CN110028799B - High-dispersion emulsifying wax and preparation method thereof - Google Patents
High-dispersion emulsifying wax and preparation method thereof Download PDFInfo
- Publication number
- CN110028799B CN110028799B CN201910297200.0A CN201910297200A CN110028799B CN 110028799 B CN110028799 B CN 110028799B CN 201910297200 A CN201910297200 A CN 201910297200A CN 110028799 B CN110028799 B CN 110028799B
- Authority
- CN
- China
- Prior art keywords
- wax
- solvent
- preparing
- solid
- pressure
- 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.)
- Active
Links
- 239000006185 dispersion Substances 0.000 title claims abstract description 16
- 239000008387 emulsifying waxe Substances 0.000 title claims description 39
- 238000002360 preparation method Methods 0.000 title description 12
- 238000000034 method Methods 0.000 claims abstract description 64
- 239000002245 particle Substances 0.000 claims abstract description 50
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 14
- 239000001993 wax Substances 0.000 claims description 210
- 239000002904 solvent Substances 0.000 claims description 115
- 238000000605 extraction Methods 0.000 claims description 66
- 239000007787 solid Substances 0.000 claims description 43
- 239000002994 raw material Substances 0.000 claims description 37
- 238000000926 separation method Methods 0.000 claims description 32
- 239000000839 emulsion Substances 0.000 claims description 26
- 235000011837 pasties Nutrition 0.000 claims description 25
- 239000012188 paraffin wax Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 12
- 238000004945 emulsification Methods 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- 238000011084 recovery Methods 0.000 claims description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 230000001804 emulsifying effect Effects 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 34
- 238000003756 stirring Methods 0.000 abstract description 31
- 238000000194 supercritical-fluid extraction Methods 0.000 abstract description 21
- 239000002131 composite material Substances 0.000 abstract description 10
- 239000012153 distilled water Substances 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 5
- 239000003960 organic solvent Substances 0.000 abstract description 5
- 238000001704 evaporation Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000012467 final product Substances 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 40
- 238000010438 heat treatment Methods 0.000 description 20
- 230000009471 action Effects 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 3
- 229920000053 polysorbate 80 Polymers 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 229920001214 Polysorbate 60 Polymers 0.000 description 2
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000010297 mechanical methods and process Methods 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 239000004530 micro-emulsion Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011094 fiberboard Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012169 petroleum derived wax Substances 0.000 description 1
- 235000019381 petroleum wax Nutrition 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000007762 w/o emulsion Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2391/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
- C08J2391/06—Waxes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Colloid Chemistry (AREA)
Abstract
The invention belongs to the technical field of emulsified wax production, and particularly relates to a method for preparing emulsified wax based on a supercritical extraction technology and a high-dispersion emulsified wax product prepared by the method. The method for preparing the high-dispersion emulsified wax comprises the steps of firstly preparing nano-scale superfine wax particles as an emulsified wax precursor by utilizing a supercritical extraction process, then mixing the nano-scale superfine wax particles with a single emulsifier or a prepared composite emulsifier and distilled water according to a required proportion and sequence, stirring and mixing uniformly, and simultaneously evaporating an organic solvent in a system to directly obtain a final product emulsified wax. The uniformity and the particle size of wax particles in the emulsified wax prepared based on the method are both not achieved by the traditional mode, and the stability of the emulsified wax is superior to that of the emulsified wax prepared by the traditional mode.
Description
Technical Field
The invention belongs to the technical field of emulsified wax production, and particularly relates to a method for preparing emulsified wax based on a supercritical extraction technology and a high-dispersion emulsified wax product prepared by the method.
Background
The wax generally refers to oil produced by animals, plants or minerals, is a solid insoluble in water at normal temperature, becomes soft at a slightly high temperature, becomes hard at a reduced temperature, and has certain plasticity. Currently, the waxes used more frequently include paraffin, Fischer-Tropsch wax or other natural and synthetic waxes, and are widely used in the fields of lubrication, fiber boards, coatings, food, fruit preservation, and the like. However, since wax is mainly solid at room temperature and is inconvenient to use, research on emulsifying wax has been conducted to overcome the disadvantage of insufficient fluidity.
Emulsified wax is a homogeneous fluid containing wax and water, which is prepared by uniformly dispersing various waxes including petroleum wax in water, by means of the directional adsorption of an emulsifier, and by emulsification under the action of mechanical external force. The emulsified wax is in a fluid state at normal temperature, can be diluted for use as required, can be used at normal temperature, does not need to be dissolved by a solvent during use, and has the advantages of good coverage, safety, economy, convenience and the like. Therefore, compared with common solid wax, the emulsifying wax is easier to be applied to the fields of plate production, printing ink, agricultural preservation, daily chemical products and the like, and has better application effect.
In the prior art, the methods for controlling the formation of wax particles in the process of preparing emulsified wax mainly comprise a mechanical stirring method, a static mixing method, a colloid mill method, a high-pressure homogenizer method, a high-speed shearing emulsification method and the like. The mechanical stirring method is that wax is crushed into particles through the rapid rotation of a stirring paddle; the static mixing method mainly completes wax granulation through high-speed flow impact of liquid; the colloid mill method is to crush and granulate wax by centrifugal action and interaction between a stator and a rotor of the colloid mill; the high-pressure homogenizer method is to atomize the material by the shearing action of wax in a pressure cavity formed inside the homogenizer; high shear emulsification is the principle of micronization of materials by hydraulic shearing and pressure wave action. The method is to atomize the solid wax or the melted wax under the action of mechanical force, and then complete the emulsification process with the emulsifier. However, the wax particles prepared by the above mechanical method have the problem of uneven particle size distribution in the process of preparing emulsified wax by emulsification, and further, the stability of the emulsified wax product is not ideal, and the wide application of the emulsified wax product is limited to a certain extent.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide a method for preparing emulsified wax based on a supercritical extraction technology, so as to solve the problems that the particle unevenness exists in the wax particle preparation by a mechanical method in the prior art and the stability of the emulsified wax product is not ideal;
the second technical problem to be solved by the invention is to provide a high-dispersion emulsifying wax prepared by the method.
In order to solve the technical problems, the method for preparing the high-dispersion emulsifying wax comprises the following steps:
(1) putting the solid wax raw material into a high-pressure extraction device for later use;
(2) continuously injecting a solvent into the high-pressure extraction device, and simultaneously adjusting the temperature and the pressure in the high-pressure extraction device to enable the solvent to reach a supercritical or subcritical state, so that the solid wax raw material is rapidly dissolved in the solvent;
(3) continuously flowing the solvent in which the solid wax feed is dissolved out of the high pressure extraction apparatus while maintaining the entire system in a supercritical or subcritical state; the supercritical or subcritical state of the wax-containing solvent flowing out of the high-pressure extraction device is released along with the change of pressure and temperature, and the ultrafine wax particles dissolved in the solvent are separated out from the solvent to obtain wax-containing particle slurry;
(4) and (3) uniformly mixing an emulsifier and water with the wax-containing particle slurry for emulsification, and removing the solvent to obtain the required high-dispersion emulsified wax.
Specifically, in the step (1), the solid wax raw material comprises paraffin wax, Fischer-Tropsch wax, natural wax or synthetic wax;
the feeding method of the solid wax raw material into the high-pressure extraction device comprises a solid feeding method directly performed by the crushed solid wax raw material, a liquid feeding method after the solid wax raw material is heated and melted to be in a flowing state, or a solid-liquid mixing feeding method after the solid wax raw material is crushed and mixed with a solvent.
Preferably, the step (1) further comprises the step of preheating the high-pressure extraction device to the critical temperature of the solvent +/-50 ℃.
Specifically, in the step (2), the solvent includes at least one of alkane, aromatic hydrocarbon, alcohol or gas solvent.
Preferably, the solvent is selected from normal alkanes, more preferably normal alkane solvents with a boiling point below 100 ℃.
Preferably, the step (2) further comprises the step of preheating the solvent to the critical temperature of the solvent ± 50 ℃.
Preferably, the temperature of the high-pressure extraction device is set to be higher than or equal to the critical or subcritical temperature of the solvent, preferably within the range of +/-50 ℃ of the critical temperature of the solvent, and the pressure is set to be within the range of the critical pressure or subcritical pressure of the solvent, preferably the pressure is 3-10 MPa.
Preferably, the step (3) further comprises a step of feeding the wax-containing solvent flowing out of the high-pressure extraction apparatus into a separation tank, and adjusting the pressure and temperature in the separation tank to release the supercritical or subcritical state, so that the ultra-fine wax particles dissolved in the solvent are separated out from the solvent and are accumulated at the bottom of the separation tank in the form of pasty wax, or adjusting the flow rate of the solvent flowing out of the separation tank to make the separated ultra-fine wax particles flow into a solvent recovery tank along with the solvent to form an emulsion, and selecting the pasty wax and/or the emulsion as wax-containing particle slurry for subsequent treatment.
Preferably, the mass ratio of the emulsifier to the water to the solid wax raw material is 10-100: 400-2400: 800-820.
Specifically, the step (4) comprises the steps of preparing a W/O type emulsifying wax or preparing an O/W type emulsifying wax;
the step of preparing the W/O type emulsifying wax is to gradually add water into the wax-containing particle slurry for emulsification;
the step of preparing the O/W type emulsifying wax is to gradually add the wax-containing particle slurry into water for emulsification.
Like the prior art, after the nano-scale wax particles are obtained by supercritical extraction, under the action of a corresponding single emulsifier or a corresponding composite emulsifier, the nano-scale wax particles are mixed with distilled water in different orders, and then the organic solvent in a mixed system is removed by evaporation, so that the corresponding type of emulsifying wax can be obtained. During the preparation process of the emulsifying wax, the wax is called oil phase, the aqueous solution is called water phase, and water-in-oil (W/O) type or oil-in-water (W/O) type emulsifying wax can be prepared according to the proportion of oil and water and the mixing sequence during the preparation. When water is gradually added into the oil phase, the water phase is dispersed in the continuous phase in a uniform bead form to form W/O type inverse microemulsion; when the oil phase is gradually added into water, the oil phase is dispersed in the water phase in a uniform bead form to form the O/W normal phase microemulsion. It can be seen that there is a difference in the order of addition of the water phase and the oil phase during the formulation of the two types of emulsifying waxes.
Specifically, the method for preparing the high-dispersion emulsifying wax comprises the following steps:
in the step of preparing the W/O type emulsifying wax, the HLB value of the emulsifier is 3-6;
in the step of preparing the O/W type emulsifying wax, the HLB value of the emulsifier is 8-18.
Emulsifiers are key to the preparation of emulsifying waxes, each emulsifier having a specific HLB value (i.e. hydrophilic-lipophilic balance, HLB being the hydrophilicity of the hydrophilic group/lipophilicity of the lipophilic group), the greater the HLB value the more hydrophilic, and the smaller the HLB value the more lipophilic. The HLB value of the nonionic surfactant is additive, and the HLB value of the mixture of more than two surfactants can be represented by the formula HLBAB＝(HLBA×WA+HLBB×WB)/(WA+WB) And (4) calculating. The preferred emulsifiers of the invention for O/W emulsions usually have HLB values of between 8 and 18, and for W/O emulsions usually have HLB values of between 3 and 6. In the preparation of emulsifying waxes, in addition to the choice of emulsifiers according to the type of emulsion to be obtained, the different nature of the oil phase used also places different requirements on the HLB value of the emulsifier, which should be in accordance with the requirements of the oil phase to be emulsified.
The invention also discloses the high-dispersion emulsifying wax prepared by the method.
The method for preparing the high-dispersion emulsified wax uses paraffin wax or Fischer-Tropsch wax or other natural and synthetic waxes as raw materials, is based on a supercritical extraction technology, utilizes the principle that an organic solvent shows extremely strong solubility in a supercritical state, adopts a supercritical solvent extraction method to dissolve a solid wax raw material, and separates wax particles from the solvent when the supercritical state is released by changing the state of the solvent, so that the wax particles with the particle size of nanometer level and uniform distribution can be generated in the dissolving-separating process of the wax, and the obtained nanometer wax particles can be uniformly distributed in the corresponding solvent, thereby being beneficial to preparing the emulsified wax product with better dispersion and more stable performance.
The method for preparing the high-dispersion emulsified wax comprises the steps of firstly preparing nano-scale superfine wax particles as an emulsified wax precursor by utilizing a supercritical extraction process, then mixing the nano-scale superfine wax particles with a single emulsifier or a prepared composite emulsifier and distilled water according to a required proportion and sequence, stirring and mixing uniformly, and simultaneously evaporating an organic solvent in a system to directly obtain a final product emulsified wax. The uniformity and the particle size of wax particles in the emulsified wax prepared based on the method are both not achieved by the traditional mode, and the stability of the emulsified wax is superior to that of the emulsified wax prepared by the traditional mode.
The emulsified paraffin prepared by the invention is milky white in appearance, is milky white homogeneous liquid in appearance, contains 30-50% of O/W type emulsified wax solid matter wax, 60-80% of W/O type emulsified wax solid wax, has a pH value of 7-9, has a wax particle diameter of less than 1 mu m, is stable in emulsion, does not delaminate after standing for six months, does not delaminate after being diluted by any proportion when in use, does not demulsify or agglomerate, has good dispersibility, and is a qualified emulsified paraffin product.
Drawings
In order that the present disclosure may be more readily and clearly understood, the following detailed description of the present disclosure is provided in connection with specific embodiments thereof and the accompanying drawings, in which,
FIG. 1 is a schematic view of the process equipment for the supercritical extraction step of the present invention;
FIG. 2 is a schematic view of the process equipment for the step of formulating an emulsifying wax according to the present invention;
the reference numbers in the figures denote: the method comprises the following steps of 1-an extraction device, 2-a rectifying column, 3-a filter, 4-a control valve, 5-a buffer tank, 6-a separation tank, 7-a condenser, 8-a solvent recovery tank, 9-a collection tank, 10-a high-pressure solvent pump, 11-a preheater, 12-a stirring kettle and 13-a product tank.
Detailed Description
The method for preparing the high-dispersion emulsified wax in the following embodiments of the invention is to prepare pasty wax or wax emulsion by supercritical extraction according to the flow chart shown in fig. 1, and to prepare the emulsified wax according to the schematic chart shown in fig. 2.
As shown in fig. 1, a solid wax raw material and a solvent preheated by the preheater 11 are fed into the extraction apparatus 1, the temperature and pressure conditions in the extraction apparatus 1 are controlled so that the fed solvent is in a supercritical state, and the solid wax raw material therein is subjected to continuous supercritical extraction treatment so that the solid wax raw material is completely dissolved in the solvent; after extraction is finished, the solvent containing wax flows out of the extraction device 1, and after primary filtration through a rectifying column 2 and a filter 3, through the regulation control of the control valve 4 via the buffer tank 5 and further into the separation tank 6, in the separation tank 6, the supercritical state of the whole solvent system is then released by changing the temperature and pressure of the whole system, and at this time, the ultra fine wax particles dissolved in the solvent are separated out from the solvent and accumulated at the bottom of the separation tank 6 to form cream wax and collected by the collection tank 9, the separated solvent is further condensed by a condenser 7 and then enters a solvent recovery tank 8 to be collected, wherein a small part of the ultra-fine wax particles enter the solvent recovery tank 8 along with the solvent to form emulsion, and the recovered solvent is treated by a high-pressure solvent pump 10 and then enters the preheater 11 for preheating and is circularly put into the extraction device 1 for circular extraction.
As shown in fig. 2, the cream wax collected in the collection tank 9 or the emulsion formed in the solvent recovery tank 8 is put into the stirring kettle 12, and a selected amount of emulsifier and water are added to stir, mix and emulsify, so that the formed emulsified wax product enters the product tank 13, and the partially evaporated solvent enters the solvent recovery tank 8 through the condenser 7 to be recovered.
Example 1
The preparation method of the highly dispersed emulsified wax according to this embodiment includes a step of preparing a pasty wax or a wax emulsion based on a supercritical extraction technique according to a flowchart shown in fig. 1, and a step of preparing an emulsified wax according to a schematic diagram shown in fig. 2, and specifically includes the following steps:
(1) preparing 8.10kg of paraffin into emulsion, feeding the emulsion into a supercritical extraction device, and preheating an extraction device system by heating to 220 ℃;
(2) selecting n-pentane as a dissolving solvent, wherein the critical temperature is 196.6 ℃, and the critical pressure is 3.37 MPa; continuously injecting an n-pentane solvent preheated to 220 ℃ into the extraction kettle, and simultaneously controlling the internal pressure of the extraction device to rise to 6MPa, wherein the n-pentane solvent is in a supercritical state, and continuously extracting a paraffin raw material to quickly dissolve the paraffin raw material in the n-pentane solvent; then adjusting an outlet valve of the extraction device to stabilize the system pressure at 6MPa, keeping the temperature and pressure state for continuous extraction, wherein the extraction time is 1h, and ensuring that the whole dissolution process needs to control the whole system to be always in a supercritical state;
(3) continuously flowing the solvent in which the solid wax raw material is dissolved out of the high-pressure extraction device and feeding the solvent into a separation tank while maintaining the whole system in a supercritical or subcritical state; in the separation tank, the supercritical state of the whole system is relieved by adjusting the pressure and the temperature in the separation tank, at the moment, superfine wax particles dissolved in the solvent are separated out from the solvent and are gathered at the bottom of the separation tank in the form of pasty wax, and after the detection and the extraction are finished, pasty paraffin containing 7.98kg of paraffin is obtained;
(4) uniformly mixing 0.033kg of span 60 with the HLB value of 4.7 and 0.081kg of Tween 80 with the HLB value of 15 to obtain a compound emulsifier with the HLB value of 12 for later use;
adding 14.72kg of distilled water into a stirring kettle, adding the composite emulsifier, adding the prepared pasty wax, simultaneously starting stirring and heating, setting the stirring speed to be 600r/min, setting the heating temperature to be 65 ℃, stirring and heating for 35min, discharging out of the stirring kettle to obtain 22.81kg of O/W type emulsified wax product, wherein no solvent residue exists in the system. The emulsifier was determined to have a mass fraction of 0.5 wt% in the emulsified wax product.
The obtained emulsified wax is a milky homogeneous liquid, is transparent, has the solid wax content of 35.0 percent, the average particle size of 0.1 mu m and the water content of 64.5 percent, does not delaminate, demulsify or agglomerate within 35 days under the experimental test conditions, can be mixed with water in any proportion, and is a qualified O/W type emulsified wax product.
Example 2
The preparation method of the highly dispersed emulsified wax according to this embodiment includes a step of preparing a pasty wax or a wax emulsion based on a supercritical extraction technique according to a flowchart shown in fig. 1, and a step of preparing an emulsified wax according to a schematic diagram shown in fig. 2, and specifically includes the following steps:
(1) preparing 8.16kg of Fischer-Tropsch wax into emulsion, feeding the emulsion into a supercritical extraction device, and preheating an extraction device system by heating the extraction device system to 220 ℃;
(2) selecting n-pentane as a dissolving solvent, wherein the critical temperature is 196.6 ℃, and the critical pressure is 3.37 MPa; continuously injecting an n-pentane solvent preheated to 220 ℃ into the extraction kettle, and simultaneously controlling the internal pressure of the extraction device to rise to 6MPa, wherein the n-pentane solvent is in a supercritical state, and continuously extracting the Fischer-Tropsch wax raw material, so that the Fischer-Tropsch wax raw material is quickly dissolved in the n-pentane solvent; then adjusting an outlet valve of the extraction device to stabilize the system pressure at 6MPa, keeping the temperature and pressure state for continuous extraction, wherein the extraction time is 1h, and ensuring that the whole dissolution process needs to control the whole system to be always in a supercritical state;
(3) continuously flowing the solvent in which the solid wax raw material is dissolved out of the high-pressure extraction device and feeding the solvent into a separation tank while maintaining the whole system in a supercritical or subcritical state; in the separation tank, the supercritical state of the whole system is relieved by adjusting the pressure and the temperature in the separation tank, at the moment, the superfine wax particles dissolved in the solvent are separated out from the solvent and are gathered at the bottom of the separation tank in the form of pasty wax, and after the detection and the extraction are finished, pasty Fischer-Tropsch wax containing 8.04kg of Fischer-Tropsch wax is obtained;
(4) 0.026kg of span 60 with HLB value of 4.7 and 0.108kg of Tween 80 with HLB value of 15 are taken and evenly mixed to obtain a compound emulsifier with HLB value of 13 for later use;
adding 18.60kg of distilled water into a stirring kettle, adding the composite emulsifier, adding the prepared pasty Fischer-Tropsch wax, simultaneously starting stirring and heating, setting the stirring speed at 600r/min and the heating temperature at 65 ℃, after stirring and heating for 35min, discharging out of the stirring kettle to obtain 26.77kg of O/W type emulsified wax product, wherein no solvent remains in the system. The emulsifier was determined to have a mass fraction of 0.5 wt% in the emulsified wax product.
The obtained emulsified wax is a milky homogeneous liquid, is transparent, has the solid wax content of 30.0 percent, the average particle size of 0.1 mu m and the water content of 69.5 percent, does not delaminate, demulsify or agglomerate after 30 days of experimental test, can be mixed with water in any proportion, and is a qualified O/W type emulsified wax product.
Example 3
The preparation method of the highly dispersed emulsified wax according to this embodiment includes a step of preparing a pasty wax or a wax emulsion based on a supercritical extraction technique according to a flowchart shown in fig. 1, and a step of preparing an emulsified wax according to a schematic diagram shown in fig. 2, and specifically includes the following steps:
(1) preparing 8.04kg of Fischer-Tropsch wax into emulsion, feeding the emulsion into a supercritical extraction device, and preheating an extraction device system by heating the extraction device system to 220 ℃;
(2) selecting n-pentane as a dissolving solvent, wherein the critical temperature is 196.6 ℃, and the critical pressure is 3.37 MPa; continuously injecting an n-pentane solvent preheated to 220 ℃ into the extraction kettle, and simultaneously controlling the internal pressure of the extraction device to rise to 6MPa, wherein the n-pentane solvent is in a supercritical state, and continuously extracting the Fischer-Tropsch wax raw material, so that the Fischer-Tropsch wax raw material is quickly dissolved in the n-pentane solvent; then adjusting an outlet valve of the extraction device to stabilize the system pressure at 6MPa, keeping the temperature and pressure state for continuous extraction, wherein the extraction time is 1h, and ensuring that the whole dissolution process needs to control the whole system to be always in a supercritical state;
(3) continuously flowing the solvent in which the solid wax raw material is dissolved out of the high-pressure extraction device and feeding the solvent into a separation tank while maintaining the whole system in a supercritical or subcritical state; in the separation tank, the supercritical state of the whole system is relieved by adjusting the pressure and the temperature in the separation tank, at the moment, the superfine wax particles dissolved in the solvent are separated out from the solvent and are gathered at the bottom of the separation tank in the form of pasty wax, and after the detection and the extraction are finished, 7.95kg of pasty wax containing Fischer-Tropsch wax is obtained;
(4) uniformly mixing 0.031kgHLB value of span 60 of 4.7 and 0.297kg of Tween 80 of HLB value of 15 to obtain a compound emulsifier of HLB value of 14 for later use;
adding 23.80kg of distilled water into a stirring kettle, adding the composite emulsifier, adding the prepared pasty wax, simultaneously starting stirring and heating, setting the stirring speed to be 600r/min, setting the heating temperature to be 65 ℃, stirring and heating for 35min, discharging out of the stirring kettle to obtain 32.08kg of O/W type emulsified wax product, wherein no solvent residue exists in the system. The emulsifier was determined to have a mass fraction of 1 wt% in the emulsified wax product.
The obtained emulsified wax is a milky homogeneous liquid, is transparent, has the solid wax content of 25.0 percent, the average particle size of 0.1 mu m and the water content of 74.0 percent, is not layered, demulsified and agglomerated after being placed in a sealing way for 28 days, can be mixed with water in any proportion, and is a qualified O/W type emulsified wax product.
Example 4
The preparation method of the highly dispersed emulsified wax according to this embodiment includes a step of preparing a pasty wax or a wax emulsion based on a supercritical extraction technique according to a flowchart shown in fig. 1, and a step of preparing an emulsified wax according to a schematic diagram shown in fig. 2, and specifically includes the following steps:
(1) preparing 8.04kg of paraffin into emulsion, feeding the emulsion into a supercritical extraction device, and preheating an extraction device system by heating to 220 ℃;
(2) selecting n-pentane as a dissolving solvent, wherein the critical temperature is 196.6 ℃, and the critical pressure is 3.37 MPa; continuously injecting an n-pentane solvent preheated to 220 ℃ into the extraction kettle, and simultaneously controlling the internal pressure of the extraction device to rise to 6MPa, wherein the n-pentane solvent is in a supercritical state, and continuously extracting a paraffin raw material to quickly dissolve the paraffin raw material in the n-pentane solvent; then adjusting an outlet valve of the extraction device to stabilize the system pressure at 6MPa, keeping the temperature and pressure state for continuous extraction, wherein the extraction time is 1h, and ensuring that the whole dissolution process needs to control the whole system to be always in a supercritical state;
(3) continuously flowing the solvent in which the solid wax raw material is dissolved out of the high-pressure extraction device and feeding the solvent into a separation tank while maintaining the whole system in a supercritical or subcritical state; in the separation tank, the supercritical state of the whole system is relieved by adjusting the pressure and the temperature in the separation tank, at the moment, superfine wax particles dissolved in the solvent are separated out from the solvent and are gathered at the bottom of the separation tank in the form of pasty wax, and after the detection and the extraction are finished, pasty paraffin containing 7.95kg of paraffin is obtained;
(4) uniformly mixing 0.115kg of span 80 with the HLB value of 4.3 and 0.008kg of Tween 60 with the HLB value of 14.5 to obtain a composite emulsifier with the HLB value of 5 for later use;
adding the prepared pasty wax into a stirring kettle, adding the composite emulsifier, adding 4.2kg of distilled water, simultaneously starting stirring and heating, setting the stirring speed at 600r/min and the heating temperature at 65 ℃, stirring and heating for 35min, discharging out of the stirring kettle to obtain 12.27kg of W/O type emulsified wax product, wherein no solvent residue exists in the system. The emulsifier was determined to have a mass fraction of 1 wt% in the emulsified wax product.
The obtained emulsified wax is a milky homogeneous liquid, has the solid wax content of 65.0 percent, the average particle size of 0.1 mu m and the water content of 34.5 percent, is not layered, demulsified and agglomerated after being placed in a sealing way for 35 days, can be mixed with oil in any proportion, and is a qualified W/O type emulsified wax product.
Example 5
The preparation method of the highly dispersed emulsified wax according to this embodiment includes a step of preparing a pasty wax or a wax emulsion based on a supercritical extraction technique according to a flowchart shown in fig. 1, and a step of preparing an emulsified wax according to a schematic diagram shown in fig. 2, and specifically includes the following steps:
(1) preparing 8.01kg Fischer-Tropsch wax into emulsion, feeding the emulsion into a supercritical extraction device, and preheating an extraction device system by heating to 220 ℃;
(2) selecting n-pentane as a dissolving solvent, wherein the critical temperature is 196.6 ℃, and the critical pressure is 3.37 MPa; continuously injecting an n-pentane solvent preheated to 220 ℃ into the extraction kettle, and simultaneously controlling the internal pressure of the extraction device to rise to 6MPa, wherein the n-pentane solvent is in a supercritical state, and continuously extracting the Fischer-Tropsch wax raw material, so that the Fischer-Tropsch wax raw material is quickly dissolved in the n-pentane solvent; then adjusting an outlet valve of the extraction device to stabilize the system pressure at 6MPa, keeping the temperature and pressure state for continuous extraction, wherein the extraction time is 1h, and ensuring that the whole dissolution process needs to control the whole system to be always in a supercritical state;
(3) continuously flowing the solvent in which the solid wax raw material is dissolved out of the high-pressure extraction device and feeding the solvent into a separation tank while maintaining the whole system in a supercritical or subcritical state; in the separation tank, the supercritical state of the whole system is relieved by adjusting the pressure and the temperature in the separation tank, at the moment, the superfine wax particles dissolved in the solvent are separated out from the solvent and are gathered at the bottom of the separation tank in the form of pasty wax, and after the detection and the extraction are finished, pasty Fischer-Tropsch wax containing 7.91kg of Fischer-Tropsch wax is obtained;
(4) uniformly mixing 0.110kg of span 80 with the HLB value of 4.3 and 0.022kg of Tween 60 with the HLB value of 14.5 to obtain a composite emulsifier with the HLB value of 6 for later use;
adding the prepared pasty wax into a stirring kettle, adding the composite emulsifier, adding 5.08kg of distilled water, simultaneously starting stirring and heating, setting the stirring speed at 600r/min and the heating temperature at 65 ℃, stirring and heating for 35min, discharging out of the stirring kettle to obtain 13.12kg of W/O type emulsified wax product, wherein no solvent residue exists in the system. The emulsifier was determined to have a mass fraction of 1 wt% in the emulsified wax product.
The obtained emulsified wax is a milky homogeneous liquid, contains 60.0% of solid wax, has an average particle size of 0.1 mu m and a water content of 39.0%, is not layered, demulsified and agglomerated after being placed in a sealed manner for 28 days, can be mixed with oil in any proportion, and is a qualified W/O type emulsified wax product.
Examples of the experiments
The properties of the emulsified wax products prepared in the above examples 1 to 5 were measured according to the conventional measurement method in the prior art, and the specific measurement indexes and measurement results are shown in table 1 below.
Table 1 emulsifying wax product performance test results.
From the data in the table, the method for preparing the emulsifying wax by extracting the solid wax raw material with the organic solvent based on the supercritical extraction technology has the advantages that the prepared emulsifying wax product is milky white in appearance, the appearance is milky homogeneous liquid, the content of the O/W type emulsifying wax solid matter wax is 30-50%, the content of the W/O type emulsifying wax solid matter wax is 60-80%, and the pH value is 7-9; in the whole emulsified wax product, the wax exists in the form of nano-scale particles, the diameter of the wax particles is less than 1 mu m, the emulsion is stable, the emulsion is not layered after standing for six months, the product stability is good, and the emulsified wax product is superior to the emulsified wax product prepared by the traditional method; when in use, the wax is diluted by any proportion without layering, demulsification and agglomeration, has good dispersibility, and is a qualified emulsified wax product.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (8)
1. A method for preparing high-dispersion emulsifying wax is characterized by comprising the following steps:
(1) putting a solid wax raw material into a high-pressure extraction device, and preheating the high-pressure extraction device to the critical temperature +/-50 ℃ of a required solvent for later use;
(2) preheating the solvent to the critical temperature +/-50 ℃ of the solvent, continuously injecting the solvent into the high-pressure extraction device, and simultaneously adjusting the temperature and the pressure in the high-pressure extraction device to enable the solvent to reach a supercritical or subcritical state, so that the solid wax raw material is quickly dissolved in the solvent;
(3) continuously flowing the solvent in which the solid wax feed is dissolved out of the high pressure extraction apparatus while maintaining the entire system in a supercritical or subcritical state; the supercritical or subcritical state of the wax-containing solvent flowing out of the high-pressure extraction device is released along with the change of pressure and temperature, and the ultrafine wax particles dissolved in the solvent are separated out from the solvent to obtain wax-containing particle slurry;
(4) uniformly mixing and emulsifying an emulsifier and water with the wax-containing particle slurry, and controlling the mass ratio of the emulsifier to the water to the solid wax raw material to be 10-100: 400-2400: 800 and 820, and removing the solvent to obtain the required high-dispersion emulsifying wax.
2. The method for preparing a highly dispersed emulsified wax according to claim 1, wherein in the step (1), the solid wax raw material comprises paraffin wax, Fischer-Tropsch wax, natural wax or synthetic wax;
the feeding method of the solid wax raw material into the high-pressure extraction device comprises a solid feeding method directly performed by the crushed solid wax raw material, a liquid feeding method after the solid wax raw material is heated and melted to be in a flowing state, or a solid-liquid mixing feeding method after the solid wax raw material is crushed and mixed with a solvent.
3. The method for preparing a highly dispersed emulsifying wax according to claim 2, wherein in the step (2), the solvent comprises at least one of alkane, aromatic hydrocarbon, alcohol or gas solvent.
4. The method for preparing highly dispersed emulsifying wax of claim 3, wherein in the step (2), the solvent is an n-alkane solvent having a boiling point of less than 100 ℃ and a critical pressure of 3 to 10 MPa.
5. The method for preparing highly dispersed emulsified wax as claimed in claim 4, wherein the step (3) further comprises the step of feeding the wax-containing solvent flowing out of the high-pressure extraction apparatus into a separation tank, and releasing the supercritical or subcritical state of the wax-containing solvent by adjusting the pressure and temperature in the separation tank, wherein the ultra-fine wax particles dissolved in the solvent are separated out from the solvent and accumulated at the bottom of the separation tank in the form of pasty wax, or wherein the separated ultra-fine wax particles are fed into a solvent recovery tank with the solvent to form an emulsion by adjusting the flow rate of the solvent flowing out of the separation tank, and the pasty wax and/or the emulsion is selected as wax-containing particle slurry for subsequent treatment.
6. The method for preparing a highly dispersed emulsifying wax according to any one of claims 1 to 5, wherein the step (4) comprises a step of preparing a W/O type emulsifying wax or preparing an O/W type emulsifying wax;
the step of preparing the W/O type emulsifying wax is to gradually add water into the wax-containing particle slurry for emulsification;
the step of preparing the O/W type emulsifying wax is to gradually add the wax-containing particle slurry into water for emulsification.
7. The method for preparing a highly dispersed emulsifying wax according to claim 6, wherein:
in the step of preparing the W/O type emulsifying wax, the HLB value of the emulsifier is 3-6;
in the step of preparing the O/W type emulsifying wax, the HLB value of the emulsifier is 8-18.
8. A highly dispersed emulsifying wax obtainable by the process of any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910297200.0A CN110028799B (en) | 2019-04-12 | 2019-04-12 | High-dispersion emulsifying wax and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910297200.0A CN110028799B (en) | 2019-04-12 | 2019-04-12 | High-dispersion emulsifying wax and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110028799A CN110028799A (en) | 2019-07-19 |
| CN110028799B true CN110028799B (en) | 2020-05-22 |
Family
ID=67238261
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910297200.0A Active CN110028799B (en) | 2019-04-12 | 2019-04-12 | High-dispersion emulsifying wax and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110028799B (en) |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4349617B2 (en) * | 2003-11-21 | 2009-10-21 | ミヨシ油脂株式会社 | Water-in-oil emulsion for spray |
| CN101967396B (en) * | 2009-07-27 | 2013-10-16 | 新奥科技发展有限公司 | Method for extracting montan wax |
| CN102649845B (en) * | 2011-02-28 | 2013-08-21 | 南京天诗实验微粉有限公司 | Preparation method of polymer wax ultrafine powder |
| TWI630018B (en) * | 2015-09-07 | 2018-07-21 | 喬治 斯特徹夫 | Extraction apparatus and method thereof |
| CN108546566B (en) * | 2018-04-04 | 2019-06-21 | 中国矿业大学(北京) | A kind of continuous supercritical extraction method recycled and refine F- T synthesis slag wax |
| CN108530768B (en) * | 2018-04-27 | 2021-05-07 | 西南科技大学 | Phase-change latex and preparation method thereof |
-
2019
- 2019-04-12 CN CN201910297200.0A patent/CN110028799B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110028799A (en) | 2019-07-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE1965934C3 (en) | Process for the production of a latex from a dispersion of a high polymer | |
| DE60315489T2 (en) | Particles are obtained by extracting an emulsion by means of a supercritical fluid | |
| EP2406176B1 (en) | Micronized sulphur powder and method of production of same | |
| EP0156486A2 (en) | Preparation of emulsions | |
| JP2009533501A (en) | Method for preparing artificial latex | |
| JPS61167401A (en) | Drying polymer and its production | |
| US20140193324A1 (en) | Micronized sulphur powder and method of production of same | |
| EP0162591B1 (en) | Bituminous emulsions | |
| AU2009200227A1 (en) | Method for the production of particles | |
| CN110028799B (en) | High-dispersion emulsifying wax and preparation method thereof | |
| CN101415752B (en) | Process for the preparation of an artificial latex | |
| US5670087A (en) | Method of preparing HIPR bituminous emulsions | |
| CN112042928B (en) | Method for synergistically and efficiently preparing protein-based nano emulsion by using polyhydroxy alcohol as molecular chaperone and prepared protein-based nano emulsion | |
| CN111939779A (en) | Supergravity preparation method of W/O/W type multiple emulsion | |
| CN111218008A (en) | High-stability SBS emulsion for emulsified asphalt | |
| JP3403703B2 (en) | Method for producing emulsified and dispersed composition and emulsified and dispersed composition obtained by the method | |
| CN114181731B (en) | Micelle dispersion type oil slurry settling agent and preparation method thereof | |
| JP3884242B2 (en) | Method for producing emulsified composition | |
| JPH0559391A (en) | Method for producing purified propolis and purified propolis component-containing o/w type emulsion | |
| CN113875968A (en) | Preparation method of oil-soluble plant extract emulsion | |
| AT365626B (en) | METHOD FOR PROCESSING, IN PARTICULAR IN THE FORM OF STABLE EMULSIONS OR. DISPERSIONS PRESENT, MIXED | |
| DE1283537B (en) | Production of latices from solutions of hydrocarbon polymers | |
| AT251865B (en) | Process for making a hydrocarbon polymer latex | |
| SU318381A1 (en) | SHETENA I | |
| CN117924739A (en) | Tea dreg protein high internal phase pickering emulsion and preparation method and application thereof |
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 | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20191225 Address after: 100083 Beijing City, Haidian District Institute of Rutosids No. 11 Applicant after: China University of Mining and Technology (Beijing) Applicant after: Shanxi Luan Mining (Group) Co., Ltd. Address before: 100083 Beijing City, Haidian District Institute of Rutosids No. 11 Applicant before: China University of Mining and Technology (Beijing) |
|
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20200108 Address after: 046299 Hou Town, Xiangyuan County, Changzhi, Shanxi Applicant after: Shanxi Luan Mining (Group) Co., Ltd. Applicant after: China University of Mining and Technology (Beijing) Address before: 100083 Beijing City, Haidian District Institute of Rutosids No. 11 Applicant before: China University of Mining and Technology (Beijing) Applicant before: Shanxi Luan Mining (Group) Co., Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |