CN103102868A - Hydrocarbon phase change heat storage material and preparation method thereof with natural acid as raw material - Google Patents
Hydrocarbon phase change heat storage material and preparation method thereof with natural acid as raw material Download PDFInfo
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- CN103102868A CN103102868A CN2011103534539A CN201110353453A CN103102868A CN 103102868 A CN103102868 A CN 103102868A CN 2011103534539 A CN2011103534539 A CN 2011103534539A CN 201110353453 A CN201110353453 A CN 201110353453A CN 103102868 A CN103102868 A CN 103102868A
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Abstract
The invention relates to a hydrocarbon phase change heat storage material and a preparation method thereof with natural acid as a raw material. According to the invention, a natural acid raw material and a solvent are mixed and then undergo a hydrogenation reaction in the presence of a catalyst and hydrogen so as to prepare corresponding n-alkanes with an even carbon number and high purity, and the n-alkanes with an even carbon number and a mixture thereof are a high performance hydrocarbon phase change heat storage material which is especially applicable to preparation of a 5-DEG C to 10-DEG C heat storage material needed by refrigeration of an air-conditioner. Compared with the prior art, the invention has the following advantages: the preparation method is simple, and the prepared hydrocarbon phase change heat storage material has great latent heat of phase change.
Description
Technical field
The invention belongs to the special wax technical field, particularly relate to natural acid and prepare high performance hydro carbons phase change heat storage material through suitable treatment.
Background technology
Power supply take mineral fuel such as oil, Sweet natural gas, coals as main, along with minimizing, the price rising of these Nonrenewable resources reserves, is constantly strengthened the research of various substitute energys in the world; And the environmental problem of using these mineral fuel to cause is on the rise, and is in widespread attention to utilizing of energy-conservation and sun power etc.Simultaneously, along with the development of society, people are more and more higher to the requirement of residence comfort, and this requires again to consume the more energy.
Both at home and abroad utilize phase change material (be called for short PCM, Phase Change Material) store sun power and at a low price the research of electric energy aspect be very active at present field.These researchs are to utilize phase change material temperature variation in fusing or process of setting little, but the very large characteristic of latent heat that absorbs or discharge, it is combined with material of construction, can play reduce indoor temperature fluctuation, utilize solar heating with reduce air-conditioning and heating system energy consumption or utilize night at a low price electric energy keep the effects such as indoor temperature, thereby accomplish and take full advantage of the energy, reduce the purpose of polluting and satisfy comfortable for living.Simultaneously, phase change material is also underway for the research of the numerous areas such as fabric, electric prospection.
By the difference of chemical constitution, phase change material can be divided into inorganic phase-changing material and organic phase change material, in 5 ℃ of can touch in mankind's daily life～30 ℃ scope, organic phase change material more has superiority.Compare with phase change materials such as other alcohol, acid, esters, the hydro carbons phase change heat storage material has the advantages such as latent heat of phase change is high, price is relatively low.
The preparation method of normal paraffin mainly contains at present: (1) takes molecular sieve or urea dewaxing to prepare the mixture of normal paraffin; (2) take the symmetrical normal paraffin of Woertz reaction preparation; (3) adopt the alkane iodide method of reducing; (4) use sherwood oil and normal hexane, normal heptane to make solvent link haloalkane method.Although above method can access corresponding normal paraffin monomer, all there is certain problem in each method: as first method processing condition more complicated, require very high to some equipment, material; Second method is only applicable to symmetry even number alkane, and generating article needs ether solvent repeatedly to extract; Third and fourth kind method operational danger is large, and sherwood oil is very easily eruption in sodium Metal 99.5 and haloalkane vigorous reaction, and safety coefficient is low, and cost is higher.
Can prepare alkane with the higher fatty acid ester through hydrogenation, but in hydrogenation process, a large amount of decarboxylic reaction and decarbonylation reaction can occur, make reaction product form complicated, can produce the alkane that more carbon number reduces, be unfavorable for improving on the one hand the productive rate of purpose product, decarboxylic reaction and decarbonylation reaction can produce carbon monoxide or carbonic acid gas on the other hand, can produce adverse influence to hydrogenation reaction.In addition, during for the higher product of the single carbon number normal paraffin of needs purity, what aforesaid method obtained is to mix normal paraffin, and boiling point is close, not easily separated.a kind of method of preparing alkane by high fatty acid ester is disclosed as CN200910100260.5, take the fatty acid methyl ester that contains 8～22 carbon atoms or the fatty-acid ethyl ester that contains 8～22 carbon atoms as raw material, carry out hydrogenation reaction and produce alkane, but can find out, in the alkane product that obtains, carbon in lipid acid still has major part to be removed, as take stearic acid methyl ester (stearic acid is as 18 carbon carboxylic acids) as raw material, the heptadecane hydrocarbon that obtains and the total recovery of octodecane hydrocarbon only have 75%, therefore, the yield of the product of decarburization direct hydrogenation (octodecane hydrocarbon) can be not lower.Simultaneously, the boiling point of heptadecane hydrocarbon and octodecane hydrocarbon differs very little, further obtains the octodecane hydrocarbon by isolation technique very difficult.
Preparing Wax take oil as raw material need to be through complicated purification and treating process, not only production cost is high, and still have the non-suitable component of some amount for the hydro carbons phase-transition heat-storage, as oils etc., the existence of these non-suitable components has affected the use properties of phase change heat storage material.Simultaneously, compare with even carbon number normal paraffin, the latent heat of phase change of odd-carbon number normal paraffin is less than normal.If adopt the precise distillation mode to extract various monomer normal paraffins, more even carbon number normal paraffin be mixed with transformation temperature continually varying phase change material, because cost is too high, can not practical application.
Summary of the invention
For the deficiencies in the prior art, the invention provides and a kind ofly prepare the method for hydro carbons phase change heat storage material and the hydro carbons phase change heat storage material that the method obtains with natural acid, the inventive method technique is simple, and the product latent heat of phase change is large.
Hydro carbons phase change heat storage material of the present invention comprises positive structure tetradecane hydrocarbon and normal cetane hydrocarbon, and the mass ratio of positive structure tetradecane hydrocarbon and normal cetane hydrocarbon is 1:99～99:1.
The transformation temperature of phase change material is 5～18 ℃.The latent heat of phase change of phase change material is 180～220J/g.
Positive structure tetradecane hydrocarbon is the n-tetradecane hydrocarbon that tetradecanoic acid obtains at Pd/MWCNTs catalyzer (palladium/multi-walled carbon nano-tubes catalyzer) hydrogenation.The normal cetane hydrocarbon is the n-hexadecane hydrocarbon that palmitinic acid obtains at Pd/MWCNTs catalyzer (palladium/multi-walled carbon nano-tubes catalyzer) hydrogenation.Can contain the normal paraffin of other a small amount of carbon number in hydrogenation products, need not separate, so may contain the normal paraffin of a small amount of other carbon number in the finished product.
Can contain other suitable component in hydro carbons phase change heat storage material of the present invention, as antioxidant, sanitas etc.
Preparation method's process take natural acid as raw material of hydro carbons phase change heat storage material of the present invention comprises: tetradecanoic acid or palmitinic acid and solvent, carry out hydrogenation reaction under catalyzer and hydrogen exist, reaction product is isolated to be mixed in proportion after unreacting material and is the hydro carbons phase change heat storage material; Catalyzer is palladium/multi-walled carbon nano-tubes catalyzer, and the reaction pressure of hydrogenation reaction is 1～10MPa, is preferably 2～8MPa, and temperature of reaction is 220～320 ℃, is preferably 260～300 ℃, and the reaction times is 3～10 hours, is preferably 4～7 hours.
In hydro carbons phase change heat storage material preparation method of the present invention, hydrogenation process can adopt intermittent reaction, also can adopt continuous reaction.When adopting intermittent reaction, be preferably under agitation condition and carry out, natural acid raw material (tetradecanoic acid or palmitinic acid) is l.0～2.5:0.2～0.5 with the volume ratio of catalyzer.When adopting continuous reaction, hydrogen and liquid phase (natural acid raw material and the solvent) volume ratio under standard state is 100:1～1200:1, is preferably 300:1～800:1.
In the inventive method, preferably contain the NH of 5～50 μ L/L in the hydrogen that hydrogenation reaction is used
3, be preferably 10～20 μ L/L, to improve the selectivity of purpose product.
In the inventive method, the natural acid raw material is n-teradecanoic acid (tetradecanoic acid) or Palmiticacid (palmitinic acid).
In the inventive method, solvent is one or more in normal hexane, normal heptane, octane or dodecane, and the volume ratio of natural acid raw material and solvent is: l.0～2.5:7～20.
In the inventive method, catalyzer is take multi-walled carbon nano-tubes as carrier, take the palladium of quality percentage composition 2%～10% as active ingredient.Multi-walled carbon nano-tubes is common commercial goods.
The preparation method of used catalyst of the present invention is as follows: under 50～100 ℃ of conditions, with the HNO of 2～8Mol/L
3Multi-walled carbon nano-tubes is carried out oxide treatment 1～5h, then filter, be washed to neutrality, 100～150 ℃ of oven dry; Then be added to the water, ultra-sonic dispersion adds H by the quality percentage composition 2%～10% of palladium in catalyzer
2PdC1
4Solution adds formaldehyde solution after stirring, and regulates PH value to 8～11 with Na0H solution, and stirring, filtration, washing, oven dry obtain the Pd/MWCNTs catalyzer.
Find through large quantity research, method of hydrotreating of the present invention has very high catalytic activity and purpose selectivity of product to the hydrogenation deoxidation of natural acid, and decarboxylic reaction and decarbonylation reaction are seldom, when particularly containing a small amount of ammonia in hydrogen, the selectivity of purpose product is higher.Compared with prior art, the present invention has: the catalyzer preparation is simple, can be recycled; Temperature of reaction is low; Solvent is cheap, consumption is few, be easy to recycling; Process operation is flexible; Purpose product selectivity high.
In the inventive method, adopt the relatively large even carbon number normal paraffin of latent heat of phase change to mix, can prepare the high performance hydro carbons phase change heat storage material of transformation temperature continually varying between 5～18 ℃.Compared with prior art, preparation technology of the present invention is simple, and the product latent heat of phase change is large.
Embodiment
Embodiment 1
(1) catalyzer preparation
Use 6M HNO in 80 ℃ of oil baths
3Multi-walled carbon nano-tubes (commercial goods, purity〉95%, diameter 40～60nm, length 5～15 μ m, nanometer port, Shenzhen company limited provides) is carried out oxide treatment 2h; Then filter, be washed to neutrality, 120 ℃ of oven dry; Get the carbon nanotube that above-mentioned oxide treatment is crossed, add 70mL water, ultra-sonic dispersion; Palladium by quality percentage composition 2%～10% is that active ingredient adds H
2PdC1
4Solution adds formaldehyde solution after stirring, and regulates pH value to 9 with 1M NaOH solution, stirs 25min, filter, and massive laundering, oven dry obtains Pd/ multi-walled carbon nano-tubes catalyzer (Pd/MwCNTs).
Prepare as stated above two kinds of catalyzer: catalyzer 1(palladium mass content is 4%) and catalyzer 2(palladium mass content be 7%).
(2) tetradecanoic acid hydrogenation deoxidation
2.0 parts of (parts by volume, lower same) tetradecanoic acids, 0.5 part of Pd/MwCNTs catalyzer 2 and 18 parts of normal hexanes are added in the 100mL reactor, be filled with the hydrogen (NH that contains 20 μ L/L
3), initial hydrogen pressure 6.0MPa opens and stirs and heating, stopped reaction after 300 ℃ of reaction 7h,, to be cooled to room temperature, filter to isolate catalyzer.
With gas-chromatography, product is carried out detection by quantitative, the transformation efficiency of tetradecanoic acid is 97% as can be known, and the yield of product n-tetradecane is 97%.
Product is carried out DSC detect, transformation temperature is 5.7 ℃, and heat of phase transformation is 200.8J/g.
(3) palmitinic acid hydrogenation deoxidation
1.5 parts of palmitinic acids, 0.4 part of Pd/MwCNTs catalyzer 2 and 16 parts of normal hexanes are added in the 100mL reactor, be filled with the hydrogen (NH that contains 5 μ L/L
3), initial hydrogen pressure 5.0MPa opens and stirs and heating, and stopped reaction after 260 ℃ of reaction 7h is to be cooled to room temperature, filters to isolate catalyzer.
With gas-chromatography, product is carried out detection by quantitative, the transformation efficiency of palmitinic acid is 98% as can be known, and the yield of product n-hexadecane is 96%.
Product is carried out DSC detect, transformation temperature is 18.5 ℃, and heat of phase transformation is 220.5J/g.
(4) hydro carbons phase change heat storage material preparation
N-tetradecane and the n-hexadecane of above-mentioned preparation are pressed the 90:10(weight ratio) mix.
Product detects through DSC, and transformation temperature is 6.9 ℃, and heat of phase transformation is 182.5J/g.
Change the blending ratio of n-tetradecane and the n-hexadecane of above-mentioned preparation, can prepare transformation temperature high performance phase change material of continually varying between 5～18 ℃.
Embodiment 2
(1) catalyzer preparation (with embodiment 1)
(2) tetradecanoic acid hydrogenation.
With 2.5 parts of (parts by volume, down together) tetradecanoic acid, 0.3 part of Pd/MwCNTs catalyzer 1 and 20 parts of normal hexanes add in the 100mL reactor, be filled with hydrogen, initial hydrogen pressure 2.5MPa, open and stir and heating, stopped reaction after 280 ℃ of reaction 6h, to be cooled to room temperature, filter to isolate catalyzer.With gas-chromatography, product is carried out detection by quantitative, the transformation efficiency of raw meat myristic acid is 82% as can be known, and the total recovery of the product tetradecane is the 76%(molar yield, and the product n-tetradecane accounts for the per-cent of raw meat myristic acid, and is lower same).
(3) palmitinic acid hydrogenation deoxidation.
With 2.5 parts of (parts by volume, down together) Palmiticacid, 0.3 part of Pd/MwCNTs catalyzer 1 and 20 parts of octanes add in the 100mL reactor, be filled with hydrogen, initial hydrogen pressure 5.0MPa, open and stir and heating, stopped reaction after 280 ℃ of reaction 6h, to be cooled to room temperature, filter to isolate catalyzer.With gas-chromatography, product is carried out detection by quantitative, the transformation efficiency of raw material Palmiticacid is 99% as can be known, and the total recovery of product n-hexadecane hydrocarbon is the 91%(molar yield, and product n-hexadecane hydrocarbon accounts for the per-cent of raw material Palmiticacid).
(4) hydro carbons phase change heat storage material preparation
N-tetradecane and the n-hexadecane of above-mentioned preparation are pressed the 25:75(weight ratio) mix.
Product detects through DSC, and transformation temperature is 15.8 ℃, and heat of phase transformation is 193.6J/g.
Comparative example:
As described in patent CN200910204257.8, take fischer-tropsch synthesis product as raw material, carry out hydrocracking under catalyzer exists, then be the phase change material of 15.8 ℃ through the transformation temperature that distillation prepares, its latent heat of phase change is 157.0J/g.The transformation temperature of the phase change material of the embodiment of the present invention 2 preparations is 15.8 ℃, and heat of phase transformation is 193.6J/g.
Claims (10)
1. hydro carbons phase change heat storage material, it is characterized in that: the hydro carbons phase-transition heat-storage comprises positive structure tetradecane hydrocarbon and normal cetane hydrocarbon, the mass ratio of positive structure tetradecane hydrocarbon and normal cetane hydrocarbon is 1:99～99:1.
2. according to hydro carbons phase change heat storage material claimed in claim 1, it is characterized in that: the transformation temperature of hydro carbons phase change heat storage material is 5～18 ℃.
3. according to the described hydro carbons phase change heat storage material of claim 1 or 2, it is characterized in that: the latent heat of phase change of hydro carbons phase change heat storage material is 180～220J/g.
4. according to hydro carbons phase change heat storage material claimed in claim 1, it is characterized in that: positive structure tetradecane hydrocarbon is the tetradecanoic acid n-tetradecane hydrocarbon that hydrogenation obtains on the Pd/MWCNTs catalyzer, and the normal cetane hydrocarbon is the palmitinic acid n-hexadecane hydrocarbon that hydrogenation obtains on the Pd/MWCNTs catalyzer.
5. the preparation method of the described hydro carbons phase change heat storage material of claim 1, it is characterized in that: tetradecanoic acid or palmitinic acid and solvent, carry out hydrogenation reaction under catalyzer and hydrogen exist, reaction product is isolated to be mixed in proportion after unreacting material and is the hydro carbons phase change heat storage material; Catalyzer is palladium/multi-walled carbon nano-tubes catalyzer, and the reaction pressure of hydrogenation reaction is 1～10MPa, and temperature of reaction is 220～320 ℃, and the reaction times is 3～10 hours.
6. in accordance with the method for claim 5, it is characterized in that: the reaction pressure of hydrogenation reaction is 2～8MPa, and temperature of reaction is 260～300 ℃, and the reaction times is 4～7 hours.
7. in accordance with the method for claim 5, it is characterized in that: hydrogenation process adopts intermittent reaction, perhaps adopts continuous reaction; When adopting intermittent reaction, be preferably under agitation condition and carry out, the volume ratio of tetradecanoic acid or palmitinic acid and catalyzer is l.0～2.5:0.2～0.5; When adopting continuous reaction, hydrogen and the liquid phase volume ratio under standard state is 100:1～1200:1.
8. it is characterized in that in accordance with the method for claim 5: the NH that contains 5～50 μ L/L in the hydrogen that hydrogenation reaction is used
3, be preferably 10～20 μ L/L, to improve the selectivity of purpose product.
9. in accordance with the method for claim 5, it is characterized in that: solvent is one or more in normal hexane, normal heptane, octane or dodecane, and the volume ratio of tetradecanoic acid or palmitinic acid raw material and solvent is: l.0～2.5:7～20.
10. in accordance with the method for claim 5, it is characterized in that: catalyzer is take multi-walled carbon nano-tubes as carrier, take the palladium of quality percentage composition 2%～10% as active ingredient.
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Cited By (4)
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| CN109628069A (en) * | 2018-12-24 | 2019-04-16 | 北京三聚环保新材料股份有限公司 | A kind of phase-changing energy storage material and preparation method thereof |
| CN109762528A (en) * | 2018-12-24 | 2019-05-17 | 北京三聚环保新材料股份有限公司 | A kind of phase-changing energy storage material and preparation method thereof |
| US11377598B2 (en) | 2018-05-11 | 2022-07-05 | Sabic Global Technologies B.V. | Method related to heat transfer for exothermic reactions |
| CN115247050A (en) * | 2021-04-27 | 2022-10-28 | 协同油脂株式会社 | Cold and heat storage agent composition |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US11377598B2 (en) | 2018-05-11 | 2022-07-05 | Sabic Global Technologies B.V. | Method related to heat transfer for exothermic reactions |
| CN109628069A (en) * | 2018-12-24 | 2019-04-16 | 北京三聚环保新材料股份有限公司 | A kind of phase-changing energy storage material and preparation method thereof |
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| CN115247050A (en) * | 2021-04-27 | 2022-10-28 | 协同油脂株式会社 | Cold and heat storage agent composition |
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