CN107954868A - 1- glycerol monobutyraltes and preparation method thereof - Google Patents
1- glycerol monobutyraltes and preparation method thereof Download PDFInfo
- Publication number
- CN107954868A CN107954868A CN201711247087.2A CN201711247087A CN107954868A CN 107954868 A CN107954868 A CN 107954868A CN 201711247087 A CN201711247087 A CN 201711247087A CN 107954868 A CN107954868 A CN 107954868A
- Authority
- CN
- China
- Prior art keywords
- preparation
- acid
- glycerol
- molar ratio
- monobutyraltes
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 166
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims abstract description 79
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 46
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000004327 boric acid Substances 0.000 claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 26
- 125000005456 glyceride group Chemical group 0.000 claims abstract description 25
- 239000011949 solid catalyst Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000010992 reflux Methods 0.000 claims abstract description 16
- 239000012024 dehydrating agents Substances 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 14
- 239000000706 filtrate Substances 0.000 claims abstract description 10
- 235000011187 glycerol Nutrition 0.000 claims description 75
- 229910052810 boron oxide Inorganic materials 0.000 claims description 15
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 15
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 11
- 239000012153 distilled water Substances 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003674 animal food additive Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 239000000047 product Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 229920005862 polyol Polymers 0.000 abstract description 5
- 150000003077 polyols Chemical class 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 239000002253 acid Substances 0.000 description 6
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 3
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 2
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid group Chemical group S(N)(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- UPBLAVFWWWKVAJ-UHFFFAOYSA-N [Cl].CCC Chemical compound [Cl].CCC UPBLAVFWWWKVAJ-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/10—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond
- C07C67/11—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond being mineral ester groups
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/10—Organic substances
- A23K20/105—Aliphatic or alicyclic compounds
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/10—Organic substances
- A23K20/158—Fatty acids; Fats; Products containing oils or fats
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
- A23L29/10—Foods or foodstuffs containing additives; Preparation or treatment thereof containing emulsifiers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
- C07C69/22—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety
- C07C69/30—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety esterified with trihydroxylic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Zoology (AREA)
- Animal Husbandry (AREA)
- Health & Medical Sciences (AREA)
- Nutrition Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
A kind of 1 glycerol monobutyralte and preparation method thereof, is related to chemical industry synthesis field.The preparation method of 1 glycerol monobutyralte of the embodiment of the present invention is by boric acid double glyceride, butyric acid, and solid dehydrating agent and solid catalyst KF/ZnO, and under conditions of 120~130 DEG C, stirring condensing reflux reacts 90~120min；Hydrochloric acid is added, is filtered under room temperature after 30~90min of stirring reaction, filtrate is distilled, remainder is 1 glycerol monobutyralte, and this method operating process is simple, is advantageously implemented industrialized production, and high conversion rate, product purity are high；Obtained 1 glycerol monobutyralte can be directly appended in feed as polyol type nonionic surface active agent.
Description
Technical field
The present invention relates to chemical industry synthesis field, and more particularly to a kind of 1- glycerol monobutyraltes and preparation method thereof.
Background technology
1- glycerol monobutyraltes are a kind of short-chain aliphatic esters, its molecular formula is C15H26O6, it is a kind of polyol type nonionic
Type surfactant.Using glycerol monobutyralte as a kind of new emulsifying agent, it is added in feed, it is easy to use, it is safe and nontoxic
Side effect, glycerol monobutyralte also have special fragrance, have not only solved the characteristics of butyric acid is difficult to addition for liquid, but also improve straight
Connect using butyric acid the smell is awful the shortcomings that.
At present, the synthetic method of butyric acid monoglyceride is mainly the following：Direct esterification, butyric anhydride method, epoxy chlorine
Propane method, glycidol method etc..Wherein, direct esterification reaction efficiency is too low, and product purity is not high；Butyric anhydride method centering control
It is more demanding, and butyric anhydride property is unstable, explosive；Epoxychloropropane method needs to use epoxychloropropane, but the thing
Matter toxicity is larger；The raw material sources of glycidol method are more difficult.
A variety of synthetic methods all restrict the industrialization of butyric acid monoglyceride above, therefore, develop a kind of high conversion, height
Product purity and easy to operate butyric acid monoglyceride novel synthesis seems very necessary.
The content of the invention
It is an object of the invention to provide a kind of preparation method of 1- glycerol monobutyraltes, operating process is simple, is conducive to reality
Existing industrialized production, and high conversion rate, product purity are high.
Another object of the present invention is to provide a kind of 1- glycerol monobutyraltes, as polyol type non-ionic surfactant
Agent, can be directly appended in feed.
The present invention is solved its technical problem and is realized using following technical scheme.
The present invention proposes a kind of preparation method of 1- glycerol monobutyraltes, it comprises the following steps：
By boric acid double glyceride, butyric acid, and solid dehydrating agent and solid catalyst KF/ZnO, in 120~130 DEG C of bar
Under part, stirring condensing reflux reacts 90~120min；
Hydrochloric acid is added, filters, filtrate is distilled, remainder is 1- after 30~90min of stirring reaction under room temperature
Glycerol monobutyralte.
Further, in present pre-ferred embodiments, the preparation method of boric acid double glyceride is：Glycerine and boric acid are pressed
Molar ratio 2~4：1, under conditions of 110~120 DEG C, stirring 90~150min of reaction, obtains boric acid double glyceride.
Further, in present pre-ferred embodiments, the molar ratio of boric acid double glyceride and butyric acid is 1：2~4.
Further, in present pre-ferred embodiments, the usage amount of solid catalyst KF/ZnO is the 2% of butyric acid quality
~4%.
Further, in present pre-ferred embodiments, solid dehydrating agent includes at least one in sulfamic acid, boron oxide
Kind.
Further, in present pre-ferred embodiments, if solid dehydrating agent is sulfamic acid, butyric acid and sulfamic acid
Molar ratio is 1：0.5~2；If solid dehydrating agent is boron oxide, the molar ratio of butyric acid and boron oxide is 1：0.3~0.5.
Further, in present pre-ferred embodiments, the preparation method of solid catalyst KF/ZnO is：By Metal Supported
Amount 10%~15% weighs KF2H2O and ZnO, adds distilled water, stirs 2~4.5h；Dried under conditions of 101~109 DEG C
It is dry, smash, be calcined 2~4.5h in 500~650 DEG C, be cooled to room temperature, obtain solid catalyst KF/ZnO.
Further, in present pre-ferred embodiments, the molar ratio of boric acid double glyceride and hydrochloric acid is 6：1.0~1.4,
Concentration of hydrochloric acid is 2mol/L.
A kind of 1- glycerol monobutyraltes, it is made using the preparation method of above-mentioned 1- glycerol monobutyraltes.
Further, in present pre-ferred embodiments, 1- glycerol monobutyraltes can be directly appended to as feed addictive
In feed.
The beneficial effect of the 1- glycerol monobutyraltes of the embodiment of the present invention and preparation method thereof is：The 1- fourths of the embodiment of the present invention
The preparation method of acid glyceride be by boric acid double glyceride, butyric acid, and solid dehydrating agent and solid catalyst KF/ZnO,
Under conditions of 120~130 DEG C, stirring condensing reflux reacts 90~120min；Add hydrochloric acid, under room temperature stirring reaction 30~
Filtered after 90min, filtrate is distilled, remainder is 1- glycerol monobutyraltes, and this method operating process is simple, is advantageously implemented
Industrialized production, and high conversion rate, product purity are high；Obtained 1- glycerol monobutyraltes are as polyol type non-ionic surface
Activating agent, can be directly appended in feed.
Embodiment
, below will be in the embodiment of the present invention to make the purpose, technical scheme and advantage of the embodiment of the present invention clearer
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, builds according to normal condition or manufacturer
The condition of view carries out.Reagents or instruments used without specified manufacturer, is the conventional production that can be obtained by commercially available purchase
Product.
1- glycerol monobutyraltes of the embodiment of the present invention and preparation method thereof are specifically described below.
The embodiment of the present invention provides a kind of preparation method of 1- glycerol monobutyraltes, it comprises the following steps：
S1, add boric acid double glyceride, butyric acid, and solid dehydrating agent and solid catalyst KF/ZnO in reaction kettle,
The molar ratio of boric acid double glyceride and butyric acid is 1：2~4, it is preferably 1：The usage amount of 2, solid catalyst KF/ZnO are butyric acid matter
The 2%~4% of amount, is preferably 3%, opens condensation reflux unit, under conditions of 120~130 DEG C, stirring condensing reflux reaction
90~120min.
In the present embodiment, the preparation method of boric acid double glyceride is：By glycerine and boric acid in molar ratio 2~4：1 is (corresponding
, the molar ratio of glycerine and butyric acid is 1~2：1~2), under conditions of 110~120 DEG C, stirring 90~150min of reaction, obtains
To boric acid double glyceride.
Solid dehydrating agent includes at least one of sulfamic acid, boron oxide.If solid dehydrating agent is sulfamic acid, butyric acid
Molar ratio with sulfamic acid is 1：0.5~2, it is preferably 1：1；If solid dehydrating agent is boron oxide, butyric acid and boron oxide rub
You are than being 1：0.3~0.5, it is preferably 1：0.35.
The preparation method of solid catalyst KF/ZnO is：KF2H is weighed by content of metal 10%~15%2O and ZnO,
Distilled water is added, stirs 2~4.5h, preferably 3h；At 101~109 DEG C, dry, smash under conditions of preferably 105 DEG C, in
500~650 DEG C of 2~4.5h of calcination, are preferable over 600 DEG C of calcination 3h, are cooled to room temperature, obtain solid catalyst KF/ZnO.
The molar ratio of S2, addition hydrochloric acid, boric acid double glyceride and hydrochloric acid is 6：1.0~1.4 (correspondingly, glycerine and hydrochloric acid
Molar ratio be 12~24：1.0~1.4) mistake after 30~90min is reacted in, concentration of hydrochloric acid 2mol/L, at ambient temperature stirring
Filter, filtrate is distilled, and it is 1- glycerol monobutyraltes to remove contained humidity and a small amount of hydrochloric acid, remainder.Boric acid in filter residue with
Solid catalyst KF/ZnO can not only reduce cost, but also can reduce the discharge of solid waste, energy-saving ring with recycling
Protect.
The embodiment of the present invention also provides a kind of 1- glycerol monobutyraltes, it is the preparation side using above-mentioned 1- glycerol monobutyraltes
Method is made, which is substantially 1- glycerol monobutyraltes, reduces the possibility for generating other isomers, the 1- butyric acid glycerine
Ester can be directly appended in feed as feed addictive.
The feature and performance of the present invention are described in further detail with reference to embodiments.
Embodiment 1
The present embodiment provides a kind of 1- glycerol monobutyraltes, it is made according to following preparation method：
(1) glycerine 55.9g is added into 500mL four-hole boiling flasks, (molar ratio of glycerine and boric acid is 2 to boric acid 18.8g：1),
120 DEG C are warming up to, 120min is stirred, obtains boric acid double glyceride.
(2) condensation reflux unit is accessed on above-mentioned flask, and butyric acid 53.4g (glycerine and fourth are added into above-mentioned flask
The molar ratio of acid is 1：1), (molar ratio of butyric acid and sulfamic acid is 1 to sulfamic acid 59.2g：1), solid catalyst KF/ZnO
1.6g (usage amount is the 3% of butyric acid quality), rises to 130 DEG C, while stirring condensing reflux 90min by temperature.
(3) temperature of reaction system is down to room temperature, added into above-mentioned flask 2mol/L hydrochloric acid 35ml (glycerine and hydrochloric acid
Molar ratio is 12：1.4) filtered after, stirring 60min.
(4) filtrate is taken, is distilled under the conditions of 0.1MP negative pressure, 75 DEG C, until no cut is separated into only, it is remaining
Part is 1- glycerol monobutyraltes.
Through gas chromatographic detection：The content of 1- glycerol monobutyraltes is 98.2%, and net yield is 94.7%.
Embodiment 2
The present embodiment provides a kind of 1- glycerol monobutyraltes, it is made according to following preparation method：
(1) glycerine 36.6g is added into 500mL four-hole boiling flasks, (molar ratio of glycerine and boric acid is 2 to boric acid 12.5g：1),
110 DEG C are warming up to, 120min is stirred, obtains boric acid double glyceride.
(2) condensation reflux unit is accessed on above-mentioned flask, and butyric acid 35.0g (glycerine and fourth are added into above-mentioned flask
The molar ratio of acid is 1：1), (molar ratio of butyric acid and boron oxide is 1 to boron oxide 9.7g：0.35), solid catalyst KF/ZnO
1.1g (usage amount is the 3.1% of butyric acid quality), rises to 120 DEG C, while stirring condensing reflux 120min by temperature.
(3) temperature of reaction system is down to room temperature, added into above-mentioned flask 2mol/L hydrochloric acid 20ml (glycerine and hydrochloric acid
Molar ratio is 12：1.2) filtered after, stirring 60min.
(4) filtrate is taken, is distilled under the conditions of 0.1MP negative pressure, 75 DEG C, until no cut is separated into only, it is remaining
Part is 1- glycerol monobutyraltes.
Through gas chromatographic detection：The content of 1- glycerol monobutyraltes is 97.8%, its net yield is 93.7%.
Embodiment 3
The present embodiment provides a kind of 1- glycerol monobutyraltes, it is made according to following preparation method：
(1) glycerine 460.0g is added into 2000mL four-hole boiling flasks, (molar ratio of glycerine and boric acid is 1 to boric acid 309.0g：
1) 120 DEG C, are warming up to, 120min is stirred, obtains boric acid double glyceride.
(2) condensation reflux unit is accessed on above-mentioned flask, and butyric acid 440.0g (glycerine and fourth are added into above-mentioned flask
The molar ratio of acid is 1：1), (molar ratio of butyric acid and boron oxide is 1 to boron oxide 122.5g：0.35), solid catalyst KF/ZnO
13.3g (usage amount is the 3% of butyric acid quality), rises to 130 DEG C, while stirring condensing reflux 90min by temperature.
(3) temperature of reaction system is down to room temperature, 2mol/L hydrochloric acid 150ml (glycerine and hydrochloric acid is added into above-mentioned flask
Molar ratio be 20：1.2) filtered after, stirring 60min.
(4) filtrate is taken, is distilled under the conditions of 0.1MP negative pressure, 75 DEG C, until no cut is separated into only, it is remaining
Part is 1- glycerol monobutyraltes.
Through gas chromatographic detection：The content of 1- glycerol monobutyraltes is 96.8%, its net yield is 94.1%.
Embodiment 4
The present embodiment provides a kind of 1- glycerol monobutyraltes, it is made according to following preparation method：
(1) glycerine 55.9g is added into 500mL four-hole boiling flasks, (molar ratio of glycerine and boric acid is 3 to boric acid 12.5g：1),
115 DEG C are warming up to, 150min is stirred, obtains boric acid double glyceride.
(2) condensation reflux unit is accessed on above-mentioned flask, and butyric acid 106.9g (glycerine and fourth are added into above-mentioned flask
The molar ratio of acid is 1：2), (molar ratio of butyric acid and sulfamic acid is 1 to sulfamic acid 59.2g：0.5), solid catalyst KF/
ZnO 2.1g (usage amount is the 2% of butyric acid quality), rise to 125 DEG C, while stirring condensing reflux 100min by temperature.
(3) temperature of reaction system is down to room temperature, 2mol/L hydrochloric acid 12.5ml (glycerine and hydrochloric acid is added into above-mentioned flask
Molar ratio be 12：0.5) filtered after, stirring 90min.
(4) filtrate is taken, is distilled under the conditions of 0.1MP negative pressure, 75 DEG C, until no cut is separated into only, it is remaining
Part is 1- glycerol monobutyraltes.
Through gas chromatographic detection：The content of 1- glycerol monobutyraltes is 98.5%, and net yield is 95.1%.
Embodiment 5
The present embodiment provides a kind of 1- glycerol monobutyraltes, it is made according to following preparation method：
(1) glycerine 36.6g is added into 500mL four-hole boiling flasks, (molar ratio of glycerine and boric acid is 4 to boric acid 6.3g：1),
115 DEG C are warming up to, 100min is stirred, obtains boric acid double glyceride.
(2) condensation reflux unit is accessed on above-mentioned flask, and butyric acid 17.5g (glycerine and fourth are added into above-mentioned flask
The molar ratio of acid is 2：1), (molar ratio of butyric acid and boron oxide is 1 to boron oxide 4.85g：0.35), solid catalyst KF/ZnO
0.7g (usage amount is the 4% of butyric acid quality), rises to 125 DEG C, while stirring condensing reflux 110min by temperature.
(3) temperature of reaction system is down to room temperature, added into above-mentioned flask 2mol/L hydrochloric acid 20ml (glycerine and hydrochloric acid
Molar ratio is 12：1.2) filtered after, stirring 60min.
(4) filtrate is taken, is distilled under the conditions of 0.1MP negative pressure, 75 DEG C, until no cut is separated into only, it is remaining
Part is 1- glycerol monobutyraltes.
Through gas chromatographic detection：The content of 1- glycerol monobutyraltes is 97.5%, its net yield is 93.4%.
In conclusion the operating process of the preparation method of the 1- glycerol monobutyraltes of the embodiment of the present invention is simple, be conducive to reality
Existing industrialized production, and high conversion rate, product purity are high；Obtained 1- glycerol monobutyraltes are as the non-ionic table of polyol type
Face activating agent, can be directly appended in feed.
Embodiments described above is part of the embodiment of the present invention, instead of all the embodiments.The reality of the present invention
The detailed description for applying example is not intended to limit the scope of claimed invention, but is merely representative of the selected implementation of the present invention
Example.Based on the embodiments of the present invention, those of ordinary skill in the art are obtained without creative efforts
Every other embodiment, belongs to the scope of protection of the invention.
Claims (10)
1. a kind of preparation method of 1- glycerol monobutyraltes, it is characterised in that it comprises the following steps：
By boric acid double glyceride, butyric acid, and solid dehydrating agent and solid catalyst KF/ZnO, in 120~130 DEG C of condition
Under, stirring condensing reflux reacts 90~120min；
Hydrochloric acid is added, filters, filtrate is distilled, remainder is 1- butyric acid after 30~90min of stirring reaction under room temperature
Glyceride.
2. the preparation method of 1- glycerol monobutyraltes according to claim 1, it is characterised in that the boric acid double glyceride
Preparation method is：By glycerine and boric acid in molar ratio 2~4：1, under conditions of 110~120 DEG C, stirring reaction 90~
150min, obtains the boric acid double glyceride.
3. the preparation method of 1- glycerol monobutyraltes according to claim 1, it is characterised in that the boric acid double glyceride with
The molar ratio of the butyric acid is 1：2~4.
4. the preparation method of 1- glycerol monobutyraltes according to claim 1, it is characterised in that the solid catalyst KF/
The usage amount of ZnO is the 2%~4% of the butyric acid quality.
5. the preparation method of 1- glycerol monobutyraltes according to claim 1, it is characterised in that the solid dehydrating agent includes
At least one of sulfamic acid, boron oxide.
6. the preparation method of 1- glycerol monobutyraltes according to claim 5, it is characterised in that if the solid dehydrating agent is
The molar ratio of sulfamic acid, the butyric acid and the sulfamic acid is 1：0.5~2；If the solid dehydrating agent is boron oxide, institute
The molar ratio for stating butyric acid and the boron oxide is 1：0.3~0.5.
7. the preparation method of 1- glycerol monobutyraltes according to claim 1, it is characterised in that the solid catalyst KF/
The preparation method of ZnO is：KF2H is weighed by content of metal 10%~15%2O and ZnO, addition distilled water, stirring 2~
4.5h；Dry, smash under conditions of 101~109 DEG C, be calcined 2~4.5h in 500~650 DEG C, be cooled to room temperature, obtain
To the solid catalyst KF/ZnO.
8. the preparation method of 1- glycerol monobutyraltes according to claim 1, it is characterised in that the boric acid double glyceride with
The molar ratio of the hydrochloric acid is 6：1.0~1.4, the concentration of hydrochloric acid is 2mol/L.
9. a kind of 1- glycerol monobutyraltes, it is characterised in that it is to use such as 1- butyric acid described in any item of the claim 1 to 8
The preparation method of glyceride is made.
10. 1- glycerol monobutyraltes according to claim 9, it is characterised in that the 1- glycerol monobutyraltes can be used as feed
Additive is directly appended in feed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711247087.2A CN107954868A (en) | 2017-12-01 | 2017-12-01 | 1- glycerol monobutyraltes and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711247087.2A CN107954868A (en) | 2017-12-01 | 2017-12-01 | 1- glycerol monobutyraltes and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107954868A true CN107954868A (en) | 2018-04-24 |
Family
ID=61962298
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711247087.2A Pending CN107954868A (en) | 2017-12-01 | 2017-12-01 | 1- glycerol monobutyraltes and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107954868A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109566863A (en) * | 2019-01-18 | 2019-04-05 | 湖北华扬科技发展有限公司 | Feed addictive and its preparation method and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106518670A (en) * | 2016-09-19 | 2017-03-22 | 湖北神舟化工有限公司 | Method for synthesizing butyrin |
-
2017
- 2017-12-01 CN CN201711247087.2A patent/CN107954868A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106518670A (en) * | 2016-09-19 | 2017-03-22 | 湖北神舟化工有限公司 | Method for synthesizing butyrin |
Non-Patent Citations (2)
| Title |
|---|
| J. M. CODDINGTON ET AL.: "High Field11B and 13C Nmr Investigations of Aqueous Borate Solutions and Borate-Diol Complexes", 《JOURNAL OF COORDINATION CHEMISTRY》 * |
| 李利军等: "KF /ZnO 固体碱催化合成月桂酸甘油单酯", 《粮油加工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109566863A (en) * | 2019-01-18 | 2019-04-05 | 湖北华扬科技发展有限公司 | Feed addictive and its preparation method and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100721467B1 (en) | Method for Production of Formic Acid | |
| CN103833780B (en) | A kind of continuous reaction rectification prepares the processing method of trimethyl borate | |
| CN102186805A (en) | Method of preparing of 60% or more cis-di(c4-c20)alkyl cyclohexane-1,4-dicarboxylate | |
| NO165914B (en) | PROCEDURE FOR THE PREPARATION OF PURE DIMETYLETS. | |
| CN101870648B (en) | Method for recovering benzoic acid from PTA oxidation residue | |
| CN103827072A (en) | Method for recovering acetic acid | |
| CN108929221A (en) | A kind of preparation method of n propyl propionate | |
| CN101289395B (en) | Method for preparing methyl ethyl carbonate | |
| CN107954868A (en) | 1- glycerol monobutyraltes and preparation method thereof | |
| CN102105430A (en) | Continuous process for obtaining a lactic ester | |
| CN103058984B (en) | Synthesis method of watermelon ketone | |
| CN101602748B (en) | Method for purifying high-purity piperidine | |
| CN104650013B (en) | A kind of high selective (S)-beta-hydroxy-gamma-butyrolactone simple and convenient process for preparing | |
| CN101434539A (en) | Preparation of benzyl acetate | |
| CN114805064B (en) | Method for synthesizing alpha-hydroxy carboxylic ester | |
| CN103342643B (en) | Method for preparing alkoxylated polyol acrylate | |
| US4254291A (en) | Allylic rearrangement process | |
| CN115896188A (en) | Preparation method of high-purity (S) -5-chloro-2-methoxycarbonyl-2-hydroxy-1-indanone | |
| CN1244538C (en) | Production of isobutyl isobutyrate from isobutyraldehyde by condensation | |
| CN103642010B (en) | A kind of method utilizing recovery alcohol to prepare hexanodioic acid kind polyester polyvalent alcohol | |
| CN106831493A (en) | The synthetic method of tetrabutyl urea | |
| CN105817228B (en) | The method for directly preparing cyclohexanone glycol ketal compounds using flyash catalysis | |
| CN104326890B (en) | A kind of Carroll reacts continuous process method | |
| WO2007073240A1 (en) | Catalyst, a method for the production thereof and a dihydroxyalkane production method | |
| CN109574847A (en) | A kind of green synthesis process of 11 ester of preservative nipalgin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180424 |