CN101786944B - Preparation method of high-quality polyglycerol - Google Patents
Preparation method of high-quality polyglycerol Download PDFInfo
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- CN101786944B CN101786944B CN 201010011323 CN201010011323A CN101786944B CN 101786944 B CN101786944 B CN 101786944B CN 201010011323 CN201010011323 CN 201010011323 CN 201010011323 A CN201010011323 A CN 201010011323A CN 101786944 B CN101786944 B CN 101786944B
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Abstract
The invention discloses a preparation method of polyglycerol, which comprises the following steps: putting glycerol and basic catalyst in an impermeable reactor; gradually heating the reactor until the temperature in the reactor is 210-260 DEG C, and ensuring that the pressure in the reactor is kept to be positive pressure by regulating the speed of exhausting the steam; at the same time cooling and collecting the exhausted steam, lowering the temperature and finishing the reaction when the collected water is weighted to be 12-18% of the weight of the glycerol; adding stearic acid until the temperature in the reactor is lowered at 180-200 DEG C and evenly stirring; and when the temperature in the reactor is lower than 100 DEG C, showing an obvious interface of the product in the reactor, wherein the upper layer is stearic acid, and the lower layer is polyglycerol; and exhausting the lower product, and packing to obtain the polyglycerol product. The method of the invention is simple and practical, has high yield, low cost, small investments and no emission of three wastes, and is particular suitable for the production of medium-sized and small enterprises; and the prepared polyglycerol has low content of salt and light color, and can be widely applied in the fields with high requirements on the product quality such as cosmetics, foods, daily health products and the like.
Description
Technical field
The present invention relates to a kind of preparation method of high-quality Polyglycerine; Belong to field of fine chemical.
Background technology
The main raw material of Polyglycerine (Polyglycerine) product is glycerine, is reproducible animal and plant source resource, can be effectively compatible with physiological environment etc.At present, Polyglycerine and derived product polyglycerol ester thereof have obtained using widely in various fields such as food, makeup, daily use chemicals, medicine, washing composition, tamanori; As, Polyglycerine successfully be used for wetting Agent for Printing Inks at cosmetic field, than readjust agent, water-based control slowly-releasing auxiliary agent etc.
It is the preparation polyglycerol fatty acid ester that Polyglycerine is used the most widely at field of food.The span of control of the HLB value of polyglycerol ester does not wait from 1～18, gets final product water-in-oil, but also oil-in-water almost can satisfy the demand of all different purposes of market, also is simultaneously the food emulsifier that minority can be dissolved in organic solvent such as ethanol.Its purposes is much better than mono-glycerides, and is fresh-keeping etc. as foaming, froth breaking, the crystallization of adjusting grease, starch quality improvement, food storing, to stearoyl lactate similar multiple action arranged in dough.In liquid milk product, as emulsifying agent good effect, excellent performance are arranged.Many new purposes that await developing are also still arranged, and application is very widely, can be considered to a kind of outstanding product that attracts people's attention, and its usage quantity is in the trend of rising at home, estimates that annual growth is about 10%.
The production method search time of Polyglycerine is longer.As far back as 1913, Niviere just adopted molecular distillation technique to separate to obtain Polyglycerine and the acetic ester thereof of the higher various polymerization degree of purity, and had characterized their physical constant in detail.
1984, Behrens once did detailed narration to the polymerization of glycerine, and what relatively be suitable for suitability for industrialized production mainly is to be raw material with glycerine, the polymerization of dewatering under alkaline catalysts and 200～300 ℃ of hot conditionss; Change reaction conditions and can regulate polymerization degree n, but note that the Polyglycerine that obtains thus is not single composition, but have the mixture that certain molecular weight distributes.
The preparation Polyglycerine has several different methods.Reaction conditions comprises temperature (250-270 ℃), but also useful low temperature (120-128 ℃).Reaction times (1.5h-18h), pressure (normal pressure and decompression are arranged. the latter is the 0.05mm mercury column), catalyzer (sulfuric acid, sodium-acetate or potassium hydroxide, sodium hydroxide, consumption are 0.3%-1.0%), feed inert gas, the water that generates with except dereaction time the and improve the product color and luster.For example glycerine (4500kg) hydro-oxidation sodium (12Kg) heats to 260 ℃, reaction 18h, and product is Polyglycerine.Also useful following operational condition: heat 120-145 ℃, decompression 0.05mm mercury column adds 0.08%-0.3% sulfuric acid and 0.5%-5.0% single triacetin.Neutralize with sodium hydroxide when reaction finishes, remove the glycerine of not participating in reaction by distillation.Regulate pH to 3.1 with HCl then, add 3% activated carbon in succession, keep 80 ℃, stir 30min, decolour.Use molecular distillation method at last, get Polyglycerine.
By also can make the Polyglycerine of high molecular with the sodium hydroxide hydrolysis epoxy chloropropane.Also useful boron fluoride or sulfuric acid are made catalyzer in addition, heat common glycerine to 100 ℃, to make the method for Polyglycerine.
All in all, synthetic Polyglycerine technological process and technical parameter difference are bigger, and particularly the mean polymerisation degree of Polyglycerine, institute's salt concentration and contaminant characteristics etc. have been brought difficulty to purification.Lewisc had once carried out analysis than system to the composition of Polyglycerine, and had inquired into various purifications such as solvent extraction, sulfonation, high temperature depolymerization and utilized method, but was difficult to realize industrialization.After synthetic Polyglycerine was consistent, the impurity in the Polyglycerine mainly was salts substances such as sodium-chlor.
At present, VITAMIN company etc. is ground all at active development with produce this series products purification preparation method as sun chemistry, this medicine company of slope, Mitsubishi's foodization, KAO. Corp. SA, the reason of Japan by more international major companies.But up to the present, its Polyglycerine purification techniques also rests among the method for " strengthening water gaging dilution (amount of water can reach 50% usually)-electrodialytic desalting-ion-exchange makes with extra care-decolorizing with activated carbon-thermal dehydration " such some " helpless " mostly, not only can cause product loss, energy consumption, also have a large amount of waste water to produce.
Summary of the invention
Deficiency at existing Polyglycerine preparation technology the purpose of this invention is to provide a kind of high-quality Polyglycerine preparation method.Utilize the inventive method gained Polyglycerine product saltiness low, of light color, can be widely used in fields such as the exigent makeup of quality product, food, daily use chemicals.
The preparation method of Polyglycerine of the present invention, step comprises:
(1) in weight part, get 100 parts of glycerine, basic catalyst potassium hydroxide 0.5-5 part places in the stopping property reactor, heats up under 120 ± 20 rev/mins agitation condition;
(2) slow reactor heating to 100 ℃ makes reactor pressure keep malleation to regulate exhaust mode therebetween, in case the reactor outer air enters;
(3) continuing reactor heating makes temperature rise to 210-260 ℃, have water and generate this moment in the reactor, and discharge with the form of water vapour, the speed of regulating drainage water steam makes reactor pressure keep malleation, cool off and collect the water vapor of discharge simultaneously, when water to be collected reaches the 12%-18% of glycerine weight through weighing, the cooling termination reaction;
When (4) temperature is down to 180-200 ℃ in the question response device, add the stearic acid of 20-100 weight part, and fully stirred 30-40 minute with 120 ± 20 rev/mins rotating speed;
When (5) temperature was cooled to below 100 ℃ naturally in the question response device, product had sharp interface to occur in the device, and the upper strata is stearic acid, and lower floor is Polyglycerine, emits lower floor's product, can, namely gets the Polyglycerine product.
Among the preparation method of above-mentioned Polyglycerine: the preferred 1.5-2 weight part of the described basic catalyst potassium hydroxide of step (1).Preferred 120 rev/mins of the described mixing speed of step (1).Step (2) is described to make reactor pressure preferably maintain 0.02 ± 0.005MPa to regulate exhaust mode.The speed of the described adjusting drainage water of step (3) steam makes reactor pressure preferably maintain 0.05 ± 0.005MPa, to prevent the volatility of raw material loss.Preferred 50 ± 2 weight parts of stearic acid of the described adding of step (4).Preferred 120 rev/mins of the described mixing speed of step (4), preferred 30 minutes of churning time.When the described reactor temperature of step (5) preferably was cooled to 80 ℃ naturally, product had sharp interface to occur in the device.
Among the preparation method of above-mentioned Polyglycerine: the amount of the described water of collecting of step (3) is relevant with the polymerization degree of Polyglycerine product, it is dimerization that two molecule glycerine take off a part water, it is trimerization that three molecule glycerine take off two molecular waters, and it is four poly-that four molecule glycerine take off trihyarol, and the rest may be inferred.
Among the preparation method of above-mentioned Polyglycerine: mainly contain stearic acid, stearate in the stearic acid of the described upper strata of step (5).The upper strata stearic acid can with common Polyglycerine compound probability Polyglycerine stearate.Stearate plays catalyst action just in Polyglycerine stearate building-up process.Described Polyglycerine stearate can be used as asphalt emulsifier, farm chemical emulgent, plastic plasticizer etc.
It is low, of light color that the high-quality Polyglycerine that utilizes the inventive method to obtain has saltiness, can be widely used in fields such as the exigent makeup of quality product, food, daily use chemicals.
The preparation method of the high-quality Polyglycerine that the present invention relates to is easy, practical, productive rate is high, cost is low, little, the three-waste free discharge of investment, is specially adapted to the production of medium-sized and small enterprises.
Embodiment
The invention will be further described below in conjunction with embodiment, but the present invention is not limited only to this.
Embodiment 1:
(1) get 100kg glycerine, 1.5kg potassium hydroxide places in the 500L stopping property reactor, heats up under 120 rev/mins of stirrer agitation conditions;
(2) slow reactor heating to 100 ℃, if produce pressure in the reactor, the about 0.02MPa of reactor pressure is kept in suitably exhaust therebetween;
(3) continue reactor heating and make temperature rise to 240 ℃, adjust draining vapour speed, keeping reactor pressure is 0.05MPa;
(4) with water cooling collection, the weighing of discharging, when being about 13.4kg to the water of collecting, the cooling termination reaction;
(5) temperature is down to 180 ℃ in the question response device, adds the 50kg stearic acid, and 120 rev/mins of stirrers stirred 30 minutes;
When (6) temperature was cooled to 80 ℃ naturally in the question response device, product had sharp interface to occur in the device, and the upper strata is stearic acid, and lower floor is Polyglycerine, emits lower floor's product, can, namely gets high-quality trimerization Polyglycerine product.
Its index of correlation of trimerization Polyglycerine that makes is as follows:
The polymerization degree: 3
Hydroxyl value: about 1160
Colourity:＜80Hz
Acid number: (mgKOH/g)＜1.0
Glycerol content:＜2%
Polyglycerine content:＞98%
Trimerization glycerol content:＞70%
Burning decrement:＜0.5%
Arsenic:＜3 μ g/g
Heavy metal content:＜5 μ g/g.
Embodiment 2:
(1) get 100kg glycerine, 1.5kg potassium hydroxide places in the 500L stopping property reactor, heats up under 120 rev/mins of stirrer agitation conditions;
(2) slow reactor heating to 100 ℃, if produce pressure in the reactor, the about 0.02MPa of reactor pressure is kept in suitably exhaust;
(3) continue to be warming up to 260 ℃ of reactions, adjust draining vapour speed, keep the about 0.05MPa of reactor pressure;
(4) with water cooling collection, the weighing of discharging, when being about 16.3kg to the water of collecting, the cooling termination reaction;
(5) temperature is down to 200 ℃ in the question response device, adds the 70kg stearic acid, and 120 rev/mins of stirrers stirred 30 minutes;
When (6) temperature was cooled to 80 ℃ naturally in the question response device, product had sharp interface to occur in the device, and the upper strata is stearic acid, and lower floor is Polyglycerine, emits lower floor's product, can, namely got high-quality six poly-Polyglycerine products.
Six poly-its indexs of correlation of Polyglycerine that make are as follows:
The polymerization degree: 6
Hydroxyl value: about 960
Colourity:＜80Hz
Acid number: (mgKOH/g)＜1.0
Glycerol content:＜0.5%
Polyglycerine content:＞98%
Six Polyglycerine content:＞55%
Burning decrement:＜0.5%
Arsenic:＜3 μ g/g
Heavy metal content:＜5 μ g/g.
Embodiment 3:
(1) get 100kg glycerine, 2kg potassium hydroxide places in the 500L stopping property reactor, heats up at 120 rev/mins of stirrer agitation conditions;
(2) slow reactor heating to 100 ℃, if produce pressure in the reactor, the about 0.02MPa of reactor pressure is kept in suitably exhaust;
(3) continue to be warming up to 250 ℃ of reactions, adjust draining vapour speed, keep the about 0.05MPa of reactor pressure;
(4) with water cooling collection, the weighing of discharging, when being about 14.8kg to the water of collecting, the cooling termination reaction;
(5) temperature is down to 170 ℃ in the question response device, adds the 60kg stearic acid, and 120 rev/mins of stirrers stirred 30 minutes;
When (6) temperature was cooled to 80 ℃ naturally in the question response device, product had sharp interface to occur in the device, and the upper strata is stearic acid, and lower floor is Polyglycerine, emits lower floor's product, can, namely gets high-quality Polyglycerine product.
Claims (7)
1. the preparation method of a Polyglycerine, step comprises:
(1) in weight part, get 100 parts of glycerine, basic catalyst potassium hydroxide 0.5-5 part places in the stopping property reactor, heats up under 120 ± 20 rev/mins agitation condition;
(2) slow reactor heating to 100 ℃ makes reactor pressure keep malleation to regulate exhaust mode therebetween, in case the reactor outer air enters;
(3) continuing reactor heating makes temperature rise to 210-260 ℃, have water and generate this moment in the reactor, and discharge with the form of water vapour, the speed of regulating drainage water steam makes reactor pressure keep malleation, cool off and collect the water vapor of discharge simultaneously, when water to be collected reaches the 12%-18% of glycerine weight through weighing, the cooling termination reaction;
When (4) temperature is down to 180-200 ℃ in the question response device, add the stearic acid of 20-100 weight part, and fully stirred 30-40 minute with 120 ± 20 rev/mins rotating speed;
When (5) temperature was cooled to below 100 ℃ naturally in the question response device, product had sharp interface to occur in the device, and the upper strata is stearic acid, and lower floor is Polyglycerine, emits lower floor's product, can, namely gets the Polyglycerine product;
Wherein, above-mentioned steps (2) makes reactor pressure maintain 0.02 ± 0.005MPa to regulate exhaust mode; The speed that above-mentioned steps (3) is regulated drainage water steam makes reactor pressure maintain 0.05 ± 0.005MPa, to prevent the volatility of raw material loss.
2. the preparation method of Polyglycerine according to claim 1, it is characterized in that: the described basic catalyst potassium hydroxide of step (1) is the 1.5-2 weight part.
3. the preparation method of Polyglycerine according to claim 1, it is characterized in that: the described mixing speed of step (1) is 120 rev/mins.
4. the preparation method of Polyglycerine according to claim 1, it is characterized in that: the amount of the described water of collecting of step (3) is relevant with the polymerization degree of Polyglycerine product, it is dimerization that two molecule glycerine take off a part water, it is trimerization that three molecule glycerine take off two molecular waters, it is four poly-that four molecule glycerine take off trihyarol, and the rest may be inferred.
5. the preparation method of Polyglycerine according to claim 1, it is characterized in that: the stearic acid of the described adding of step (4) is 50 ± 2 weight parts.
6. the preparation method of Polyglycerine according to claim 1, it is characterized in that: the described mixing speed of step (4) is 120 rev/mins, and churning time is 30 minutes.
7. the preparation method of Polyglycerine according to claim 1, it is characterized in that: when the described reactor temperature of step (5) was cooled to 80 ℃ naturally, product had sharp interface to occur in the device.
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| CN 201010011323 CN101786944B (en) | 2010-01-11 | 2010-01-11 | Preparation method of high-quality polyglycerol |
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| CN 201010011323 CN101786944B (en) | 2010-01-11 | 2010-01-11 | Preparation method of high-quality polyglycerol |
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| CN101786944B true CN101786944B (en) | 2013-08-21 |
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| CN106084209B (en) * | 2016-07-22 | 2018-05-22 | 广州煌垅生物科技有限公司 | A kind of production technology of polyglyceryl fatty acid ester |
| CN113025207A (en) * | 2021-05-08 | 2021-06-25 | 四川环图材料科技有限公司 | Anti-sagging modified asphalt waterproof coating and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5041688A (en) * | 1988-12-19 | 1991-08-20 | Deutsche Solvay-Werke Gmbh | Process for the preparation of polyglycerols |
| CN1717381A (en) * | 2002-11-28 | 2006-01-04 | 大赛璐化学工业株式会社 | Polyglycerols, polyglycerol/fatty acid ester, and processes for producing these |
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2010
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5041688A (en) * | 1988-12-19 | 1991-08-20 | Deutsche Solvay-Werke Gmbh | Process for the preparation of polyglycerols |
| CN1717381A (en) * | 2002-11-28 | 2006-01-04 | 大赛璐化学工业株式会社 | Polyglycerols, polyglycerol/fatty acid ester, and processes for producing these |
Non-Patent Citations (2)
| Title |
|---|
| 聚甘油及其油酸酯的合成;谢汝文等;《福建化工》;20021231(第1期);第8-9,14页 * |
| 谢汝文等.聚甘油及其油酸酯的合成.《福建化工》.2002,(第1期),第8-9,14页. |
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Application publication date: 20100728 Assignee: Shijiazhuang Hui get Science and Technology Ltd. Assignor: Jinan Dongrun Fine Chemical Technology Co., Ltd. Contract record no.: 2014130000078 Denomination of invention: Preparation method of high-quality polyglycerol Granted publication date: 20130821 License type: Exclusive License Record date: 20140523 |
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