CN108884383A - Chemical heat accumulation granule and its manufacturing method - Google Patents
Chemical heat accumulation granule and its manufacturing method Download PDFInfo
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- CN108884383A CN108884383A CN201780022073.2A CN201780022073A CN108884383A CN 108884383 A CN108884383 A CN 108884383A CN 201780022073 A CN201780022073 A CN 201780022073A CN 108884383 A CN108884383 A CN 108884383A
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- C09K5/16—Materials undergoing chemical reactions when used
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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Abstract
Present invention offer causes the chemical heat accumulation granule for being dehydrated the endothermic reaction and high intensity in 100~350 DEG C of low-temperature region.A kind of chemical heat accumulation granule,It is characterized in that,It is the oxide to be selected from magnesium,The hydroxide of magnesium,At least one kind of compound in the composite oxides of magnesium and the complex hydroxide of magnesium,Selected from lithium compound,At least one kind of compound in potassium compound and sodium compound,And the chemical heat accumulation granule that carbon compound is constituted for principal component,In the case that carbon content in chemical heat accumulation granule is 12~35 mass %,Range relative to the Mg in afore mentioned chemical accumulation of heat granule in 0.1~50mol% includes Li,K,And/or Na,And then the composite oxides of aforementioned magnesium and the complex hydroxide of magnesium include to be selected from Ni in the range of 1~40mol% relative to Mg,Co,At least one kind of element in Cu and Al,The excellent durability of the dehydration endothermic reaction is shown in 100~350 DEG C of low-temperature region.
Description
Technical field
Cause to be dehydrated the endothermic reaction the present invention relates to the low-temperature region at 100~350 DEG C and recycles the excellent change of patience
Learn accumulation of heat granule.
Background technique
In recent years, it is controlled since carbon dioxide is discharged, it is desirable that the use for cutting down fossil fuel needs the energy conservation in each technique
The utilization of heat extraction is carried out on the basis of change.Utilization method as heat extraction, it is known to be stored using 100 DEG C of warm water below of water
Heat.But warm water accumulation of heat has following problem etc.：It (1), cannot long-time accumulation of heat due to there is radiation loss；(2) due to aobvious
Heat is small, it is therefore desirable to a large amount of water, the miniaturization difficult of thermal storage equipment；(3) output temperature is non-constant according to utilization, meeting
It is gradually reduced.Therefore, in order to which the people's livelihood for carrying out such heat extraction utilizes, the higher heat storage technology of development efficiency is needed.
As high-efficient heat storage technology, chemical heat accumulation method can be enumerated.Since chemical heat accumulation method can be with the suction of substance
The chemical changes such as attached, hydration, therefore compared with the regenerative process of latent heat, sensible heat based on material itself (water, fuse salt etc.), every list
The amount of stored heat of position quality is got higher.As chemical heat accumulation method, the water vapour of the adsorption/desorption based on the water vapour in atmosphere is proposed
The absorption (ammino-complex generate reaction) of adsorption/desorption method, ammonia in metal salt, the adsorption/desorption based on organic matters such as alcohol
Reaction etc..If considering burden, the simplicity of device to environment, capillary pressure/desorption method is best.It is steamed as water
Chemical heat-accumulating material used in vapour adsorption/desorption method, it is known to magnesia.
Magnesia will not work in 100~300 DEG C of low-temperature region as practical heat-storing material.This is because magnesium
Hydroxide will not cause effective dehydration in above-mentioned low-temperature region.In order to solve these problems, propose make Mg and
At least one kind of metal component Composite in the group being made of Ni, Co, Cu and Al, can accumulation of heat at 100~300 DEG C or so
Chemical heat-accumulating material (patent document 1).In addition it proposes, by adding the hygroscopicity gold formed by lithium chloride into magnesium hydroxide
Belong to salt, the amount of stored heat of per unit mass or unit volume is high, 100~350 DEG C or so can accumulation of heat chemical heat-accumulating material (patent
Document 2).And then disclose, in the chemical heat-accumulating material based on calcium hydroxide, by forming the skeleton knot based on sepiolite etc.
Structure body, the aggregation of chemical heat-accumulating material layer when being able to suppress dehydration, to when hydration reaction transition after dehydration, energy
Hydration reaction is enough carried out, the invertibity (patent document 3) of dehydration and hydration reaction is maintained.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2007-309561 bulletin
Patent document 2：Japanese Unexamined Patent Publication 2009-186119 bulletin
Patent document 3：Japanese Unexamined Patent Publication 2009-256517 bulletin
Summary of the invention
Problems to be solved by the invention
But the technology for being recorded in patent document 1 and 2, when being directly used as chemical heat-accumulating material with powder, due to work
Repeatedly, in micronization post-concentration collection, response area can be reduced, to have as accumulation of heat for hydration reaction and dehydration in work
The problem of reactivity of system reduces.In addition, the chemical heat-accumulating material recorded in patent document 3 is by forming based on sepiolite etc.
Skeleton structure body, it is suppressed that the aggregation of chemical heat-accumulating material layer when dehydration, but the intensity of skeleton structure body is weak, chemical
The aggregation of heat-storing material layer inhibits insufficient.
Therefore, the purpose of the present invention is to provide the low-temperature region at 100~350 DEG C cause be dehydrated the endothermic reaction and
Recycle the excellent chemical heat accumulation body of patience.
The solution to the problem
To solve the above-mentioned problems, various researchs are repeated in the present inventor, as a result, it has been found that, following chemical heat accumulation granule
Cause to be dehydrated the endothermic reaction in 100~350 DEG C of low-temperature regions and there is sufficient intensity, circulation patience is excellent, thus complete
At the present invention, the chemical heat accumulation granule is characterized in that, is selected from the oxide of magnesium, the hydroxide of magnesium, magnesium
Composite oxides and magnesium complex hydroxide at least one kind of magnesium compound, be selected from lithium compound, potassium compound and sodium
The chemical heat accumulation granule that at least one kind of alkali metal compound and carbon compound in object are constituted for principal component is closed, chemistry stores
Carbon content in hot granule is 12~35 mass %.
The present invention has excellent sufficient intensity in mode below, and it is excellent to recycle patience.
Purport is that a kind of chemical heat accumulation granule is to be selected from answering for the oxide of magnesium, the hydroxide of magnesium, magnesium
Close at least one kind of compound in the complex hydroxide of oxide and magnesium, in lithium compound, potassium compound and sodium compound
At least one kind of compound and carbon compound be principal component and constitute, the carbon content in chemical heat accumulation granule be 12~35
Quality %.
The effect of invention
Chemical heat accumulation granule of the invention causes to be dehydrated the endothermic reaction and have in 100~350 DEG C of low-temperature region
Sufficient intensity, it is excellent to recycle patience is because being 12~35 mass %, knot by the carbon content control in chemical heat accumulation granule
Compared with prior art, the intensity of chemical heat accumulation granule is high for fruit, can be defined according to cyclic test measurement result (percent of pass).Cause
This also can inhibit micronization bring aggregation, it is possible to provide heat storage performance does not drop even if accumulation of heat dehydration hydrating cycle is repeated
Low chemical heat-accumulating material.In the present invention, aforementioned magnesium composite oxides and magnesium complex hydroxide relative to Mg with 1~
The wide scope of 40mol% includes at least one kind of element in Ni, Co, Cu and Al, causes in 100~350 DEG C of low-temperature regions
It is dehydrated the endothermic reaction, and has sufficient intensity, circulation patience excellent.In addition, relative to afore mentioned chemical accumulation of heat granule
In Mg with the wide scope of 0.1~50mol% contain Li, K and/or Na, 100~350 DEG C of low-temperature regions cause dehydration inhale
Thermal response, and have sufficient intensity, circulation patience excellent.
Specific embodiment
[chemical heat accumulation granule]
Chemical heat accumulation granule is selected from the oxide of magnesium, the hydroxide of magnesium, the composite oxides of magnesium and answering for magnesium
Close hydroxide at least one kind of compound, at least one kind of compound in lithium compound, potassium compound and sodium compound,
And carbon compound is principal component and constitutes, and relative to the Mg in afore mentioned chemical accumulation of heat granule, containing Li, K and/or Na,
And the carbon content in chemical heat accumulation granule is 12~35 mass %.
Herein, as selected from the oxide of magnesium, the hydroxide of magnesium, the composite oxides of magnesium and the complex hydroxide of magnesium
In at least one kind of compound, can enumerate magnesia, magnesium hydroxide or their mixture, or relative to Mg include 1~
Composite oxides, the complex hydroxide of the magnesium of at least one kind of element of the 40mol% in the group being made of Ni, Co, Cu and Al
Or their mixture.
As lithium compound, potassium compound and sodium compound, if for hygroscopicity, absorption atmosphere in moisture or
The compound that corresponding hydrate can be generated, can be used any compound.As lithium compound, potassium compound and sodium
Compound, preferably meet above-mentioned important document and the easy chloride of processing, hydroxide, oxide, bromide, nitrate or
Sulfate.As lithium compound, more preferably lithium halide or lithium hydroxide, further preferably lithium chloride, lithium bromide or hydrogen-oxygen
Change lithium.As potassium compound, more preferably potassium halide or potassium hydroxide, further preferably potassium chloride, potassium bromide or hydroxide
Potassium.As sodium compound, more preferably sodium halide or sodium hydroxide, further preferably sodium chloride, sodium bromide or hydroxide
Sodium.By in the complex hydroxide of the hydroxide of oxide, magnesium, the composite oxides of magnesium and magnesium selected from magnesium at least
At least one kind of compound of the addition in lithium compound, potassium compound and sodium compound in a kind of compound, to show deficiency
350 DEG C of dehydration endothermic temperature, and the temperature changes according to addition ratio.
As carbon compound, as long as not changing in hydration dehydration temperaturre region, can be used macromolecule
Roasting carbide and inorganic carbon compound etc. made of compound roasts in inert atmosphere.
For chemical heat accumulation granule, when the carbon content in chemical heat accumulation granule is 12~35 mass %, then in Li, K
And/or Na relative to the Mg in chemical heat accumulation granule be 0.1~50mol% range play as defined in effect, Li, K and/or
The content of Na ranges preferably from 2~45mol%, more preferably 3~30mol%.The content of Li, K and/or Na are insufficient
In the case where 0.1mol%, even if the carbon content in chemical heat accumulation granule is 12~35 mass %, it also cannot get dehydration temperaturre
The effect of low temperature, more than 50mol% in the case where, the dehydration hydration reaction of magnesium hydroxide itself, per unit matter can be hindered
The amount of stored heat of amount or unit volume is reduced, and heat storage performance reduces.Carbon content ranges preferably from 13~33 mass %, is more preferably
14~30 mass %.In the case that carbon content is less than 12 mass %, there cannot be the skeleton structure of enough intensity, more than 35
In the case where quality %, the amount of stored heat of per unit mass or unit volume is reduced, and heat storage performance reduces.
Chemical heat accumulation granule refers to, using the adhesive comprising carbon component that the powder formed by single or multicomponent is former
Material be processed into it is bigger than raw material it is granular after, carried out made of carbonization treatment in inert atmosphere.Chemical heat accumulation of the invention is made
Plastochondria carries out carbonization treatment after being granulated by using the high-molecular compound for constituting carbon compound as adhesive to obtain.
It is 0.2~1.0g/cm that chemical heat accumulation granule, which can be bulk density,3Pellet (pellet) shape of left and right.Change of the invention
The intensity for learning the heat-storing material of accumulation of heat granule improves, even if accumulation of heat dehydration hydrating cycle is repeated, can also inhibit micro mist
Change bring aggregation, heat storage performance will not reduce.
Chemical heat accumulation granule can be granulated the mixture comprising chemical heat-accumulating material by using pelletizer, into
Row carbonization treatment manufactures.Prilling process does not limit, and dry type granulation can be used or wet type is granulated to carry out.Wet type is carried out to make
It is dry after being granulated in the case where grain, after sieve, carbonization treatment is carried out, chemical heat accumulation granule is thus obtained.
As long as the partial size of chemical heat accumulation granule be can be used as chemical heat-accumulating material come using size, preferably 1~20mm.Grain
In the case that diameter is less than 1mm, have in chemical heat pump system, water vapour imports worry of the blocking such as piping to occlude.
In the case that partial size is more than 20mm, in order to pass through water vapour, big pore is needed, in this case, chemical heat accumulation granule
Intensity can reduce, chemical heat accumulation granule becomes easy rupture.
Carbon compound in chemical heat accumulation granule is preferably formed as porous structure.Porous structure, which refers to, has very more pores
Solid structure, as make water vapour by flow path work.The porosity of porous body can be 10~80% or so, from
It sets out in terms of reaction efficiency, preferably pore is dispersed randomly in the structure in chemical heat accumulation granule.
Chemical heat accumulation granule can be manufactured by carrying out carbonization treatment at 400~800 DEG C in inert atmosphere,
Porous structure is formed by being carbonized.In the case that maturing temperature is less than 400 DEG C, the macromolecule chemical combination of carbon compound is constituted
Object is not carbonized, and in the case where 800 DEG C, the activity of magnesia is reduced, and hydration reaction reduces.Constitute carbon compound
High-molecular compound is the high-molecular compounds such as Residual carbon height, and/or the resin of three-dimensional structure easy to form in carbonization treatment
?.As the high-molecular compound for constituting carbon compound, preferably by phenolic resin, melamine resin, urea resin, epoxy
The heat-curing resins such as resin, furane resins, polyamide, polyester resin, polyvinyl resin, acrylic resin, polyphenyl second
The heat such as olefine resin, acrylic resin, vinyl chloride resin, fluororesin, polyacetal resin, polycarbonate resin, polyurethane resin
One kind or two or more in plastic resin or cellulose is used in mixed way, more preferably selected from by phenolic resin, melamine resin
And at least one kind of high-molecular compound in the group of cellulose composition.
In order to which porous structure is more readily formed, it can add in inert atmosphere, be easy at 400~800 DEG C in turn
The high-molecular compound of volatilization.As readily volatilized high-molecular compound, preferably potato starch, cornstarch, sweet potato is formed sediment
Powder, tapioca, sago starch, rice starch, amaranth starch etc..
By selected from least one kind of in the group being made of Ni, Co, Cu and Al comprising 1~40mol% relative to aforementioned Mg
The chemical heat accumulation granule that the composite oxides of the magnesium of element and at least one kind of compound in complex hydroxide are formed is benefit
With the substance of the reversible reaction of the magnesia recorded in patent document 1 and 2/water-based chemical heat-accumulating material as follows.
The △ H of Co and Ni is 50~60kJ/mol, lower than Mg, and Cu and Al are also showed that with equivalence, therefore are shown same
Function and effect.Compound magnesium compound comprising at least one kind of element in the group being made of Ni, Co, Cu and Al is shown not
The dehydration endothermic temperature of 350 DEG C of foot, and the temperature changes according to compound composition ratio.As element, preferably Ni, Co or
Al, more preferable Ni or Co.As the content of element, preferably 3~30mol%, more preferable 10~25mol%.The content of element is not
In the case where sufficient 1mol%, cannot get the effect of dehydration temperaturre low temperature, in the case where 40mol%, per unit mass or
The amount of stored heat of unit volume can reduce.
As long as aforementioned at least one kind of element source in the group being made of Ni, Co, Cu and Al can be mixed and be easy with water
Chloride, hydroxide, oxide, oxycarbide, nitrate, and/or sulfate can be used in the substance of processing, excellent
It is selected as chloride, nitrate, and/or sulfate, more preferably chloride.In the case where using chloride, dissolution in water
Degree is high, rich in treatability, is easy to be uniformly dispersed.
The sieve of the sizing grid for the chemical heat accumulation granule that 80~99 mass % can be left is used to chemical heat accumulation granule
Son, after the small chemical heat accumulation granule removal of partial size, in the 500mL plastic containers of the nylon ball equipped with 5 diameter 15mm,
It is put into chemical heat accumulation granule and has passed through the aforementioned change that partial size is small after turntable was with 148rpm rotation 2 hours to 250mL
The amount for learning the sieve used when the removal of accumulation of heat granule is preferably 40 mass % or less.The case where throughput is more than 40 mass %
Under, the intensity of chemical heat accumulation granule is insufficient, if accumulation of heat dehydration hydrating cycle is repeated, due to being micronized bring
Aggregation, heat storage performance reduce.
(manufacturing method of chemical heat accumulation granule)
The manufacturing method of chemical heat accumulation granule includes：
Process (A)：Prepare the hydroxide of magnesium, or prepare include relative to Mg 1~40mol% be selected from by Ni, Co, Cu and
The magnesium complex hydroxide of at least one kind of element in the group of Al composition；
Process (B)：By the hydroxide of the magnesium prepared in process (A) or the complex hydroxide of magnesium, include relative to Mg
At least one kind of compound in lithium compound, potassium compound and sodium compound of 0.1~50mol%, and relative to magnesium
100 mass parts of complex hydroxide of hydroxide or magnesium are the high-molecular compound of the composition carbon compound of 15~60 mass parts
Mixing；
Process (C)：To obtained in process (B) include magnesium hydroxide or magnesium complex hydroxide mixture into
Row is granulated；
Process (D)：To obtained in process (C) include magnesium hydroxide or magnesium complex hydroxide granules into
Row classification；And
Process (E)：By the compound hydrogen-oxygen of the hydroxide comprising magnesium or magnesium that prepare in process (D) in inert atmosphere
The mixture of compound carries out roasting for 1~24 hour at 400~800 DEG C.
The process of the hydroxide for obtaining magnesium of preferable process (A) comprises the following steps：
Prepare the magnesium chloride brine of 1~10mol/L of concentration and the sodium hydroxide solution or calcium hydroxide of 1~18mol/L
Dispersion liquid, while putting into the sodium hydroxide solution or calcium hydroxide dispersion of magnesium chloride brine and reactivity for 80~150%
It is allowed to react, obtains magnesium hydroxide slurry, gained magnesium hydroxide slurry is filtered, wash, is dried, obtain the hydroxide of magnesium
Object.
The process of the complex hydroxide for obtaining magnesium of preferable process (A) comprises the following steps：
Prepare the magnesium chloride brine of 1~10mol/L of concentration, 0.1~10mol/L of concentration comprising selected from by Ni, Co, Cu
And the aqueous solution of at least one kind of element and the sodium hydroxide solution of 1~18mol/L or calcium hydroxide point in the group of Al composition
Dispersion liquid mixes magnesium chloride brine and the solution comprising at least one kind of element in the group being made of Ni, Co, Cu and Al,
And then put into reactivity and be allowed to react for 80~150% sodium hydroxide solution or calcium hydroxide dispersion, obtain compound hydrogen-oxygen
Change magnesium slurry, the compound magnesium hydroxide slurry of gained is filtered, wash, is dried, the complex hydroxide of magnesium is obtained.
Process (B) is to include by the complex hydroxide of the hydroxide of the magnesium prepared in process (A) or magnesium, relative to Mg
At least one kind of compound in lithium compound, potassium compound and sodium compound of 0.1~50mol% and relative to magnesium
100 mass parts of complex hydroxide of hydroxide or magnesium are the high-molecular compound of the composition carbon compound of 15~60 mass parts
Omnipotent mixing and blending machine, ribbon mixer (ribbon Mixer), Spartan can be used in mixing in mixed process
Reuser (ス パ Le タ Application リ ュ ー ザ ー) etc..
Process (C) is the mixture to the complex hydroxide of the hydroxide or magnesium that include magnesium obtained in process (B)
Wet type extruding granulator DOME GRAN (ド ー system グ ラ Application can be used in granulation in the process being granulated), granulating disc
(disk pelleter), pellet processing machine etc..
[embodiment]
The present invention is using specific using Ni and Co as representative, the embodiment as alkali metal using Li as representative as metallic element
Ground is illustrated the intensity and circulation patience of granule, and the present invention is in the composite oxides of aforementioned magnesium and the compound hydroxide of magnesium
Object is enough strong relative to having in the wide scope that Mg includes at least one kind of element of the 1~40mol% in Ni, Co, Cu and Al
Degree, circulation patience are excellent.In addition, relative to the Mg in afore mentioned chemical accumulation of heat granule contain 0.1~50mol%Li, K and/
Or have sufficient intensity, circulation patience excellent in the wide scope of Na.Therefore, it is not limited to the following embodiments.
[evaluation]
(1) measuring method of Mg, Li, K, Na, Ni, Co, Cu, Al
Sample will be measured and be added in the hydrochloric acid (reagent is superfine) and perchloric acid (reagent is superfine) of 12N and carry out heating makes it
After being completely dissolved, ICP emission spectrographic analysis device (PS3520VDD Hitachi High-Tech Science is used
Corporation system) it is measured.
(2) measuring method of carbon content
Other than Mg, Li, K, Na, Ni, Co, Cu, the Al measured in (1), also measurement Fe, Ba, Ti, Zn, P, Si, B
Content, about Li, K, Na, by using compound conversion calculate, other elements are calculated by oxide conversion, false
If other ingredients are not present, by subtracting this from 100% in chemical heat accumulation granule other than these chemical components and C
A little chemical component values, calculate carbon content (%).
(3) the durability evaluation method of chemical heat accumulation granule
Chemical heat accumulation granule after drying 12 hours, is measured into 200g, at 120 DEG C for the chemical heat accumulation that partial size is small
Granule removal is removed the small chemical heat accumulation granule of partial size using that can leave sieve of 80~99 mass % on sieve.So
Afterwards, investment eliminates the measurement sample of the small chemical heat accumulation granule of partial size to 250mL, in turn in the plastic containers of 500mL
The nylon ball of 5 diameter 15mm is packed into container, with porcelain jar ball mill turntable with 148rpm rotation 2 hours.In order to making
The dusting of plastochondria is studied, and the sieve used when being removed using the aforementioned chemical heat accumulation granule that partial size is small, measurement is passed through
Measurement sample weight, calculate percent of pass.
(4) measuring method of partial size
The partial size that 20 chemical heat accumulation granules are measured with vernier removes minimum value and maximum value, calculates average value.It will
The diameter of the granule of cylindrical shape is as partial size.
(5) the durability evaluation method after cyclic test
After measuring chemical heat accumulation granule 30g, (i) is kept for 80 minutes at 350 DEG C, oxide is made, (ii) is at 140 DEG C
Lower placement is 40 minutes cooling, and (iii) is kept for 80 minutes at 140 DEG C under water vapour circulation, hydroxide is made, (iv) exists
It is 40 minutes dry at 140 DEG C.After the process for implementing (i)~(iv) of 10 circulations, the sieve for the use of sieve pore being 1mm, measurement is led to
The weight for the measurement sample crossed, calculates percent of pass.
(manufacture of chemical heat accumulation granule)
[embodiment 1]
Dissolve the anhydrous magnesium chloride of 98 mass % of purity with pure water, in the side for becoming 2.0mol/L with Mg ion concentration
Following solution is put into the magnesium chloride brine that formula is adjusted so that Ni ion makes relative to Mg ion is 20mol%
Mixed solution, the solution are that pure water is added in the nickel chloride solution of 97 mass % of purity to become Ni ion concentration
The solution adjusted to 0.8mol/L.
Using occlusion pump, in such a way that sodium hydroxide becomes 90% relative to the reactivity of magnesium chloride, with 5mL/ minutes to
Pure water is added in the sodium hydroxide solution of reagent superfine and is adjusted to concentration 2.0mol/L's for the mixed solution and dripping of production
Solution is stirred with 300rpm, is reacted 1 hour at 30 DEG C.The dispersion liquid of compound magnesium hydroxide after reaction was carried out
After filter, washing, drying in 12 hours is carried out at 120 DEG C, obtains compound magnesium hydroxide.
Following substance is put into omnipotent mixing and blending machine (DULTON CO., LTD. system by magnesium hydroxide compound for gained
5DM-r type) container in：The lithium chloride for being 10mol% relative to Mg；Relative to compound 100 mass parts of magnesium hydroxide, powder shaped
20 mass parts of phenolic resin, with pure water 7.3 mass parts of melamine resin are adjusted to melamine made of 77% solution
240 mass parts of resin solution and pure water are stirred 10 minutes under conditions of revolution speed 62rpm, rotational velocity 141rpm, are obtained
To using compound magnesium hydroxide as the mixture of principal component.
Then, wet type extruding granulator DOME GRAN (Fuji will be marginally put into every time in claylike mixture
Paudal Co., Ltd. DG-L1 type) hopper in, in screw speed 40rpm, dome mold aperture be 3.0mm, plate thickness is
1.0mm, aperture efficiency are granulated under conditions of being 22.7%.Drying in 24 hours is carried out after granulation at 100 DEG C, by sieve,
The compound magnesium hydroxide for being about 2~5mm using partial size is obtained as the granule of principal component.
Then, by gained granule in atmosphere displaced type electric furnace (MARUSHO DENKI CO., LTD. SPX1518-
In 17V), while making nitrogen circulate with 0.25L/ minutes flow velocitys, while the condition in 600 DEG C, 1 hour carries out carbonization treatment, obtain
Carbon content is the chemical heat accumulation granule of 14.4 mass %.
[embodiment 2]
Nickel chloride aqueous solution is changed to cobalt chloride solution, in addition to this, passes through method system similarly to Example 1
It makes, obtains the chemical heat accumulation granule that carbon content is 19.6 mass %.
[embodiment 3]
Ni is not added, in addition to this, is manufactured by method similarly to Example 1, obtaining carbon content is 28.3 matter
Measure the chemical heat accumulation granule of %.
[embodiment 4]
Relative to Mg ion, Co ion is set as 5mol%, in addition to this, is carried out by method similarly to Example 1
Manufacture obtains the chemical heat accumulation granule that carbon content is 20.6 mass %.
[embodiment 5]
Relative to compound 100 mass parts of magnesium hydroxide, the phenolic resin of powder shaped is set as 50 mass parts, in addition to this,
It is manufactured by method similarly to Example 4, obtains the chemical heat accumulation granule that carbon content is 32.2 mass %.
[embodiment 6]
Relative to compound 100 mass parts of magnesium hydroxide, the phenolic resin of powder shaped is set as 10 mass parts, in addition to this,
It is manufactured by method similarly to Example 4, obtains the chemical heat accumulation granule that carbon content is 14.5 mass %.
[embodiment 7]
Melamine resin is replaced to be manufactured in addition to this by method similarly to Example 4 using cellulose,
Obtain the chemical heat accumulation granule of 20.6 mass % of carbon content.
[embodiment 8]
Lithium chloride is replaced to be manufactured by method similarly to Example 1 in addition to this, obtain carbon using lithium bromide
The chemical heat accumulation granule of 26.4 mass % of content.
[comparative example 1]
Phenolic resin and melamine are replaced using 27.3 mass parts sepiolites relative to compound 100 mass parts of magnesium hydroxide
Resin is manufactured by method similarly to Example 3 in addition to this, obtains chemical heat accumulation granule.
[comparative example 2]
Without using the high-molecular compound for constituting carbon compound, manufactured by method similarly to Example 3, it cannot
Form granule.
[comparative example 3]
Relative to compound 100 mass parts of magnesium hydroxide, the phenolic resin of powder shaped is set as 5 mass parts, in addition to this, is led to
The method crossed similarly to Example 4 is manufactured, and the chemical heat accumulation granule of 10.9 mass % of carbon content is obtained.
[comparative example 4]
Relative to compound 100 mass parts of magnesium hydroxide, the phenolic resin of powder shaped is set as 70 mass parts, in addition to this,
It is manufactured by method similarly to Example 4, obtains the chemical heat accumulation granule of 38.9 mass % of carbon content.
Result is summarized in table 1.
[table 1]
* 1 for determine, using in chemical heat accumulation granule not including carbon can accumulation of heat part be used as heat storage, general
Its content be 65% or more situation be denoted as zero, by less than 65% the case where be denoted as ×.When lower than 65%, regenerative capacity is reduced.
* the heat storage content of 2 comparative examples 1 is to subtract the sepiolite used in mixing and calculate.
It can define according to the result of table 1, and use sepiolite come (comparative example 1) the case where replacing carbon compound and do not made
It is compared with (comparative example 2) the case where the high-molecular compound for constituting carbon compound, chemical heat accumulation granule intensity of the invention is bright
Aobvious chemical heat accumulation granule high, that high intensity can be obtained.
Industrial availability
Accumulation of heat granule of the invention can cause to be dehydrated the endothermic reaction and intensity in 100~350 DEG C of low-temperature region
It is high.Therefore, suitable for efficiently using the heat from the exhaust gas of the discharges such as engine, fuel cell.For example, the heat of exhaust gas can be applied to
The shortening of the warm-operation of automobile, the raising of the comfort of passenger, the improvement of fuel consumption and the active of exhaust gas catalyst improve band
The low evilization of exhaust gas etc. come.Especially in the case where engine, since operating bring burden is non-constant, exhaust exports also not
Stablize, therefore exhaust heat is directly inconvenient with non-efficiency using inevitable.If using chemical heat accumulation system as the present invention,
Then by carrying out temporary chemical accumulation of heat to exhaust heat, and thermal output is carried out according to heat demand, can be realized more preferably exhaust heat
It utilizes.
Claims (9)
1. a kind of chemical heat accumulation granule, which is characterized in that it is to be with magnesium compound, alkali metal compound and carbon compound
Principal component and the chemical heat accumulation granule constituted, the carbon content in chemical heat accumulation granule is 12~35 mass %, the magnesium
It closes at least one kind of in the complex hydroxide that object is oxide selected from magnesium, the hydroxide of magnesium, the composite oxides of magnesium and magnesium
Magnesium compound, the alkali metal compound are at least one kind of alkali metal in lithium compound, potassium compound and sodium compound
Close object.
2. chemical heat accumulation granule according to claim 1, which is characterized in that the carbon compound in chemical heat accumulation granule
Form porous structure.
3. chemical heat accumulation granule according to claim 1 or 2, wherein the carbon compound of the porous structure be selected from
At least one kind of resin in the group being made of phenolic resin, melamine resin and cellulose, roasting in inert atmosphere
Object.
4. chemical heat accumulation granule according to claim 1, wherein the alkali metal compound is the chlorine of lithium, potassium and sodium
The form of compound, hydroxide, oxide, bromide, nitrate and/or sulfate, and be granulated relative to the chemical heat accumulation
Mg in body, Li, K and/or Na containing 0.1~50mol%.
5. chemical heat accumulation granule according to claim 1, which is characterized in that the Magnesium coumpoud oxide or the compound hydrogen of magnesium
Oxide contained in the form of chloride, hydroxide, oxide, oxycarbide, nitrate and/or sulfate selected from by Ni,
At least one kind of element source in the group of Co, Cu and Al composition, contain 1 relative to the Mg in the chemical heat accumulation granule~
Ni, Co, Cu and/or Al of 40mol%.
6. chemical heat accumulation granule according to any one of claims 1 to 5, wherein use chemical heat accumulation granule
The sieve that the sizing grid of the chemical heat accumulation granule of 80~99 mass % can be left removes the small chemical heat accumulation granule of partial size
After removing, in the 500mL plastic containers of the nylon ball equipped with 5 diameter 15mm, chemical heat accumulation granule is put into 250mL, is used
After turntable was with 148rpm rotation 2 hours, the sieve that is used when by removing the small chemical heat accumulation granule of the partial size
Amount is 40% mass or less.
7. a kind of manufacturing method of chemical heat accumulation granule comprising：
Process (A)：Prepare the hydroxide of magnesium, or prepares to include that 1~40mol% is selected from by Ni, Co, Cu and Al group relative to Mg
At group at least one kind of element magnesium complex hydroxide；
Process (B)：By the hydroxide of the magnesium prepared in process (A) or the complex hydroxide of magnesium, relative to Mg be 0.1~
At least one kind of compound in lithium compound, potassium compound and sodium compound of 50mol%, and the hydrogen-oxygen relative to magnesium
Compound or 100 mass parts of complex hydroxide of magnesium are that the high-molecular compound of the composition carbon compound of 15~60 mass parts is mixed
It closes；
Process (C)：The mixture of the complex hydroxide of the hydroxide or magnesium that obtained in process (B) include magnesium is made
Grain；
Process (D)：The granules of the complex hydroxide of the hydroxide or magnesium that obtained in process (C) include magnesium are divided
Grade；And
Process (E)：By the complex hydroxide of the hydroxide comprising magnesium or magnesium that prepare in process (D) in inert atmosphere
Mixture 400~800 DEG C carry out 1~24 hour roast.
8. the manufacturing method of chemical heat accumulation body according to claim 7, wherein the process (A) obtains the hydrogen-oxygen of magnesium
The process of compound comprises the following steps：
Prepare sodium hydroxide solution or the calcium hydroxide dispersion of the magnesium chloride brine and 1~18mol/L of 1~10mol/L of concentration
Liquid, while putting into magnesium chloride brine and reactivity and being allowed to for 80~150% sodium hydroxide solution or calcium hydroxide dispersion
Reaction, obtains magnesium hydroxide slurry, is filtered, washes, dries to gained magnesium hydroxide slurry, obtain the hydroxide of magnesium.
9. the manufacturing method of chemical heat accumulation body according to claim 7, wherein process (A) obtains the compound hydrogen-oxygen of magnesium
The process of compound comprises the following steps：
Prepare the magnesium chloride brine of 1~10mol/L of concentration, 0.1~10mol/L of concentration comprising selected from by Ni, Co, Cu and Al
The aqueous solution of at least one kind of element and the sodium hydroxide solution of 1~18mol/L or calcium hydroxide dispersion in the group of composition,
Magnesium chloride brine is mixed with the solution comprising at least one kind of element in the group being made of Ni, Co, Cu and Al, in turn
The sodium hydroxide solution or calcium hydroxide dispersion that investment reactivity is 80~150% are allowed to react, and obtain compound magnesium hydroxide
Slurry is filtered the compound magnesium hydroxide slurry of gained, washes, dries, obtains the complex hydroxide of magnesium.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016072404 | 2016-03-31 | ||
| JP2016-072404 | 2016-03-31 | ||
| JP2017057010A JP7036335B2 (en) | 2016-03-31 | 2017-03-23 | Chemical heat storage granulation and its manufacturing method |
| JP2017-057010 | 2017-03-23 | ||
| PCT/JP2017/012707 WO2017170582A1 (en) | 2016-03-31 | 2017-03-28 | Chemical heat storage granules and production process therefor |
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| CN108884383A true CN108884383A (en) | 2018-11-23 |
| CN108884383B CN108884383B (en) | 2022-02-25 |
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|---|---|
| KR (1) | KR102380429B1 (en) |
| CN (1) | CN108884383B (en) |
| SA (1) | SA518400077B1 (en) |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109777368A (en) * | 2019-03-07 | 2019-05-21 | 宁波石墨烯创新中心有限公司 | A kind of porous carbon composite phase-change material and preparation method thereof |
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| JP2009186119A (en) * | 2008-02-07 | 2009-08-20 | Tokyo Institute Of Technology | Chemical heat pump |
| JP2011162746A (en) * | 2010-02-15 | 2011-08-25 | Nagoya Electrical Educational Foundation | Molded article of chemical heat storage material and method for producing the same |
| JP2013112706A (en) * | 2011-11-25 | 2013-06-10 | Tokyo Institute Of Technology | Chemical thermal storage medium and chemical heat pump |
| JP2013216763A (en) * | 2012-04-06 | 2013-10-24 | Toyota Central R&D Labs Inc | Chemical heat storage material, and reaction device, heat storage device, and vehicle |
| JP2018168225A (en) * | 2017-03-29 | 2018-11-01 | タテホ化学工業株式会社 | Chemical thermal storage medium and method for producing the same |
| JP2018168223A (en) * | 2017-03-29 | 2018-11-01 | タテホ化学工業株式会社 | Chemical thermal storage medium and method for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5327729B2 (en) | 2008-04-18 | 2013-10-30 | 株式会社豊田中央研究所 | Chemical heat storage material and manufacturing method thereof |
| JP2015048393A (en) * | 2013-08-30 | 2015-03-16 | 株式会社金星 | Heat reservoir |
-
2017
- 2017-03-28 KR KR1020187030375A patent/KR102380429B1/en active IP Right Grant
- 2017-03-28 CN CN201780022073.2A patent/CN108884383B/en active Active
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| JP2007309561A (en) * | 2006-05-17 | 2007-11-29 | Tokyo Institute Of Technology | Chemical heat pump |
| JP2009186119A (en) * | 2008-02-07 | 2009-08-20 | Tokyo Institute Of Technology | Chemical heat pump |
| JP2011162746A (en) * | 2010-02-15 | 2011-08-25 | Nagoya Electrical Educational Foundation | Molded article of chemical heat storage material and method for producing the same |
| JP2013112706A (en) * | 2011-11-25 | 2013-06-10 | Tokyo Institute Of Technology | Chemical thermal storage medium and chemical heat pump |
| JP2013216763A (en) * | 2012-04-06 | 2013-10-24 | Toyota Central R&D Labs Inc | Chemical heat storage material, and reaction device, heat storage device, and vehicle |
| JP2018168225A (en) * | 2017-03-29 | 2018-11-01 | タテホ化学工業株式会社 | Chemical thermal storage medium and method for producing the same |
| JP2018168223A (en) * | 2017-03-29 | 2018-11-01 | タテホ化学工業株式会社 | Chemical thermal storage medium and method for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109777368A (en) * | 2019-03-07 | 2019-05-21 | 宁波石墨烯创新中心有限公司 | A kind of porous carbon composite phase-change material and preparation method thereof |
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| KR20180123132A (en) | 2018-11-14 |
| WO2017170582A1 (en) | 2017-10-05 |
| SA518400077B1 (en) | 2023-02-28 |
| CN108884383B (en) | 2022-02-25 |
| KR102380429B1 (en) | 2022-03-31 |
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