple compared with traditional post-processing approach
It is single.
Brief description of the drawings
Fig. 1 is reaction scheme schematic diagram of the present invention.
Fig. 2 is phenyl phosphate class catalyst structure schematic diagram.
Fig. 3 is phosphinylidyne trifluoromethanesulfonic acid amine diphenyl ester (PAA), pyrophosphoric acid catalyst (IDPA) synthesis schematic diagram.
Embodiment
According to following embodiments, the present invention may be better understood.However, as it will be easily appreciated by one skilled in the art that real
Apply the content described by example and be merely to illustrate the present invention, without should be also without limitation on sheet described in detail in claims
Invention.
Fig. 1 is reaction scheme schematic diagram of the present invention, and 1 is material pot A, and 2 be material pot B, and 3 be pump A, and 4 be pump B, and 5 be micro- knot
Structure blender, 6 be structural response device, and 7 be acylation reaction kettle, and 8 be the reactor that is concentrated under reduced pressure.
Glycerine and benzene are mixed in material pot A, acetic acid and bionic catalyst, benzene mixed in material pot B, then distinguishes
Squeezed into by pump A and pump B in microstucture mixer, then flow into esterification is carried out in micro-structured reactor, esterification liquid pump
Enter in acylation reaction kettle and to carry out acylation reaction with acetic anhydride, finally separate triacetyl glycerine being concentrated under reduced pressure in reactor.
The program mainly passes through two-step reaction, be respectively in micro passage reaction glycerine and acetic acid in bionic catalyst phosphorus
The catalysis of acid phenenyl ester class is lower to occur esterification, reacts the product terminated and occurs acylation reaction with acetic anhydride in a kettle., is made
The higher triacetyl glycerine of purity.Microstucture mixer is slit plate mixer wherein in the reaction unit of microchannel
LH25(Hastelloy C)；Model 0109-4-0004-F.
Heretofore described microchannel reaction unit includes：Microstucture mixer, micro passage reaction, described micro- knot
Structure blender is connected with micro passage reaction, a diameter of 1.5mm of the micro passage reaction, and volume is 150ml.
Embodiment 1：
The preparation of phenyl phosphate class bionic catalyst：Diphenyl phosphate (DPP), diphenylphosphoric acid (DPA) can be from me
Bought commercially available from fourth reagent, the preparation of phosphinylidyne trifluoromethanesulfonic acid imines diphenyl ester (PAA)：Chlorine phosphoric acid hexichol is taken in anhydrous and oxygen-free environment
Ester 2mmol adds 3mmol trifluoromethanesulfonic acid amine thereto in 50ml flasks at -78 DEG C, reacts 2h, after reaction terminates, moves
Except cryostat, product vacuum is dried, and carries out column chromatography and purifies to obtain product (dichloromethane makees eluant, eluent).
The preparation of pyrophosphoric acid catalyst (IDPA)：Diphenyl ester phosphamide is synthesized first, and chlorine phosphorus is taken in anhydrous and oxygen-free environment
Diphenyl phthalate 3mmol is passed through ammonia thereto in 50ml flasks at -78 DEG C, reacts 2h, after reaction terminates, removes cryostat,
Product vacuum is dried, and carries out column chromatography and purifies to obtain product (dichloromethane makees eluant, eluent).Take 2mmol diphenyl esters phosphamide with
2mmol diphenyl phosphate chlorides add 5mmol 60% hydrogen thereto in addition with 50ml flasks, 5ml THF are added thereto
Sodium hydroxide solution, is stirred at room temperature 14h, and reaction adds the hydrochloric acid of 10ml 10% and 10ml dichloromethane (DCM), stirring after terminating
1h, takes out organic phase, carries out column chromatography and purifies to obtain product.
Embodiment 2：
4mol/L glycerine benzole soln 100ml is configured as material pot 1,12mol/L, 16mol/L, 20mol/ is respectively configured
L acetic acid solution 100ml adds bionic catalyst pyrophosphoric acid catalyst (IDPA) 0.4mol, thing thereto as material pot 2
Batch can 1 is with material pot 2 according to 1:1 velocity ratio, which is pumped at micro passage reaction, 70 DEG C, retains 30min, after reaction terminates, takes stream
Go out liquid and make liquid phase detection, determine each component content.
Influence of the acetic acid concentration of table 1 to glycerol conversion yield and acylation reaction acetate selectivity
| Acetic acid concentration | Glycerol conversion yield | Monoacetate selectivity | Diacetate selectivity | Triacetate selectivity |
| 12mol/L | 86% | 23.7% | 25.7% | 50.6% |
| 16mol/L | 95% | 10.4% | 30.7% | 58.9% |
| 20mol/L | 100% | 3.4% | 17.8% | 78.8% |
Embodiment 3：
4mol/L glycerine benzole soln 100ml is configured as material pot 1,20mol/L acetic acid solution 100ml conducts are configured
Material pot 2, and bionic catalyst pyrophosphoric acid catalyst (IDPA) 0.4mol is added thereto, material pot 1 is with material pot 2 according to 1:
1 velocity ratio, which is pumped at micro passage reaction, 60,70,80 DEG C, retains 30min (embodiment 5,6,7), after reaction terminates, takes stream
Go out liquid and make liquid phase detection, determine each component content.
Influence of the micro passage reaction temperature of table 2 to glycerol conversion yield and acylation reaction acetate selectivity
Embodiment 4：
4mol/L glycerine benzole soln 100ml is configured as material pot 1,20mol/L acetic acid solution 100ml conducts are configured
Material pot 2, and bionic catalyst pyrophosphoric acid catalyst (IDPA) 0.4mol is added thereto, material pot 1 is with material pot 2 according to 1:
1 velocity ratio, which is pumped at micro passage reaction, 70 DEG C, retains 20min, 30min, 40min, after reaction terminates, takes efflux to make liquid
Mutually detect, determine each component content.
Influence of the micro passage reaction retention time of table 3 to glycerol conversion yield and acylation reaction acetate selectivity
Embodiment 5：
4mol/L glycerine benzole soln 100ml is configured as material pot 1,20mol/L acetic acid solution 100ml conducts are configured
Material pot 2, and bionic catalyst diphenyl phosphate (DPP), diphenylphosphoric acid (DPA), phosphinylidyne trifluoromethanesulfonic acid are added thereto
Amine diphenyl ester (PAA), pyrophosphoric acid catalyst (IDPA) each 0.4mol, material pot 1 is with material pot 2 according to 1:1 velocity ratio is pumped into
Micro passage reaction, 30min is retained at 70 DEG C, after reaction terminates, takes efflux to make liquid phase detection, determines each component content.
Influence of the bionic catalyst type of table 4 to glycerol conversion yield and acylation reaction acetate selectivity
Embodiment 6：
The efflux of micro passage reaction before is placed in reactor to the acetic anhydride for adding 15mol, is stirred vigorously, instead
2h should be reacted at 100 DEG C, 120 DEG C, 150 DEG C respectively.After reaction terminates, reaction solution in reactor is taken to carry out liquid phase detection, really
Determine each component content.
Influence of the acylation reaction temperature of table 5 to glycerol conversion yield and esterification acetate selectivity
| Acylation reaction temperature | Glycerol conversion yield | Monoacetate selectivity | Diacetate selectivity | Triacetate selectivity |
| 100℃ | 100% | 0.3% | 1.7% | 98.0% |
| 120℃ | 100% | 0.7% | 1.2% | 98.1% |
| 150℃ | 100% | 0% | 1.2% | 98.8% |
Embodiment 7：
Reaction terminates rear to be cooled to room temperature, and addition 400ml water, is stirred vigorously the acetic anhydride of hydrolysed residual thereto, quiet
Put layering, lower floor's liquid outflow, 70 DEG C of moisture that are concentrated under reduced pressure away, catalyst and remaining acetic acid reuse, upper organic phase, 80
DEG C be concentrated under reduced pressure removing benzene, and remaining is product triacetyl glycerine.
Claims (11)
1. a kind of method that utilization phenyl phosphate class catalyst continuously produces acetoglyceride, it is characterised in that by glycerine, second
Acid, catalyst, solvent pump enter in micro passage reaction, occur esterification under phenyl phosphate class catalyst, will obtain
Product and acetic anhydride occur acylation reaction, obtain acetoglyceride.
2. the method that utilization phenyl phosphate class catalyst according to claim 1 continuously produces acetoglyceride, its feature
It is, the solvent is benzene.
3. the method that utilization phenyl phosphate class catalyst according to claim 1 continuously produces acetoglyceride, its feature
It is, the phenyl phosphate class catalyst is diphenyl phosphate, diphenylphosphoric acid, phosphinylidyne trifluoromethanesulfonic acid amine diphenyl ester, burnt phosphorus
One or more of mixtures in acid.
4. the method that utilization phenyl phosphate class catalyst according to claim 1 continuously produces acetoglyceride, its feature
Be, phenyl phosphate class catalyst, glycerine, acetic acid and mol ratio be 1：(8~10)：(30-50).
5. the method that utilization phenyl phosphate class catalyst according to claim 3 continuously produces acetoglyceride, its feature
It is, glycerine is mixed with benzene, obtain material I, acetic acid, phenyl phosphate class catalyst is mixed with benzene, material II, material is obtained
The flow velocity that I is pumped into micro passage reaction is 0.5~2mL/min, material II be pumped into the flow velocity of micro passage reaction for 0.5~
2.4mL/min。
6. the method that utilization phenyl phosphate class catalyst according to claim 4 continuously produces acetoglyceride, its feature
It is, material I is 1 according to velocity ratio with material II：(1~1.2) is pumped into micro passage reaction.
7. the method that utilization phenyl phosphate class catalyst according to claim 1 continuously produces acetoglyceride, its feature
It is, in micro passage reaction, the temperature of esterification is 60~80 DEG C, and the reaction time is 20~40min.
8. the method that utilization phenyl phosphate class catalyst according to claim 1 continuously produces acetoglyceride, its feature
It is, during acylation reaction, the mol ratio of acetic anhydride and glycerine in esterification is (3~5)：1.
9. the method that utilization phenyl phosphate class catalyst according to claim 1 continuously produces acetoglyceride, its feature
It is, the temperature of acylation reaction is 100~150 DEG C, and the reaction time is 2~3h.
10. the method that utilization phenyl phosphate class catalyst according to claim 1 continuously produces acetoglyceride, its feature
It is, acylation reaction adds water after terminating, remaining acetic anhydride is hydrolyzed to acetic acid.
11. the method that utilization phenyl phosphate class catalyst according to claim 1 continuously produces acetoglyceride, its feature
It is, described microchannel reaction unit includes：Microstucture mixer, micro passage reaction, described microstucture mixer with
Micro passage reaction is connected, a diameter of 1.5mm of the micro passage reaction, and volume is 150ml.
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| CN108640835A (en) * | 2018-04-23 | 2018-10-12 | 南京工业大学 | A kind of method that organic catalysis prepares triacetyl glycerine |
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| CN102115444A (en) * | 2010-01-06 | 2011-07-06 | 江苏瑞佳化学有限公司 | Process and device for continuously producing glyceryl triacetate |
| CN103965045A (en) * | 2014-05-06 | 2014-08-06 | 江苏瑞晨化学有限公司 | Preparation process and device for glycerol triacetate |
| CN104130125A (en) * | 2014-08-07 | 2014-11-05 | 南京工业大学 | Method for synthesizing glycerol triacetate through microchannel reactor |
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