Molecule distillating monoglyceride technique and device are produced in a kind of use immobilization bed serialization
Technical field
The present invention relates to the fine chemistry industry production field, aim to provide a kind of use immobilization bed serialization and produce molecule distillating monoglyceride technique and device.
Technical background
The full name of mono-glycerides is monoglyceride, adopts the refining mono-glycerides product of molecular distillation technique to be called molecule distillating monoglyceride.Molecule distillating monoglyceride is a kind of efficient tensio-active agent, can play the effects such as emulsification, foaming, dispersion, froth breaking, resisting starch ageing, therefore as food emulsifier, be widely used in field of food, usage quantity has surpassed 50% of food emulsifier total amount at present.Except field of food, mono-glycerides also is widely used in the industry such as makeup, medicine, fine chemistry industry, washing composition, plastics.
Ester-interchange method is mainly adopted in the production of current molecule distillating monoglyceride, namely use hydrogenated oil and fat and glycerine in pyroreaction 1 ~ 2 hour under the feed ratio of about 1:2 in molar ratio under the basic catalyst condition, obtain approximately containing glycerine, mono-glycerides and two or three ester mixtures of 40 ~ 50% mono-glyceridess; By molecular distillation equipment, glycerine, mono-glycerides, two or three esters are separated, obtained monoester content at the molecule distillating monoglyceride product 90% or more, wherein the glycerine, two or three esters that obtain of separation can continue reuse and enter esterification.Patent CN101724508A has just mentioned a kind of technique that two or three esters that obtain after molecular distillation is continued to get back to esterification, and the glycerine that its use accounts for total reaction material quality 25-35% reacts under the sheet base catalysis with grease or reuse two or three esters.In this type of technique, due to the existence of a small amount of soap (basic catalyst reacts appearance with grease) in the product after esterification, if directly entered molecular distillation, not only can affect distillation efficiency, make the easy gum deposit of molecular distillation equipment; And the transesterification reaction occurred due to glycerine and grease shows as reversible balanced reaction, under the catalyzer existence condition, molecular distillation removes the glycerine afterreaction easily to reverse movement, monoester content is reduced and contain higher free glycerol.After therefore existing production technique esterification finishes, need to adopt acid by the basic catalyst neutralization, and by stratification, partial glycerol and catalyzer are removed, will increase the operation to this part end glycerin treatment like this, also increased production cost.
Summary of the invention
The objective of the invention is to overcome the deficiency of above-mentioned background technology, a kind of technique and device that uses the serialization of immobilization bed to produce molecule distillating monoglyceride is provided, this technique and device should have and can be continuously produced, and reduce energy consumption, the characteristics of enhancing productivity.
The objective of the invention is by realizing by the following technical solutions:
A kind of technique of using the serialization of immobilization bed to produce molecule distillating monoglyceride, carry out in the steps below successively:
A, grease, two or three esters, glycerine be from temporary tank output separately, by volume pump, through static mixer, tentatively mixes, after interchanger heat absorption, heater heats, enters ultrasound reactor continuously by a certain percentage; Wherein glycerine is 10% ~ 30% of the part by weight that always feeds intake;
B, mixture in ultrasound reactor after ultrasonication, directly enter the immobilization bed bioreactor that is filled with basic catalyst and carry out esterification, esterification reaction temperature is 200 ~ 240 ℃, reaction time is 10 ~ 120min;
C, absorb heat through interchanger from immobilization bed bioreactor esterification reaction product out, be cooled to 150 ~ 180 ℃, after the temporary tank of thick ester is temporary, directly enters the molecular distillation system and carry out molecular distillation;
Successively thin film distillation removes the processing of water and low-boiling-point substance, secondary molecular distillation separation of glycerin, three grades of molecule fractionation by distillation two or three esters and mono-glycerides through one-level in the molecular distillation system for D, described esterification reaction product;
The glycerine that after secondary, three grades of molecules distilled, separation obtained and two or three esters enter respectively keeps in tank separately to do reuse, and three grades of molecules distill the monoesters obtained and be the finished product molecule distillating monoglyceride after the processing of dusting;
Two or three esters in described steps A, step D, refer to the lipid acid diester after molecular distillation, the mixture of lipid acid three esters;
In described step D, the temperature of one-level thin film evaporation is 150 ~ 180 ℃, vacuum tightness 1-10KPa, and secondary molecular distillation temperature is 150 ~ 180 ℃, vacuum tightness 1 ~ 50Pa, three grades of molecule distillation temperatures are 150 ~ 180 ℃, vacuum tightness 1 ~ 10Pa.
In described steps A, grease is one or more mixing of hydrogenated palm kernel oil, hydrogenated lard.
In described steps A, the ultrasonic frequency of ultrasound reactor is 10
5~ 10
6Hz.
In described step B, material reaction time in the immobilization bed bioreactor is 10 ~ 30min.
Described immobilization bed bioreactor is connected in series by a plurality of immobilization bed bioreactors; Material residence time in single immobilization bed bioreactor is 5 ~ 10min.
In described step B, the esterification in the immobilization bed bioreactor adopts vacuum or N
2Protection, vacuum pressure is 1 ~ 10KPa, N
2Protection pressure is 0.1 ~ 0.3MPa.
In described step B, the solid basic catalyst of filling in immobilization bed bioreactor or flowing bed reactor is CaO, MgO, magnalium stone flour, aluminium lithium stone flour and self-control alkali solid catalyst; The self-control solid basic catalyst is MgO-CaO/SiO
2, its Mg:Ca ratio is 8:2.
In described step C, the mixture after the interchanger absorbing and cooling temperature, wherein glycerol content is controlled at 5 ~ 8%, and monoester content is controlled at 50 ~ 70%.
In described step D, the temperature of one-level thin film evaporation is 150 ~ 180 ℃, vacuum tightness 1-10KPa, and secondary molecular distillation temperature is 150 ~ 180 ℃, vacuum tightness 1 ~ 50Pa, three grades of molecule distillation temperatures are 150 ~ 180 ℃, vacuum tightness 1 ~ 10Pa.
A kind of device that uses the serialization of immobilization bed to produce molecule distillating monoglyceride is characterized in that in this device:
1) grease is kept in tank, tank kept in by glycerine and two or three esters are kept in each pipeline of the outputting material of tank, parallel connection accesses static mixer after volume pump separately respectively, perhaps, by access static mixer in parallel after a bull proportioning pump, then access interchanger; The delivery conduit of immobilization bed bioreactor also accesses interchanger;
2) two of interchanger delivery conduits, wherein a road is communicated with well heater; The temporary tank of two or three esters is connected after connecting successively the temporary tank of thick ester and comprising the molecular distillation system of one-level thin film evaporation unit, secondary molecular distillation apparatus, three grades of molecule water distilling apparatus again in another road;
3) delivery conduit of well heater is sequentially connected ultrasound reactor, immobilization bed bioreactor, then accesses interchanger;
Above-mentioned secondary molecular distillation apparatus carries the delivery conduit of glycerine to connect into the temporary tank of glycerine, and three grades of molecule water distilling apparatus carry the delivery conduit of mono-glycerides separately to connect the collection storing unit.
The immobilization bed bioreactor that described immobilization bed bioreactor is two or more serial connections, also be connected in series a ultrasound reactor between two adjacent immobilization bed bioreactors.
The pipeline of described immobilization bed bioreactor, the temporary tank of thick ester, the temporary tank of glycerine and the temporary tank configuration of two or three esters all is equipped with transferpump.
Described ultrasound reactor can be liquid whistle formula ultrasonic reactor, sound horn immerseable reactor.Wherein according to the particle properties of catalyzer, sound horn immerseable reactor can be installed on the immobilization bed bioreactor.
Described one-level thin film evaporation unit also can be flash distillation plant.
Described secondary molecular distillation apparatus, three grades of molecule water distilling apparatus are state type, falling film type, scraped film type or centrifugal; Can a plurality of molecular distillation equipment serial or parallel connections.
The present invention compared with prior art, has following outstanding advantages and positively effect:
1, select immobilization bed bioreactor and solid basic catalyst, esterification reaction product, without further acid treatment, has been simplified production technique.
2, immobilization bed bioreactor and ultrasound reactor coupling, make the abundant contact reacts of grease and glycerine, reaction times, 1 ~ 2h by common process shortened to 15-30min, and in thick ester, the content of monoesters brings up to 50 ~ 70% by 40 ~ 50% of common process, has greatly improved reaction efficiency.
The accompanying drawing explanation
Fig. 1 is that molecule distillating monoglyceride system structure of device figure is produced in use immobilization bed serialization of the present invention.
In figure:
1 is the temporary tank of grease, and 2 is grease metering pump, and 3 are the temporary tank of glycerine, 4 is the glycerine volume pump, and 5 is the temporary tanks of two or three esters, and 6 is two or three ester volume pumps, 7 is static mixer, and 8 is interchanger, and 9 is well heater, 10 is ultrasound reactor, and 11 are the immobilization bed bioreactor, and 12 is the temporary tank of thick ester, 13 is the one-level thin film evaporation unit, and 14 is the secondary molecular distillation apparatus, and 15 is three grades of molecule water distilling apparatus, 16 is mono-glycerides, and 17 is water and low-boiling-point substance.
Embodiment
For understanding better the present invention, the present invention is further illustrated below in conjunction with drawings and Examples, but the scope of protection of present invention is not limited to the scope of case representation.
In the present invention, the pan feeding speed of the grease of steps A, glycerine and two or three esters is determined according to production capacity; The ratio of grease and two or three esters is according to how many decisions that have two or three esters.
Immobilization bed bioreactor in the present invention also available flowing bed reactor substitutes.
In the industrial production of mono-glycerides, the most generally adopt grease and glycerine to carry out trans-esterification processes production, this reaction is reversible balanced reaction, its reaction product is the mixture (thick ester) of single, double, triglyceride and excess of glycerol, the current suitability for industrialized production of separating-purifying monoesters generally to adopt molecular distillation method.During molecular distillation, generally first by glycerine from reaction product, separating, then monoesters is separated with two or three esters, at this moment in system if any the existence of catalyzer, molecular distillation removes the glycerine afterreaction easily to reverse movement, monoester content is reduced and contain higher free glycerol.After therefore existing production technique esterification end, need to adopt acid by the basic catalyst neutralization, and with the salt of rear catalyst, remove in by stratification, partial glycerol being reached, will increase the operation to this part end glycerin treatment like this.
The present invention adopts the immobilization bed bioreactor, selects solid basic catalyst, has effectively avoided the existence of thick ester neutral and alkali catalyzer.And by the ultrasound reactor be connected in series, greatly improved transformation efficiency, reduced the reaction times (reaction times, 1 ~ 2h by common process shortened to 15-30min), in thick ester, the content of monoesters brings up to 50 ~ 70% by 40 ~ 50% of common process, has greatly improved reaction efficiency.
The size of described immobilization bed bioreactor determines according to production capacity and the residence time, and material is preferred 5 ~ 10min of the residence time in single immobilization bed bioreactor, can be connected in series by a plurality of immobilization bed bioreactors.
Shown in figure, the whole flow process of this system is: grease, glycerine and two or three esters enter static mixer 7 by volume pump (grease metering pump 2, glycerine volume pump 4,23 ester volume pumps 6) by certain speed from temporary tank (grease keep in tank 1, temporary tank 3,23 esters of glycerine are kept in tank 5) separately tentatively to be mixed, again via interchanger 8 heat absorptions, well heater 9 heating, be warming up to 200 ~ 240 ℃, via ultrasound reactor 10, enter the immobilization bed bioreactor 11 that is filled with solid basic catalyst and carry out transesterification, reaction time is 15 ~ 30min.Thick ester after reaction finishes (thick ester is the mixture of glycerine, fatty acid monoester, lipid acid diester and lipid acid three esters), through interchanger 9 absorbing and cooling temperatures to 150 ~ 180 ℃, enters the temporary rear molecular distillation system of directly going of tank 12 of thick ester.
Thick ester is in one-level thin film evaporation unit 13, Separation of Water and low-boiling-point substance 17, separation of glycerin in secondary molecular distillation apparatus 14, in three grades of molecule water distilling apparatus 15, monoesters is separated with two or three esters, wherein separate the glycerine and two or three esters that obtain and all get back to temporary tank recycle separately, mono-glycerides 16 obtains molecule distillating monoglyceride via after dusting.
Below in conjunction with embodiment, further illustrate.
Embodiment 1
Hydrogenated palm kernel oil is pressed the speed of 1.2t/h, two or three esters are pressed the speed of 0.5t/h, glycerine is squeezed into reactive system from keeping in separately tank through volume pump respectively by the speed of 0.3t/h, material tentatively mixes via static mixer, interchanger heat absorption is warming up to 190 ℃, and heater heats is warming up to 230 ℃ of two groups of ultrasound reactors and immobilization bed bioreactors that enter serial connection in twos and carries out transesterification.Wherein ultrasound reactor is selected liquid whistle formula ultrasonic reactor, and ultrasonic frequency is controlled to be 10
5Hz; In the immobilization bed bioreactor, be filled with MgO as solid basic catalyst, the effective residence time of material in single immobilization bed bioreactor is controlled at 10min, and Controlling System vacuum tightness is 5KPa.The thick ester of reaction gained is cooled to rapidly 160 ℃ via interchanger, and its glycerol content is about 6%, and monoester content is about 60%.After thick ester enters the temporary tank of thick ester, do not stop direct flow velocity by 2t/h and enter the molecular distillation system.
The one-level thin film evaporation is controlled 160 ℃ of vaporization temperatures, and vacuum tightness 5KPa steams except a small amount of water and low-boiling-point substance in material; The wiped film molecular distillation post is selected in three grades of molecule distillations of secondary, and it is 165 ℃ that the secondary molecular distillation is controlled vaporization temperature, steams the about 120kg/h of glycerine speed; It is 170 ℃ that vaporization temperature is controlled in three grades of molecule distillations, and vacuum tightness is 3.0Pa, and the speed that steams the finished product molecule distillating monoglyceride is about 1.2t/h.
The quality index of gained molecule distillating monoglyceride:
Project |
Index |
Outward appearance |
Oyster white or light yellow waxy solid |
Content, % |
92.3 |
Fusing point, ℃ |
61.8 |
Free acid, % |
0.9 |
Embodiment 2
Hydrogenated lard is pressed the speed of 1.5t/h, two or three esters are pressed the speed of 0.65t/h, glycerine is squeezed into reactive system from keeping in separately tank through volume pump respectively by the speed of 0.35t/h, material tentatively mixes via static mixer, the interchanger heat absorption is warming up to 190 ℃, and heater heats is warming up to 230 ℃ of immobilization bed bioreactors that enter two series connection and carries out transesterification; Wherein ultrasound reactor selects sound horn immerseable reactor to be installed in the immobilization bed bioreactor, and ultrasonic frequency is controlled to be 10
6Hz.In the immobilization bed bioreactor, be filled with self-control solid basic catalyst (MgO-CaO/SiO
2) as solid basic catalyst, the effective residence time of material in single immobilization bed bioreactor is controlled at 10min.The thick ester of reaction gained is cooled to rapidly 160 ℃ via interchanger, and its glycerol content is about 6%, and monoester content is about 60%.After thick ester enters the temporary tank of thick ester, do not stop direct flow velocity by 2.5t/h and enter the molecular distillation system.
The one-level thin film evaporation is controlled 160 ℃ of vaporization temperatures, and vacuum tightness 5KPa steams except a small amount of water and low-boiling-point substance in material; The wiped film molecular distillation post is selected in three grades of molecule distillations of secondary, and it is 165 ℃ that the secondary molecular distillation is controlled vaporization temperature, and vacuum tightness is 5.0Pa, steams the about 150Kg/h of glycerine speed; It is 170 ℃ that vaporization temperature is controlled in three grades of molecule distillations, and vacuum tightness is 3.0Pa, and the speed that steams the finished product molecule distillating monoglyceride is about 1.5t/h.
The quality index of gained molecule distillating monoglyceride:
Project |
Index |
Outward appearance |
Oyster white or light yellow waxy solid |
Content, % |
93.5 |
Fusing point, ℃ |
61.8 |
Free acid, % |
0.9 |