CN102417168B - Method for producing calcium nitride powder - Google Patents
Method for producing calcium nitride powder Download PDFInfo
- Publication number
- CN102417168B CN102417168B CN 201110249949 CN201110249949A CN102417168B CN 102417168 B CN102417168 B CN 102417168B CN 201110249949 CN201110249949 CN 201110249949 CN 201110249949 A CN201110249949 A CN 201110249949A CN 102417168 B CN102417168 B CN 102417168B
- Authority
- CN
- China
- Prior art keywords
- powder
- reactor
- cacl2
- ball
- producing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000843 powder Substances 0.000 title claims abstract description 89
- 239000011575 calcium Substances 0.000 title claims abstract description 37
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 36
- -1 calcium nitride Chemical class 0.000 title claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 75
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 37
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 238000000498 ball milling Methods 0.000 claims abstract description 17
- 239000000654 additive Substances 0.000 claims abstract description 14
- 230000000996 additive effect Effects 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims abstract description 12
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 12
- 239000010439 graphite Substances 0.000 claims abstract description 12
- 238000007873 sieving Methods 0.000 claims abstract description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 59
- 239000001110 calcium chloride Substances 0.000 claims description 59
- 235000011148 calcium chloride Nutrition 0.000 claims description 59
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 59
- 238000002485 combustion reaction Methods 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
- 150000003863 ammonium salts Chemical class 0.000 claims description 10
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 8
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 4
- 229910001120 nichrome Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 29
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract 2
- 239000002184 metal Substances 0.000 abstract 2
- 239000003085 diluting agent Substances 0.000 abstract 1
- 229920002635 polyurethane Polymers 0.000 abstract 1
- 239000004814 polyurethane Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 18
- 238000005303 weighing Methods 0.000 description 17
- 238000002156 mixing Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000005049 combustion synthesis Methods 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 229910052582 BN Inorganic materials 0.000 description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 235000011089 carbon dioxide Nutrition 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005121 nitriding Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000882 Ca alloy Inorganic materials 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Abstract
The invention discloses a method for producing calcium nitride powder. The method comprises the following steps: adding the following components by weight percent: 30-50% of metal calcium powder, 30-50% of diluting agent and 10-20% of additive, wherein the metal calcium powder is used as a raw material; placing a proportioned mixture in a polyurethane tank to carry out ball milling for 1-4 hours, and sieving with a screen after ball milling; putting the mixture powder in a graphite boat, and then placing the graphite boat in a self-propagating reactor; vacuumizing to 400-600 Pa, and then introducing nitrogen, maintaining the pressure in the self-propagating reactor to be 4-8MPa, igniting and carrying out self-propagating synthesis; and when the pressure in the self-propagating reactor is reduced to 4-8MPa, finishing the self-propagating reaction, releasing the gas in the reactor, and then introducing nitrogen to the self-propagating reactor for 1-5 minutes, and opening the reactor so as to obtain the calcium nitride powder finished product. The calcium nitride powder prepared by using the method disclosed by the invention has wide raw material resources, high phase content and high purity; the method disclosed by the invention has simple and reliable process; and by using the method, energy is saved.
Description
Technical field
The present invention relates to a kind of method of producing CaCl2, relate in particular to a kind of method of producing the CaCl2 powder, belong to technical field of inorganic nonmetallic materials.
Background technology
CaCl2 (Ca
3N
2) powder is a kind of brown ceramic powder, density 2.63g/cm
3(17 ℃), 1195 ℃ of fusing points, ionic compound.CaCl2 can be widely used in fields such as semiconductor material, fine ceramics and high-end refractory materials, in the solid state reaction of the many type materials (for example boron nitride, silicon nitride) with advantageous property of preparation, CaCl2 is indispensable sintering aid, and for example CaCl2 can promote hexagonal boron nitride to the conversion of cubic boron nitride under High Temperature High Pressure.CaCl2 also can be used for preparing special stupalith and special glass, also can be used for the additive of high-strength steel smelting etc.Simultaneously, it was one of storage hydrogen series material by the M-N-H of extensive concern (M refers to I.IV family and some magnesium-yttrium-transition metals) in recent years still.In addition, generally believe that at present the CaCl2 powder is the direct band-gap semicondictor material, bandwidth is about 2.8eV, and therefore, CaCl2 has potential using value aspect photodiode and the laser diode.
CaCl2 has multiple preparation method, as metallic calcium powder and nitrogen direct reaction method, metallic calcium powder and ammonia direct reaction method, Low Pressure Chemical Vapor Deposition etc., wherein preceding two kinds of methods are fit to scale operation, cost is also cheap relatively, has the method that industrial production is worth, and above-mentioned two kinds of methods all are to be 700 ℃～1050 ℃ at nitriding temperature, reacted 1 hour with metallic calcium powder and flowing nitrogen (or ammonia), preparation CaCl2 powder, the reaction times is longer, and energy consumption is bigger.Chinese patent literature (CN1665744A) discloses French Buddhist Lang Keyisi Ren and has adopted the zinc calcium alloy of droplet to make CaCl2 in nitrogen environment, the raw material costliness that this method adopts, and contain a spot of zinc element impurity in the powder of preparation.
Summary of the invention
The objective of the invention is to overcome the deficiency of above-mentioned prior art, a kind of phase content height is provided, the purity height, operation is simple and reliable, is easy to realize the method for the production CaCl2 powder of scale operation.
Technical solution of the present invention is: a kind of method of producing the CaCl2 powder the steps include:
(1) batching: be raw material with the metallic calcium powder, add thinner, additive, its weight percent proportioning is:
Metallic calcium powder: 30～50%,
Thinner 30～50%,
Additive 10～20%,
(2) mix: the mixture of batching is placed in the urethane jar, is medium with the abrading-ball, ball milling 1～4 hour;
(3) mix powder behind the ball milling sieves with screen cloth;
(4) from climing combustion reaction: the mix powder after above-mentioned the sieving is contained in the graphite boat, is placed in climing combustion reactor again, be evacuated to inflated with nitrogen behind 400～600Pa, remain on 4～8MPa from climing combustion reactor pressure, igniting is synthesized from climing combustion;
(5) obtain finished product: when the pressure in climing combustion reactor drops to 4～8MPa, finish from climing combustion reaction, the gas in the releasing reactor to fill 1～5 minute nitrogen in climing combustion reactor, is opened reactor then, namely obtains CaCl2 powder finished product.
The granularity of the described metallic calcium powder in the above-mentioned steps (1) is 100～600 orders.
Described thinner in the above-mentioned steps (1) is the CaCl2 powder, purity＞97%, and median size is 1～20 micron.
The described additive of above-mentioned steps (1) is ammonium salt or urea.
Described ammonium salt is any one or its arbitrary combination in ammonium chloride, Neutral ammonium fluoride, the volatile salt.
Described abrading-ball in the above-mentioned steps (2) is alumina balls, zirconia ball, silicon nitride ball, and ball radius is 5～20 millimeters, and the mixture of batching and the weight ratio of abrading-ball are 1: 5～10.
The purity of institute's inflated with nitrogen is＞99.999% in the above-mentioned steps (4).
The aperture of screen cloth is 40～60 orders in the above-mentioned steps (3).
The purity of institute's inflated with nitrogen is＞99.9% in the above-mentioned steps (5).
Above-mentioned steps (4) igniting is by spirrillum nichrome wire or tungsten filament energising heating igniting.
The technique effect that the present invention has: the present invention adopts and to prepare the CaCl2 powder from climing combustion, is to utilize between metallic calcium powder and the additive ammonium salt exothermic heat of reaction and conduction mode certainly to synthesize nitrogenize calcium powder body.Starting material of the present invention adopt metallic calcium powder, and as the CaCl2 powder of thinner with as the ammonium salt of additive, starting material wide material sources.When metallic calcium powder and additive ammonium salt in case ignited, just can be from trend unreacted regional spread still, building-up reactions is rapid, the production efficiency height, entire reaction period (comprise batch mixing, building-up reactions, synthetics handle) 50～60 minutes is easy to suitability for industrialized production.Reactant is in case ignited, just can be from trend unreacted regional spread still, until reacting completely, except ignition reaction, whole process needs the external world that any energy is provided hardly, and namely building-up reactions relies on raw material id reaction liberated heat just can keep from climing combustion, therefore, present method can be saved the energy, reduces production costs, and is suitable for the LED industry.Because the temperature of control reaction preferably is 900～1100 ℃, the transformation efficiency height of reaction has reached more than 95%, and uses from the synthetic nitrogenize calcium powder body purity height of climing combustion high temperature, purity＞97%, crystal grain rule.It is good that the CaCl2 powder of the present invention's preparation also has fillibility, stable performance, and with low cost, technology is simple, the characteristics of less investment.Therefore, the method for preparing the CaCl2 powder from climing combustion of the present invention, the product purity height that obtains, the phase content height is by design and adjustment reactant system, select suitable additive, mainly be ammonium salt, in heat-processed, the additive ammonium salt decomposes the absorption heat, control is reflected at suitable temperature range well, can obtain high phase content.The present invention adds a certain amount of thinner CaCl2 powder, control the temperature of reaction on the one hand, the temperature field at each position of control reaction mass system evenly distributes, adjusted the porosity of material simultaneously, be beneficial to the nitriding reaction, realized the complete nitrogenize of calcium powder, guaranteed from climing combustion reacting balance, continued, carry out rapidly.In addition, the present invention vacuumizes processing before climing combustion reaction, reduced the oxygen level of synthesis gas, has reduced the foreign matter content of calcium oxide (CaO) in the reactant.
Description of drawings
1, Fig. 1 is from climing combustion reaction unit synoptic diagram
1, Fig. 2 is that embodiment 1 is from the CaCl2 powder X-ray diffractogram of climing combustion synthetic product sampling.
2, Fig. 3 is that embodiment 2 is from the CaCl2 powder X-ray diffractogram of climing combustion synthetic product sampling.
3, Fig. 4 is that embodiment 3 is from the CaCl2 powder X-ray diffractogram of climing combustion synthetic product sampling.
4, Fig. 5 is that embodiment 4 is from the CaCl2 powder X-ray diffractogram of climing combustion synthetic product sampling.
5, Fig. 6 is that embodiment 5 is from the CaCl2 powder X-ray diffractogram of climing combustion synthetic product sampling.
Among the figure: 1, cooling water circulation water jacket, 2, reaction mass, 3, graphite boat, 4, portfire, 5, nitrogen inlet, 6, nitrogen outlet.
Embodiment
The present invention adopts the method for preparing the CaCl2 powder from climing combustion, from climing combustion high temperature synthetic technology (Self-propagation High-temperature Synthesis, abbreviation SHS), also claim combustion synthesis technology (Combustion Synthesis, the CS that writes), be to utilize exothermic heat of reaction and conduction mode certainly between the reactant to come a kind of mode of synthetic materials.When reactant is ignited, just can be from trend unreacted regional spread still, until reacting completely, whole process needs the external world to provide any energy and reaction times very fast hardly, and it is simple to have technology, and energy consumption is low, product purity height, the characteristics of less investment.With synthesizing CaCl2 ceramic powder purity height from climing combustion high temperature, fillibility is good, and stable performance is with low cost.
In order to understand better and to implement, describe in detail below in conjunction with specific embodiment.
Embodiment 1
Take by weighing metallic calcium powder 1000 gram (account for raw material gross weight 50%) by weight ratio, this metallic calcium powder particle is 100 orders, purity＞99%; Take by weighing CaCl2 powder 800 gram (account for raw material gross weight 40%), this CaCl2 powder median size 20 μ m, purity＞98%; Take by weighing volatile salt (NH
4)
2CO
3200 grams (account for raw material gross weight 10%), after the mixing, (chemical formula: Si3N4) ball is ball-milling medium with silicon nitride, the silicon nitride ball diameter is 20 millimeters, be placed in 8 liters the urethane jar, the weight ratio of above-mentioned raw materials and silicon nitride abrading-ball is 1: 10, be placed on the jar mill dry ball milling 1 hour, the present embodiment jar mill adopts the GM8 of Zibo Qimingxing New Material Co., Ltd. to produce, carry out mechanize and do mixed the stirring, ball milling and mix after material cross 40 eye mesh screens, material after sieving is positioned in the half-terete graphite boat of porous equably, the present embodiment graphite boat adopts the product of Yantai graphite product factory, put into then from climing combustion synthesis reactor, after being evacuated down to 400Pa, the high pure nitrogen (nitrogen gas purity is＞99.999%) that charges into 8MPa reacts, in reactor, make heating element with the spirrillum nichrome wire of 0.6 millimeter of diameter, feed 40 amperes electric current, 4 seconds time length, make coil heating, temperature has reached the temperature of reaction (450 ℃) of metallic calcium powder and nitrogen in the raw mix, chemical reaction mode with climing combustion in material successively advances then, reaction times continues 18 minutes, reactor pressure begins to descend, the logical recirculated water cooling of reactor this moment, when the pressure of reactor drops to 8MPa, (gas contains unreacted nitrogen to have the gas of pressure in the releasing reactor, and the ammonia of volatile salt pyrolytic decomposition generation and carbonic acid gas etc.), the gas of release is eliminated remaining small amount of ammonia gas NH by water
3, to reduce topsoil, in reactor, fill 1 minute ordinary nitrogen (purity of nitrogen is＞99.9%, charges into the gaseous tension 1MPa of ordinary nitrogen) then, eliminate remaining small amount of ammonia gas NH
3, opening the product that reactor takes out loose shape then is the CaCl2 powder, and the product integral body that obtains is brown, and the CaCl2 purity that obtains is greater than 98%, reaction yield＞95%, product weight reaches 2108 grams.
The X-ray diffraction analysis of synthetic product CaCl2 powder is seen Fig. 2 in this example, and calculating its purity is 98.5% (weight ratio).
Take by weighing 600 gram metallic calcium powders (account for raw material gross weight 30%) by weight ratio, this metallic calcium powder particle is 600 orders, purity＞95%; Take by weighing 1000 gram CaCl2 powders (account for raw material gross weight 50%), this CaCl2 powder median size 20 μ m, purity＞98%; Take by weighing 400 gram ammonium chloride (NH
4)
2Cl (account for raw material gross weight 20%), after the mixing, be that 10 millimeters alumina balls are ball-milling medium with diameter, be placed in the urethane jar, above-mentioned raw materials and alumina balls weight ratio are 1: 10, be placed on the jar mill ball milling 4 hours, material after mixing is crossed 60 eye mesh screens, material after sieving is positioned in the half-terete graphite boat of porous equably, put into then from climing combustion synthesis reactor, after being evacuated to 600Pa, charge into the high pure nitrogen of 4MPa, tungsten filament with 0.6 millimeter of diameter is made heating element, feed 20 amperes electric current, 15 seconds time length, make coil heating, temperature has reached the temperature of reaction of metallic calcium powder and nitrogen in the raw mix, chemical reaction mode with climing combustion in material successively advances then, reaction times continues 8 minutes, and reactor pressure begins to descend, the logical recirculated water cooling of reactor this moment, when the pressure of reactor drops to 4MPa, the gas that has pressure in the releasing reactor (mainly be ammonium chloride decompose generate hydrogenchloride and ammonia gas and unreacted nitrogen) fills 1 minute ordinary nitrogen to reactor, eliminates remaining small amount of ammonia gas NH
3, open the product that reactor takes out loose shape then, the product integral body that obtains is brown, and product weight has reached 1688 grams, and the CaCl2 purity that obtains after the fine grinding is greater than 96%.
The X-ray diffraction analysis of synthetic product CaCl2 powder is seen Fig. 3 in this example.Calculating its purity is 96.3% (weight ratio).
Embodiment 3
Take by weighing 900 gram metallic calcium powders (account for raw material gross weight 45%) by weight ratio, this metallic calcium powder particle is 240 orders, purity＞97%; Take by weighing 700 gram CaCl2 powders (account for raw material gross weight 35%), this CaCl2 powder median size 10 μ m, purity＞98%; Take by weighing 400 gram urea CO (NH
2)
2(account for raw material gross weight 20%), after the mixing, be that 5 millimeters zirconia ball is ball-milling medium with diameter, be placed in the urethane jar, above-mentioned raw materials and zirconia ball weight ratio are 1: 8, be placed on the jar mill ball milling 3 hours, material after mixing is crossed 60 eye mesh screens, material after sieving is positioned in the half-terete graphite boat of porous equably, put into then from climing combustion synthesis reactor, after being evacuated to 600Pa, charge into the high pure nitrogen of 6MPa, tungsten filament with 1 millimeter of diameter is made heating element, feed 30 amperes electric current, 15 seconds time length, make coil heating, temperature has reached the temperature of reaction of metallic calcium powder and nitrogen in the raw mix, chemical reaction mode with climing combustion in material successively advances then, reaction times continues 10 minutes, and reactor pressure begins to descend, the logical recirculated water cooling of reactor this moment, when the pressure of reactor drops to 6MPa, the gas that has pressure in the releasing reactor (mainly is unreacted nitrogen, and the ammonia that generates of urea pyrolytic decomposition and carbonic acid gas etc.), reactor is filled 5 minutes ordinary nitrogen, eliminate remaining small amount of ammonia gas NH
3, open the product that reactor takes out loose shape then, the product integral body that obtains is brown, and product weight has reached 2460 grams, and the CaCl2 purity that obtains after the fine grinding is greater than 97%.
The X-ray diffraction analysis of synthetic product CaCl2 powder is seen Fig. 4 among the embodiment 3, and calculating its purity is 97.3% (weight ratio).
Embodiment 4
Take by weighing 700 gram metallic calcium powders (account for raw material gross weight 35%) by weight ratio, this metallic calcium powder particle is 120 orders, purity＞98%; Take by weighing 1000 gram CaCl2 powders (account for raw material gross weight 50%), this CaCl2 powder median size 10 μ m, purity＞98%; Take by weighing 300 gram Neutral ammonium fluoride NH
4F (account for raw material gross weight 15%).After the mixing, be that 15 millimeters zirconia ball and diameter is that 20 millimeters alumina balls (weight ratio is 1: 1) are ball-milling medium with diameter, be placed in the urethane jar, above-mentioned raw materials is 1: 5 with the ball weight ratio, be placed on the jar mill ball milling 2.5 hours, material after mixing is crossed 60 eye mesh screens, material after sieving is positioned in the half-terete graphite boat of porous uniformly, put into then from climing combustion synthesis reactor, after being evacuated to 500Pa, charge into the high pure nitrogen of 7MPa, tungsten filament with 0.6 millimeter of diameter is made heating element, feed 30 amperes electric current, 15 seconds time length, make coil heating, temperature has reached the temperature of reaction of metallic calcium powder and nitrogen in the raw mix, chemical reaction mode with climing combustion in material successively advances then, reaction times continues 10 minutes, reactor pressure begins to descend, the logical recirculated water cooling of reactor this moment, when the pressure of reactor dropped to 7MPa, the gas that has pressure in the releasing reactor (mainly was unreacted nitrogen, and the ammonia of Neutral ammonium fluoride pyrolytic decomposition generation and hydrofluoric acid etc.), reactor is filled 5 minutes ordinary nitrogen, eliminate remaining small amount of N H
3, open the product that reactor takes out loose shape then, the product integral body that obtains is brown, and product weight has reached 1832 grams, and the CaCl2 purity that obtains after the fine grinding is greater than 97%.
The X-ray diffraction analysis of synthetic product CaCl2 powder is seen Fig. 5 in this example.Calculating its purity is 98.3% (weight ratio).
Embodiment 5
Take by weighing 800 gram metallic calcium powders (account for raw material gross weight 40%) by weight ratio, this metallic calcium powder particle is 120 orders, purity＞98%; Take by weighing 900 gram CaCl2 powders (account for raw material gross weight 45%), this CaCl2 powder median size 10 μ m, purity＞98%; Take by weighing the volatile salt (NH of 100 grams
4)
2CO
3, take by weighing 100 the gram Neutral ammonium fluoride NH
4F, take by weighing 100 gram urea CO (NH
2)
2(amount to 300 grams, account for the raw material gross weight 15%).After the mixing, be that 5 millimeters alumina balls and diameter is that 14 millimeters silicon nitride balls (weight ratio is 1: 1) are ball-milling medium with diameter, be placed in the urethane jar, above-mentioned raw materials and silicon nitride ball weight ratio are 1: 5, be placed on the jar mill ball milling 2.5 hours, material after mixing is crossed 60 eye mesh screens, material after sieving is positioned in the half-terete graphite boat of porous uniformly, put into then from climing combustion synthesis reactor, after vacuumizing, charge into the high pure nitrogen of 7MPa, tungsten filament with 0.6 millimeter of diameter is made heating element, feed 30 amperes electric current, 15 seconds time length, make coil heating, temperature has reached the temperature of reaction of metallic calcium powder and nitrogen in the raw mix, chemical reaction mode with climing combustion in material successively advances then, reaction times continues 10 minutes, reactor pressure begins to descend, the logical recirculated water cooling of reactor this moment, when the pressure of reactor dropped to 7MPa, the gas that has pressure in the releasing reactor (mainly was unreacted nitrogen, and ammonia and carbonic acid gas and the hydrofluoric acid of the generation of additive pyrolytic decomposition), reactor is filled 5 minutes ordinary nitrogen, eliminate remaining small amount of N H
3, open the product that reactor takes out loose shape then, the product integral body that obtains is brown, and product weight has reached 1854 grams, and the CaCl2 purity that obtains after the fine grinding is greater than 97%.
The X-ray diffraction analysis of synthetic product CaCl2 powder is seen Fig. 6 in this example.Calculating its purity is 98.1% (weight ratio).
The gas that specific embodiment discharges is by water, and to eliminate remaining small amount of ammonia gas, to reduce topsoil, the specific embodiment ammonium salt is chemical grade.
Claims (7)
1. a method of producing the CaCl2 powder is characterized in that, the steps include:
(1) batching: be raw material with the metallic calcium powder, add thinner, additive, its weight percent proportioning is:
Metallic calcium powder: 30～50%, the granularity of described metallic calcium powder is 100～600 orders,
Thinner 30～50%, described thinner are the CaCl2 powder, purity＞98%, and median size is 10～20 microns,
Additive 10～20%, described additive are ammonium salt or urea,
(2) mix: the mixture of batching is placed in the urethane jar, is medium with the abrading-ball, ball milling 1～4 hour;
(3) mix powder behind the ball milling sieves with screen cloth;
(4) from climing combustion reaction: the mix powder after above-mentioned the sieving is contained in the graphite boat, is placed in climing combustion reactor again, be evacuated to inflated with nitrogen behind 400～600Pa, remain on 4～8MPa from climing combustion reactor pressure, igniting is synthesized from climing combustion;
(5) obtain finished product: when the pressure in climing combustion reactor drops to 4～8MPa, finish from climing combustion reaction, the gas in the releasing reactor to fill 1～5 minute nitrogen in climing combustion reactor, is opened reactor then, namely obtains CaCl2 powder finished product.
2. according to the described a kind of method of producing the CaCl2 powder of claim 1, it is characterized in that: described step (1) ammonium salt is any one or its arbitrary combination in ammonium chloride, Neutral ammonium fluoride, the volatile salt.
3. according to the described a kind of method of producing the CaCl2 powder of claim 1, it is characterized in that: the described abrading-ball in the step (2) is alumina balls, zirconia ball, silicon nitride ball, ball radius is 5～20 millimeters, and the mixture of batching and the weight ratio of abrading-ball are 1: 5～10.
4. according to the described a kind of method of producing the CaCl2 powder of claim 1, it is characterized in that: the purity of institute's inflated with nitrogen is＞99.999% in the step (4).
5. according to the described a kind of method of producing the CaCl2 powder of claim 1, it is characterized in that: the aperture of screen cloth is 40～60 orders in the step (3).
6. according to the described a kind of method of producing the CaCl2 powder of claim 1, it is characterized in that: the purity of institute's inflated with nitrogen is＞99.9% in the step (5).
7. according to the described a kind of method of producing the CaCl2 powder of claim 1, it is characterized in that: step (4) igniting is by spirrillum nichrome wire or tungsten filament energising heating igniting.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110249949 CN102417168B (en) | 2011-08-19 | 2011-08-19 | Method for producing calcium nitride powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110249949 CN102417168B (en) | 2011-08-19 | 2011-08-19 | Method for producing calcium nitride powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102417168A CN102417168A (en) | 2012-04-18 |
| CN102417168B true CN102417168B (en) | 2013-08-21 |
Family
ID=45941849
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110249949 Active CN102417168B (en) | 2011-08-19 | 2011-08-19 | Method for producing calcium nitride powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102417168B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017176463A1 (en) * | 2016-04-07 | 2017-10-12 | First Solar, Inc. | Devices and methods for making polycrystalline alloys |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103159190B (en) * | 2013-03-11 | 2016-01-20 | 烟台同立高科新材料股份有限公司 | A kind of superpure nitrogen compound raw powder's production technology |
| CN114163254B (en) * | 2022-02-11 | 2022-04-26 | 北京利尔高温材料股份有限公司 | Blast furnace iron tap channel main channel castable |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5693305A (en) * | 1995-10-19 | 1997-12-02 | Advanced Refractory Technologies, Inc. | Method for synthesizing aluminum nitride whiskers |
| US5846508A (en) * | 1997-05-09 | 1998-12-08 | National Science Council | Method for preparing aluminum nitride powders |
| FR2841893B1 (en) * | 2002-07-02 | 2004-08-27 | Francois Lacoste | CALCIUM NITRIDE SYNTHESIS PROCESS |
-
2011
- 2011-08-19 CN CN 201110249949 patent/CN102417168B/en active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017176463A1 (en) * | 2016-04-07 | 2017-10-12 | First Solar, Inc. | Devices and methods for making polycrystalline alloys |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102417168A (en) | 2012-04-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hargreaves | Heterogeneous catalysis with metal nitrides | |
| CN101214934A (en) | Self-combustion non-pollution fast preparation method for alpha-phase silicon nitride powder | |
| CN101445223A (en) | Method for preparing low-oxygen high-alpha phase silicon nitride powder by auto-igniting synthesis | |
| CN103237599A (en) | Ammonia synthesis catalyst and ammonia synthesis method | |
| CN102583276A (en) | Method for producing regularly shaped alpha-phase silicon nitride powder | |
| CN106744967B (en) | A kind of preparation method of silicon carbide powder | |
| CN111908922A (en) | Low-temperature synthesized rare earth hafnate high-entropy ceramic powder and preparation method thereof | |
| CN102417168B (en) | Method for producing calcium nitride powder | |
| CN101891215A (en) | Method for preparing nano titanium diboride polycrystalline powder | |
| CN110526249A (en) | A kind of reactor assembly producing silane mixture | |
| CN103771359A (en) | Method for preparing submicron-order high-alpha-phase silicon nitride powder body by virtue of combustion synthesis without using additive | |
| CN101863663B (en) | Combustion method for preparing submicron grade titanium carbide polycrystal powder | |
| JPS6112844B2 (en) | ||
| Rao et al. | Rapid solid-state-precursor synthesis of crystalline boron nitride | |
| CN101445224A (en) | Method for preparing low-oxygen aluminum nitride powder by auto-igniting synthesis | |
| CN101318637A (en) | Process for producing nano-silicon nitride ceramics powder | |
| CN103159190B (en) | A kind of superpure nitrogen compound raw powder's production technology | |
| CN1307089C (en) | Temperature-controlling activated self-spreading combustion process of synthesizing alpha-phase SiN powder | |
| CN101774809A (en) | Method for preparing silicon nitride and silicon carbide compounded powder through self-propagating combustion | |
| CN106232523B (en) | Mayenite compound containing imino group anion and preparation method thereof | |
| JPS5913442B2 (en) | Manufacturing method of high purity type silicon nitride | |
| CN1696076A (en) | Temperature controlled combustion method for synthesizing powder of silicon nitride in alpha phase | |
| US5665326A (en) | Method for synthesizing titanium nitride whiskers | |
| CN101798083A (en) | Method for preparing tungsten carbide powder through self-propagating process | |
| CN102583379B (en) | Method for producing nano-tungsten carbide powder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: YANTAI TOMLEY HI-TECH NEW MATERIALS CO., LTD. Free format text: FORMER OWNER: YANTAI TOMLEY HI-TECH. IND. + TRA. CO., LTD. Effective date: 20130225 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20130225 Address after: 264000 No. 17 Intel street, Fushan District, Shandong, Yantai Applicant after: YANTAI TOMLEY HI-TECH NEW MATERIALS Co.,Ltd. Address before: 264000 Shandong Yantai Zhifu District Huang office resident Applicant before: Yantai Tongligaoke Industry & Trade Co.,Ltd. |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C53 | Correction of patent of invention or patent application | ||
| C56 | Change in the name or address of the patentee | ||
| CB03 | Change of inventor or designer information |
Inventor after: Guo Dawei Inventor after: Sun Hongliang Inventor after: Sun Weiping Inventor after: Wang Qian Inventor before: Guo Dawei Inventor before: Chen Xiaoguang Inventor before: Sun Hongliang |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: GUO DAWEI CHEN XIAOGUANG SUN HONGLIANG TO: GUO DAWEI SUN HONGLIANG SUN WEIPING WANG QIAN |
|
| CP02 | Change in the address of a patent holder |
Address after: 264000 No. 20 Intel Road, Fushan District, Shandong, Yantai Patentee after: YANTAI TOMLEY HI-TECH NEW MATERIALS Co.,Ltd. Address before: 264000 No. 17 Intel street, Fushan District, Shandong, Yantai Patentee before: YANTAI TOMLEY HI-TECH NEW MATERIALS Co.,Ltd. |
|
| DD01 | Delivery of document by public notice | ||
| DD01 | Delivery of document by public notice |
Addressee: YANTAI TOMLEY HI-TECH NEW MATERIALS Co.,Ltd. Person in charge of patentsThe principal of patent Document name: payment instructions |