CN106905929A - A kind of solid heat storage material and preparation method and application - Google Patents
A kind of solid heat storage material and preparation method and application Download PDFInfo
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Abstract
The invention belongs to high-temperature material field, more particularly to a kind of solid heat storage material and its preparation method and application.Its raw materials by weight portion proportioning composition is as follows：14 parts of 5 95 parts of iron ore, 5 50 parts of magnesium grey iron block, 5 20 parts of iron scale, 5 20 parts of carborundum dust-removing powder, 1 20 parts of aluminium nitride, 15 parts of beryllium nitride, 0.5 5 parts of boron mud, 1 2.5 parts of calgon, 12 parts of magnalium high temperature cementing agent and water.The lower cost for material, high specific heat adjusts the height of thermal conductivity factor according to different charge ratios, so as to adapt to the demand of different thermal storage equipments.
Description
Technical field
The invention belongs to high-temperature material field, more particularly to a kind of solid heat storage material and its preparation method and application.
Background technology
In recent years, as the phenomenon of China's various regions haze weather is increasingly sharpened, reducing even eliminate PM2.5 indexes as ring
The focus of guarantor department, haze weather not only brings many inconvenience to people's daily life, while serious harm people
It is healthy.Research shows that PM2.5 has 6 important sources, be respectively soil dirt, fire coal, biomass combustion, vehicle exhaust with
Waste incineration, industrial pollution and secondary inorganic aerosol, wherein coal-fired accounting is about 18%.Shape of the pollution that caused by coal burning to haze weather
Into generating tremendous influence.In order to reduce winter pollution that caused by coal burning, improve air quality, many cities of northern China start to promote
" coal changes electricity ", and a series of policies subsidy also accordingly come out of the stove, excitation relevant industries research and development focus are turned on into " coal changes electricity " political affairs
In plan.Solid electricity thermal storage equipment has been used widely, wherein being with solid electricity heat-storage heating device and solid electricity heat storage boiler
Main, at the same time, the market demand of solid heat storage brick is increasing.According to incompletely statistics, national gitter brick demand is every
Annual meeting reaches 400,000 tons, and with progressively implementing for national " coal changes electricity " policy, this numeral can continue to increase.At present, it is existing
Solid heat storage material main component is magnesia, and magnesia gitter brick is worked into from magnesite stone ore according to current production technology,
The existing market demand, and existing gitter brick can not be met, 200 DEG C of temperature diffusivity is 2.8w/ ㎡ .s, heat release
Too fast, solid thermal storage electric heater can not meet the heat release demand on daytime.900 DEG C of temperature diffusivity is 0.9w/ ㎡ .s, in high temperature
Section 800-1000 DEG C when, under human intervention heat release it is very undesirable.Therefore, for different thermal storage equipments, improve or drop
The guide temp of low solid heat storage material, reduces cost, improving output turns into the problem that the field must solve.
The content of the invention
Regarding to the issue above, a kind of new solid heat storage material of present invention offer, the lower cost for material, high specific heat,
The height of thermal conductivity factor is adjusted according to different charge ratios, so as to adapt to the demand of different thermal storage equipments.
To achieve these goals, the heat-storing material that the present invention is provided, its raw materials by weight portion proportioning composition is as follows：Iron
Ore 5-95 parts, 5-50 parts of magnesium grey iron block, iron scale 5-20 parts, 5-20 parts of carborundum dust-removing powder, aluminium nitride 1-20 parts, beryllium nitride 1-5
Part, boron mud 0.5-5 parts, calgon 1-2.5 parts, 1-2 parts and water 1-4 parts of magnalium high temperature cementing agent.
Preferably, described magnesium grey iron block composition and weight fraction proportioning be magnesia 84.2%, di-iron trioxide 8.6%,
Silica 3.13%, calcium oxide 1.85%, alundum (Al2O3) 2.22%；It is preferred that the waste and old magnesium grey iron block of cement kiln.
Described magnalium high temperature cementing agent composition and weight fraction proportioning be magnesia 45%, alundum (Al2O3) 50.5%,
Silica 2%, di-iron trioxide 1%, calcium oxide 1.5%.
To achieve these goals, the present invention provides the preparation method of the heat-storing material, specifically includes following steps：By group
Weight portion into raw material weighs each raw material, and iron ore is broken into particle diameter for 3-5mm particles first, standby；Magnesium grey iron block is crushed
It is not more than the particle of 3mm into particle diameter, it is standby；Carborundum dust-removing powder is pulverized, granularity is 200 mesh, standby；Iron phosphorus is broken into
No more than 5mm particle diameters, standby；Merge the standby raw material of above-mentioned preparation, be subsequently adding other raw materials, in 60-120 revs/min of condition
Lower stirring 15-60min, is sufficiently mixed each raw material；Take compound and be pressed into adobe under 600-800 tons of forcing press, be placed in temperature
Spend in 200-240 DEG C of drying kiln, to dry 16 hours, obtain final product.
The solid heat storage materials application is in paddy electricity thermal storage equipment.
Beneficial effects of the present invention.
Heat-storing material low cost of the invention, it is with short production cycle, with high specific heat, good thermal shock stability, long service life
The advantages of.The present invention provides a kind of new solid heat storage brick, and main component is iron ore and waste and old magnesium grey iron block；Due to iron ore
It is 300 yuan/ton or so with the waste and old magnesium grey iron block head of cement kiln, it is with low cost；Traditional high temperature firing process is not needed, drying is only needed
Can come into operation afterwards, with short production cycle, production capacity reaches annual millions of tons；Service condition regulation heat conduction according to distinct device
The height of coefficient, hot stored electric heating gitter brick, mean coefficient of heat conductivity can be reduced to 3.6w/m.k by original 8.5w/m.k；It is high
Intermediate temperature regenerator boiler gitter brick can bring up to 16.8w/m.k by original 9.2w/m.k, and enhancing is artificial handling, so as to meet work
Condition leads warm demand.
The main component of waste and old magnesium grey iron block is magnesia, and content of magnesia can reach more than 80%, in metal oxide,
The specific heat capacity of magnesia is highest, and high temperature resistant, and stable performance is nontoxic, tasteless, non-volatile, is preferable solid heat storage material
Expect, but the thermal conductivity factor of magnesia can drastically decline with the increase of temperature, and in the range of 20-1200 DEG C, thermal conductivity factor is just
Differ nearly 6 times；13w/m.k under from normal temperature is changed into 2.2w/m.k；The drastically decline of thermal conductivity factor, causes high-temp solid electricity accumulation of heat
Equipment, greatly improves in the manipulation difficulty of high temperature exothermic stage human intervention, and the heat of storage can not effectively discharge.With waste and old
Magnesium grey iron block not only solves pollution of the industrial waste to environment as raw material, can also turn waste into wealth, and reduces solid heat storage material
Production cost；Addition iron ore and iron scale, can effectively reduce heat-storing material heat conductivility so that middle temperature solid electricity accumulation of heat
Equipment can greatly increase the time of release heat；Addition carborundum dust-removing powder, can improve the mechanical strength of heat-storing material；Add
Plus aluminium nitride, the thermal conductivity of heat-storing material can be significantly improved, magnesia is made up in 900-1100 DEG C of thermal conductivity of high temperature section
The weak point of energy difference；Addition boron mud, improves the normal temperature cure intensity of compound；Addition beryllium nitride, improves the hard of heat-storing material
Degree, peels off in high speed hot air circulation operating mode without dust；It is aided with the preferable calgon of high temperature mechanical strength and magnalium glue
Knot agent composite binder, after compound is dried into base, in high temperature section, not only ensure that specific heat, and heat conduction also possesses very
Good mechanical strength and hardness, so as to reach, equipment working condition is macrocyclic to store heat release demand.
Solid electricity thermal storage equipment gitter brick main component be magnesia, due to magnesia thermal conductivity high temperature with
Low temperature deviation is very big, and 100 DEG C of thermal conductivity factors of accumulation of heat magnesia brick are 13.5w/m.k, and the thermal conductivity factor of 1000 DEG C of accumulation of heat magnesia bricks is
3.2w/m.k so that its low-temperature zone heat is put and discharges too fast, does not reach preferable heat release duration, such as hot stored electric heating；Accumulation of heat
7-8 hour, heat release duration only has 10 hours or so.There is a big chunk heat because the problem of heat storage thermal conductivity, and do not have
There is storage to heat storage the inside, adiabator layer is reached by heat storage, considerably increase thermal losses, cause the secondary of electric energy
Waste.Using heat-storing material of the invention, by adjusting formula rate, the low heat conduction accumulation of heat material for meeting electric heater can be produced
Material, can reach regenerator temperature, and heat, the gitter brick of equal quality, in same power output persistently can be uniformly discharged again
Under the premise of, the sustainable heat release of gitter brick of the invention 15 hours, heat release duration is obviously improved.It is existing in high temperature solid heat accumulator
There are the prevailing temperatures such as electric heating thermal source, nickel filament, ferrum-chromium-aluminum, Elema can be more than 1200 DEG C, but the gitter brick highest temperature can only
Accomplish 800 DEG C；If being raised to more than 1000 DEG C, the temperature diffusivity of gitter brick only has 0.5w/ ㎡ .k；When needing heat, release
Can do not put out, human intervention effect extreme difference, the problem for taking hot hardly possible never has preferable solution；Using accumulation of heat of the invention
Material, by reducing content of magnesia, is mixed into the aluminium nitride of high heat conduction, and thermal conductivity factor is 175w/m.k, is remarkably improved accumulation of heat
The guide temp of material.Due to greatly improving for high temperature section thermal conductivity so that the override of human intervention is significantly improved, and may be such that this
Heat-storing material high temperature section can discharge heat rapidly under human intervention.
It is raw material that heat-storing material of the invention uses various industrial wastes, and raw material sources are extensive, simple production process, cycle
It is short, it is easy to operate, it is capable of achieving to produce in enormous quantities；It is the ideal product for substituting existing solid heat storage material, solves thermal storage equipment
Exotherm is fast, and high temperature takes the problem of hot hardly possible, and for the manufacture of high-temperature heat storage equipment provides premise guarantee, such as high-temperature heat accumulation steams
Vapour stove.Heat release efficiency is improve, electric energy has been saved, the secondary waste of the energy is effectively prevent.
Specific embodiment
The present invention is described in detail with reference to specific embodiment.
Embodiment 1.
Solid heat storage material, the weight portion of its constitutive material is：10 parts of the waste and old magnesium grey iron block of 30 parts of iron ore, cement kiln, nitrogen
10 parts of aluminium of change, 10 parts of iron scale, 20 parts of carborundum dust-removing powder, 2 parts of beryllium nitride, 2 parts of boron mud, 2.5 parts of calgon, magnalium is efficient
2.8 parts of 1.4 parts of cementing agent and water.
The preparation method of solid heat storage material, comprises the following steps.
（1）Each raw material is weighed by the weight portion of constitutive material, iron ore, mineral hot furnace furnace bottom waste material are broken into particle diameter first
3-5mm particles, it is standby；（2）The waste and old magnesium grey iron block of cement kiln is broken into the particle of particle diameter 1-3mm, standby；（3）Carborundum dust-removing powder
Pulverize, the mesh of fineness 200 is standby；（4）Iron phosphorus is broken into 1-5mm particle diameters, standby；（5）Merge（1）（2）（3）（4）It is standby
Material, is subsequently adding other remaining combination raw materials, is stirred 15 minutes at 60-120 revs/min, is sufficiently mixed each raw material.（6）Take mixed
Close material and be pressed into adobe under 600-800 tons of forcing press, enter temperature for 200-240 DEG C dries kiln drying 12 hours, obtain final product.
Solid heat storage material data obtained in above-described embodiment 1：Caustic soda 0.18%, SiO2：8.96%, Fe2O3：69.11%,
Al2O3：3.06%, MgO：16.73%, CaO：1.96%；Bulk density 3.72g/cm3, cold crushing strength（110℃x24h）
76.3MPa；Specific heat capacity（100℃）0.96Kj/（kg.k）,（400℃）1.02Kj/（kg.k）,（700℃）1.08Kj/（kg.k）,
Thermal conductivity factor（100℃）4.6w/（m.k）,（400℃）3.8w/（m.k）（700℃）3.2w/（m.k）.
The gitter brick even particle distribution, shaping is good, surface flawless, and brick strength is greatly reinforced after drying.Highest
732 DEG C of heating-up temperature, brick body is rubescent, and brick laying structure is unchanged, after vacant 24 hours, is placed in 2 hours in boiling water, then to soak 72 small
When, vacant 120 days after taking-up, brick strength is unchanged, anhydrous.
Embodiment 2.
Solid heat storage material, the weight portion of its constitutive material is：30 parts of the waste and old magnesium grey iron block of 5 parts of iron ore, cement kiln, iron scale
15 parts, 20 parts of carborundum dust-removing powder, 15 parts of aluminium nitride, 5 parts of beryllium nitride, 2 parts of boron mud, 1.5 parts of calgon, the efficient glue of magnalium
4 parts of 1 part of knot agent and water.
Solid heat storage material data obtained in above-described embodiment 2：Caustic soda 0.13%, SiO2 46.52%, SiC 9.13%,
Fe2O35.01%, MgO 38.25%, CaO 0.96%.Bulk density 3.16g/cm3, cold crushing strength（110℃x24h）
108.32MPa；Specific heat capacity（100℃）1.01Kj/（kg.k）,（400℃）1.08Kj/（kg.k）,（700℃）1.16Kj/
（kg.k）, thermal conductivity factor（100℃）19.5w/（m.k）,（400℃）17.4w/（m.k）（700℃）16.8w/（m.k）.
The gitter brick even particle distribution, shaping is good, surface flawless；After drying, cut without discovery with brick cutting machine
Weight base；1073 DEG C of maximum heating temperature, insulation is taken out after 12 hours, and brick laying structure is unchanged, after vacant 12 hours, is placed in boiling water
In 2 hours, then soak 72 hours, vacant 120 days after taking-up, brick strength is unchanged, anhydrous.
Embodiment 3.
Solid heat storage material, the weight portion of its constitutive material is：50 parts of the waste and old magnesium grey iron block of 5 parts of iron ore, cement kiln, carbonization
10 parts of silicon dust-removing powder, 10 parts of iron scale, 5 parts of aluminium nitride, 1 part of beryllium nitride, 2 parts of boron mud, 1 part of calgon, magnalium are efficiently cementing
3.5 parts of 2 parts of agent and water.
Solid heat storage material data obtained above：Caustic soda 0.23%, SiO2 14.02%, Al2O31.13%, Fe2O3
16.01%, MgO 66.35%, CaO 2.20%, other 0.06%；Bulk density 3.22g/cm3, cold crushing strength（110℃*
24h）68.32MPa；Specific heat capacity（100℃）1.08Kj/（kg.k）,（400℃）1.12Kj/（kg.k）,（700℃）1.21Kj/
（kg.k）, thermal conductivity factor（100℃）10.3w/（m.k）,（400℃）4.6w/（m.k）（700℃）3.4w/（m.k）.
The gitter brick even particle distribution, shaping is good, surface flawless；After drying, cut without discovery with brick cutting machine
Weight base.823 DEG C of maximum heating temperature, insulation is taken out after 10 hours, and brick laying structure is unchanged, after vacant 12 hours, is placed in boiling water
In 2 hours, then soak 72 hours, vacant 90 days after taking-up, brick strength is unchanged, anhydrous.
Commercially available common magnesium iron gitter brick heat-storing material data：Caustic soda 0.27%, SiO2 2.86%, Al2O32.69%, Fe2O3
8.76%, MgO 83.64%, CaO 1.78%.Bulk density 2.91g/cm3, cold crushing strength（110℃*24h）88.32MPa；
Specific heat capacity（100℃）1.13Kj/（kg.k）,（400℃）1.18Kj/（kg.k）,（700℃）1.24Kj/（kg.k）, thermal conductivity factor
（100℃）13.3w/（m.k）,（400℃）5.3w/（m.k）（700℃）3.7w/（m.k）.
Learnt by above-mentioned heat-storing material data, the gitter brick of same volume, the normal temperature amount of stored heat of example 1 is：0.96×3.72=
3.57, and the normal temperature amount of stored heat of commercially available magnesium iron gitter brick is：1.13 × 2.9=3.227, the former improves than the amount of stored heat of the latter
10.3%.High-temperature heat accumulation amount example 1：1.08 × 3.72=4.01, commercially available high temperature magnesium iron gitter brick amount of stored heat is：1.24×2.9=
3.59, the former improves 11.6% than the amount of stored heat of the latter.It is low because the thermal conductivity factor change of the normal temperature of example 1 to high temperature section is smaller
The thermal conductivity factor of temperature section example 1 only has 4.6/13.3=0.34 times of magnesium iron gitter brick thermal conductivity factor, it is possible to uniform release
Heat.The time for discharging heat is longer, can significantly improve the short problem of current hot stored electric heating Exotherm Time.
The normal temperature amount of stored heat of example 2 is：1.01 × 3.16=3.19, and the normal temperature amount of stored heat of commercially available magnesium iron gitter brick is：
1.13 × 2.9=3.227, the amount of stored heat of the former with the latter remains basically stable.High-temperature heat accumulation amount example 2：1.16 × 3.16=3.66, city
Selling high temperature magnesium iron gitter brick amount of stored heat is：1.24 × 2.9=3.59, the amount of stored heat of the former with the latter remains basically stable.Due to example 2
The thermal conductivity factor change of normal temperature to high temperature section is smaller, and the thermal conductivity factor of high temperature section example 2 is magnesium iron gitter brick thermal conductivity factor
16.8/3.7=4.54 again, so high temperature section can rapidly discharge heat under artificial manipulation, current accumulation of heat grill pan is significantly improved
Stove discharges problem not out in high temperature section heat.
The indices of example 3 are essentially identical with commercially available magnesium iron gitter brick；It is that low heat conduction and high heat conduction gitter brick are provided
Data supporting.
Claims (5)
1. a kind of solid heat storage material, it is characterised in that its raw materials by weight portion proportioning includes：Iron ore 5-95 parts, magnesium iron
Brick 5-50 parts, 5-20 parts of iron unicorn, 5-20 parts of carborundum dust-removing powder, aluminium nitride 1-20 parts, beryllium nitride 1-5 parts, 0.5-5 parts of boron mud,
Calgon 1-2.5 parts, 1-2 parts and water 1-4 parts of magnalium high temperature cementing agent.
2. solid heat storage material as claimed in claim 1, it is characterised in that composition and the weight fraction proportioning of described magnesia brick
It is magnesia 84.2%, di-iron trioxide 8.6%, silica 3.13%, calcium oxide 1.85%, alundum (Al2O3) 2.22%；Described
The waste and old magnesium grey iron block of the preferred cement kiln of magnesia brick.
3. solid heat storage material as claimed in claim 1, it is characterised in that the composition and weight of described magnalium high temperature cementing agent
Amount fraction proportioning is magnesia 45g, alundum (Al2O3) 50.5g, silica 2g, di-iron trioxide 1g, calcium oxide 1.5g.
4. the solid heat storage material as described in claim 1-3, it is characterised in that specifically include following steps：By constitutive material
Weight portion weigh each raw material, iron ore is broken into particle diameter for 3-5mm particles first, it is standby；Magnesium grey iron block is broken into particle diameter
No more than the particle of 3mm, standby；Carborundum dust-removing powder is pulverized, granularity is 200 mesh, standby；Iron phosphorus is broken into no more than
5mm particle diameters, it is standby；Merge the standby raw material of above-mentioned preparation, be subsequently adding other raw materials, 1 is stirred under the conditions of 60-120 revs/min
Hour, it is sufficiently mixed each raw material；Take compound and be pressed into adobe under 600-800 tons of forcing press, be placed in temperature for 200-240
In DEG C drying kiln, dry 16 hours, obtain final product.
5. the solid heat storage material as described in claim 1-4 is any, it is characterised in that can apply to paddy electricity thermal storage equipment.
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| CN109504353A (en) * | 2018-12-24 | 2019-03-22 | 中国有色集团晋铝耐材有限公司 | A kind of high specific heat capacity heat-storing material and preparation method thereof |
| CN115321947A (en) * | 2022-08-11 | 2022-11-11 | 北京华厚能源科技有限公司 | Iron-based heat storage brick and preparation method thereof |
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| CN115321947A (en) * | 2022-08-11 | 2022-11-11 | 北京华厚能源科技有限公司 | Iron-based heat storage brick and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN106905929B (en) | 2019-09-20 |
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