CN107513419B - The production method of high latent heat phase-change material - Google Patents
The production method of high latent heat phase-change material Download PDFInfo
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- CN107513419B CN107513419B CN201610432987.3A CN201610432987A CN107513419B CN 107513419 B CN107513419 B CN 107513419B CN 201610432987 A CN201610432987 A CN 201610432987A CN 107513419 B CN107513419 B CN 107513419B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G73/00—Recovery or refining of mineral waxes, e.g. montan wax
- C10G73/36—Recovery of petroleum waxes from other compositions containing oil in minor proportions, from concentrates or from residues; De-oiling, sweating
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G73/00—Recovery or refining of mineral waxes, e.g. montan wax
- C10G73/38—Chemical modification of petroleum
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G73/00—Recovery or refining of mineral waxes, e.g. montan wax
- C10G73/40—Physical treatment of waxes or modified waxes, e.g. granulation, dispersion, emulsion, irradiation
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G73/00—Recovery or refining of mineral waxes, e.g. montan wax
- C10G73/42—Refining of petroleum waxes
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Abstract
The invention discloses a kind of production methods of high latent heat phase-change material.This method is on the basis of common sweating process, liquid composition is carried out to force separation solids fraction and liquid composition by wax layer using air-flow in sweating effort, preferably raw material and water or salting liquid are emulsified simultaneously, it is also beneficial to the quick discharge of liquid composition, so that this solvent-free separation method of sweating be allow to produce high latent heat phase-change material.The method of the present invention has many advantages, such as that equipment investment is low, production process is simple and operating cost is low, safety, energy conservation, solvent-free pollution.
Description
Technical field
The invention belongs to Wax special production technical fields, more particularly to a kind of production method of high latent heat phase-change material.
Background technique
Temperature change is not in fusing or process of setting for phase-change material (Phase Change Material, abbreviation PCM)
Greatly, the latent heat for absorbing or discharging but in the temperature range of very little is very big, this characteristic make its constant temperature, in terms of have
It is widely applied.Generally phase-change material is required to have phase transition temperature appropriate and high latent heat of phase change.
According to the difference of phase transition temperature, phase-change material can be generally 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, generally phase-change material can be divided into inorganic phase-changing material and organic phase change material.
According to the difference of material phase-state change in thermal energy storage process, phase-change material can be generally divided into solid-gas phase-change material, liquid-gas phase
Become material, solid-liquid phase-change material, solid-solid phase change material.Hydro carbons phase-change material is common organic, middle low-temperature space
Gu-liquid phase-change material.
Pertroleum wax is crude oil by all kinds of wax products obtained after the processing of the processes such as dewaxing, de-oiling, purification and molding
General name, including atoleine, soap manufacturing paraffin, paraffin and microwax.Paraffin typically contains C20~C50N-alkane, isoparaffin
With the components such as a small amount of cycloalkane, usual fusing point is 50 DEG C~74 DEG C, has coarse flaky crystal structure under solid-state.Microwax one
As by C30~C60Isoparaffin and a small amount of n-alkane, cycloalkane composition, usual dropping point be 65 DEG C~92 DEG C, under solid-state
With the needle-like crystal structure more tiny than paraffin.
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.Since the fusing point of hydrocarbon mixture is the various components of its composition
Concentrated expression, thus can consider that the fusing point of hydro carbons is any adjustable within the scope of -20~100 DEG C, this is exactly hydro carbons phase transformation material
The sharpest edges of material.The temperature region is also the range most often contacted in people's daily life simultaneously, and hydro carbons is chemically
Matter is stable, non-corrosive, free from environmental pollution, thus has unrivaled advantage when as phase-change material.But commodity oil wax
Containing the components such as isoparaffin and cycloalkane, and carbon number distribution is wider, and it is low (generally below to be directly used as latent heat when phase-change material
200J/g), phase transformation section is wider.Therefore, pertroleum wax must be purified to improve normal paraffin content and to reduce carbon number distribution wide
Degree just can serve as hydro carbons phase-change material.
In terms of pertroleum wax production technology, the common manufacturing process that separates has distillation, solvent separation, sweating separation etc..
Distillation is to achieve the purpose that 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 influenced on normal paraffin content is improved less, simultaneously because distillation process is needed raw material
It is heated to boiling point or more, consumes a large amount of energy.And fusing point 70 DEG C or more of hydro carbons boiling point 500 DEG C (normal pressures) with
On, efficiency is greatly reduced when being separated using distillating method.
Solvent fractionation method is using n-alkane and isoparaffin in selective solvent (acetone, benzene and toluene mixture；
Or acetone, toluene；Or methyl ethyl ketone, toluene) in the property of different solubility separated, can effectively improve in product just
Structure Determination of Alkane Content, but the influence to carbon distribution width is little, while solvent separation investment of production equipment is big；It is needed in production process
Solvent is largely used, recycling design needs to consume a large amount of energy；Contain benzene homologues in solvent, environment can be impacted；It is molten
Agent is inflammable, be easy to cause production accident.
Sweating separation method carries out separating-purifying using hydrocarbon components various in wax property with different melting points.Pertroleum wax
In molecular weight and the structure of various components Bu Tong can all make its fusing point different.When being all n-alkane, molecular weight is biggish just
The fusing point of structure alkane is higher, and the fusing point of the lesser n-alkane of molecular weight is lower；When molecular weight is identical, isoparaffin and cycloalkanes
The fusing point of hydrocarbon will be lower than n-alkane, and isomery degree more high-melting-point is lower.So sweating separation method can reduce product
The width of carbon distribution can improve normal paraffin content again.
Compared with distillating method, since the melting temperature of various hydro carbons is far below boiling temperature, so sweating separation process
Energy consumption far below distillation；Compared with solvent fractionation method, sweating separation process does not use solvent, so sweating separation process is pacified
Entirely, energy conservation and on environment without influence, and sweating method can reduce the width of product carbon distribution and can improve n-alkane again and contain
Amount, so sweating separating technology is at two aspect of production process and properties of product for the hydro carbons phase-change material for producing high latent heat
It is all advantageous.
Common sweating process mainly comprises the steps that (1) preparation: pad water is (with water full of sweatbox ware plate
Lower space) charge (raw material is heated to being packed into sweatbox when fusing point or more is in a liquid state) afterwards；(2) it crystallizes: by raw material with little
10~20 DEG C of its fusing point or less are progressively cooled in the rate of temperature fall of 4 DEG C/h.In cooling procedure, various components are by fusing point by height
It is successively crystallized to low sequence and forms solid；(3) it sweating: after wax layer temperature reaches preset cooling final temperature, bleeds off
Pad water；Raw material is slowly heated to preset sweating final temperature again.In sweating effort, various components by fusing point by as low as
High sequence, which is successively fused into liquid and flows out the wax layer residue (on wax) finally obtained (under wax), to be exactly high-melting-point, low contains
The wax of oil；(4) it refines: collection crude product (continue to increase temperature after sweating effort, be taken out on wax with fusing, as thick production
Product), (predetermined temperature, mistake after addition carclazyte and constant temperature were stirred to the predetermined time are warming up to after melting crude product through clay-filtered
Filter) after, reshaping, packaging are purpose product.
Common sweating process can produce soap manufacturing paraffin and low melt point paraffin of the fusing point at 40 DEG C~60 DEG C, and it is molten to be not suitable for production
O'clock in 70 DEG C or more of wax product.When common sweating process produces 40 DEG C~60 DEG C of soap manufacturing paraffin and low melt point paraffin, sweating
In journey although solids fraction (wax of higher melt) and liquid composition (oil and the wax compared with low melting point) two class components are respectively at solid
Two kinds of phases of body and liquid, but be also difficult to be kept completely separate.To make final products meet the requirements, extension sweating sessions are generallyd use
And the method for improving sweating final temperature, but will lead to production cycle length and product yield decline in this way；Experiments have shown that common hair
Sweat technique produces the carbon dispersion of distribution and normal paraffin content and receipts of the fusing point in 70 DEG C or more of wax product, on sweating later period wax
Rate is unrelated, i.e., the carbon dispersion of distribution on wax does not decline with the decline of yield, normal paraffin content also not with the decline of yield and
It improves, so common sweating separating technology is not suitable for producing hydro carbons phase-change material of the fusing point at 70 DEG C or more.
Compared with solvent fractionation method, sweating process is intermittently operated, and product yield is lower, the production cycle is longer, but
Be sweating process have equipment investment is few, production process is simple, operating cost is low, production process is safe, it is energy saving and to environment without
The advantages that pollution, still has part of the manufacturer producing soap manufacturing paraffin product using this method at present.
For many years, sweating method has obtained some development in production equipment and process aspect, such as CN89214332(vertical type square
Shape multipul sections spacer diaphoresis tank), CN94223980.6(ware type sudorific device), CN98233254.8(Paraffin sweating pot),
CN200920033500.X(novel paraffin sweating tank), a kind of Efficient paraffin sweatbox of CN201210508905.0(),
CN201320127680.4(tubular type paraffin deoiler) etc., it is improved in sweating production equipment；CN91206202(is a kind of
High-efficient sweat pot for paraffin wax) it is improved on sweating process, but these methods cannot still produce hydro carbons of the fusing point at 70 DEG C or more
Phase-change material.
Sweating process is the unique solvent-free separation method being currently known for commercial scale wax product, green advocating
Color low-carbon, environmental protection and energy saving today, using sweating process production phase transition temperature in 70 DEG C or more, latent heat of phase change in 210J/g or more
High latent heat phase-change material demand it is more urgent.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of production method of high latent heat phase-change material, specifically
Using sweatbox, on the basis of common sweating process, carried out after emulsion preferably is made with water or salting liquid in paraffin
Sweating is conducive to the discharge of liquid composition；And liquid composition is carried out to force by wax layer using air-flow in sweating effort
Solids fraction and liquid composition are separated, separating effect is enhanced and accelerates separating rate；And increase the high-temperature constant of crystallization process
Thermophase and cryogenic thermostat stage and the constant temperature stage of sweating effort produce this solvent-free separation method of sweating
Phase transition temperature is greater than the high latent heat phase-change material product of 210J/g in 70 DEG C or more, latent heat of phase change.The method of the present invention has equipment
Invest that low, production process is simple and operating cost is low, energy-saving safe and the advantages that solvent-free pollution.
A kind of production method of high latent heat phase-change material of the invention, including the following contents:
A: emulsification
(A1) prepared by oil phase material: using fusing point be 60 DEG C~74 DEG C, paraffin of the oil content less than 2.0 mass % is raw material, is added
Heat fusing；Oil soluble emulsifying agent is added, stirs evenly, forms oil phase material；
(A2) prepared by water-phase material: water or salting liquid being heated, water-phase material is formed；
(A3) prepared by emulsion: water-phase material being added in oil phase material under agitation, is continued after all adding
Stirring 5~60 minutes；
B: sweating
(B1) emulsion of (A3) preparation preparation: is packed into sweatbox；
(B2) crystallize: first with 5.0 DEG C/h~35.0 DEG C/h rate by emulsion be cooled to+4 DEG C of raw material fusing point~fusing point+
Within the scope of 10 DEG C, then wax layer is cooled to by proper temperature with 1.0 DEG C/h~3.0 DEG C/h rate, high temperature constant temperature is for a period of time；Again
5 DEG C~20 DEG C of raw material fusing point or less of cooling final temperature, and cryogenic thermostat are cooled to 0.5 DEG C/h~2.5 DEG C/h rate
For a period of time；
(B3) sweating: with the heating of 0.5 DEG C/h~2.5 DEG C/h rate；Wax layer reaches predetermined temperature and constant temperature for a period of time
After stop sweating；Wax layer is forced air flow through in sweating effort；
(B4) it refines: collecting on wax, be high latent heat phase-change material product after refining.
In method of the invention, the oil content (in mass) of the sweating raw material paraffin is less than 2.0%；Fusing point is general
It is 60 DEG C~74 DEG C, preferably 66 DEG C~74 DEG C.
In method of the invention, the oil soluble emulsifying agent is selected from nonionic surface active agent, anionic surface
In one group of substance that activating agent, cationic surface active agent, amphoteric surfactant, response type surfactant active are constituted
It is at least one.The HLB value of oil soluble emulsifying agent is 1~10, preferably 3~8；The freezing point or fusing point of the surfactant are low
Maximum temperature (predetermined temperature that sweating heats up i.e. in step (B3)) is heated up in sweating.
Wherein, it is stearic to be selected from sorbitan monooleate, anhydrous sorbitol list for the nonionic surface active agent
Acid esters, diethylene glycol aliphatic ester, diethylene glycol monolaurate, sorbitan monopalmitate, tetraethylene glycol list are stearic
One group of substance that acid esters, polyoxypropylene stearate, sorbitan mono-laurate, polyoxyethylene fatty acid ester are constituted；Yin
Ionic surfactant is selected from fatty alcohol sulfate monoethanolamine salt, pareth sulfate, oleamide yl carboxylic acid
Sodium, sodium alkyl benzene sulfonate, N- methyl oleoyl taurate, sodium butylnaphthalenesulfonate, Disodium sulfosuccinate, suitable succinate monoester
One group of substance that sodium sulfonate is constituted.The cationic surface active agent is selected from benzyl quaternary ammonium salt, dodecyl dimethyl benzyl
Ammonium chloride, dodecyl trimethyl ammonium chloride, cetyl trimethylammonium bromide, octadecyltrimethylammonium chloride, three second
One group of substance that amide oleate is constituted；Amphoteric surfactant is selected from empgen BB, dodecyl dimethyl oxygen
Change ammonium, aliphatic group imidazolidine derivatives, alkyl imidazoline derivatives, derivative of fatty acid, amphoteric modified epoxy ethane to add
The one group of substance constituted at object.
The response type surfactant active can be reacted with ammonia water by organic acid, and Organic Alcohol is added and is made.Specifically:
Organic acid and ammonium hydroxide are stirred to react 5 under conditions of 10~30 DEG C~generate organic acid ammonium salt after sixty minutes；In 60~70 DEG C of item
Under part, Organic Alcohol is added into the organic acid ammonium salt prepared, stirring is uniformly mixed it.The organic acid is
Saturation and unsaturated acids of the carbon number 1~36, preferably unitary organic acid of the carbon number 8~20, can be caprylic acid, the positive tenth of the twelve Earthly Branches acid,
N-capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitinic acid, stearic acid, linoleic acid, oleic acid, nonadecanoic acid,
Or mixtures thereof one of arachidic acid；Be also possible to the oxalic acid of polyacid, malic acid, citric acid, maleic acid, in fumaric acid
Or mixtures thereof one kind.The mass concentration of the ammonium hydroxide is 1%~28%, preferably 5%~15%.The Organic Alcohol is carbon number 1
Or mixtures thereof one of~12 saturated monohydroxy alcohol, preferably methanol, ethyl alcohol.The mixing speed is 50~1500r/
Min, preferably 100~1000r/min.It uses in the sweating effort of reactive emulsifier with the mass ratio of the acid such as sulfuric acid, nitric acid
Ammonia is absorbed for 2%~20% aqueous solution.
The oil soluble emulsifying agent is preferably the compound emulsifying agent that two or more surfactants are constituted.
In method of the invention, the salting liquid be any water-soluble salt solution, preferably chemical property it is stable, it is nontoxic,
It is non-corrosive, without special odor, salting liquid cheap and easy to get, such as can be molten selected from sodium chloride solution, Klorvess Liquid, sodium carbonate
At least one of one group of salting liquid that liquid, solution of potassium carbonate, metabisulfite solution and potassium sulfate solution are constituted.Concentration of salt solution is
1%~20%(mass, similarly hereinafter), preferably 5%~15%.
The emulsion ratio are as follows: paraffin 60.0%~90.0%, preferably 65.0%~84.0%；Water or salting liquid 9.9%
~30.0%, preferably 15.0%~30.0%；Compound emulsifying agent 0.1%~10.0%, preferably 1.0%~5.0%.The emulsification condition
To be mixed 5~60 minutes with 50~1500 revs/min of mixing speed, preferably at 85 DEG C~95 DEG C at 85 DEG C~98 DEG C
Under, it is mixed 10~30 minutes with 100~1000 revs/min of mixing speed.
In method of the invention, the preferred sweating ware of the sweatbox, and in wax layer pressurizing device added above and/or
Increase vacuum plant below wax layer.In step (B3) sweating effort, the wax layer that forces air flow through is used in wax layer
Top increases air pressure and/or reduces air pressure below wax layer, so that wax layer upper and lower is formed pressure difference and realizes.The pressure difference
Generally 0.1~5.0 atmospheric pressure, preferably 0.2~2.0 atmospheric pressure, to force air flow through wax layer.
In method of the invention, in the temperature-fall period of step (B2) described crystallization, preferred raw material wax layer is first with 10.0 DEG C/h
The rate of~30.0 DEG C/h is cooled within the scope of+4 DEG C of raw material fusing point~+8 DEG C of fusing point；Thereafter the cooling before high-temperature constant temperature section
Rate preferably 1.5 DEG C/h~2.5 DEG C/h.The proper temperature of the high-temperature constant temperature section of the temperature-fall period is paraffin fusing point -1.0
DEG C~+4.0 DEG C of fusing point, preferably paraffin fusing point~+2.0 DEG C of fusing point.The time of the high-temperature constant temperature section of cooling procedure be 0.1~
4.0 hours, preferably 0.5~4.0 hour, more preferably 1.0~4.0 hours.
In method of the invention, rate of temperature fall of the temperature-fall period of step (B2) described crystallization after high-temperature constant temperature section is excellent
Select 1.0 DEG C/h~2.0 DEG C/h.The cooling final temperature is preferably 8 DEG C~15 DEG C of starting paraffin fusing point or less.The drop
After temperature to final temperature, increasing the cryogenic thermostat stage so that solid crystal is more abundant, the time in cryogenic thermostat stage is 0.1~
3.0 hours, preferably 0.5~3.0 hour, more preferably 1.0~3.0 hours.
In method of the invention, the heating rate preferably 1.0 DEG C/h~2.0 DEG C/h of step (B3) described sweating effort.Institute
The predetermined temperature (i.e. final temperature) for stating heating is lower than 1 DEG C~10 DEG C of fusing point of purpose product.The sweating is warming up to predetermined
After temperature, increasing the constant temperature stage can be such that solids fraction separates with liquid composition more sufficiently, time in constant temperature stage for 0.1~
5.0 hours, preferably 0.5~5.0 hour, most preferably 1.0~5.0 hours.
In method of the invention, the heating rate and cooling rate of said wax layer can pass through air bath, water-bath, oil bath
Or other feasible modes are controlled, it is preferred to use water-bath or oil bath.Wax layer heating is controlled using water-bath or oil bath mode
When rate and rate of temperature fall, collet can be increased outside sweating ware, collet is connected with removable coil pipe and the circulatory system, collet, disk
Pipe etc. can make wax layer lifting/lowering temperature process faster, wax layer more uniform temperature；The circulatory system has program cooling/heating function, circulation
The substances such as water or conduction oil are added as circulatory mediator in system.
In method of the invention, wax layer is forced air flow through described in step (B3) can be in sweating effort any stage
Implement, preferably implements at sweating initial stage.
In method of the invention, wax layer is forced air flow through described in step (B3) and is utilized in increase gas above wax layer
What pressure was realized, it can such as apply the pressure of 0.2~2.0 atmospheric pressure (gauge pressure) above wax layer, and normal pressure is remained below wax layer.
In method of the invention, wax layer is forced air flow through described in step (B3) and is utilized in reduction gas below wax layer
What pressure was realized, normal pressure can be such as kept above wax layer, and the pressure of -0.2~-0.8 atmospheric pressure (gauge pressure) is maintained below wax layer
Power.
Sweating separation method is separated using various hydrocarbon molecules property with different melting points, for petroleum wax sweating
Process studies have shown that in sweating effort, liquid composition is gradually discharged along crystalline portion, be similar to liquid in capillary
The case where middle flowing.But the high melting point paraffin product for fusing point at 70 DEG C or so, due to isoparaffin and cycloalkanes in raw material
The substances such as hydrocarbon increase, and chemical composition is complicated, cause crystals upon crystallization structure more fine and compact, are formed to the discharge of liquid composition
Huge filter flow resistance power, this is resulted in only, and solids fraction is difficult to liquid composition in the common sweating effort of gravity natural separation
It is kept completely separate.Therefore common sweating process cannot prepare high latent heat hydro carbons phase-change material product of the fusing point at 70 DEG C or more.
The present invention is in order to allow this solvent-free separation method of sweating to produce the hydro carbons phase-change material of high latent heat, by right
Hydro carbons phase-change material performance and the relationship of its chemical composition and the further investigation of common sweating effort, for common petroleum wax product
It is that latent heat of phase change is small when it being caused to be used as hydro carbons phase-change material that carbon number distribution is lower compared with wide and normal paraffin content in chemical composition
And the reason that phase transformation range is wide, carbon number distribution width is reduced using sweating method and improves normal paraffin content simultaneously；For common
Solids fraction is difficult to the reason of separating with liquid composition in sweating effort, forces air flow through wax by using in sweating effort
Layer, and increase high temperature constant temperature stage and the processes such as cryogenic thermostat stage and the constant temperature stage of sweating effort in crystallization process；
Further preferably raw material and water or salting liquid are made emulsion and carry out sweating again simultaneously, these measures can satisfy the performance of product
The technical requirements of high latent heat phase-change material.
It is difficult to the reason of separating for solids fraction in sweating effort and liquid composition, by using gas in sweating effort
Stream forces the separation of solids fraction and liquid composition by the method that wax layer carries out liquid composition, enhances separating effect and adds
Fast separating rate；Increasing the high temperature constant temperature stage in crystallization process can make the crystallization of wax bigger, be conducive in sweating effort
The discharge of liquid composition.For wax crystallization process studies have shown that the chemical composition of wax be determine crystal habit it is main because
Element, while the condition of cooling procedure also will affect crystal habit, especially near fusing point at a temperature of cooling condition to knot
The influence of crystalline form state is most obvious.When being cooled near fusing point, the n-alkane of larger molecular weight has formed crystallization and has been precipitated wax, this
Partially crystallizable body can be used as the nucleus for being subsequently formed crystallization, increases the high temperature constant temperature stage at this time, nucleus can be enable abundant
Increase, forms larger sized crystal, although this larger sized crystal is coarse not as good as the crystallization of low melt point paraffin,
Be to the sweating stage discharge liquid composition be also highly beneficial.Simultaneously further preferably by raw material and water or salting liquid in appropriate HLB
W/o type emulsion is formed under the compound emulsifying agent effect of value, water or salting liquid is made to be evenly distributed on sweating in the form of fine particle
In raw material；Using air-flow on the one hand it is micro- to be formed in wax layer can be carried by wax layer for water outlet or salting liquid in sweating effort
Small space, these short spaces are easy to be formed several tiny channels in sweating effort in wax layer, are conducive to sweating effort
The discharge of middle liquid composition；Another aspect air-flow can carry out liquid composition to force separation solids fraction and liquid composition, from
And it enhances separating effect and accelerates separating rate.It selects salting liquid as water phase, increases the difference in specific gravity of water phase with oily phase,
It can accelerate the velocity of discharge of the water phase in sweating effort, to form the channel of discharge liquid composition as early as possible.Selected surfactant
Fusing point or freezing point are lower than the maximum temperature of sweating effort, and contain functional group, poor with the intermiscibility of paraffin, can be in sweating
It is discharged in the process with liquid composition.The cryogenic thermostat stage for being aided with crystallization process again keeps solid crystal more abundant, Yi Jifa
It is the methods of more abundant that the constant temperature stage of sweat process separates solids fraction with liquid composition, and sweating separating technology is allow to produce phase
Temperature is greater than the high latent heat phase-change material product of 210J/g in 70 DEG C or more, latent heat of phase change.
This have the advantage that: the side by carrying out liquid composition by wax layer using air-flow in sweating effort
Method forces the separation of solids fraction and liquid composition, enhances separating effect and accelerates separating rate；Increased using high temperature crystallization
Big crystalline size, while evenly dispersed short space is formed in wax layer using water or salting liquid, it is also beneficial to liquid composition
Quick discharge；And increase the processes such as the cryogenic thermostat stage of crystallization process and the constant temperature stage of sweating effort, to make to send out
Sweat technique can produce high latent heat phase-change material.Method of the invention is low with plant investment, production process is simple and operating cost
The advantages that with low, safety, energy conservation and solvent-free pollution environment.
Specific embodiment
Sweating ware top connects dismountable sealing device and connect with pressurized buffer tank and compressor, and/or in sweating
Ware lower part connects pressure-reducing cushioning tank and vacuum pump；Sweating ware is packed into after raw material and the emulsification of water or salting liquid；Wax layer is controlled with water-bath
Heating-cooling speed；Wax layer temperature be down to raw material melting temperature nearby and high temperature constant temperature for a period of time；Continue to be cooled to preset temperature
And cryogenic thermostat is for a period of time；In sweating effort, start compressor in wax layer positive pressure formed above, and/or starting vacuum
Pump is in wax layer negative pressure formed below, to force air flow through wax layer；When wax layer temperature reaches preset temperature and one section of constant temperature
Between after stop sweating effort；It is high latent heat phase-change material product after refining on wax.
1-4 illustrates the production method of the high latent heat phase-change material of the present invention by the following examples.In following instance, such as
Without special instruction, related % is mass percent.
Embodiment 1
The present embodiment includes: A: emulsification and B: sweating two parts.
A: emulsification
This part includes the preparation of (A1) oil phase material, the preparation of (A2) water-phase material, (A3) emulsion three steps of preparation.
(A1) prepared by oil phase material
Take No. 66 paraffin (Sinopec Jinan branch company, 66.35 DEG C of fusing point, oil content 0.71%, normal paraffin content
58.72%；Latent heat of phase change 186.37J/g) 80.0Kg, sorbitan monostearate is added after being heated to 90 DEG C of fusings
1.5Kg, diethylene glycol aliphatic ester 1.0Kg, tetraethylene glycol monostearate 0.5Kg, stir evenly.
(A2) prepared by water-phase material
The water of 17.0Kg is heated to 95 DEG C.
(A3) prepared by emulsion
With the oil phase material prepared in the speed stirring (A1) of 500r/min, and (A2) middle water-phase material prepared is slow
It is added in oil phase material, continues to stir 30min, form water-in-oil type emulsion.
B: sweating
This part includes (B1) preparation, (B2) cooling-high temperature constant temperature-cooling-cryogenic thermostat crystallization, (B3) liter
Temperature-constant temperature sweating, (B4) refine four steps.
(B1) preparation
The sealing system of sweating ware and pressurized buffer tank and compressor are connected；Pressure-reducing cushioning is installed in sweating ware lower part
Tank simultaneously connects vacuum pump；Sweating ware collet and removable coil pipe are connect with the circulatory system, coil pipe is fixed on sweating ware；With
Water is heat-conducting medium；The heating function for starting the circulatory system, makes recirculated water be warming up to 71 DEG C.Water is padded below sweating ware ware plate.It will
(A3) sweating ware is added in the emulsion prepared in.
(B2) cooling-high temperature constant temperature-cooling-cryogenic thermostat crystallization
Emulsion stands the refrigerating function of the starting circulatory system after 1.0h, makes wax layer temperature with the rate of temperature fall of 2.0 DEG C/h
67.3 DEG C and 2.0 hours progress high temperature constant temperatures of constant temperature are dropped to, so that crystal sufficiently increases；Again with the rate of temperature fall of 1.5 DEG C/h
Wax layer temperature is set to drop to 56.0 DEG C and 1.0 hours progress cryogenic thermostats of constant temperature, so that crystallization is more abundant.Close the circulatory system
Refrigerating function.
(B3) heating-constant temperature sweating
Sweating ware is discharged and pads water.Sweating ware outlet connection intermediate storage tank (I) is to receive under wax；The close of sweating ware top is installed
Envelope system；Starting compressor simultaneously keeps pressurized buffer pressure inside the tank to stablize in 1.4~1.6 atmospheric pressure (gauge pressure), sweating ware ware
Normal pressure is kept below plate；Start circulation system function, so that wax layer temperature is increased to 64.0 with the heating rate of 1.5 DEG C/h
℃.Stop compressor.
It opens vacuum pump and pressure-reducing cushioning pressure inside the tank is kept to stablize on -0.5~-0.7 atmospheric pressure (gauge pressure), wax layer
Square air pressure keeps normal pressure；Wax layer temperature is set to be increased to 70.0 DEG C and constant temperature 4.0 hours with the heating rate of 1.0 DEG C/h, so that wax
Solids fraction in layer is sufficiently separated with liquid composition.Stop vacuum pump, terminates sweating effort.
Sweating ware exports changing-over crude product storage tank (I) to receive on wax；Continue the temperature of raising recirculated water to 85 DEG C, with molten
Change and take out on wax, as crude product (I).
(B4) it refines
Crude product (I) is high latent heat phase-change material product (I) after clay-filtered.
High latent heat phase-change material product (I) property: fusing point (DSC method): 73.16 DEG C；Latent heat of phase change: 220.36J/g；Just
Structure Determination of Alkane Content 73.18%.The yield of high latent heat phase-change material product (I) is 10.2%(relative to No. 66 paraffin of raw material).
Embodiment 2
The present embodiment includes: A: emulsification and B: sweating two parts.
A: emulsification
This part includes the preparation of (A1) oil phase material, the preparation of (A2) water-phase material, (A3) emulsion three steps of preparation.
(A1) prepared by oil phase material
No. 66 paraffin (with embodiment 1) 80.0Kg are taken, diethylene glycol aliphatic ester is added after being heated to 90 DEG C of fusings
1.5Kg, sorbitan monostearate 1.0Kg, 0.5 Kg of Emulphor FM, stir evenly.
(A2) prepared by water-phase material
By the Na of 2.0Kg2CO3It is dissolved in the water of 15.0 Kg, and is heated to 95 DEG C.
(A3) prepared by emulsion
With the oil phase material prepared in the speed stirring (A1) of 500 r/min, and (A2) middle water-phase material prepared is slow
Slowly it is added in oil phase material, continues to stir 30min, form water-in-oil type emulsion.
B: sweating
With embodiment 1.
The present embodiment prepares high latent heat phase-change material product (II) property: fusing point (DSC method): 72.87 DEG C；Phase transformation is latent
Heat: 225.21J/g；Normal paraffin content 76.37%.The yield of high latent heat phase-change material product (II) is 12.5%(relative to original
Expect No. 66 paraffin).
Embodiment 3
The present embodiment includes: A: emulsification and B: sweating two parts.
A: emulsification
This part includes the preparation of (A1) oil phase material, the preparation of (A2) water-phase material, (A3) emulsion three steps of preparation.
(A1) prepared by oil phase material
No. 66 paraffin (with embodiment 1) 80.0Kg are taken, sorbitan monopalmitate is added after being heated to 90 DEG C of fusings
1.5Kg, sorbitan monooleate 0.5Kg, empgen BB 0.5Kg, stir evenly.
(A2) prepared by water-phase material
By the K of 2.0Kg2CO3It is dissolved in the water of 15.5 Kg, and is heated to 95 DEG C.
(A3) prepared by emulsion
With the oil phase material prepared in the speed stirring (A1) of 800 r/min, and (A2) middle water-phase material prepared is slow
Slowly it is added in oil phase material, continues to stir 50min, form water-in-oil type emulsion.
B: sweating
With embodiment 1.
High latent heat phase-change material product (III) property manufactured in the present embodiment: fusing point (DSC method): 72.36 DEG C；Phase transformation is latent
Heat: 224.35J/g；Normal paraffin content 75.69%.The yield of high latent heat phase-change material product (III) is 12.8%(relative to original
Expect No. 66 paraffin).
Embodiment 4
The present embodiment includes: A: the preparation of emulsifier, B: emulsification and C sweating three parts.
A: the preparation of emulsifier
The oleic acid of the linoleic acid and 2Kg that weigh 3Kg is placed in reaction kettle, and 10% ammonium hydroxide is added after being warming up to 30 DEG C
2.5Kg, starting are stirred, mixing speed 500r/min, and temperature is risen to 60 DEG C after reaction 60min, the ethyl alcohol of 0.75Kg is added,
It is stand-by after mixing to continue stirring 30min.
B: emulsification
This part includes the preparation of (B1) oil phase material, the preparation of (B2) water-phase material, (B3) emulsion three steps of preparation.
(B1) prepared by oil phase material
No. 66 paraffin (with embodiment 1) 80.0Kg are taken, emulsifier prepared by A process is added after being heated to 90 DEG C of fusings
1.0Kg, sorbitan mono-laurate 0.5Kg, 0.5 Kg of diethylene glycol aliphatic ester, stir evenly.
(B2) prepared by water-phase material
The KCl of 2.0Kg is dissolved in the water of 16.0 Kg, and is heated to 95 DEG C.
(B3) prepared by emulsion
With the oil phase material prepared in the speed stirring (B1) of 300 r/min, and (B2) middle water-phase material prepared is slow
Slowly it is added in oil phase material, continues to stir 60min, form water-in-oil type emulsion.
C: sweating
With 5%H in sweating effort2SO4Solution absorbs ammonia, remaining is the same as embodiment 1.
Product (IV) property manufactured in the present embodiment: fusing point (DSC method): 72.53 DEG C；Latent heat of phase change: 221.39J/g；
Normal paraffin content 75.08%.The yield of high latent heat phase-change material product (IV) is 11.9%(relative to No. 66 paraffin of raw material).
The production method that can be seen that the high latent heat phase-change material of the present invention by embodiment 1-4, by increase pressurization and/
Or the improvement to sweatbox such as vacuum facility；Evenly dispersed small sky is formed in wax layer using the water or salting liquid of emulsification
Between, force air flow through in sweating effort wax layer, increase crystallization and constant temperature stage of sweating effort etc. sweating process is changed
Into；It enhances the separating effect of solids fraction and liquid composition and accelerates separating rate, to make sweating separating technology can be with
Produce phase transition temperature 70 DEG C or more, latent heat of phase change 210J/g or more high latent heat phase-change material.
Claims (24)
1. a kind of production method of high latent heat phase-change material, including the following contents:
A: emulsification
(A1) prepared by oil phase material: using fusing point be 60 DEG C~74 DEG C, the paraffin less than 2.0 mass % of oil content is raw material, heating
Fusing；Oil soluble emulsifying agent is added, stirs evenly, forms oil phase material；
(A2) prepared by water-phase material: water or salting liquid being heated, water-phase material is formed；The salting liquid be selected from sodium chloride solution,
In one group of salting liquid that Klorvess Liquid, sodium carbonate liquor, solution of potassium carbonate, metabisulfite solution and potassium sulfate solution are constituted extremely
Few one kind；
(A3) prepared by emulsion: water-phase material being added in oil phase material under agitation, continues stirring 5 after all adding
~60 minutes；
B: sweating
(B1) emulsion of (A3) process preparation preparation: is packed into sweatbox；
(B2) it crystallizes: emulsion is cooled to by+4 DEG C of raw material fusing point~+10 DEG C of fusing point model with 5.0 DEG C/h~35.0 DEG C/h rate
In enclosing, then wax layer is cooled to by proper temperature with 1.0 DEG C/h~3.0 DEG C/h rate, high temperature constant temperature 0.1~4.0 hour；Again with
The rate of 0.5 DEG C/h~2.5 DEG C/h is cooled to 5 DEG C~20 DEG C of raw material fusing point or less of cooling final temperature, and cryogenic thermostat 0.1
~3.0 hours；The proper temperature is -1.0 DEG C of starting paraffin fusing point~+4.0 DEG C of fusing point；
(B3) sweating: with the heating of 0.5 DEG C/h~2.5 DEG C/h rate；Wax layer reaches predetermined temperature and constant temperature 0.1~5.0 hour
After stop sweating；Wax layer is forced air flow through in sweating effort；The predetermined temperature is lower than purpose product fusing point 1 DEG C~10
℃；
(B4) it refines: collecting on wax, be high latent heat phase-change material product after refining.
2. according to the method for claim 1, which is characterized in that the oil soluble emulsifying agent is living selected from non-ionic surface
Property agent, anionic surfactant, cationic surface active agent, amphoteric surfactant, response type surfactant active
The one group of substance constituted；The HLB value of oil soluble emulsifying agent is 1~10, and the fusing point or freezing point of the oil soluble emulsifying agent are lower than
Sweating heating maximum temperature.
3. according to the method for claim 2, which is characterized in that the nonionic surface active agent is selected from Sorbitan
Alcohol monoleate, sorbitan monostearate, diethylene glycol aliphatic ester, sorbitan monopalmitate, tetrem two
Alcohol monostearate, polyoxypropylene stearate, sorbitan mono-laurate, polyoxyethylene fatty acid ester constitute one group
Substance；The anionic surfactant be selected from fatty alcohol sulfate monoethanolamine salt, pareth sulfate,
Oleamide yl carboxylic acid sodium, sodium alkyl benzene sulfonate, N- methyl oleoyl taurate, sodium butylnaphthalenesulfonate, Disodium sulfosuccinate,
The one group of substance constituted along succinate monoester sodium sulfonate；The cationic surface active agent is selected from benzyl quaternary ammonium salt, 12
Zephiran, dodecyl trimethyl ammonium chloride, cetyl trimethylammonium bromide, octadecyl trimethyl
One group of substance that ammonium chloride, triacetamide oleate are constituted；The amphoteric surfactant be selected from empgen BB,
Dodecyldimethyl ammonium oxide, aliphatic group imidazolidine derivatives, alkyl imidazoline derivatives, derivative of fatty acid, both sexes
One group of substance that type modified epoxy ethane additive product is constituted.
4. according to the method for claim 2, which is characterized in that the oil soluble emulsifying agent is two or more surface-actives
The compound emulsifying agent that agent is constituted.
5. according to the method for claim 1, which is characterized in that the mass concentration of the salting liquid is 1%~20%.
6. according to the method for claim 1, which is characterized in that mixing speed described in step (A3) is 50~1500
Rev/min, the preparation temperature of emulsion is 85 DEG C~98 DEG C.
7. according to the method for claim 1, which is characterized in that step (A3) obtains the composition of emulsion are as follows: starting paraffin
Mass percent is 60.0%~90.0%, and the mass percent of water or salting liquid is 9.9%~30.0%, the quality percentage of emulsifier
Number is 0.1%~10.0%.
8. according to the method for claim 7, which is characterized in that the composition of the emulsion are as follows: starting paraffin quality percentage
Number is 65.0%~84.0%, and the mass percent of water or salting liquid is 15.0%~30.0%, and the mass percent of emulsifier is
1.0%~5.0%.
9. according to the method for claim 1, which is characterized in that proper temperature described in step (B2) is molten for starting paraffin
Point~+2.0 DEG C of fusing point.
10. according to the method for claim 1, which is characterized in that the predetermined temperature of cooling described in step (B2) is raw material
8 DEG C~15 DEG C below paraffin melting point.
11. according to the method for claim 1, which is characterized in that force air flow through wax layer described in step (B3) and exist
Sweating initial stage implements.
12. according to the method for claim 1, which is characterized in that force air flow through wax layer described in step (B3) and adopt
Increase air pressure above wax layer and/or reduce air pressure below wax layer, so that wax layer upper and lower is formed pressure difference and realize, it is described
Pressure difference is 0.1~5.0 atmospheric pressure.
13. according to the method for claim 12, which is characterized in that force air flow through wax layer described in step (B3) and adopt
Increase air pressure above wax layer to realize, applies the gauge of 0.2~2.0 atmospheric pressure above wax layer, and below wax layer
Remain normal pressure.
14. according to the method for claim 12, which is characterized in that force air flow through wax layer described in step (B3) and adopt
Air pressure is reduced below wax layer and realizes that air pressure keeps normal pressure above wax layer, and -0.2~-0.8 is maintained below wax layer
The gauge of atmospheric pressure.
15. according to the method for claim 2, which is characterized in that the response type surfactant active is by organic acid and ammonia
Water reaction, and Organic Alcohol is added and is made: organic acid and ammonium hydroxide is stirred to react 5 under conditions of 10~30 DEG C~it generates after sixty minutes
Organic acid ammonium salt；Under conditions of 60~70 DEG C, Organic Alcohol is added into the organic acid ammonium salt prepared, stirring makes it in 5~30 minutes
It is uniformly mixed to get response type surfactant active is arrived.
16. according to the method for claim 15, which is characterized in that the organic acid be carbon number 1~36 saturation and
Unsaturated acids.
17. according to the method for claim 16, which is characterized in that the organic acid is selected from caprylic acid, acid of the positive tenth of the twelve Earthly Branches, the positive last of the ten Heavenly stems
Acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitinic acid, stearic acid, linoleic acid, oleic acid, nonadecanoic acid, peanut
Acid, oxalic acid, malic acid, citric acid, maleic acid, fumaric acid constitute one or more of one group of substance.
18. according to the method for claim 15, which is characterized in that the mass concentration of the ammonium hydroxide is 1%~25%.
19. according to the method for claim 15, which is characterized in that the Organic Alcohol is saturation one of the carbon number 1~12
First alcohol.
20. according to the method for claim 1, which is characterized in that the sweatbox is sweating ware.
21. according to the method for claim 5, which is characterized in that the mass concentration of the salting liquid is 5%~15%.
22. according to the method for claim 12, which is characterized in that the pressure difference is 0.2~2.0 atmospheric pressure.
23. according to the method for claim 16, which is characterized in that the organic acid be carbon number 8~20 unitary or
Multicomponent organic acid.
24. according to the method for claim 19, which is characterized in that the Organic Alcohol is methanol and/or ethyl alcohol.
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| GB687235A (en) * | 1950-03-24 | 1953-02-11 | Bataafsche Petroleum | Improvements in and relating to the treatment of paraffin wax |
| 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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| GB687235A (en) * | 1950-03-24 | 1953-02-11 | Bataafsche Petroleum | Improvements in and relating to the treatment of paraffin wax |
| 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 |
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