Catalytic phase change dielectric sphere for methanol combustion and preparation method therefor

Abstract

The present invention discloses a catalytic phase change dielectric sphere for methanol combustion and a preparation method therefor. The catalytic phase change dielectric sphere for methanol combustion is mainly prepared from a high-temperature phase change material, an active material, a carrier material, a catalyst, a nano-semiconductor material, a nano-transition metal and an adhesive. A catalytic phase change dielectric solid sphere is prepared with a mixed pressing and sintering process, the methanol energy conversion rate reaches 87.5%, the furnace temperature of methanol combustion reaches 900° C. or higher, and waste heat recovery is realized; or, a catalytic phase change dielectric microporous hollow sphere is prepared through electrostatic adsorption and in-site redox reaction, the methanol energy conversion rate reaches 99% or higher, the furnace temperature of methanol combustion reaches 1000° C. or higher, and waste heat recovery is realized.

Claims

1. A catalytic phase change dielectric sphere for methanol combustion, prepared from the following part by weight of raw materials (measured by 100 parts by weight): 8-12 parts of high-temperature phase change material, 0.05-0.30 part of active material, 75.2-81.7 parts of carrier material, 0.10-0.20 part of catalyst material, 0.10-0.20 part of nano-semiconductor material, 0.05-0.10 part of nano-transition metal and 10-12 parts of adhesive.

2. The catalytic phase change dielectric sphere for methanol combustion according to claim 1, wherein the high-temperature phase change material is a binary-molten-salt high-temperature phase, change material consisting of sodium carbonate and sodium chloride, a binary-molten-salt high-temperature phase change material consisting of sodium carbonate and potassium carbonate, a ternary-molten-salt high-temperature phase change material consisting of sodium carbonate, potassium chloride and sodium chloride or a high-temperature phase change material consisting of sodium carbonate, potassium carbonate, lithium carbonate and magnesium oxide.

3. The catalytic phase change dielectric sphere for methanol combustion according to claim 2, wherein the mass ratio of sodium carbonate to sodium chloride in the binary-molten-salt high-temperature phase change material consisting of sodium carbonate and sodium chloride is 0.5-1:0.75-1; the mass ratio of sodium carbonate to potassium carbonate in the binary-molten-salt high-temperature phase change material consisting of sodium carbonate and potassium carbonate is 0.5-1:0.75-1; the mass ratio of sodium carbonate to potassium chloride and sodium chloride in the ternary-molten-salt high-temperature phase change material consisting of sodium carbonate, potassium chloride and sodium chloride is 0.5-1:0.75-1:0.75-1; and the mass ratio of sodium carbonate to potassium carbonate, lithium carbonate and magnesium oxide in the high-temperature phase change material consisting of sodium carbonate, potassium carbonate, lithium carbonate and magnesium oxide is 0.5-1:0.5-1:1:0.3-0.65.

4. A preparation method for the catalytic phase change dielectric sphere for methanol combustion, comprising preparing a solution 1 and a solution 2, wherein the preparation of solution 1 comprises the following steps: 1) weighing each raw material according to the part by weight of the raw materials of the catalytic phase change dielectric sphere for methanol combustion according to claim 3; 2) uniformly mixing the active material, the carrier material, the catalyst material, the nano-semiconductor material and the nano-transition metal, grinding the mixture to be ultra-fine micron powder, adding to the high-temperature phase change material, uniformly dispersing, and obtaining a premix material; 3) adding adhesive and an appropriate amount of water to the premix material, stirring, dispersing and mixing, granulating, and obtaining an initial product of the dielectric sphere; and 4) firing the initial product of the dielectric sphere, molding, and obtaining a solid sphere of the catalytic phase change dielectric sphere for methanol combustion; and the preparation of solution 2 comprises the following steps: 1) weighing each raw material according to the part by weight of the raw materials of the catalytic phase change dielectric sphere for methanol combustion according to claim 3; 2) dividing the carrier material into two parts, preparing the first part of carrier material into a hollow sphere, adhering the high-temperature phase change material to the surface of the hollow sphere by the adhesive, drying; 3) mixing and reacting with the active material, the second part of carrier material, the catalyst material, the nano-semiconductor material and the nano-transition metal, obtaining a double-shell structure; and 4) firing the double-shell structure, and obtaining a hollow microporous sphere of the catalytic phase change dielectric sphere for methanol combustion.

5. A preparation method for the catalytic phase change dielectric sphere for methanol combustion according to claim 4, wherein the high-temperature phase change material in the solution 1 or solution 2 is prepared by the following steps: 1) uniformly mixing the raw materials of the high-temperature phase change material according to the mass ratio, drying and then grinding the mixture to be ultra-fine micron powder, and obtaining raw material powder for later use; 2) firing the raw material powder to a molten state, obtaining a mixed molten salt material; and 3) adding magnesium oxide, adhesive and water to, the mixed molten salt material, uniformly mixing and then firing, and obtaining the high-temperature phase change material.

6. A preparation method for the catalytic phase change dielectric sphere for methanol combustion according to claim 5, wherein in the step 3), the mass percentages of the mixed molten salt material, the magnesium oxide, the adhesive and the water are 55%, 36%, 8.5% and 0.5% respectively.

7. The catalytic phase change dielectric sphere for methanol combustion according to claim 1, wherein the active material is one or a combination of platinum, palladium, rhodium or iridium; the carrier material is one or a combination of α-Al2O3, kyanite, spinel, silicon carbide, silicon nitride, silicon phosphide, boron carbide, boron nitride, boron phosphide, mullite; the catalyst material is one or a combination of magnesium oxide, cerium dioxide, copper oxide, manganese oxide; the nano-semiconductor material is one or a combination of nano titanium dioxide, nano zinc oxide, nano tin oxide, nano cadmium oxide, nano ferric oxide, nano aluminium oxide, nano chromium oxide and nano aluminium trioxide; the nano-transition metal is one or a combination of nano cerium oxide, nano cobaltous oxide and nano tungsten oxide; and the adhesive is one or a combination of silica sol, potassium silicate, sodium silicate, silicone resin, phenolic resin, urea-formaldehyde resin, high-temperature-resistant epoxy resin and polyimide resin.

8. A preparation method for the catalytic phase change dielectric sphere for methanol combustion according to claim 5, wherein in the step 1), the drying temperature is 115-125° C., the duration is 24-30 h; and in the step 3), the firing operation is performed for 1-1.5 h at 730-750° C.

9. A preparation method for the catalytic phase change dielectric sphere for methanol combustion according to claim 4, wherein in the step 2) of the solution 1, the dispersing duration is 30-35 min, the rotational speed is 3500-5000 r/min; in the step 3), the granulating diameter is 6-19 mm, the granulating pressure is 13-17 mpa; and the adding amount of water accounts for 0.5%-0.8% of the gross weight of the raw materials of the catalytic phase change dielectric sphere for methanol combustion; and in the step 4), the firing operation is performed for 1-1.5 h at 730-750° C.

10. A preparation method for the catalytic phase change dielectric sphere for methanol combustion according to claim 4, wherein in the solution 2, the mass ratio of the first part of carrier material to the second part of carrier material is 0.5-1:1; in the step 2), an adhering thickness of the high-temperature phase change material is 18-20 μm; and the drying operation is performed for 30-32 min at 80-85° C.; in the step 3), the mixing and reacting duration is 15-30 min; and in the step 4), the firing operation is performed for 1-1.5 h at 730-750° C.

Description

DETAILED DESCRIPTION

(1) The technical solution in embodiments of the present invention will be clearly and fully described below. The described embodiments are merely part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments in the present invention, all other embodiments obtained by those ordinary skilled in the art without contributing creative labor will belong to the protection scope of the present invention.

(2) In the following embodiments, the high-temperature phase change material is prepared by the following steps: 1) uniformly mixing the raw materials of the high-temperature phase change material according to mass ratio drying for 24 h at 120° C., grinding to ultra-fine micron powder, and obtaining raw material powder for later use; 2) firing the raw material powder to a molten state and obtaining a mixed molten salt material; and 3) adding magnesium oxide, adhesive and water to the mixed molten salt material, wherein the mixture contains: 55% mixed molten salt, 36% magnesium oxide, 8.5% adhesive and 0.5% water respectively, uniformly mixing, firing for 1 h at 750° C., and obtaining the high-temperature phase change material.

(3) The specific operation of the combustion test is as follows: paving solid spheres of the catalytic phase change dielectric sphere at the combustion port of the methanol combustion furnace with the paving thickness of 5-10 mm, preferably 6 mm, and observing and recording methanol combustion state.

Embodiment 1

(4) A preparation method for the catalytic phase change dielectric sphere for methanol combustion, comprising the following steps: 1) weighing all raw materials according to the following mass: 8 g of binary-molten-salt high-temperature phase change material consisting of sodium carbonate and sodium chloride in the mass ratio of 1:1, 0.05 g of palladium, 81.6 g of a-Al.sub.2O.sub.3, 0.15 g of cerium dioxide, 0.15 g of nano titanium dioxide, 0.05 g of nano cerium oxide, and 10 g of sodium silicate; 2) uniformly mixing the palladium, the a-Al.sub.2O.sub.3, the cerium dioxide, the nano titanium dioxide and the nano cerium oxide, grinding the mixture to ultra-fine micron powder, adding to the binary-molten-salt high-temperature phase change material, dispersing for 30 min at the rotational speed of 3500 r/min to be uniform, and obtaining a premix material; 3) adding sodium silicate and water to the premix material, fully stirring, dispersing and mixing, granulating, wherein the granulating diameter is 16 mm, and the granulating pressure is 15 mpa, and obtaining an initial product of the dielectric sphere, wherein the adding amount of water is 0.5 g; and 4) firing the initial product of the dielectric sphere for 1 h at 750° C., molding, and obtaining a solid sphere of the catalytic phase change dielectric sphere for methanol combustion.

(5) When a professional methanol combustion furnace is used to conduct combustion test, solid spheres of the catalytic phase change dielectric sphere are paved at the combustion port of the methanol combustion furnace with the paving thickness of 6 mm, the test results are as follows: (according to the heat (Kcal) required for increasing the indoor area of 20000 m.sup.2 by 1° C. (indoor height is 3 m)

(6) TABLE-US-00001 Test Indexes Test Results Methanol conversion rate 87.3% Average temperature reached by combustion furnace 788° C. Methanol consumption (kg/h) 1.8 Operating cost of methanol (yuan/h) (the unit price of 5.40 methanol is calculated at 3 yuan/kg) Power consumption of methanol combustion furnace 1.50 (kW/h) Power consumption cost (yuan/h) (electricity price: 0.75 0.5 yuan/kWh) Direct operating cost, (methanol + power) (yuan/h) 6.15 Year-on-year power fare used (yuan/h) 13.50

Embodiment 2

(7) A preparation method for the catalytic phase change dielectric sphere for methanol combustion, comprising the following steps: 1) weighing all raw materials according to the following mass: 8 g of binary-molten-salt high-temperature phase change material consisting of sodium carbonate and sodium chloride in the mass ratio of 1:1, 0.05 g of palladium, 81.6 g of a-Al.sub.2O.sub.3, 0.15 g of cerium dioxide, 0.15 g of nano titanium dioxide, 0.05 g of nano cerium oxide, and 10 g of sodium silicate; 2) dividing the a-Al.sub.2O.sub.3 into two parts, wherein the mass ratio of the first part of a-Al.sub.2O.sub.3 to the second part of a-Al.sub.2O.sub.3 is 0.5, preparing the first part of a-Al.sub.2O.sub.3 into a hollow sphere, adhering the binary-molten-salt high-temperature phase change material to the surface of the hollow sphere by sodium silicate, the thickness being 20 um, and drying for 30 min at 80° C.; 3) mixing and reacting with the palladium, the second part a-Al.sub.2O.sub.3, the cerium dioxide, the nano titanium dioxide and the nano cerium oxide for 15 min, and obtaining a double-shell structure; and 4) firing the double-shell structure for 1 h at 750° C., and obtaining a hollow microporous sphere of the catalytic phase change dielectric sphere for methanol combustion.

(8) When a professional methanol combustion furnace is used to conduct combustion test, solid spheres of the catalytic phase change dielectric sphere are paved at the combustion port of the methanol combustion furnace with the paving thickness of 5 mm, the test results are as follows: (according to the heat (Kcal) required for increasing the indoor area of 20000 m.sup.2 by 1° C. (indoor height is 3 m)

(9) TABLE-US-00002 Test Indexes Test Results Methanol conversion rate 99.3% Average temperature reached by 1001° C. combustion furnace Methanol consumption (kg/h) 1.6 Operating cost of methanol (yuan/h) (the unit price 4.80 of methanol is calculated at 3 yuan/kg) Power consumption of methanol combustion furnace 1.20 (kW/h) Power consumption cost (yuan/h) (electricity price 0.60 0.5 yuan/kWh) Direct operating cost, (methanol + power) (yuan/h) 5.40 Year-on-year power fare used (yuan/h) 13.50

Embodiment 3

(10) A preparation method for the catalytic phase change dielectric sphere for methanol combustion, comprising the following steps: 1) weighing all raw materials according to the following mass: 9.6 g of high-temperature phase change material obtained by mixing sodium carbonate, potassium carbonate, lithium carbonate and magnesium oxide in the mass ratio of 1:1:1:0.65, 0.05 g of rhodium, 80.06 g of a-Al.sub.2O.sub.3, 0.15 g of copper oxide, 0.15 g of mixture of nano stannic oxide and nano cadmium oxide in the mass ratio of 2:1, 0.05 g of nano tungsten oxide, and 10 g of silicone resin; 2) uniformly mixing the rhodium, the a-Al.sub.2O.sub.3, the copper oxide, and the mixture of nano stannic oxide and nano cadmium oxide in the mass ratio of 2:1 with the nano tungsten oxide, grinding the mixture to ultra-fine, micron power, adding to the high-temperature phase change material, dispersing for 30 min at the rotational speed of 5000 r/min to be uniform, and obtaining a premix material; 3) adding silicone resin and water to the premix material, fully stirring, dispersing and mixing, granulating, wherein the granulating diameter is 6 mm, and the granulating pressure is 15 mpa, and obtaining an initial product of the dielectric sphere, wherein the adding amount of water is 0.8 g; and 4) firing the initial product of the dielectric sphere for 1 h at 750° C., molding, and obtaining a solid sphere of the catalytic phase change dielectric sphere for methanol combustion.

(11) When a professional methanol combustion furnace is used to conduct combustion test, solid spheres of the catalytic phase change dielectric sphere are paved at the combustion port of the methanol combustion furnace with the paving thickness of 10 mm, the test results are as follows: (according to the heat (Kcal) required for increasing the indoor area of 20000 m.sup.2 by 1° C. (indoor height is 3 m)

(12) TABLE-US-00003 Test Indexes Test Results Methanol conversion rate 88% Average temperature reached 971° C. by combustion furnace Methanol consumption (kg/h) 1.70 Operating cost of methanol (yuan/h) 5.10 (the unit price of methanol is calculated at 3 yuan/kg) Power consumption of methanol 1.20 combustion furnace (kW/h) Power consumption cost (yuan/h) 0.6 (electricity price: 0.5 yuan/kWh) Direct operating cost, (methanol + power) (yuan/h) 5.70 Year-on-year power fare used (yuan/h) 13.50

Embodiment 4

(13) A preparation method for the catalytic phase change dielectric sphere for methanol combustion, comprising the following steps: 1) weighing all raw materials according to the following mass: 9.6 g of high-temperature phase change material obtained by mixing sodium carbonate, potassium carbonate, lithium carbonate and magnesium oxide in the mass ratio of 1:1:1:0.65, 0.05 g of rhodium, 80.0 g of a-Al.sub.2O.sub.3, 0.15 g of copper oxide, 0.15 g of mixture of nano stannic oxide and nano cadmium oxide in the mass ratio of 2:1, 0.05 g of nano tungsten oxide, and 10 g of silicone resin; 2) dividing the a-Al.sub.2O.sub.3 into two parts, wherein the mass ratio of the first part of a-Al.sub.2O.sub.3 to the second part of a-Al.sub.2O.sub.3 is 1:1, preparing the first part of a-Al.sub.2O.sub.3 into a hollow sphere, adhering the high-temperature phase change material to the surface of the hollow sphere by silicone resin, the thickness being 20 um, and drying for 30 min at 80° C.; 3) mixing and reacting with the rhodium, the second part a-Al.sub.2O.sub.3, the copper oxide, the mixture of nano stannic oxide and nano cadmium oxide in the mass ratio of 2:1 and nano tungsten oxide for 30 min, and obtaining a double-shell structure; and 4) firing the double-shell structure for 1 h at 750° C., and obtaining a hollow microporous sphere of the catalytic phase change dielectric sphere for methanol combustion.

(14) When a professional methanol combustion furnace is used to conduct combustion test, solid spheres of the catalytic phase change dielectric sphere are paved at the combustion port of the methanol combustion furnace with the paving thickness of 7 mm, the test results are as follows: (according to the heat (Kcal) required for increasing the indoor area of 20000 m.sup.2 by 1° C. (indoor height is 3 m)

(15) TABLE-US-00004 Test Indexes Test Results Methanol conversion rate 99.5% Average temperature reached 1012° C. by combustion furnace Methanol consumption (kg/h) 1.6 Operating cost of methanol (yuan/h) 4.80 (the unit price of methanol is calculated at 3 yuan/kg) Power consumption of methanol combustion furnace 0.60 (kW/h)/h) Power consumption cost (yuan/h) 0.30 (electricity price: 0.5 yuan/kWh) Direct operating cost, (methanol + power) (yuan/h) 5.10 Year-on-year power fare used (yuan/h) 13.50

Embodiment 5

(16) A preparation method for the catalytic phase change dielectric sphere for methanol combustion, comprising the following steps: 1) weighing all raw materials according to the following mass: 8.3 g of binary-molten-salt high-temperature phase change material consisting of sodium carbonate and potassium carbonate in the mass ratio of 1:1, 0.05 g of iridium, 81.3 g of a-Al2O.sub.3, 0.15 g of mixture of magnesium oxide and cerium dioxide in the mass ratio of 1:1, 0.15 g of nano ferric oxide, 0.05 g of nano tungsten oxide and 10 g of potassium silicate; 2) uniformly mixing the iridium, the a-Al.sub.2O.sub.3, the mixture of magnesium oxide and cerium dioxide in the mass ratio of 1:1, the nano ferric oxide and the nano tungsten oxide, grinding the mixture to ultra-fine micron powder, adding to the binary-molten-salt high-temperature phase change material, dispersing for 30 min at the rotational speed of 4000 r/min to be uniform, and obtaining a premix material; 3) adding potassium silicate and water to the premix material, fully stirring, dispersing and mixing, granulating, wherein the granulating diameter is 6 mm, and the granulating pressure is 15 mpa, and obtaining an initial product of the dielectric sphere, wherein the adding amount of water is 0.8 g; and 4) firing the initial product of the dielectric sphere for 1 h at 750° C., molding, and obtaining a solid sphere of the catalytic phase change dielectric sphere for methanol combustion.

(17) When a professional methanol combustion furnace is used to conduct combustion test, solid spheres of the catalytic phase change dielectric sphere are paved at the combustion port of the methanol combustion furnace with the paving thickness of 8 mm, the test results are as follows: (according to the heat (Kcal) required for increasing the indoor area of 20000 m.sup.2 by 1° C. (indoor height is 3 m)

(18) TABLE-US-00005 Test Indexes Test Results Methanol conversion rate 89.9% Average temperature reached 987° C. by combustion furnace Methanol consumption (kg/h) 1.50 Operating cost of methanol (yuan/h) 4.50 (the unit price of methanol is calculated at 3 yuan/kg) Power consumption of methanol combustion furnace 1.10 (kW/h) Power consumption cost (yuan/h) 0.55 (electricity price: 0.5 yuan/kWh) Direct operating cost, (methanol + power) (yuan/h) 5.05 Year-on-year power fare used (yuan/h) 13.50

Embodiment 6

(19) A preparation method for the catalytic phase change dielectric sphere for methanol combustion, comprising the following steps: 1) weighing all raw materials according to the following mass: 8.3 g of binary-molten-salt high-temperature phase change material consisting of sodium carbonate and potassium carbonate in the mass ratio of 1:1, 0.05 g of iridium, 81.3 g of a-Al.sub.2O.sub.3, 0.15 g of mixture of magnesium oxide and cerium dioxide in the mass ratio of 1:1, 0.15 g of nano ferric oxide, 0.05 g of nano tungsten oxide and 10 g of potassium silicate; 2) dividing the a-Al.sub.2O.sub.3 into two parts, wherein the mass ratio of the first part of a-Al.sub.2O.sub.3 to the second part of a-Al.sub.2O.sub.3 is 0.8:1, preparing the first part of a-Al.sub.2O.sub.3 into a hollow sphere, adhering the binary-molten-salt high-temperature phase change material to the surface of the hollow sphere by potassium silicate, the thickness being 20 um, and drying for 30 min at 80° C.; 3) mixing and reacting with the iridium, the second part a-Al.sub.2O.sub.3, the mixture of magnesium oxide and cerium dioxide in the mass ratio of 1:1, the nano ferric oxide and the nano tungsten oxide for 25 min, and obtaining a double-shell structure; and 4) firing the double-shell structure for 1 h at 750° C., and obtaining a hollow microporous sphere of the catalytic phase change dielectric sphere for methanol combustion.

(20) When a professional methanol combustion furnace is used to conduct combustion test, solid spheres of the catalytic phase change dielectric sphere are paved at the combustion port of the methanol combustion furnace with the paving thickness of 6 mm, the test results are as follows: (according to the heat (Kcal) required for increasing the indoor area of 20000 m.sup.2 by 1° C. (indoor height is 3 m)

(21) TABLE-US-00006 Test Indexes Test Results Methanol conversion rate 99.9% Average temperature reached 1048° C. by combustion furnace Methanol consumption (kg/h) 1.40 Operating cost of methanol (yuan/h) 4.20 (the unit price of methanol is calculated at 3 yuan/kg) Power consumption of methanol combustion furnace 0.60 (kW/h) Power consumption cost (yuan/h) 0.30 (electricity price: 0.5 yuan/kWh) Direct operating cost, (methanol + power) (yuan/h) 4.50 Year-on-year power fare used (yuan/h) 13.50