CN105802666B - A kind of production method of wax class phase-change material - Google Patents
A kind of production method of wax class phase-change material Download PDFInfo
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- CN105802666B CN105802666B CN201410825741.3A CN201410825741A CN105802666B CN 105802666 B CN105802666 B CN 105802666B CN 201410825741 A CN201410825741 A CN 201410825741A CN 105802666 B CN105802666 B CN 105802666B
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Abstract
The invention discloses a kind of production method of wax class phase-change material.This method adds low-boiling point liquid in the feed, the proper temperature increase high temperature constant temperature stage during cooling, and carries out liquid composition by wax layer using air-flow in the sweating effort that heats up, and enhances separating effect and accelerates separating rate.For the present invention on the basis of common sweating method, the process that liquid composition separates with solids fraction is forced in increase, this solvent-free de-oiling method of sweating is produced wax class phase-change material product.The inventive method has the advantages that plant investment is low, production process is simple and operating cost is low, solvent-free pollution.
Description
Technical field
The invention belongs to special wax production technical field, more particularly to a kind of production method of wax class phase-change material.
Background technology
Phase-change material（Phase Change Material, abbreviation PCM）Temperature change is not in fusing or process of setting
Greatly, but in the temperature range of very little the latent heat for absorbing or discharging is quite big, and this characteristic makes it in constant temperature, energy storage etc.
It is widely used.Typically require that phase-change material has appropriate phase transition temperature and larger latent heat of phase change.Twentieth century 80 years
Just phase-change material was applied to aerospace field and obtained good application effect by the U.S., is then widely used in military affairs generation
Field.Late nineteen eighties, phase-change material start to be applied to civilian aspect, and some products are in US and European market sale.
According to the difference of phase transition temperature, phase-change material can be typically divided into high temperature phase change material (pcm), medium temperature phase-change material and low
Warm phase-change material.According to the difference of chemical composition, typically phase-change material can be divided into inorganic phase-changing material and organic phase change material.
According to the difference of energy storage process in which materials phase-state change, phase-change material can be typically divided into solid-gas phase-change material, liquid-gas phase
Become material, solid-liquid phase-change material, solid-solid phase change material.Gu commonly used in constant temperature, thermal energy storage process is solid-liquid, solid-two kinds
Phase-change material.Wax class phase-change material be it is conventional it is organic in, low temperature solid-liquid phase change material.
The general name of the pertroleum wax obtained all kinds of wax products that are crude oil after refining is processed from wax-containing distillate, including liquid
Body paraffin, paraffin and microwax.It is liquid under atoleine normal temperature, usual melting point of paraffin wax is 52 DEG C~74 DEG C, microwax
Fusing point is 65 DEG C~90 DEG C.Commodity oil wax is the hydro carbons mixing of the n-alkane, isoparaffin, cycloalkane of a variety of carbon numbers etc.
Thing, its carbon number distribution is wider, and normal paraffin content is relatively low.
Compared with isoparaffin and cycloalkane, the latent heat of phase change of n-alkane is big.With the increase of n-alkane chain length,
Its fusing point increases, and the fusing point of common n-alkane is -20~100 DEG C.Because the fusing point of pertroleum wax is the various components of its composition
Concentrated expression, thus can consider that the fusing point of pertroleum wax is any adjustable in the range of -20~100 DEG C, this is exactly that pertroleum wax is used
Make the sharpest edges of phase-change material.The temperature province is also the scope most often contacted in people's daily life simultaneously, and oil
It is wax chemical property stabilization, non-corrosiveness, free from environmental pollution, thus pertroleum wax is used as phase-change material has unrivaled advantage.
But general goods pertroleum wax contains the components such as isoparaffin and cycloalkane, and carbon number distribution is wider, when being directly used as phase-change material
Latent heat is smaller, and phase transformation section is wider.
Pertroleum wax purified must just can serve as phase-change material to improve normal paraffin content and reduce carbon number distribution width.
The pertroleum wax separation manufacturing process commonly used in terms of pertroleum wax production technology mainly has distillation, solvent deoiling, sweating etc..
Distillation is to reach the purpose of separating-purifying using the boiling point difference of different hydrocarbons, and the boiling range for reducing distillation can be effective
The width of product carbon distribution is reduced, but is influenceed on improving normal paraffin content less, simultaneously because still-process is needed oil
Wax is heated to more than boiling point, consumes substantial amounts of energy.
Solvent deoiling method is to reach separating-purifying using n-alkane and the different solubility of isoparaffin in a solvent
Purpose, can effectively improve the normal paraffin content in product, but the influence that width is distributed to carbon is little, while solvent deoiling
Investment of production equipment is big；Need largely to use solvent in production process, recycling design needs to consume substantial amounts of energy；Contain in solvent
There are benzene homologues, environment can be impacted；Solvent is inflammable, easily causes production accident.
Sweating method is to carry out separating-purifying using the different property of various hydrocarbon component fusing points in wax.It is each in pertroleum wax
The molecular weight of kind component Bu Tong can all make its fusing point different with structure.When being all n-alkane, the larger N-alkanes of molecular weight
The fusing point of hydrocarbon is higher, and the fusing point of the less n-alkane of molecular weight is relatively low；When molecular weight is identical, isoparaffin and cycloalkane
Fusing point will be less than n-alkane, and isomery degree more high-melting-point is lower.So sweating can reduce the width of product carbon distribution
And can improves normal paraffin content.
Compared with distillation separation method, because the melting temperature of various hydro carbons is far below boiling temperature, so sweating separates
The energy consumption of process is far below separated；Compared with solvent fractionation method, sweating separation process is without using solvent, so sweating point
From process on environment without influence.And diaphoresis can reduce the width and can raising normal paraffin content of product carbon distribution, institute
So that for producing wax class phase-change material, sweating separation process is all advantageous in production process and the aspect of properties of product two.
Common sweating effort mainly includes the following steps that：（1）Preparation：Water is padded, is full of sweatbox ware plate with water
Lower space；（2）Charging：Load sweatbox when raw material is heated to more than fusing point being in a liquid state；（3）Decrease temperature crystalline：By raw material with
Rate of temperature fall no more than 4 DEG C/h progressively cools to below its fusing point 10~20 DEG C.In cooling procedure, fusing point highest component
First come out with thick fibrous crystal morphological crystal, as wax layer temperature continues to reduce, other components by fusing point from high to low
Crystallization forms solid to order successively；（4）Heat up sweating：After wax layer temperature reaches default cooling final temperature, pad is bled off
Water；Raw material is slowly heated to default sweating final temperature again.In the sweating effort that heats up, various components are by fusing point by low
Successively liquid is fused into high order and is flowed out（Under wax）, the wax layer residue that finally obtains（On wax）It is exactly high-melting-point, low
The wax of oil-containing；（5）Crude product is collected：Heating sweating effort terminates follow-up high-temperature of continuing rising, is taken out with fusing on wax, is thick production
Product；（6）Product purification, shaping, packaging：Subtractive process generally use is clay-filtered：Pre- constant temperature is warming up to after crude product is melted
Degree, add carclazyte and simultaneously filtered after constant temperature was stirred to the scheduled time；It is again purpose product through being molded, packing.
To common sweating method, the solids fraction in the sweating effort that heats up（The wax of higher melt）And liquid composition（Oil and
Compared with the wax of low melting point）Although two class components are respectively at two kinds of phases of solid and liquid, but also be difficult to be kept completely separate.To make most
The oil content of finished product meets the requirements, and generally use extends sweating sessions and the method for improving sweating final temperature, but so meeting
Cause the production cycle long and product yield declines.
Common sweating process can produce soap wax and low melt point paraffin of the fusing point at 40 DEG C~60 DEG C, be not suitable for producing fusing point
High melting-point wax product more than 70 DEG C.There is experiment to show, high-melting-point production of the common sweating process production fusing point more than 70 DEG C
During product, the carbon dispersion of distribution and normal paraffin content on sweating later stage wax are unrelated with yield, i.e., the carbon dispersion of distribution on wax not with
The decline of yield and decline, normal paraffin content does not also improve with the decline of yield, so common sweating separating technology is uncomfortable
Preferably produce wax class phase-change material of the fusing point more than 70 DEG C.Only part producer uses sweating process production soap wax and eutectic at present
The mill runs such as the paraffin of point.
For many years, sweating process has obtained some development, such as CN89214332 in production equipment and process aspect（Vertical type square
Shape multipul sections spacer diaphoresis tank）、CN98233254.8（Paraffin sweating pot）、CN201320127680.4（Tubular type paraffin deoiler）
Deng being improved in sweating production equipment；CN91206202（A kind of high-efficient sweat pot for paraffin wax）Change on sweating process
Enter.But these improvement can not still produce wax class phase-change material of the fusing point more than 70 DEG C.
Compared with solvent deoiling technique, sweating process has the advantages such as small investment, production process are simple and operating cost is low；
Importantly, sweating process is to be currently known unique solvent-free de-oiling method for commercial scale paraffin wax product.
Green low-carbon, today of environmental protection and energy saving are advocated, the need of wax class phase-change material of the fusing point more than 70 DEG C are produced using sweating process
Ask more urgent.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of production method of wax class phase-change material, specifically with
Paraffin grade wax is raw material, using sweatbox, on the basis of common sweating method, preferably in pressure strip after raw material heating fusing
Low-boiling point liquid is mixed under part；The proper temperature increase high temperature constant temperature stage during cooling, and increase cooled
Journey terminate after the cryogenic thermostat stage and heating sweating effort the constant temperature stage；Pass through wax using air-flow in the sweating effort that heats up
Layer carries out liquid composition to force to separate solids fraction and liquid composition, enhances separating effect and accelerates separating rate.
Low-boiling point liquid is reclaimed in the sweating effort of the cryogenic thermostat process of cooling and heating and constant temperature.The inventive method makes sweating this
Solvent-free de-oiling method can produce wax class phase-change material product of the fusing point more than 70 DEG C, and low, raw with plant investment
The advantages that production process is simple and operating cost is low, solvent-free pollution.
A kind of production method of wax class phase-change material of the present invention, including herein below：
（1）Water is padded in sweatbox；
（2）Using paraffin grade wax as raw material, 3 DEG C~8 DEG C are heated to more than fusing point, raw material loads sweating dress after all melting
Put；
（3）Wax layer is cooled to by proper temperature with 1.0 DEG C/h~3.0 DEG C/h speed, high temperature constant temperature is for a period of time；Again with
0.5 DEG C/h~2.5 DEG C/h speed cools to 5 DEG C below raw material fusing point~20 DEG C of predetermined temperature, and cryogenic thermostat one
The section time；
（4）Discharge the pad water in sweatbox；Then heated up with 0.5 DEG C/h~2.5 DEG C/h speed, wax layer reaches predetermined
Constant temperature for a period of time, then stops sweating after temperature；Wax layer is wherein forced air flow through in temperature-rise period；
（5）Collect on wax；
（6）On wax wax class phase-change material product is obtained after refined, shaping, packaging.
In the production method of the wax class phase-change material of the present invention, the melting range of the paraffin grade wax is generally 60~74
DEG C, preferably fusing point scope is 66~74 DEG C.
In the production method of the wax class phase-change material of the present invention, preferably mixed under stress after raw material heating fusing
Low-boiling point liquid.Described pressure（Gauge pressure）For 0.5~20.0 atmospheric pressure, preferably 1.0~10.0 atmospheric pressure.Described
Low-boiling point liquid is organic matter, and it has preferable intersolubility with raw material, and boiling point at ambient pressure is predetermined less than what is cooled
Temperature, and boiling point under high pressure is higher than the maximum temperature of charging process.Described low-boiling point liquid can be alkane, alkene,
One or more in the suitable organic matter of the boiling points such as alkynes, alkadienes, alcohol, aldehyde, ether, ester, halogenated hydrocarbons, preferably alkane, alcohol,
Ester etc. and raw material have preferable intersolubility, without special odor and the material that has no toxic side effect.The addition of described low-boiling point liquid
Amount accounts for the 0.1%~5.0% of raw material weight, preferably 0.3%~2.0%.In the cryogenic thermostat process of cooling and heating and constant temperature
Low-boiling point liquid is reclaimed in sweating effort.
In the production method of the wax class phase-change material of the present invention, described sweatbox is generally sweating ware, and in wax layer
Dismountable sealing system added above and pressue device, to ensure to keep low-boiling point liquid to be in charging and cooling procedure
Liquid condition, described pressure（Gauge pressure）For 0.5~20.0 atmospheric pressure, preferably 1.0~10.0 atmospheric pressure.
In the production method of the wax class phase-change material of the present invention, described sweating ware is in wax layer pressue device added above
And/or increase vacuum plant below wax layer.The described wax layer that forces air flow through above wax layer using increasing pressure（Gas
Pressure）And/or pressure is reduced below wax layer（Air pressure）, wax layer upper and lower is formed pressure differential and realize.Described pressure differential is general
For 0.1~5.0 atmospheric pressure, preferably 0.2~1.5 atmospheric pressure, to force air flow through wax layer.
In the production method of the wax class phase-change material of the present invention, the drop in described temperature-fall period before high-temperature constant temperature section
Warm speed preferably 1.5 DEG C/h~2.5 DEG C/h.
In the production method of the wax class phase-change material of the present invention, the proper temperature of the high-temperature constant temperature section of described temperature-fall period
It is -1.0 DEG C of starting paraffin fusing point~+2.0 DEG C of fusing point, preferably starting paraffin fusing point~+1.0 DEG C of fusing point.Cool process
High-temperature constant temperature section time be 0~4.0 hour, preferably 0.1~4.0 hour, most preferably 1.0~4.0 hours.
In the production method of the wax class phase-change material of the present invention, cooling of the described temperature-fall period after high-temperature constant temperature section
Speed preferably 1.0 DEG C/h~2.0 DEG C/h.
In the production method of the wax class phase-change material of the present invention, described cooling final temperature is preferably starting paraffin fusing point
8 DEG C below~15 DEG C.
In the production method of the wax class phase-change material of the present invention, described cools to preset temperature, increases low temperature
The constant temperature stage is so that solid crystal is more abundant, while gradually reduces pressure to normal pressure.The cryogenic thermostat stage for the process that cools
Time be 0~3.0 hour, preferably 0.1~3.0 hour, most preferably 1.0~3.0 hours.
In the production method of the wax class phase-change material of the present invention, the heating rate preferably 1.0 of described heating sweating effort
DEG C/h~2.0 DEG C/h.The predetermined temperature of the heating（That is final temperature）To be wax class phase-change material product less than purpose product
1 DEG C~10 DEG C of fusing point.
In the production method of the wax class phase-change material of the present invention, described heating sweating to the preset temperature for producing product
Afterwards, the constant temperature stage is increased so that solids fraction separates more fully with liquid composition, the time in constant temperature stage is 0~5.0 hour, excellent
Elect 0.1~5.0 hour, most preferably 1.0~5.0 hours as.
In the method for the present invention, the programming rate and cooling rate of said wax layer, air bath, water-bath, oil bath can be passed through
Or other feasible modes are controlled, it is preferred to use water-bath or oil bath are controlled.Controlled using water-bath or oil bath mode
When wax layer heating rate and rate of temperature fall, chuck can be increased outside sweating ware, chuck is connected with removable coil pipe and the circulatory system,
The circulatory system has program cooling/heating function, and circulatory mediator is used as using the material such as water or conduction oil；Increase coil pipe can make wax layer
Lifting/lowering temperature process faster, wax layer more uniform temperature.
In the production method of the wax class phase-change material of the present invention, the described wax layer that forces air flow through can be in sweating effort
Any stage is implemented, and preferably implements initial stage in heating.
In the production method of the wax class phase-change material of the present invention, the described wax layer that forces air flow through is utilized in wax layer
Fang Zengjia pressure（Air pressure）Realize, the pressure such as applied above wax layer is 0.2~1.5 atmospheric pressure（Gauge pressure）, and wax layer
Lower section remains normal pressure.
In the wax class phase-change material production method of the present invention, the described wax layer that forces air flow through is utilized in below wax layer
Reduce pressure（Air pressure）Realize, normal pressure is such as kept above wax layer, and -0.2~-0.8 atmospheric pressure is maintained below wax layer
（Gauge pressure）Pressure.
In the wax class phase-change material production method of the present invention, described sweatbox connection recovery system, to reclaim low boiling
Point liquid.Recovery system can using liquid absorption or refrigeration system etc. it is a variety of it is feasible by the way of, preferably liquid absorption system.
Common sweating method is to carry out separation production petroleum paraffin product using the wax property different with oily fusing point, but right
In petroleum paraffin product of the fusing point at 70 DEG C or so, because the material such as cycloalkane and isoparaffin increases in raw material, chemical composition is multiple
It is miscellaneous, cause the more tiny densification of crystals upon crystallization structure, the discharge to liquid composition forms huge filter flow resistance power, and this is resulted in
Only it is difficult to be kept completely separate with liquid composition by solids fraction in the common sweating effort of gravity natural separation.Therefore common sweating work
Skill can not produce wax class phase-change material product of the fusing point more than 70 DEG C.
The present invention in order that sweating it is this it is solvent-free production pertroleum wax method can produce wax class phase-change material product, lead to
Cross to wax class phase-change material performance and the relation of its chemical composition and the further investigation of common sweating effort, for common petroleum wax
Carbon number distribution is wider in product chemical composition and normal paraffin content it is relatively low be to cause common petroleum wax product to meet wax class
The reason for phase-change material product technology requirement, improve n-alkane simultaneously by using diaphoresis reduction carbon number distribution width and contain
Amount；It is difficult to liquid composition separate reason for solids fraction in common sweating effort, by using in the sweating effort that heats up
The method that wax layer carries out liquid composition is forced air flow through, while is further preferably mixed under stress after raw material heating fusing
Low-boiling point liquid, and increase high temperature constant temperature stage, the cryogenic thermostat stage for the process that cools and liter during cooling
The processes such as the constant temperature stage after warm sweating to preset temperature, these measures significantly reduce the width of product carbon distribution and raising
Normal paraffin content, the performance of product is set to disclosure satisfy that the technical requirements of wax class phase-change material.
Research for pertroleum wax sweating effort shows, in sweating effort, liquid composition is gradually arranged along crystalline portion
Go out, situation about being flowed similar to liquid in capillary.Because fusing point is in 70 DEG C or so of the tiny fine and close crystallization of pertroleum wax
Structure, it can make to increased dramatically the filter flow resistance power that liquid composition is formed, this is resulted in only by the common of gravity natural separation process
Sweating method can not produce wax class phase-change material product.
Increasing the high temperature constant temperature stage during cooling can make the crystallization of pertroleum wax bigger, beneficial to heating sweating
The discharge of liquid composition in journey.Research for pertroleum wax crystallization process shows that its chemical composition is to determine crystal habit most
Principal element, while the condition of cooling procedure can also influence crystal habit, the cooling bar especially at the temperature near fusing point
Influence of the part to crystal habit is most obvious.Fusing point is when 70 DEG C or so of pertroleum wax is being cooled near fusing point, larger molecular weight
N-alkane formed crystallization and separated out, this partially crystallizable body can now increase high temperature as the nucleus for being subsequently formed crystallization
In the constant temperature stage, nucleus can be enable fully to increase, form larger sized crystal, although this larger sized crystal is not so good as
The crystallization of low melt point paraffin is thick like that, but it is also extremely to have that the crystal structure of this increase discharges liquid composition to the sweating stage
Profit.
Low-boiling point liquid is mixed under stress after raw material heating fusing, while forces air-flow in the sweating effort that heats up
The discharge of liquid composition in heating sweating effort is also beneficial to by wax layer.The low-boiling point liquid mixed after raw material heating fusing,
Boiling point under stress is in liquid condition higher than the now temperature of raw material, and due to having preferable intersolubility with raw material
And it is dispersed in the feed；Raw material under pressure is kept to be cooled to below fusing point 8 DEG C~15 DEG C and 0.1~3.0h of constant temperature so that wax
Layer crystallization is more abundant；Gradually reduction pressure to normal pressure, now raw material is in softer solid state in thermostatic process simultaneously, and
And temperature is higher than the boiling point under low-boiling point liquid normal pressure（Or bubble point）, low-boiling point liquid slowly declines with pressure and gradually vaporizes
（Or gradually vaporized in sweating effort behind）, dispersed micro-bubble can be formed in wax layer, these micro-bubbles
The space of formation is easy to form some tiny passages in wax layer in sweating effort, oily in sweating effort so as to be advantageous to
Discharge.The method for carrying out liquid composition by wax layer using air-flow in the sweating effort of heating and constant temperature simultaneously forces liquid
Component separates with solids fraction, enhances separating effect and accelerates separating rate.It is aided with the cryogenic thermostat rank of cooling procedure again
Section makes solid crystal more abundant, and the constant temperature stage of sweating effort makes solids fraction separate the side such as more abundant with liquid composition
Method so that sweating process can produce carbon number distribution narrow range and the high wax class phase-change material product of normal paraffin content.
It is an advantage of the invention that：Crystalline size is increased using high temperature crystallization；Liquid group is carried out by wax layer using air-flow
The method divided enhances the separating effect of solids fraction and liquid composition and accelerates separating rate；And utilize low-boiling point liquid vapour
Change forms dispersed micro-bubble in wax layer, advantageously in the quick discharge of liquid composition, further improves solid
The separating effect of state component and liquid composition.So that sweating process can produce, carbon number distribution scope is narrower and n-alkane contains
The higher petroleum paraffin product of amount, these products may be used as wax class phase-change material.The inventive method plant investment is low, production process
Simple and operating cost is low, solvent-free pollution environment.
Embodiment
Sweating ware top connects dismountable sealing device and is connected with pressurized buffer tank and compressor, and/or in sweating
Ware bottom connects pressure-reducing cushioning tank and vavuum pump；With water-bath or oil bath control wax layer heating-cooling speed；Increase folder outside sweating ware
Set, chuck are connected with removable coil pipe and the circulatory system, and the circulatory system has program cooling/heating function；Suitable with fusing point
Paraffin is raw material, and heating fusing simultaneously preferably mixes loading sweating ware after low-boiling point liquid under stress；Keep making under pressure
Wax layer temperature be down to raw material melting temperature nearby and high temperature constant temperature for a period of time；Continue to reduce wax layer temperature to design temperature and low
Warm constant temperature gradually reduces more than raw material wax layer pressure to normal pressure for a period of time, in thermostatic process；In the sweating effort that heats up, open
Dynamic compressor is with wax layer malleation formed above, and/or starts vavuum pump with wax layer negative pressure formed below, to force air-flow
Pass through wax layer；Wax layer temperature reaches preset temperature and constant temperature stops sweating effort afterwards for a period of time；Through refined, shaping, bag on wax
It is wax class phase-change material product after dress.
1-2 illustrates the production method of wax class phase-change material of the present invention by the following examples.
Embodiment 1
The present embodiment includes：（1）Preparation,（2）Charging,（3）Cooling-high temperature constant temperature-cooling-cryogenic thermostat knot
Brilliant,（4）Heating-constant temperature sweating,（5）Crude product collection,（6）The processes such as product purification.
（1）Preparation
Sweating ware chuck and removable coil pipe are connected with the circulatory system, coil pipe is fixed on sweating ware；Using water as Jie
Matter；Start the heating function of the circulatory system, water-cycling-media is warming up to 78 DEG C.
Pad water in sweating ware ware plate bottom；Sweating ware bottom connects pressure-reducing cushioning tank and vavuum pump.
（2）Charging
With No. 72 semi-refined waxs（Dalian Petrochemical Industry Company produces, and its property is：72.50 DEG C of fusing point；Oil content 0.66%；N-alkanes
Hydrocarbon content 68.25%）For raw material, sweating ware is added after being heated to 78 DEG C of fusings.
The sealing system on installation sweating ware top simultaneously connects with pressurized buffer tank and compressor；Start compressor and keep
Pressurized buffer pressure inside the tank is stable in 5.0~5.2 atmospheric pressure（Gauge pressure）.
（3）Cooling-high temperature constant temperature-cooling-cryogenic thermostat crystallization
Start the refrigerating function of the circulatory system, wax layer temperature is dropped to 73.0 DEG C and perseverance with 2.0 DEG C/h rate of temperature fall
Temperature carries out high temperature constant temperature in 2.0 hours, so that crystallization fully increases；Drop to wax layer temperature again with 1.5 DEG C/h rate of temperature fall
62.0 DEG C so that wax layer crystallizes to form solid, and constant temperature carries out cryogenic thermostat in 2.0 hours, so that crystallization is more abundant.Cryogenic thermostat
Stage controls pressurized buffer pressure inside the tank to be gradually decrease to normal pressure by emptying system.
Close the refrigerating function of the circulatory system.
（4）Heating-constant temperature sweating
Discharge sweating ware pad water.
Storage tank under sweating ware outlet connection wax；Start compressor and keep pressurized buffer pressure inside the tank stable 1.0~1.2
Individual atmospheric pressure（Gauge pressure）, and normal pressure is remained below wax layer；Start circulation system function, with 1.5 DEG C/h heating speed
Rate makes wax layer temperature be increased to 72.0 DEG C.
Stop compressor.
Open vavuum pump and keep pressure-reducing cushioning pressure inside the tank stable in -0.4~-0.6 atmospheric pressure（Gauge pressure）, and in wax
Layer top remains normal pressure；Wax layer temperature is set to be increased to 75.0 DEG C and constant temperature 4.0 hours so that wax layer with 1.5/h heating rate
In solids fraction be sufficiently separated with liquid composition.
Stop vavuum pump, terminate sweating effort.
（5）Crude product is collected
Sweating ware exports changing-over crude product storage tank（Ⅰ）To receive on wax；Continue the temperature of rise recirculated water to 90 DEG C, with molten
Change and take out on wax, as crude product.
（6）Product purification
Crude product is wax class phase-change material product after clay-filtered, shaping and packaging（Ⅰ）.
Wax class phase-change material product（Ⅰ）Property：Fusing point（DSC method）：77.51℃；Latent heat of phase change：218.52J/g；Positive structure
Determination of Alkane Content 81.47%.
Wax class phase-change material product（Ⅰ）Yield be 14.6%（Relative to No. 72 semi-refined waxs of raw material）.
Embodiment 2
The present embodiment includes：（1）Preparation,（2）Charging,（3）Cooling-high temperature constant temperature-cooling-cryogenic thermostat knot
Brilliant,（4）Heating-constant temperature sweating,（5）Crude product collection,（6）The processes such as product purification.
（1）Preparation
Sweating ware chuck and removable coil pipe are connected with the circulatory system, coil pipe is fixed on sweating ware；Using water as Jie
Matter；Start the heating function of the circulatory system, water-cycling-media is warming up to 78 DEG C.
Pad water in sweating ware ware plate bottom.
The sealing system on installation sweating ware top is simultaneously connected with pressurized buffer tank and compressor, and pressurized buffer tank is emptied
System and sweating ware lower exhaust port connect with recovery system respectively, using atoleine as absorbing medium.And under sweating ware
Portion connects pressure-reducing cushioning tank and vavuum pump.
（2）Charging
With No. 72 semi-refined waxs（Property is the same as embodiment 1）For raw material, it is heated to after 78 DEG C of fusings in 5.0~5.2 atmospheric pressure
（Gauge pressure）The methyl acetate of lower incorporation 1.0%, adds sweating ware；Keep pressurized buffer pressure inside the tank stable at 5.0~5.2
Atmospheric pressure（Gauge pressure）.
（3）Cooling-high temperature constant temperature-cooling-cryogenic thermostat crystallization
Start the refrigerating function of the circulatory system, wax layer temperature is dropped to 73.0 DEG C and perseverance with 2.0 DEG C/h rate of temperature fall
Temperature carries out high temperature constant temperature in 2.0 hours, so that crystallization fully increases；Drop to wax layer temperature again with 1.5 DEG C/h rate of temperature fall
62.0 DEG C so that wax layer crystallizes to form solid, and constant temperature carries out cryogenic thermostat in 2.0 hours, so that crystallization is more abundant.
The cryogenic thermostat stage controls pressurized buffer pressure inside the tank to be gradually decrease to normal pressure by emptying system.The gas of discharge
By atoleine to reclaim low-boiling point liquid methyl acetate.
Close the refrigerating function of the circulatory system.
（4）Heating-constant temperature sweating
Discharge sweating ware pad water.
Storage tank under sweating ware outlet connection wax；Start compressor and keep pressurized buffer pressure inside the tank stable 1.0~1.2
Individual atmospheric pressure（Gauge pressure）, and normal pressure is remained below wax layer；Start circulation system function, with 1.5 DEG C/h heating speed
Rate makes wax layer temperature be increased to 72.0 DEG C.
Stop compressor.
Open vavuum pump and keep pressure-reducing cushioning pressure inside the tank stable in -0.4~-0.6 atmospheric pressure（Gauge pressure）, and in wax
Layer top remains normal pressure；Wax layer temperature is set to be increased to 75.0 DEG C with 1.5/h heating rate, and constant temperature 4.0 hours is so that wax
Solids fraction in layer is sufficiently separated with liquid composition.
In the sweating effort of heating and constant temperature the gas discharged by atoleine to reclaim low-boiling point liquid methyl acetate.
Stop vavuum pump, terminate sweating effort.
（5）Crude product is collected
Sweating ware exports changing-over crude product storage tank（Ⅱ）To receive on wax；Continue the temperature of rise recirculated water to 90 DEG C, with
Fusing is taken out on wax, as crude product.
（6）Product purification
Crude product is wax class phase-change material product after clay-filtered, shaping and packaging（Ⅱ）.
Wax class phase-change material product（Ⅱ）Property：Fusing point（DSC method）：78.23℃；Latent heat of phase change：230.15J/g；Just
Structure Determination of Alkane Content 85.35%.
Wax class phase-change material product（Ⅱ）Yield be 14.2%（Relative to No. 72 semi-refined waxs of raw material）.
The production method of wax class phase-change material of the present invention is can be seen that by embodiment 1-2, by heating sweating effort
The middle method for carrying out liquid composition by wax layer using air-flow forces liquid composition to be separated with solids fraction, enhances separation effect
Fruit；The quick row that dispersed micro-bubble is formed in wax layer and is also beneficial to liquid composition is vaporized using low-boiling point liquid
Go out, make this solvent-free production paraffin of sweating method produce fusing point more than 70 DEG C, latent heat of phase change is more than 210J/g's
Wax class phase-change material product.
Claims (27)
1. a kind of production method of wax class phase-change material, including herein below：
（1）Water is padded in sweatbox；
（2）Using paraffin grade wax as raw material, 3 DEG C~8 DEG C are heated to more than fusing point, raw material loads sweatbox after all melting；Institute
The fusing point for stating paraffin grade wax is 60~74 DEG C；
（3）Wax layer is cooled to by proper temperature with 1.0 DEG C/h~3.0 DEG C/h speed, high temperature constant temperature is for a period of time；Again with 0.5
DEG C/h~2.5 DEG C/h speed cools to 5 DEG C below raw material fusing point~20 DEG C of predetermined temperature, and during one section of cryogenic thermostat
Between；
（4）Discharge the pad water in sweatbox；Then heated up with 0.5 DEG C/h~2.5 DEG C/h speed, wax layer reaches predetermined temperature
Constant temperature for a period of time, then stops sweating afterwards；Wax layer is wherein forced air flow through in sweating effort；
（5）Collect on wax；
（6）On wax wax class phase-change material product is obtained after refined, shaping, packaging.
2. in accordance with the method for claim 1, it is characterised in that step（2）After middle raw material heating fusing under stress
Low-boiling point liquid is mixed, the boiling point of described low-boiling point liquid at ambient pressure is less than the predetermined temperature to cool, and in high pressure
Under boiling point be higher than step（2）The maximum temperature of charging process.
3. in accordance with the method for claim 2, it is characterised in that described low-boiling point liquid be selected from alkane, alkene, alkynes,
One or more in alcohol, aldehyde, ether, ester, halogenated hydrocarbons.
4. in accordance with the method for claim 3, it is characterised in that described low-boiling point liquid in alkane, alcohol, ester one
Kind is several.
5. in accordance with the method for claim 2, it is characterised in that the addition of described low-boiling point liquid accounts for raw material weight
0.1%~5.0%.
6. in accordance with the method for claim 2, it is characterised in that in step（2）And step（3）In above wax layer apply pressure
Power, to ensure to keep low-boiling point liquid to be in liquid condition in charging and cooling procedure.
7. in accordance with the method for claim 6, it is characterised in that described pressure is 0.5~20.0 air of gauge
Pressure.
8. in accordance with the method for claim 1, it is characterised in that step（4）Described in force air flow through wax layer use
Increase air pressure above wax layer and/or air pressure is reduced below wax layer, wax layer upper and lower is formed pressure differential and realize, described pressure
Power difference is 0.1~5.0 atmospheric pressure.
9. in accordance with the method for claim 1, it is characterised in that step（3）Described temperature-fall period high-temperature constant temperature section it
Preceding rate of temperature fall is 1.5 DEG C/h~2.5 DEG C/h, and the rate of temperature fall after high-temperature constant temperature section is 1.0 DEG C/h~2.0 DEG C/h.
10. in accordance with the method for claim 1, it is characterised in that step（3）Described in proper temperature melted for starting paraffin
- 1.0 DEG C of point~+2.0 DEG C of fusing point.
11. in accordance with the method for claim 1, it is characterised in that step（3）Described in high temperature constant temperature time be 0.1
~4.0 hours.
12. in accordance with the method for claim 1, it is characterised in that step（3）Described in cooling final temperature be raw material stone
8 DEG C~15 DEG C below wax fusing point.
13. in accordance with the method for claim 1, it is characterised in that step（3）Described in cryogenic thermostat time be 0.1
~3.0 hours.
14. in accordance with the method for claim 1, it is characterised in that step（4）Described in the speed that heats up for 1.0 DEG C/h~
2.0℃/h。
15. according to the method described in claim 1 or 13, it is characterised in that pressure is gradually reduced in the cryogenic thermostat stage to normal
Pressure.
16. in accordance with the method for claim 1, it is characterised in that step（4）Described in the predetermined temperature that heats up be less than mesh
Product be wax class phase-change material product 1 DEG C~10 DEG C of fusing point.
17. in accordance with the method for claim 1, it is characterised in that step（4）Described in time of constant temperature be 0.1~5.0 small
When.
18. according to the method described in claim 1 or 8, it is characterised in that step（4）Described in force air flow through wax layer
Implement in sweating effort any stage.
19. in accordance with the method for claim 8, it is characterised in that the described wax layer that forces air flow through is used in wax layer
What Fang Zengjia air pressure was realized：Apply the gauge of 0.2~1.5 atmospheric pressure above wax layer, and remained often below wax layer
Pressure.
20. it is wanted to seek the method described in 8 according to right, it is characterised in that the described wax layer that forces air flow through is utilized in wax
Layer lower section reduces what air pressure was realized：Keep normal pressure above wax layer, and -0.2~-0.8 atmospheric pressure is maintained below wax layer
Gauge.
21. according to any described methods of claim 2-7, it is characterised in that returned in cooling thermostatic process and sweating effort
Receive low-boiling point liquid.
22. in accordance with the method for claim 21, it is characterised in that reclaimed by the way of liquid absorption or refrigeration system low
Boiling-point liquids.
23. in accordance with the method for claim 5, it is characterised in that the addition of described low-boiling point liquid accounts for raw material weight
0.3%~2.0%.
24. in accordance with the method for claim 7, it is characterised in that described pressure is 1.0~10.0 air of gauge
Pressure.
25. in accordance with the method for claim 8, it is characterised in that described pressure differential is 0.2~1.5 atmospheric pressure.
26. in accordance with the method for claim 10, it is characterised in that step（3）Described in proper temperature be starting paraffin
Fusing point~+1.0 DEG C of fusing point.
27. in accordance with the method for claim 18, it is characterised in that step（4）Described in the wax layer that forces air flow through exist
Heating is implemented initial stage.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB687235A (en) * | 1950-03-24 | 1953-02-11 | Bataafsche Petroleum | Improvements in and relating to the treatment of paraffin wax |
| CN1351094A (en) * | 2000-10-26 | 2002-05-29 | 中国石油化工股份有限公司 | Wax compositions for thermosensitive switch |
| CN1458241A (en) * | 2002-05-15 | 2003-11-26 | 中国石油化工股份有限公司 | Wax dielectric for heating temperature control valve and its preparing method |
| CN1458188A (en) * | 2002-05-15 | 2003-11-26 | 中国石油化工股份有限公司 | Wax dielectric for thermosensitive switch |
| CN1609162A (en) * | 2003-10-24 | 2005-04-27 | 中国石油化工股份有限公司 | Temerature sensitive medium for wax temperature controlling valve and its prepn process |
| CN103102971A (en) * | 2011-11-10 | 2013-05-15 | 中国石油化工股份有限公司 | Preparation method for wax temperature-sensitive medium for temperature control valve |
-
2014
- 2014-12-28 CN CN201410825741.3A patent/CN105802666B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB687235A (en) * | 1950-03-24 | 1953-02-11 | Bataafsche Petroleum | Improvements in and relating to the treatment of paraffin wax |
| CN1351094A (en) * | 2000-10-26 | 2002-05-29 | 中国石油化工股份有限公司 | Wax compositions for thermosensitive switch |
| CN1458241A (en) * | 2002-05-15 | 2003-11-26 | 中国石油化工股份有限公司 | Wax dielectric for heating temperature control valve and its preparing method |
| CN1458188A (en) * | 2002-05-15 | 2003-11-26 | 中国石油化工股份有限公司 | Wax dielectric for thermosensitive switch |
| CN1609162A (en) * | 2003-10-24 | 2005-04-27 | 中国石油化工股份有限公司 | Temerature sensitive medium for wax temperature controlling valve and its prepn process |
| CN103102971A (en) * | 2011-11-10 | 2013-05-15 | 中国石油化工股份有限公司 | Preparation method for wax temperature-sensitive medium for temperature control valve |
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|---|---|
| CN105802666A (en) | 2016-07-27 |
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