CN102993009A - Preparation method of glycerin monostearate alpha crystal - Google Patents
Preparation method of glycerin monostearate alpha crystal Download PDFInfo
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Abstract
The invention discloses a preparation method of glycerin monostearate alpha crystal. The method comprises the steps of enabling material hydrogenated palm oil and glycerol to react to generate crude monoglyceride under alkali catalysis, and then carrying out four-stage distillation to obtain the high-quality glycerin monostearate alpha crystal, wherein the content exceeds 90%. The acid value of the product disclosed by the invention is reduced to below 0.4; the freezing point is increased to 64-66 DEG C; the quality of the product is improved, and the difficult point of the prior art is overcome. Meanwhile, slag block of a pipe generated in the distillation process and the problems of disconnected production and low treatment efficiency caused by scale formation of an evaporating surface in an early technology are completely eradicated by the preparation method; and recovered glycerin and intermediate materials can be recycled. Therefore, the preparation method is low in cost, high in yield, high in controllability of the entire process, and suitable for industrial production.
Description
Technical field
The present invention relates to the invention belongs to chemical field, be specifically related to a kind of preparation method of glyceryl monostearate alpha-crystal.
Background technology
Glyceryl monostearate is a kind of tensio-active agent of non-ionic type.It existing hydrophilic have again oleophilic group because of, have the several functions such as wetting, emulsification, foaming.
Glyceryl monostearate is emulsifying agent and the additive of food; Be used as emulsifying agent in makeup and the medical paste, make lotion fine and smooth, lubricious; Be used for the emulsifying agent of industrial yarn finish and the lubricant of textiles; In plastics film, be used as drip agent and antifogging agent; In plastic working, make lubricant and static inhibitor, can be used as in other respects defoamer, dispersion agent, thickening material, wetting agent etc.
Its preparation is generally and is divided into chemical method and biological process, and wherein chemical method has following several approach:
(1) by glycerine and hydrogenated palm kernel oil esterification and get.
Hydrogenated palm kernel oil, glycerine and sodium hydroxide are added in the reactor, start stirring behind the heating and melting, pass into nitrogen.Reacting by heating.This process application is the most general, but the control condition is the key of product yield and purity in the technique, needs to continue perfect.
(2) direct esterification
Stearic acid and glycerine are pressed 1:(1.2～1.3) mol ratio, under 0.2% an acidic catalyst effect, at 180～250 ℃: the reaction 2～4h; Reactant speed is chilled to 100 ℃, adds the alkali catalyst neutralisation, must contain the product of monoesters 40%～60% after washing with water.This process yield is low, and product purity is low, the aftertreatment difficulty, and relative cost is high.
(3) ester-interchange method
Hydrogenated palm kernel oil and glycerine are at 0.06%～0.1% Cu (OH)
2Under the existence, at 170～240 ℃ of reaction 1～2h, pass into nitrogen protection in the reaction process, reactant obtains containing the product of monoesters 40%～60% after decompression deodorization, acid neutralize, make with extra care.This technique can be converted into glyceryl monostearate with many stearins, but scale is limited, and product yield is low, and cost is high.
(4) Racemic glycidol saponification method
Racemic glycidol and stearic acid at 100～130 ℃ of reaction 30～70min, can contain the product of monoesters 80%～90% after reactant is refining under the catalysis of tetraethyl ammonium iodide.This technological reaction mild condition, productive rate is high, but cost is higher.
(5) epoxy chloropropane phase transfer catalysis process
Epoxy chloropropane and sodium stearate (2:1, mol ratio) are in toluene, under the catalysis of phase-transfer catalyst Tetrabutyl amonium bromide, at 90～110 ℃ of reaction 2h; Reactant washs with sodium chloride solution, divides and gets organic phase, and toluene is removed in distillation and unreacted epoxy chloropropane gets the stearic acid glycidyl ester, with its NaOH solution hydrolysis with 0.1mol/L, through separation, drying, get product with the normal hexane recrystallization, monoester content is more than 90%.The monoesters product of content 40%～60% can obtain high density product more than 90% through molecular distillation.The productive rate of this technique is low, and cost is high.
Biological rule adopts the synthetic glyceryl monostearate of enzyme process to be, use lipase as a kind of efficient biological catalyst (Peng Lifeng. Food science [J], 1999,04), product not only has highly-solid selectively and regiospecificity, but the optical purity product that the synthetic chemistry method is difficult to synthesize, but long reaction time, generally all more than 10 hours, and the subsequent disposal expense is higher.
The quality of glyceryl monostearate product is directly connected to its Secure Application in the fields such as medicine, food, makeup.In the prior art, the standard that product can reach is iodine number (g I
2/ 100g)≤2.0, acid number (mg KOH/g)≤2.0,60 ℃ of zero pour 55 –, saponification value (mg KOH/g) 160-175.Wherein acid number only can be controlled at below 2.0, usually more than 1.0.Along with the especially requirement of quality of demand to glyceryl monostearate of food and pharmaceutical prod, we further promote the quality of glyceryl monostearate an urgent demand.
It should be noted that in addition, glyceryl monostearate finally obtains the higher glyceryl monostearate of purity after separating through multi-step evaporator, the mono-glycerides of this moment is 100 ℃ transparent liquid state, becomes thickness after process press atomization normal temperature is air-cooled and is distributed as 20 to 100 purpose graininesses.After glyceryl monostearate becomes the particulate state finished product through press atomization, the process that when storage, can have a crystal transition, when crystal transition occurs, the meeting releases heat, if directly the glyceryl monostearate of producing is packaged in summer, top temperature can reach between 50 to 56 degree when crystal transition occurs, sensation scalds one's hand, and molten state can appear in the package centre position, the glyceryl monostearate melting range of general different content is at 63 to 66 ℃, after it finishes this process glyceryl monostearate and progressively cools off, the glyceryl monostearate finished product can seriously lump, have a strong impact on the quality of product, more can't obtain the higher glyceryl monostearate of alpha-crystal content.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, the preparation method of a kind of high yield, high quality, low cost, easy industrialized glyceryl monostearate alpha-crystal is provided.
This purpose is achieved by following technical solution.This technical scheme is that esterification is synthesized, processed the high-quality glyceryl monostearate alpha-crystal of preparation through technique, the cooling spray of level Four distilation under base catalysis.
The preparation method of this glyceryl monostearate alpha-crystal comprises the steps:
1) preparation of glyceryl monostearate crude product
At first, glycerine is joined in the esterification reaction tank, then catalyzer is slowly joined in the esterification reaction tank, be warming up to again 90 degrees centigrade, stirred 30 minutes;
Secondly, the hydrogenated liquid plam oil is joined in the above-mentioned esterification reaction tank, fully mix, be warmed up to T
0Being 210-220 ℃, control pressure P is-0.06Mpa is to-0.09Mpa, carries out esterification 30min, gets the glyceryl monostearate crude product;
Wherein, described T
0Be preferably 215-220 ℃, more preferably 218 ℃;
Described catalyzer is sodium hydroxide or potassium hydroxide, preferred sodium hydroxide.
The mass ratio of described catalyzer and glycerine is (0.1-0.5): 100, be preferably (0.2-0.4): and 100,0.275:100 more preferably.
Described hydrogenated palm kernel oil is 1:(0.98-1.3 with the ratio of the amount of substance of glycerine); Be preferably 1:(1.0-1.1), 1:1.05 more preferably.
2) neutralizing treatment
Add phosphoric acid in above-mentioned reacted glyceryl monostearate crude product, adjusting pH is 6.0-7.5, is preferably 7.0, stirs 15 minutes, then leaves standstill deslagging after 2 hours, and filtrate is the thick ester of glyceryl monostearate;
3) one-level distillation
With step 2) in the thick ester of glyceryl monostearate distill, distillation condition is as follows: temperature T
1Be 160-225 ℃, preferred T
1Be 170 ℃, vacuum P
1Be 150-200pa, preferred P
1Be 200pa, thermal oil pressure 0.25-0.3MPA.Steaming is removed most of moisture till extremely steaming without cut, gets one-level distillation feed liquid.
This step is steamed except the moisture in the feed liquid.
4) secondary distillation
Carry out second stage distillation with steaming one-level distillation feed liquid in the step 3), distillation condition is: temperature T
2Be 190-220 ℃, preferred T
2Be 195 ℃, vacuum P
2Be 3-10pa, preferred P
2Be 10pa, thermal oil pressure 0.25-0.3MPA.Steaming is steamed except most glycerine and free acid till extremely steaming without cut, gets the secondary distillation feed liquid.
5) three-stage distillation
Carry out three-stage distillation with getting the secondary distillation feed liquid in the step 4), distillation condition is: temperature T
3Be 200-220 ℃, preferred T
3Be 210 ℃, vacuum P
3Be 3-15pa, preferred P
3Be 8pa, thermal oil pressure 0.25-0.3MPA.Steaming is extracted micro-glycerine and free acid till extremely steaming without cut, gets the three-stage distillation feed liquid.
6) level Four distillation:
Three-stage distillation feed liquid in the step 5) is carried out the level Four distillation, and distillation condition is: temperature T
4Be 210-230 ℃, vacuum P
4Be 0.1-7pa, thermal oil pressure 0.25-0.3MPA.Steaming gets glyceryl monostearate liquid till extremely steaming without cut.
7) cooling spray is processed:
Glyceryl monostearate liquid is cooled to 65-73 ℃, and keeps constant;
With the processing of spraying of the glyceryl monostearate liquid after the above-mentioned cooling, and to keep the spray tower inlet temperature be 5-10 ℃, gets the glyceryl monostearate particle;
Above-mentioned glyceryl monostearate particle continues to be cooled to 25 ℃, and the control rate of cooling is at 2-5 ℃/h; Pack to get the glyceryl monostearate alpha-crystal.
The present invention utilizes reaction equation, reaction equilibrium constant and test practice, determines to produce prescription proportional quantity and the length in reaction times, controls preferably the main quality index such as acid number.In process of production, the parameters such as each material consumption, reaction times, technological temperature, vacuum tightness are controlled effectively, allow the material complete reaction, fully purify.As seen step 1) to step 6) has been established good quality base for preparation glyceryl monostearate alpha-crystal, and step 1) of the present invention is to the preferred fabulous glyceryl monostearate of quality that just can obtain of step 6) processing parameter just.
In addition, very crucial effect is also played in the formation for the glyceryl monostearate alpha-crystal treatment stage of especially it should be noted that the glyceryl monostearate cooling spray.At first, a kind of liquid glyceryl monostearate keeps 65-73 ℃ through after lowering the temperature, preferred 70 ℃, reduced the temperature that mono-glycerides enters the press atomization link, in follow-up spray process, eliminated in advance the hidden danger of easy caking, this link has directly improved 15-20% with glyceryl monostearate alpha-crystal production efficiency; Secondly, further reduce the temperature of the mono-glycerides finished particle in the spray tower by spray tower 5-10 ℃ air intake, more stable and regular through cooled mono-glycerides alpha-crystal; At last, the glyceryl monostearate particle continues to be cooled to 25 ℃, controls rate of cooling at 2-5 ℃/h, preferred 4 ℃/h, and this link has directly improved 5-10% with glyceryl monostearate alpha-crystal production efficiency; Pack to get glyceryl monostearate alpha-crystal particle.
Through detecting quality examination result of the present invention be: iodine number (g I
2/ 100g)≤2.0; Acid number (mg KOH/g)≤1.0; Zero pour: 64-66 ℃; Saponification value (mg KOH/g): 160-175.Detect through alpha-crystal, the content of glyceryl monostearate alpha-crystal of the present invention is more than 90%.
Compared with prior art, the present invention has following beneficial effect:
1) content of the glyceryl monostearate alpha-crystal of the present invention's acquisition is high, more than 90%;
2) the present invention adopts the level Four distillation method, so that the glycerine that steams and intermediate material can be recycled, saves cost.
3) the glyceryl monostearate alpha-crystal quality product that obtains is high, and whole process controllability is high, is fit to industrial production.
Embodiment
Following content is the further description of the present invention being done in conjunction with concrete preferred implementation, can not assert that implementation of the present invention is confined to these explanations.For the general technical staff of the technical field of the invention; without departing from the inventive concept of the premise; can also make some simple deduction or replace; all should be considered as belonging to protection scope of the present invention; the present invention uses but the technology and the indexing section that do not describe, is prior art.
GB15612-1995 is adopted in the glyceryl monostearate quality examination.
The measuring method of glyceryl monostearate alpha-crystal is with reference to " standard method of analysis of grease and derivative thereof " (national oil technology information center station, Li Shunlan translates, 41-44 page or leaf in 1981).
Embodiment 1
Prepare high-quality glyceryl monostearate, concrete technology is as follows:
1) preparation of glyceryl monostearate crude product
The preparation of step 1) glyceryl monostearate crude product:
At first, 122kg glycerine is joined in the esterification reaction tank, then 0.6kg sodium hydroxide slowly joins in the esterification reaction tank, is warming up to 90 degrees centigrade again, stirs 30 minutes;
Secondly, 500kg hydrogenated liquid plam oil is joined in the above-mentioned esterification reaction tank, fully mix, be warmed up to T
0Be 210 ℃, control pressure P is-0.06Mpa, carries out esterification 30min, gets the glyceryl monostearate crude product;
2) neutralizing treatment
Add phosphoric acid in the glyceryl monostearate crude product of step 1), regulating pH is 6.0, stirs 15 minutes, then leaves standstill deslagging after 2 hours, and filtrate is the thick ester of glyceryl monostearate.
3) one-level distillation
With step 2) in the thick ester feed liquid of glyceryl monostearate distill, distillation condition is as follows: temperature is 160 ℃, vacuum 150pa, thermal oil pressure 0.25-0.3MPA.Till steaming extremely steams without cut.
This step is steamed except the moisture in the feed liquid.
4) secondary distillation
Carry out second stage distillation with steaming in the step 3) except the feed liquid of moisture, steam except most free glycerol and free acid.
Distillation condition is: temperature is 190 ℃, vacuum 3pa, thermal oil pressure 0.25-0.3MPA.Steaming gets the secondary distillation feed liquid till extremely steaming without cut.
5) three-stage distillation
Secondary distillation feed liquid in the step 4) is entered three-stage distillation, extract micro-glycerine and free acid.
Distillation condition is: temperature is 200 ℃, vacuum 3pa, thermal oil pressure 0.25-0.3MPA.Steaming gets the three-stage distillation feed liquid till extremely steaming without cut.
6) level Four distillation:
Three-stage distillation feed liquid in the step 5) is entered the level Four distillation, separate glyceryl monostearate and stearic acid two glyceryl ester, glycerol stearate, obtain high-quality glyceryl monostearate.
Distillation condition is: temperature is 210 ℃, vacuum 0.1-7pa, and thermal oil pressure 0.25-0.3MPA gets glyceryl monostearate liquid.
7) cooling spray is processed:
Glyceryl monostearate liquid is cooled to 73 ℃, and keeps constant;
With the processing of spraying of the glyceryl monostearate liquid after the above-mentioned cooling, and to keep the spray tower inlet temperature be 5-10 ℃, gets the glyceryl monostearate particle;
Above-mentioned glyceryl monostearate particle continues to be cooled to 25 ℃, and the control rate of cooling is at 5 ℃/h; Pack to get the glyceryl monostearate alpha-crystal, through detecting, glyceryl monostearate alpha-crystal content is 90.5%.
The quality examination result of finished product is:
Iodine number (g I
2/ 100g)≤2.0; Acid number (mg KOH/g): 1.0; Zero pour: 65.8 ℃; Saponification value (mg KOH/g): 162.
Embodiment 2
Prepare high-quality glyceryl monostearate, concrete technology is as follows:
1) preparation of glyceryl monostearate crude product
The preparation of step 1) glyceryl monostearate crude product:
At first, 128kg glycerine is joined in the esterification reaction tank, then 0.5kg sodium hydroxide slowly joins in the esterification reaction tank, is warming up to 90 degrees centigrade again, stirs 30 minutes;
Secondly, 500kg hydrogenated liquid plam oil is joined in the above-mentioned esterification reaction tank, fully mix, be warmed up to T
0Be 215 ℃, control pressure P is-0.07Mpa, carries out esterification 30min, gets the glyceryl monostearate crude product;
2) neutralizing treatment
Add phosphoric acid in the glyceryl monostearate crude product of step 1), regulating pH is 6.5, stirs 15 minutes, then leaves standstill deslagging after 2 hours, and filtrate is the thick ester of glyceryl monostearate.
3) one-level distillation
With step 2) in the feed liquid of having removed glycerol slag distill, distillation condition is as follows: temperature is 170 ℃, vacuum 160pa, thermal oil pressure 0.25-0.3MPA.Till steaming extremely steams without cut.
This step is steamed except the moisture in the feed liquid.
4) secondary distillation
Carry out second stage distillation with steaming in the step 3) except the feed liquid of moisture, steam except most free glycerol and free acid.
Distillation condition is: temperature is 200 ℃, vacuum 5pa, thermal oil pressure 0.25-0.3MPA.Till steaming extremely steams without cut.
5) three-stage distillation
The feed liquid of steaming except most of glycerine and free acid in the step 4) is entered three-stage distillation, extract micro-glycerine and free acid.
Distillation condition is: temperature is 210 ℃, vacuum 5pa, thermal oil pressure 0.25-0.3MPA.Steaming gets the three-stage distillation feed liquid till extremely steaming without cut.
6) level Four distillation:
Three-stage distillation feed liquid in the step 5) is entered the level Four distillation, separate glyceryl monostearate and stearic acid two glyceryl ester, glycerol stearate, obtain high-quality glyceryl monostearate.
Distillation condition is: temperature is 215 ℃, vacuum 0.1pa, thermal oil pressure 0.25-0.3MPA.Get glyceryl monostearate liquid.
7) cooling spray is processed:
Glyceryl monostearate liquid is cooled to 68 ℃, and keeps constant;
With the processing of spraying of the glyceryl monostearate liquid after the above-mentioned cooling, and to keep the spray tower inlet temperature be 5-10 ℃, gets the glyceryl monostearate particle;
Above-mentioned glyceryl monostearate particle continues to be cooled to 25 ℃, and the control rate of cooling is at 2 ℃/h; Pack to get the glyceryl monostearate alpha-crystal, through detecting, glyceryl monostearate alpha-crystal content is 91.5%.
The quality examination result of finished product is:
Iodine number (g I
2/ 100g): 0.9; Acid number (mg KOH/g): 0.6; Zero pour: 65.6 ℃; Saponification value (mg KOH/g): 170.
Embodiment 3
Prepare high-quality glyceryl monostearate, concrete technology is as follows:
1) preparation of glyceryl monostearate crude product
The preparation of step 1) glyceryl monostearate crude product:
At first, 135kg glycerine is joined in the esterification reaction tank, then 0.37kg sodium hydroxide slowly joins in the esterification reaction tank, is warming up to 90 degrees centigrade again, stirs 30 minutes;
Secondly, 500kg hydrogenated liquid plam oil is joined in the above-mentioned esterification reaction tank, fully mix, be warmed up to T
0Be 218 ℃, control pressure P is-0.08Mpa, carries out esterification 30min, gets the glyceryl monostearate crude product;
2) neutralizing treatment
Add phosphoric acid in the glyceryl monostearate crude product of step 1), regulating pH is 7.0, stirs 15 minutes, then leaves standstill deslagging after 2 hours, and filtrate is the thick ester of glyceryl monostearate.
3) one-level distillation
With step 2) in the feed liquid of having removed glycerol slag distill, distillation condition is as follows: temperature is 170 ℃, vacuum 200pa, thermal oil pressure 0.25-0.3MPA.Till steaming extremely steams without cut.
This step is steamed except the moisture in the feed liquid.
4) secondary distillation
Carry out second stage distillation with steaming in the step 3) except the feed liquid of moisture, steam except most free glycerol and free acid.
Distillation condition is: temperature is 195 ℃, vacuum 10pa, thermal oil pressure 0.25-0.3MPA.Till steaming extremely steams without cut.
5) three-stage distillation
The feed liquid of steaming except most of glycerine and free acid in the step 4) is entered three-stage distillation, extract micro-glycerine and free acid.
Distillation condition is: temperature is 210 ℃, vacuum 8pa, thermal oil pressure 0.25-0.3MPA.Steaming gets the three-stage distillation feed liquid till extremely steaming without cut.
6) level Four distillation:
Three-stage distillation feed liquid in the step 5) is entered the level Four distillation, separate glyceryl monostearate and stearic acid two glyceryl ester, glycerol stearate, obtain high-quality glyceryl monostearate.
Distillation condition is: temperature is 215 ℃, vacuum 0.1pa, and thermal oil pressure 0.25-0.3MPA gets glyceryl monostearate liquid.
7) cooling spray is processed:
Glyceryl monostearate liquid is cooled to 70 ℃, and keeps constant;
With the processing of spraying of the glyceryl monostearate liquid after the above-mentioned cooling, and to keep the spray tower inlet temperature be 5-10 ℃, gets the glyceryl monostearate particle;
Above-mentioned glyceryl monostearate particle continues to be cooled to 25 ℃, and the control rate of cooling is at 4 ℃/h; Pack to get the glyceryl monostearate alpha-crystal, through detecting, glyceryl monostearate alpha-crystal content is 95.5%.
The quality examination result of finished product is:
Iodine number (g I
2/ 100g): 0.8; Acid number (mg KOH/g): 0.25; Zero pour: 65.6 ℃; Saponification value (mg KOH/g): 168.
Embodiment 4
Prepare high-quality glyceryl monostearate, concrete technology is as follows:
1) preparation of glyceryl monostearate crude product
The preparation of step 1) glyceryl monostearate crude product:
At first, 141kg glycerine is joined in the esterification reaction tank, then 0.4kg sodium hydroxide slowly joins in the esterification reaction tank, is warming up to 90 degrees centigrade again, stirs 30 minutes;
Secondly, 500kg hydrogenated liquid plam oil is joined in the above-mentioned esterification reaction tank, fully mix, be warmed up to T
0Be 218 ℃, control pressure P is-0.08Mpa, carries out esterification 30min, gets the glyceryl monostearate crude product;
2) neutralizing treatment
Glyceryl monostearate crude product to step 1) adds phosphoric acid, and regulating pH is 7.0, stirs 15 minutes, then leaves standstill deslagging after 2 hours, and filtrate is the thick ester of glyceryl monostearate.
3) one-level distillation
With step 2) in the feed liquid of having removed glycerol slag distill, distillation condition is as follows: temperature is 180 ℃, vacuum 180pa, thermal oil pressure 0.25-0.3MPA steams till steam without cut.
This step is steamed except the moisture in the feed liquid.
4) secondary distillation
Carry out second stage distillation with steaming in the step 3) except the feed liquid of moisture, steam except most extraction glycerine and free acid.
Distillation condition is: temperature is 195 ℃, vacuum 10pa, and thermal oil pressure 0.25-0.3MPA is till steaming extremely steams without cut.
5) three-stage distillation
The feed liquid of steaming except most of glycerine and free acid in the step 4) is entered three-stage distillation, extract micro-glycerine and free acid.
Distillation condition is: temperature is 210 ℃, vacuum 8pa, and thermal oil pressure 0.25-0.3MPA, steaming gets the three-stage distillation feed liquid till extremely steaming without cut.
6) level Four distillation:
Three-stage distillation feed liquid in the step 5) is entered the level Four distillation, separate glyceryl monostearate and stearic acid two glyceryl ester, glycerol stearate, obtain high-quality glyceryl monostearate.
Distillation condition is: temperature is 215 ℃, vacuum 0.1pa, and thermal oil pressure 0.25-0.3MPA,, get glyceryl monostearate liquid.
7) cooling spray is processed:
Glyceryl monostearate liquid is cooled to 73 ℃, and keeps constant;
With the processing of spraying of the glyceryl monostearate liquid after the above-mentioned cooling, and to keep the spray tower inlet temperature be 5-10 ℃, gets the glyceryl monostearate particle;
Above-mentioned glyceryl monostearate particle continues to be cooled to 25 ℃, and the control rate of cooling is at 2 ℃/h; Pack to get the glyceryl monostearate alpha-crystal, through detecting, glyceryl monostearate alpha-crystal content is 92%.
The quality examination result of finished product is:
Iodine number (g I
2/ 100g): 0.8; Acid number (mg KOH/g): 0.4; Zero pour: 66 ℃; Saponification value (mg KOH/g): 166.
Embodiment 5
Prepare high-quality glyceryl monostearate, concrete technology is as follows:
1) preparation of glyceryl monostearate crude product
The preparation of step 1) glyceryl monostearate crude product:
At first, 154kg glycerine is joined in the esterification reaction tank, then 0.3kg sodium hydroxide slowly joins in the esterification reaction tank, is warming up to 90 degrees centigrade again, stirs 30 minutes;
Secondly, 500kg hydrogenated liquid plam oil is joined in the above-mentioned esterification reaction tank, fully mix, be warmed up to T
0Be 218 ℃, control pressure P is-0.08Mpa, carries out esterification 30min, gets the glyceryl monostearate crude product;
2) neutralizing treatment
Glyceryl monostearate crude product to step 1) adds phosphoric acid, and regulating pH is 7.0, stirs 15 minutes, then leaves standstill deslagging after 2 hours, and filtrate is the thick ester of glyceryl monostearate.
3) one-level distillation
With step 2) in the feed liquid of having removed glycerol slag distill, distillation condition is as follows: temperature is 200 ℃, vacuum 190pa, thermal oil pressure 0.25-0.3MPA.Till steaming extremely steams without cut.
This step is steamed except the moisture in the feed liquid.
4) secondary distillation
Carry out second stage distillation with steaming in the step 3) except the feed liquid of moisture, steam except most extraction glycerine and free acid.
Distillation condition is: temperature is 210 ℃, vacuum 10pa, and thermal oil pressure 0.25-0.3MPA is till steaming extremely steams without cut.
5) three-stage distillation
The feed liquid of steaming except most of glycerine and free acid in the step 4) is entered three-stage distillation, extract micro-glycerine and free acid.
Distillation condition is: temperature is 210 ℃, vacuum 10pa, and thermal oil pressure 0.25-0.3MPA, steaming gets the three-stage distillation feed liquid till extremely steaming without cut.
6) level Four distillation:
Three-stage distillation feed liquid in the step 5) is entered the level Four distillation, separate glyceryl monostearate and stearic acid two glyceryl ester, glycerol stearate, obtain high-quality glyceryl monostearate.
Distillation condition is: temperature is 220 ℃, vacuum 5pa, and pressure 0.25-0.3MPA gets glyceryl monostearate liquid.
7) cooling spray is processed:
Glyceryl monostearate liquid is cooled to 67 ℃, and keeps constant;
With the processing of spraying of the glyceryl monostearate liquid after the above-mentioned cooling, and to keep the spray tower inlet temperature be 5-10 ℃, gets the glyceryl monostearate particle;
Above-mentioned glyceryl monostearate particle continues to be cooled to 25 ℃, and the control rate of cooling is at 3 ℃/h; Pack to get the glyceryl monostearate alpha-crystal, through detecting, glyceryl monostearate alpha-crystal content is 91%.
The quality examination result of finished product is:
Iodine number (g I
2/ 100g): 0.9; Acid number (mg KOH/g): 0.5; Zero pour: 64-66 ℃; Saponification value (mg KOH/g): 168.
Embodiment 6
Prepare high-quality glyceryl monostearate, concrete technology is as follows:
1) preparation of glyceryl monostearate crude product
The preparation of step 1) glyceryl monostearate crude product:
At first, 166kg glycerine is joined in the esterification reaction tank, then 0.2kg sodium hydroxide slowly joins in the esterification reaction tank, is warming up to 90 degrees centigrade again, stirs 30 minutes;
Secondly, 500kg hydrogenated liquid plam oil is joined in the above-mentioned esterification reaction tank, fully mix, be warmed up to T
0Be 220 ℃, control pressure P is-0.08Mpa, carries out esterification 30min, gets the glyceryl monostearate crude product;
2) neutralizing treatment
Add phosphoric acid in the glyceryl monostearate crude product of step 1), regulating pH is 7.5, stirs 15 minutes, then leaves standstill deslagging after 2 hours, and filtrate is the thick ester of glyceryl monostearate.
3) one-level distillation
With step 2) in the feed liquid of having removed glycerol slag distill, distillation condition is as follows: temperature is 225 ℃, vacuum 170pa, thermal oil pressure 0.25-0.3MPA steams till steam without cut.
This step is steamed except the moisture in the feed liquid.
4) secondary distillation
Carry out second stage distillation with steaming in the step 3) except the feed liquid of moisture, steam except most extraction glycerine and free acid.
Distillation condition is: temperature is 220 ℃, vacuum 10pa, and thermal oil pressure 0.25-0.3MPA is till steaming extremely steams without cut.
5) three-stage distillation
The feed liquid of steaming except most of glycerine and free acid in the step 4) is entered three-stage distillation, extract micro-glycerine and free acid.
Distillation condition is: temperature is 220 ℃, vacuum 8pa, and thermal oil pressure 0.25-0.3MPA, steaming gets the three-stage distillation feed liquid till extremely steaming without cut.
6) level Four distillation:
Three-stage distillation feed liquid in the step 5) is entered the level Four distillation, separate glyceryl monostearate and stearic acid two glyceryl ester, glycerol stearate, obtain high-quality glyceryl monostearate.
Distillation condition is: temperature is 230 ℃, vacuum 7pa, and thermal oil pressure 0.25-0.3MPA,, get glyceryl monostearate liquid.
7) cooling spray is processed:
Glyceryl monostearate liquid is cooled to 70 ℃, and keeps constant;
With the processing of spraying of the glyceryl monostearate liquid after the above-mentioned cooling, and to keep the spray tower inlet temperature be 5-10 ℃, gets the glyceryl monostearate particle;
Above-mentioned glyceryl monostearate particle continues to be cooled to 25 ℃, and the control rate of cooling is at 5 ℃/h; Pack to get the glyceryl monostearate alpha-crystal, through detecting, glyceryl monostearate alpha-crystal content is 92%.
The quality examination result of finished product is:
Iodine number (g I
2/ 100g): 1.0; Acid number (mg KOH/g): 0.8; Zero pour: 65.8 ℃; Saponification value (mg KOH/g): 165.
Claims (8)
1. the preparation method of a glyceryl monostearate alpha-crystal comprises the steps:
The preparation of step 1) glyceryl monostearate crude product
At first, glycerine is joined in the esterification reaction tank, then catalyzer is slowly joined in the esterification reaction tank, be warming up to again 90 degrees centigrade, stirred 30 minutes;
Secondly, the hydrogenated liquid plam oil is joined in the above-mentioned esterification reaction tank, fully mix, be warmed up to T
0Being 210-220 ℃, control pressure P is-0.06Mpa is to-0.09Mpa, carries out esterification 30min, gets the glyceryl monostearate crude product;
Wherein, described catalyzer is sodium hydroxide or potassium hydroxide;
The weight ratio of described catalyzer and glycerine is (0.1-0.5): 100;
The molar ratio of described hydrogenated palm kernel oil and glycerine is 1:(0.98-1.3);
Step 2) neutralizing treatment
Add phosphoric acid in above-mentioned reacted glyceryl monostearate crude product, adjusting pH is 6.0-7.5, stirs 15 minutes, then leaves standstill deslagging after 2 hours, and filtrate is the thick ester of glyceryl monostearate;
The distillation of step 3) one-level
With step 2) in the thick ester of glyceryl monostearate distill, distillation condition is: temperature T
1Be 160-225 ℃, vacuum P
1Be 150-200pa, thermal oil pressure 0.25-0.3MPA till steaming extremely steams without cut, gets one-level distillation feed liquid;
The step 4) secondary distillation
One-level distillation feed liquid in the step 3) is carried out second stage distillation, and distillation condition is: temperature T
2Be 190-220 ℃, vacuum P
2Be 3-10pa, thermal oil pressure 0.25-0.3MPA gets the secondary distillation feed liquid;
The step 5) three-stage distillation
Secondary distillation feed liquid in the step 4) is carried out three-stage distillation, and distillation condition is: temperature T
3Be 200-220 ℃, vacuum P
3Be 3-15pa, thermal oil pressure 0.25-0.3MPA gets the three-stage distillation feed liquid;
The distillation of step 6) level Four
Three-stage distillation feed liquid in the step 5) is entered the level Four distillation, and distillation condition is: temperature T
4Be 210-230 ℃, vacuum P
4Be 0.1-7pa, thermal oil pressure 0.25-0.3MPA gets glyceryl monostearate liquid;
The step 7) cooling spray is processed:
Glyceryl monostearate liquid is cooled to 65-73 ℃, and keeps constant;
With the processing of spraying of the glyceryl monostearate liquid after the above-mentioned cooling, and to keep the spray tower inlet temperature be 5-10 ℃, gets the glyceryl monostearate particle;
Above-mentioned glyceryl monostearate particle continues to be cooled to 25 ℃, and the control rate of cooling is at 2-5 ℃/h; Pack to get the glyceryl monostearate alpha-crystal.
2. the preparation method of a kind of glyceryl monostearate alpha-crystal as claimed in claim 1 is characterized in that, described T
0Be 215-220 ℃.
3. the preparation method of a kind of glyceryl monostearate alpha-crystal as claimed in claim 1 is characterized in that, described T
0Be 218 ℃, described catalyzer is sodium hydroxide.
4. the preparation method of a kind of glyceryl monostearate alpha-crystal as claimed in claim 1, it is characterized in that, the mass ratio of described catalyzer and glycerine is (0.2-0.4): 100, described hydrogenated palm kernel oil is 1:(1.0-1.1 with the ratio of the amount of substance of glycerine).
5. the preparation method of a kind of glyceryl monostearate alpha-crystal as claimed in claim 1 is characterized in that step 2) in to regulate pH be 7.0.
6. the preparation method of a kind of glyceryl monostearate alpha-crystal as claimed in claim 1 is characterized in that, described T
1Be 170 ℃, vacuum P
1Be 200pa; T
2Be 195 ℃, vacuum P
2Be 10pa; T
3Be 210 ℃, P
3Be 8pa; T
4Be 215 ℃, P
4Be 0.1pa.
7. such as the preparation method of the described a kind of glyceryl monostearate alpha-crystal of the arbitrary claim of claim 1-6, it is characterized in that, the mass ratio of described catalyzer and glycerine is 0.275:100, and described hydrogenated palm kernel oil is 1:1.05 with the ratio of the amount of substance of glycerine.
8. the preparation method of a kind of glyceryl monostearate alpha-crystal as claimed in claim 1 is characterized in that, described step 7) cooling spray treatment process is:
Glyceryl monostearate liquid is cooled to 70 ℃, and keeps constant;
With the processing of spraying of the glyceryl monostearate liquid after the above-mentioned cooling, and to keep the spray tower inlet temperature be 5-10 ℃, gets the glyceryl monostearate particle;
Above-mentioned glyceryl monostearate particle continues to be cooled to 25 ℃, and the control rate of cooling is at 4 ℃/h; Pack to get the glyceryl monostearate alpha-crystal.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105152929A (en) * | 2015-08-05 | 2015-12-16 | 广州嘉德乐生化科技有限公司 | Propylene glycol monostearate, and industrial production method and application thereof |
| CN109896954A (en) * | 2019-03-27 | 2019-06-18 | 佳力士添加剂（海安）有限公司 | A kind of synthetic method of monopalmitin |
| CN113416132A (en) * | 2021-08-06 | 2021-09-21 | 杭州富春食品添加剂有限公司 | Production process for distilling low-glycerol glycerin monostearate |
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| US2875221A (en) * | 1958-03-07 | 1959-02-24 | Hachmeister Inc | Process for preparing monoglycerides of fatty acids |
| US3102129A (en) * | 1961-05-19 | 1963-08-27 | Hachmeister Inc | Process for producing monoglycerides of fatty acids |
| CN102241586A (en) * | 2011-05-12 | 2011-11-16 | 暨南大学 | Method for synthesizing and purifying high-purity fatty acyl monoglyceride |
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| US2875221A (en) * | 1958-03-07 | 1959-02-24 | Hachmeister Inc | Process for preparing monoglycerides of fatty acids |
| US3102129A (en) * | 1961-05-19 | 1963-08-27 | Hachmeister Inc | Process for producing monoglycerides of fatty acids |
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| CN105152929A (en) * | 2015-08-05 | 2015-12-16 | 广州嘉德乐生化科技有限公司 | Propylene glycol monostearate, and industrial production method and application thereof |
| CN105152929B (en) * | 2015-08-05 | 2017-11-14 | 广州嘉德乐生化科技有限公司 | A kind of propylene glycol monostearate and its industrial process and application |
| CN109896954A (en) * | 2019-03-27 | 2019-06-18 | 佳力士添加剂（海安）有限公司 | A kind of synthetic method of monopalmitin |
| CN113416132A (en) * | 2021-08-06 | 2021-09-21 | 杭州富春食品添加剂有限公司 | Production process for distilling low-glycerol glycerin monostearate |
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