CN103773315A - Hydrocarbon phase change heat storage materials and preparation method using natural acid as raw material - Google Patents
Hydrocarbon phase change heat storage materials and preparation method using natural acid as raw material Download PDFInfo
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Abstract
The invention discloses hydrocarbon phase change heat storage materials and a preparation method using natural acid as a raw material. A natural acid raw material is mixed with a solvent for hydrogenation reaction in the presence of a catalyst and hydrogen to prepare corresponding high-purity even-carbon-number n-alkanes, the even-carbon-number n-alkanes and mixtures thereof are the high-performance hydrocarbon phase change heat storage materials, and the preparation method is particularly applicable to preparing of the hydrocarbon phase change heat storage materials at 36-45 DEG C. Compared with the prior art, the preparation method is simple, and the latent heat of phase change of a product is high.
Description
Technical field
The invention belongs to special wax technical field, particularly relate to take natural acid as raw material 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 of these Nonrenewable resources reserves raise, is constantly strengthened the research of various substitute energys in the world; And the environmental problem that uses these mineral fuel to cause is on the rise, in widespread attention to utilizing of energy-conservation and sun power etc.Meanwhile, along with social development, people are more and more higher to the requirement of residence comfort, and this requires again to consume the more energy.
Current very active field in the research that utilizes hydro carbons phase change heat storage material (being called for short PCM, Phase Change Material) to store sun power and low price electric energy aspect both at home and abroad.These researchs are to utilize hydro carbons phase change heat storage 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 maintain the effects such as indoor temperature, thereby accomplish to make full use of the energy, reduce the object of polluting and meet comfortable for living.Meanwhile, hydro carbons phase change heat storage material is also underway for the research of the numerous areas such as fabric, electric prospection.For example, CN200410046099.5 discloses a kind of Phase change heat insulation mortar of paraffin and its preparation method, introduce and will after the emulsification of wax class hydro carbons phase change heat storage material, sneak in mortar, this material has heat-accumulation temperature-adjustment function, heat-insulating property excellence, heat-proof quality is good, can be widely used in the heat insulating engineering of industry and covil construction building enclosure, is particularly useful for the heat insulating engineering of Xia Redong cryogenic region and hot summer and warm winter region buildings.CN200410101555.1 discloses a kind of mineral wax composite shape-setting hydro carbons phase change heat storage material and preparation method, utilizing transformation temperature is that the wax class hydro carbons phase change heat storage material of 44～50 ℃ is prepared without container encloses, energy storage material that can direct contact heat transfer WATER AS FLOW MEDIUM.CN200710014607.5 discloses a kind of phase-change energy-storage fibre and preparation method thereof, introduce 10～60 ℃ of transformation temperatures are sneaked into and in fiber, prepared phase-change energy-storage fibre, the method technique is simple, effectively reduce the loss of hydro carbons phase change heat storage material in fiber process process, the content that has improved hydro carbons phase change heat storage material in the fiber making, the phase change energy storage function of phase-change energy-storage fibre and the physical and mechanical properties of fiber are good.
By the difference of chemical constitution, hydro carbons phase change heat storage material can be divided into inorganic hydro carbons phase change heat storage material and organic hydrocarbon phase change heat storage material.Within the scope of 0 ℃～50 ℃, organic hydrocarbon phase change heat storage material more has superiority.Compared with the hydro carbons phase change heat storage materials such as other alcohol, acid, ester, wax class 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 alkane iodide method of reducing; (4) use sherwood oil and normal hexane, normal heptane to make solvent link haloalkane method.Although above method can obtain 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 of 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.
CN200810151995.6 discloses a kind of synthetic and New Method of Purification of NSC 62789, and the step of its preparation method comprises: mix positive structure butyl bromide (1) with bromo n-hexadecane; (2) after sherwood oil is mixed with mixed solution, add sodium, back flow reaction 1～2 hour; (3) drip after dehydrated alcohol, water, separate organic phase and be washed to neutrality; (4) cut of 320～360 ℃ is collected in distillation, through wash colourless to organic phase or be faint yellow after, be washed to neutrality; (5) by after dry organic phase rear filtration, absorption, in the middle of underpressure distillation collection, just cut obtains NSC 62789 product.
Can prepare alkane with higher fatty acid ester through hydrogenation, but in hydrogenation process, can there is a large amount of decarboxylic reaction and decarbonylation reaction, make reaction product composition complicated, can produce the alkane that more carbon number reduces, the productive rate that is unfavorable for improving on the one hand object 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.
CN200910100260.5 discloses a kind of method of preparing alkane by high fatty acid ester, 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, carries out hydrogenation reaction and produces alkane.But can find out, in the alkane product obtaining, carbon in lipid acid still has major part to be removed, as take eicosanoic acid formicester (eicosanoic acid is as 18 carbon carboxylic acids) as raw material, the heptadecane hydrocarbon obtaining 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.Meanwhile, the boiling point of heptadecane hydrocarbon and octodecane hydrocarbon differs very little, further obtains octodecane hydrocarbon by isolation technique very difficult.
Prepare Wax take oil as raw material and need to pass through complicated purification and treating process, not only production cost is high, and for hydro carbons phase change heat storage material, still there is the non-suitable component of some amount, as oils etc., the existence of these non-suitable components has affected the use properties of hydro carbons phase change heat storage material.Meanwhile, compared with even carbon number normal paraffin, the latent heat of phase change of odd-carbon number normal paraffin is less than normal.If adopt precise distillation mode to extract various monomer normal paraffins, more even carbon number normal paraffin be mixed with to transformation temperature continually varying hydro carbons phase change heat storage material, because cost is too high, can not practical application.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of method of hydro carbons phase change heat storage material and hydro carbons phase change heat storage material that the method obtains prepared take natural acid as raw material, the inventive method technique is simple, and product latent heat of phase change is large.
Hydro carbons phase change heat storage material provided by the invention, comprises positive structure eicosane hydrocarbon and positive structure docosane hydrocarbon, and its mass ratio is 1:99～99:1.The transformation temperature of hydro carbons phase change heat storage material is 36～45 ℃.The latent heat of phase change of hydro carbons phase change heat storage material is 200～230 J/g.
Wherein said positive structure eicosane hydrocarbon is that eicosanoic acid obtains at Pd/MWCNTs catalyzer (palladium/multi-walled carbon nano-tubes catalyzer) hydrogenation.Positive structure docosane hydrocarbon is that behenic acid obtains at Pd/MWCNTs catalyzer (palladium/multi-walled carbon nano-tubes catalyzer) hydrogenation.
In hydro carbons phase change heat storage material of the present invention, can contain other suitable component, as antioxidant, sanitas etc.
The present invention prepares hydro carbons phase change heat storage material process take natural acid as raw material comprises: eicosanoic acid or behenic acid and solvent, under catalyzer and hydrogen exist, carry out hydrogenation reaction, reaction product is isolated after unreacting material and is mixed in proportion and is hydro carbons phase change heat storage material.Catalyzer is palladium/multi-walled carbon nano-tubes catalyzer, and the reaction pressure of hydrogenation reaction is 1～10 MPa, is preferably 2～8 MPa, 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.While adopting intermittent reaction, be preferably under agitation condition and carry out, natural acid raw material (eicosanoic acid or behenic acid) is l.0～2.5: 0.2～0.5 with the volume ratio of catalyzer.While 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, in the hydrogen that hydrogenation reaction is used, preferably contain the NH of 5～50 μ L/L
3, preferably contain the NH of 10～20 μ L/L
3, to improve the selectivity of object product.
In the inventive method, wherein natural acid raw material is NSC 62789 acid (eicosanoic acid) and behenic acid (behenic 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, described catalyzer is take multi-walled carbon nano-tubes as carrier, take the palladium of quality percentage composition 2%～10% as active ingredient.Wherein multi-walled carbon nano-tubes is common commercial goods.
The preparation method of the present invention's Pd/MWCNTs catalyzer used is generally as follows: under 50～100 ℃ of conditions, with the HNO of 2～8mol/L
3multi-walled carbon nano-tubes is carried out to oxide treatment 1～5h, then filter, be washed to neutrality, 100～150 ℃ of oven dry; Then be added to the water, ultrasonic dispersion, adds H by the quality percentage composition 2%～10% of palladium in catalyzer
2pdC1
4solution, adds formaldehyde solution after stirring, and with NaOH solution adjusting pH value to 8～11, stirs, filters, washes, dries, and obtains Pd/MWCNTs catalyzer.
Find through large quantity research, method of hydrotreating of the present invention, has very high catalytic activity and object selectivity of product to the hydrogenation deoxidation of natural acid, and decarboxylic reaction and decarbonylation reaction are little, while particularly containing a small amount of ammonia in hydrogen, the selectivity of object product is higher.Compared with prior art, the present invention has: catalyzer preparation is simple, can be recycled; Temperature of reaction is low; Solvent cheapness, consumption be few, be easy to recycle; Process operation is flexible; Object 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 36～45 ℃.Compared with prior art, preparation technology of the present invention is simple, and the hydro carbons phase change heat storage material latent heat making is large.
Embodiment
Embodiment 1
(1) catalyzer preparation
In 80 ℃ of oil baths, use the HNO of 6M
3multi-walled carbon nano-tubes (diameter 40～60nm, length 5～15 μ m, nanometer port, Shenzhen company limited provides for commercial goods, purity >95%) is carried out to 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, ultrasonic dispersion; Add H by the content of palladium quality percentage composition 2%～10% in catalyzer
2pdC1
4solution, adds formaldehyde solution after stirring, and by the NaOH solution adjusting pH value to 9 of 1M, stirs 25min, filters, and massive laundering, dries, and 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) eicosanoic acid hydrogenation deoxidation
1.5 parts of eicosanoic acids, 1 and 16 parts of normal hexanes of 0.4 part of Pd/MwCNTs catalyzer are added in 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, isolates unreacted product.By gas-chromatography, product is carried out to detection by quantitative, known eicosanoic acid transformation efficiency is 89%, and the yield of product NSC 62789 is 85%.
Product is carried out to DSC detection, and transformation temperature is 36.2 ℃, and heat of phase transformation is 226.3J/g.
(3) behenic acid hydrogenation deoxidation
1.5 parts of behenic acids, 2 and 16 parts of normal hexanes of 0.4 part of Pd/MwCNTs catalyzer are added in 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, isolates unreacted product.By gas-chromatography, product is carried out to detection by quantitative, the transformation efficiency of known raw material behenic acid is 90%, and the yield of product n-docosane is 85%.
Product is carried out to DSC detection, and transformation temperature is 45.1 ℃, and heat of phase transformation is 228.8J/g.
(4) hydro carbons phase change heat storage material preparation
The NSC 62789 of above-mentioned preparation and n-docosane were mixed by weight 10: 90.
Product detects through DSC, and transformation temperature is 44.3.1 ℃, and heat of phase transformation is 225.7J/g.
Change the NSC 62789 of above-mentioned preparation and the blending ratio of n-docosane, can prepare the high performance hydro carbons phase change heat storage material of transformation temperature continually varying between 36～45 ℃.
Embodiment 2
(1) catalyzer preparation (with embodiment 1).
(2) eicosanoic acid hydrogenation
2.0 parts of eicosanoic acids, 2 and 18 parts of normal hexanes of 0.5 part of Pd/MwCNTs catalyzer are added in 100mL reactor, be filled with hydrogen (NH3 that contains 20 μ L/L), initial hydrogen pressure 6.0MPa, open and stir and heating, stopped reaction after 300 ℃ of reaction 7h, to be cooled to room temperature, filter to isolate catalyzer.By gas-chromatography, product is carried out to detection by quantitative, known eicosanoic acid transformation efficiency is 94%, and the yield of product NSC 62789 is 88%.
(3) behenic acid hydrogenation deoxidation
2.0 parts of behenic acids, 1 and 18 parts of normal hexanes of 0.5 part of Pd/MwCNTs catalyzer are added in 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, and stopped reaction after 300 ℃ of reaction 7h is to be cooled to room temperature, filters to isolate catalyzer, isolates unreacted product.By gas-chromatography, product is carried out to detection by quantitative, the transformation efficiency of known raw material behenic acid is 95%, and the yield of product n-docosane is 90%.
(4) NSC 62789 of above-mentioned preparation and n-docosane were mixed by weight 90: 10.
Product detects through DSC, and transformation temperature is 37.1 ℃, and heat of phase transformation is 225.3J/g.
Comparative example 1
As described in patent CN200910204257.8, take fischer-tropsch synthesis product as raw material, under catalyzer exists, carry out hydrocracking, then be the hydro carbons phase change heat storage material of 35 ℃ through the transformation temperature of distillation preparation, its latent heat of phase change is 140～220 J/g.The transformation temperature of hydro carbons phase change heat storage material prepared by the embodiment of the present invention 2 is 37.1 ℃, and heat of phase transformation is 225.3J/g.The transformation temperature of this patent product is identical with comparative example, and heat of phase transformation is greater than comparative example product.
Claims (11)
1. a hydro carbons phase change heat storage material, it is characterized in that, described hydro carbons phase change heat storage material comprises positive structure eicosane hydrocarbon and positive structure docosane hydrocarbon, and its mass ratio is 1: 99～99: 1, the transformation temperature of hydro carbons phase change heat storage material is 36～45 ℃, and latent heat of phase change is 200～230 J/g.
2. according to hydro carbons phase change heat storage material claimed in claim 1, it is characterized in that, described positive structure eicosane hydrocarbon is the positive structure eicosane hydrocarbon that eicosanoic acid carries out hydrogenation reaction acquisition under catalyzer and hydrogen existence, and positive structure docosane hydrocarbon is the positive structure docosane hydrocarbon that behenic acid carries out hydrogenation reaction acquisition under catalyzer and hydrogen existence.
3. according to the hydro carbons phase change heat storage material described in claim 1 or 2, it is characterized in that, in described hydro carbons phase change heat storage material, also contain antioxidant, sanitas.
4. the preparation method of hydro carbons phase change heat storage material described in claim 1, comprise following content: eicosanoic acid or behenic acid and solvent, under catalyzer and hydrogen exist, carry out hydrogenation reaction, reaction product is isolated after unreacting material and is mixed in proportion and is hydro carbons phase change heat storage material; Wherein catalyzer is palladium/multi-walled carbon nano-tubes catalyzer, and the reaction pressure of hydrogenation reaction is 1～10 MPa, and temperature of reaction is 220～320 ℃.
5. in accordance with the method for claim 4, it is characterized in that, described hydrogenation reaction adopts intermittent reaction, and reaction is carried out under agitation condition, and the volume ratio of eicosanoic acid or behenic acid and catalyzer is l.0～2.5: 0.2～0.5, and the reaction times is 3～10 hours.
6. in accordance with the method for claim 4, it is characterized in that, described hydrogenation reaction adopts continuous reaction, and hydrogen and the liquid phase volume ratio under standard state is 100: 1～1200: 1, volume space velocity 0.6h when liquid
-1-1.8h
-1, preferably 0.8h
-1-1.2h
-1.
7. in accordance with the method for claim 4, it is characterized in that the NH that contains 5～50 μ L/L in described hydrogen
3.
8. in accordance with the method for claim 4, it is characterized in that the NH that contains 10～20 μ L/L in described hydrogen
3.
9. in accordance with the method for claim 4, it is characterized in that, in the inventive method, described solvent is one or more in normal hexane, normal heptane, octane or dodecane, and the volume ratio of eicosanoic acid or behenic acid and solvent is l.0～2.5: 7～20.
10. in accordance with the method for claim 4, it is characterized in that, described palladium/multi-walled carbon nano-tubes catalyzer is take multi-walled carbon nano-tubes as carrier, take the palladium of quality percentage composition 2%～10% as active ingredient.
11. according to the method described in claim 4 or 10, it is characterized in that, the preparation method of described palladium/multi-walled carbon nano-tubes catalyzer is: under 50～100 ℃ of conditions, multi-walled carbon nano-tubes is carried out to oxide treatment 1～5h with the HNO3 of 2～8mol/L, then filter, be washed to neutrality, 100～150 ℃ of oven dry; Then be added to the water, ultrasonic dispersion, adds H by the quality percentage composition 2%～10% of palladium in catalyzer
2pdC1
4solution, adds formaldehyde solution after stirring, and with NaOH solution adjusting pH value to 8～11, stirs, filters, washes, dries, and obtains Pd/MWCNTs catalyzer.
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Cited By (6)
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| CN105907377A (en) * | 2016-03-21 | 2016-08-31 | 东华大学 | Disposable annular thermometer |
| CN106883822A (en) * | 2015-12-15 | 2017-06-23 | 中国石油化工股份有限公司 | A kind of method that Hydrocarbon phase change heat storage is produced with natural acid |
| CN106883823A (en) * | 2015-12-15 | 2017-06-23 | 中国石油化工股份有限公司 | A kind of method for producing phase-changing energy storage material |
| CN108102613A (en) * | 2017-11-28 | 2018-06-01 | 大连理工大学 | A kind of anti-mildew organic composite shaping phase-change material and preparation method thereof |
| WO2018225759A1 (en) * | 2017-06-06 | 2018-12-13 | 国立研究開発法人理化学研究所 | Method for producing aliphatic hydrocarbon and carbon monoxide |
| 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 |
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| CN101292064A (en) * | 2005-09-15 | 2008-10-22 | 纤维创新技术公司 | Multicomponent fiber comprising a phase change material |
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| CN101292064A (en) * | 2005-09-15 | 2008-10-22 | 纤维创新技术公司 | Multicomponent fiber comprising a phase change material |
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| CN106883822A (en) * | 2015-12-15 | 2017-06-23 | 中国石油化工股份有限公司 | A kind of method that Hydrocarbon phase change heat storage is produced with natural acid |
| CN106883823A (en) * | 2015-12-15 | 2017-06-23 | 中国石油化工股份有限公司 | A kind of method for producing phase-changing energy storage material |
| CN106883823B (en) * | 2015-12-15 | 2020-04-10 | 中国石油化工股份有限公司 | Method for producing phase change energy storage material |
| CN106883822B (en) * | 2015-12-15 | 2020-04-14 | 中国石油化工股份有限公司 | Method for producing hydrocarbon phase change heat storage material by using natural acid |
| CN105907377A (en) * | 2016-03-21 | 2016-08-31 | 东华大学 | Disposable annular thermometer |
| CN105907377B (en) * | 2016-03-21 | 2019-08-09 | 东华大学 | Disposable annulus temperature meter |
| WO2018225759A1 (en) * | 2017-06-06 | 2018-12-13 | 国立研究開発法人理化学研究所 | Method for producing aliphatic hydrocarbon and carbon monoxide |
| JP7176759B2 (en) | 2017-06-06 | 2022-11-22 | 国立研究開発法人理化学研究所 | Method for producing aliphatic hydrocarbon and carbon monoxide |
| CN108102613A (en) * | 2017-11-28 | 2018-06-01 | 大连理工大学 | A kind of anti-mildew organic composite shaping phase-change 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 |
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