CN103011271A - Method for synthesizing spherical nano-titanium-oxide by using detonation method in grain diameter controllable manner - Google Patents
Method for synthesizing spherical nano-titanium-oxide by using detonation method in grain diameter controllable manner Download PDFInfo
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- CN103011271A CN103011271A CN2012104722258A CN201210472225A CN103011271A CN 103011271 A CN103011271 A CN 103011271A CN 2012104722258 A CN2012104722258 A CN 2012104722258A CN 201210472225 A CN201210472225 A CN 201210472225A CN 103011271 A CN103011271 A CN 103011271A
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Abstract
The invention belongs to the field of physical or chemical methods and provides a formula for synthesizing spherical nano-titanium-oxide by using a detonation method in a grain diameter controllable manner and a synthetic method thereof. The method is characterized by comprising the following steps of: mixing and sensitively preparing titanium salt, ammonium nitrate and organic hydrocarbon compounds into paste with detonation property; and, after detonating the paste, carrying out drastic redox reaction among the ammonium nitrate as the oxidant and the organic hydrocarbon compounds as the reducing agent, so that a high-temperature and high-pressure environment is formed, oxidizing titanium atoms into titanium oxide, and crystallizing and gathering under the action of an inert cooling medium to form the spherical nano-titanium-oxide. The method disclosed by the invention has the advantages that the environmental pollution in the production process is low; the process is simple; the cost is low; the yield is easy to enlarge, so that industrial production is realized; the grain diameter of the spherical nano-titanium-oxide is distributed in the range of 10-100 nm and is adjustable; and the appearance of the spherical nano-titanium-oxide is a regular sphere.
Description
Technical field
The present invention relates to a kind of method of detonation synthesis nano material, more particularly, the present invention relates to prescription and the preparation method of the controlled detonation synthesizing spherical nano-titanium oxide of a kind of particle diameter.The ball shaped nano titanium oxide that generates can be used for the fields such as photochemical catalysis, uv-absorbing, makeup.
Background technology
The titanium dioxide purposes is very extensive; can be widely used in the titanium dioxide pigment exploitation, the numerous areas such as solar cell, surround lighting catalyzer, food product pack, antibacterial fiber, woodenware protective paint, the high-grade finish paint of automobile, Clear paint, makeup sun-screening agent, sensitive materials and self-cleaning functional materials.
The common method of producing nano titanium oxide can be divided into physical method and chemical process: Physical can be divided into method for constructing and comminuting method again, method for constructing but has and is difficult to scale operation and the comparatively expensive shortcoming of huge, the equipment of power consumption, and comminuting method technique simply can be produced continuously, but too simple complete processing is difficult to control the degree of uniformity of particle, also easily mixes impurity.The chemical process of synthesis of nano titanium oxide commonly used comprises vapor phase process and liquid phase method.Wherein gas-phase synthesizing method mainly comprises oxyhydrogen flame flame hydrolysis, titanium alkoxide gas phase hydrolysis method, TiCl
4Vapour phase oxidation processes etc., liquid-phase synthesis process mainly comprise sol-gel method, hydro-thermal reaction method, microemulsion method etc.The shortcomings such as these method ubiquity production costs are high, environmental pollution serious, easily reunite, energy consumption is large.
Patent CN200410020553.X has proposed and single chmical compound explosive and oxide precursor physical mixed can have been formed the explosibility mixture, and the single chmical compound explosive that contains oxide precursor by ignition prepares various oxide compounds.But it does not offer some clarification on concrete composition and the proportioning of the explosibility mixture of preparation nano-titanium oxide, and the method for control nano-titanium oxide particle diameter is not described in this patent.Patent CN200510133956.X has proposed a kind of method for preparing nano-titanium oxide with the low temperature liquid phase pyrolysis method, but the method will be used the equipment such as autoclave, and cost is higher, needs to consume a large amount of organic solvents in the preparation process, and byproduct of reaction is more.
Summary of the invention
The method that the purpose of this invention is to provide a kind of synthetic ball shaped nano titanium oxide is to solve problems of the prior art.Nano titania particle profile with the present invention's preparation is the sphere of rule, and size distribution is even, and particle diameter is adjustable between 10-100nm.Because its stable chemical nature has high specific surface area, is a kind of good photocatalyst.
Technical scheme of the present invention is: described ball shaped nano titanium oxide preparation method is comprised of following steps successively:
(a) titanium salt, ammonium nitrate and water are mixed the formation aqueous solution, be warming up to 60-65 ℃ and heat preservation for standby use; Wherein titanium salt accounts for the 7%-13% of raw material total amount; Ammonium nitrate accounts for the 40%-60% of raw material total amount; SODIUMNITRATE accounts for the 10%-20% of raw material total amount; Water accounts for the 10%-14% of raw material total amount;
(b) according to the target grain size scope of synthetic nano-titanium oxide, select corresponding tensio-active agent, with organic hydrocarbon compound and tensio-active agent fusing and be mixed into uniform solution, be warming up to 70-80 ℃ and heat preservation for standby use; Wherein tensio-active agent accounts for the 5%-8% of raw material total amount; The organic hydrocarbon compound accounts for the 3%-8% of raw material total amount;
(c) with step (a) and the solution that obtains (b) mix at 55-65 ℃, according to the particle diameter requirement of synthetic nano-titanium oxide, the rotating speed of control stirring rake forms the paste of water-in-oil-type;
When treating that (d) the water-in-oil-type paste temperature that obtains in (c) is down to 50-60 ℃, to wherein adding sensitizing agent, and make it fully to mix with paste, formation density is 1.05～1.20g/cm
3The explosibility paste; Wherein sensitizing agent accounts for the 0.2%-0.6% of raw material total amount;
(e) the explosibility paste in the usefulness cap sensitive (d) in blasting pot, acquisition contains the explosion product of ball shaped nano titanium oxide;
The explosion product that (f) will obtain in (e) carries out purification processes, obtains the finished product ball shaped nano titanium oxide;
Wherein, the organic hydrocarbon compound is comprised of one or more of compound wax, paraffin, ceresine and diesel oil etc.; Tensio-active agent is that one or more of sorbitan oleate, polyisobutene succinimide, polyoxyethylene stearic acid ester, sylvic acid polyoxyethylene ester etc. mix; Sensitizing agent is that one or more components in nitrite, supercarbonate, organic coupling compound, the resin microsphere mix; Titanium salt is titanyl sulfate.
The target grain size scope of described nano-titanium oxide and the relation of tensio-active agent and rotating speed of agitator see Table 1
| Median particle diameter | Tensio-active agent | Rotating speed of agitator |
| 10-30nm | Sorbitan oleate | 2500-3000rpm |
| 30-50nm | Polyisobutene succinimide | 2000-2500rpm |
| 50-70nm | The sylvic acid polyoxyethylene ester | 1500-2000rpm |
| 70-100nm | Polyoxyethylene stearic acid ester+sylvic acid polyoxyethylene ester | 1000-1500rpm |
The relation of the target grain size of table 1 different surfaces promoting agent and rotating speed of agitator and nano-titanium oxide
The invention has the advantages that: 1. with the aqueous solution of ammonium nitrate and titanium salt as oxygenant, organic hydrocarbon compounds etc. are prepared into the volatile paste with cap-sensitivity as reductive agent through mixing and add sensitizing agent.After it was ignited, violent redox reaction occured with reductive agent in oxygenant, forms high temperature, hyperbaric environment, makes the titanium atom in the titanium salt be oxidized to titanium oxide, and crystallization under the effect of inertia heat-eliminating medium, assembled formation ball shaped nano titanium oxide.2. the rotating speed of agitator that the present invention can be when selecting different tensio-active agents and changing preparation explosibility paste, the size of control nano-titanium oxide particle diameter.3. after the paste of preparing by the present invention exploded in blasting pot, the explosion product of acquisition was the mixture that ball shaped nano titanium oxide and a small amount of impurity form, and this mixture is carried out chemical purification can obtain the ball shaped nano titanium dioxide powder of purity more than 99.5%.Method of the present invention have that operation is simple, environmental pollution is little, with short production cycle, easily amplify output, product cut size is little, purity is high characteristics.
Description of drawings
Fig. 1 is blast sample wiring layout, and wherein 1 is the 8# commercial electric detonator; 2 is the explosibility paste; 3 is the paper shell; 4 inert medias; 5 shells.
Embodiment
Further specify the present invention below by embodiment.
Get the 100g raw material according to prescription of the present invention, wherein diesel oil 8g, tensio-active agent (sorbitan oleate) 5g, sensitizing agent (Sodium Nitrite) 0.6g, ammonium nitrate 40g, SODIUMNITRATE 20g, titanyl sulfate 13g, water 13.4g.
Ammonium nitrate, titanyl sulfate, SODIUMNITRATE are mixed with water, heating for dissolving, keeping the temperature of solution is 65 ℃; With diesel oil and sorbitan oleate fusing, mix, keeping solution temperature is 80 ℃; The adjusting rotating speed of agitator is 2500r/min, and above two kinds of solution are mixed the paste that forms water-in-oil-type;
When the temperature for the treatment of paste is 50 ~ 60 ℃, in the paste of above-mentioned water-in-oil-type, adds Sodium Nitrite, and make it fully to mix with paste; With the preparation the paste can in paper roll, charge density is 1.15g/cm
3According to accompanying drawing 1 No. 8 commercial electric detonators, explosibility paste powder stick and inertia heat-eliminating mediums are assembled, then put into blasting pot and ignite.Explosion product is taken out from blasting pot, remove large granular impurity through water washing, filtration, under 120 ℃ of temperature, dry.Pretreated explosion product is carried out purification processes, and every gram solid adds 1mL nitric acid (65%), 1.5mL hydrochloric acid (36%), 5mL water, 80-90 ℃ of lower reaction 12 hours, then extremely neutral with deionized water wash, put into baking oven and dry, namely get ball shaped nano titanium oxide finished product.
With D8 ADVANCE type X-ray diffractometer sample is detected.The diffracting spectrum characteristic peak of sample is at 25.42 °, and 37.88 °, 48.18 °, 55.22 °, sample is without assorted peak.The product that proof generates is the isometric system titanium oxide.Use the field emission microscopy observation sample, its appearance is spherical; With BT-9300H laser fineness gage specimen granularity, its size-grade distribution interval is in the 10nm-100nm scope, and median particle diameter is d50=20-30nm.With the foreign matter content of plasma emission spectrum (ICP) specimen, foreign matter content is less than 0.5%.
Prove by above test, product is purer ball shaped nano titanium oxide, and the purity of product is more than 99.5%.
Get the 100g raw material according to prescription of the present invention, wherein compound wax 7.4g, tensio-active agent (polyisobutene succinimide) 6g, sensitizing agent (resin microsphere) 0.6g, ammonium nitrate 50g, SODIUMNITRATE 18g, titanyl sulfate 10g, water 8g.
Ammonium nitrate, SODIUMNITRATE, titanyl sulfate and water are mixed, heating for dissolving, keeping the temperature of solution is 60 ℃; With compound wax and polyisobutene succinimide fusing, mix, keeping solution temperature is 75 ℃; The adjusting rotating speed of agitator is 2000r/min, and above two kinds of solution are mixed the paste that forms water-in-oil-type;
When the temperature for the treatment of paste is 50 ~ 60 ℃, in the paste of above-mentioned water-in-oil-type, adds resin microsphere, and make it fully to mix with paste; With the preparation the paste can in paper roll, charge density is controlled to be 1.05g/cm
3According to accompanying drawing 1 No. 8 commercial electric detonators, explosibility paste powder stick and inertia heat-eliminating mediums are assembled, then put into blasting pot and ignite.Explosion product is taken out from blasting pot, through washing, removing by filter except large granular impurity, under 120 ℃ of temperature, dry.Pretreated explosion product is carried out purification processes, and every gram solid adds 1mL nitric acid (65%), 1.5mL hydrochloric acid (36%), 5mL water, 80-90 ℃ of lower reaction 12 hours, then extremely neutral with deionized water wash, put into baking oven and dry, namely get ball shaped nano titanium oxide finished product
With D8 ADVANCE type X-ray diffractometer sample is detected.The diffracting spectrum characteristic peak of sample is at 25.42 °, and 37.88 °, 48.18 °, 55.22 °, sample is without assorted peak.The product that proof generates is the isometric system titanium oxide.Use the field emission microscopy observation sample, its appearance is spherical; With BT-9300H laser fineness gage specimen granularity, its size-grade distribution interval is in the 20nm-60nm scope, and median particle diameter is d50=30-40nm.With the foreign matter content of plasma emission spectrum (ICP) specimen, foreign matter content is less than 0.5%.
Prove by above test, product is purer ball shaped nano titanium oxide, and the purity of product is more than 99.5%.
Get the 100g raw material according to prescription of the present invention, wherein paraffin 3g, diesel oil 4g, tensio-active agent (polyoxyethylene stearic acid ester+sylvic acid polyoxyethylene ester) 8g, sensitizing agent (supercarbonate+organic coupling compound) 0.5g, ammonium nitrate 57.5g, SODIUMNITRATE 10g, titanyl sulfate 7g, water 10g.
Ammonium nitrate, SODIUMNITRATE, titanyl sulfate and water are mixed, heating for dissolving, keeping the temperature of solution is 60 ℃; With paraffin, diesel oil, tensio-active agent fusing, mix, keeping solution temperature is 75 ℃; The adjusting rotating speed of agitator is 1000r/min, and above two kinds of solution are mixed the paste that forms water-in-oil-type;
When the temperature for the treatment of paste is 50 ~ 60 ℃, in the paste of above-mentioned water-in-oil-type, adds sensitizing agent, and make it fully to mix with paste; With the preparation the paste can in paper roll, charge density is controlled to be 1.12g/cm
3According to accompanying drawing 1 No. 8 commercial electric detonators, explosibility paste powder stick and inertia heat-eliminating mediums are assembled, then put into blasting pot and ignite.Explosion product is taken out from blasting pot, through washing, removing by filter except large granular impurity, pretreated explosion product is carried out purification processes, every gram solid adds 1mL nitric acid (65%), 1.5mL hydrochloric acid (36%), 5mL water, 80-90 ℃ of lower reaction 12 hours, then extremely neutral with deionized water wash, put into baking oven and dry, namely get ball shaped nano titanium oxide finished product.
With D8 ADVANCE type X-ray diffractometer sample is detected.The diffracting spectrum characteristic peak of sample is at 225.42 °, and 37.88 °, 48.18 °, 55.22 °, sample is without assorted peak.The product that proof generates is the isometric system titanium oxide.Use the field emission microscopy observation sample, its appearance is spherical; With BT-9300H laser fineness gage specimen granularity, its size-grade distribution interval is in the 40nm-100nm scope, and median particle diameter is d50=80-100nm.With the foreign matter content of plasma emission spectrum (ICP) specimen, foreign matter content is less than 0.5%.
Prove by above test, product is purer ball shaped nano titanium oxide, and the purity of product is more than 99.5%.
Claims (10)
1.
The method of the detonation synthesizing spherical nano-titanium oxide that a kind of particle diameter is controlled may further comprise the steps:
A mixes the formation aqueous solution with titanium salt, ammonium nitrate, SODIUMNITRATE and water, heats up and heat preservation for standby use;
B is with organic hydrocarbon compound and tensio-active agent fusing and be mixed into uniform solution, heats up and heat preservation for standby use;
C mixes the solution that obtains among step a and the b, stirs, and forms the paste of water-in-oil-type;
The water-in-oil-type paste cooling that d treats to obtain among the step c to wherein adding sensitizing agent, and makes it fully to mix with paste, forms the explosibility paste;
E with the explosibility paste in the cap sensitive steps d, obtains to contain the explosion product of ball shaped nano titanium oxide in blasting pot;
The explosion product that f will obtain in step e is purified, and obtains the finished product ball shaped nano titanium oxide.
2. method according to claim 1 is characterized in that: titanium salt accounts for the 7%-13% of raw material total amount in the step (a); Ammonium nitrate accounts for the 40%-60% of raw material total amount; SODIUMNITRATE accounts for the 10%-20% of raw material total amount; Water accounts for the 10%-14% of raw material total amount; Be warming up to after 60-65 ℃ heat preservation for standby use.
3. method according to claim 1 is characterized in that: tensio-active agent accounts for the 5%-8% of raw material total amount in the step (b); The organic hydrocarbon compound accounts for the 3%-8% of raw material total amount; Be warming up to after 70-80 ℃ heat preservation for standby use.
4. method according to claim 1, it is characterized in that: the mixing temperature in the step (c) is 55-65 ℃, rotating speed of agitator is 1000-3000rpm.
5. method according to claim 1 is characterized in that: add sensitizing agent when water-in-oil-type paste temperature is down to 50-60 ℃ in the step (d); Wherein sensitizing agent accounts for the 0.2%-0.6% of raw material total amount; Described explosibility paste density is 1.05～1.20g/cm
3
6. method according to claim 1 is characterized in that: the organic hydrocarbon compound is one or two or more kinds the mixture in compound wax, paraffin, ceresine and the diesel oil.
7. method according to claim 1 is characterized in that: tensio-active agent is one or two or more kinds the mixture in sorbitan oleate, polyisobutene succinimide, polyoxyethylene stearic acid ester, the sylvic acid polyoxyethylene ester.
8. method according to claim 1 is characterized in that: described sensitizing agent is by one or two or more kinds the mixture in nitrite, supercarbonate, organic coupling compound, the resin microsphere.
9. method according to claim 1, it is characterized in that: described titanium salt is titanyl sulfate.
10. method according to claim 1, it is characterized in that: the particle diameter of formed nano-titanium oxide can be controlled in 10-100nm.
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| CN1034264A (en) * | 1987-05-22 | 1989-07-26 | 淮南矿业学院 | Low density grainy emulsified explosive |
| CN1569617A (en) * | 2004-05-13 | 2005-01-26 | 大连理工大学 | Detonation method for synthesizing oxide powder |
| CN101152992A (en) * | 2006-09-29 | 2008-04-02 | 鞍钢集团矿业公司 | Emulsifying blasting agent produced on blasting agent mixing vehicle |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1034264A (en) * | 1987-05-22 | 1989-07-26 | 淮南矿业学院 | Low density grainy emulsified explosive |
| CN1569617A (en) * | 2004-05-13 | 2005-01-26 | 大连理工大学 | Detonation method for synthesizing oxide powder |
| CN101152992A (en) * | 2006-09-29 | 2008-04-02 | 鞍钢集团矿业公司 | Emulsifying blasting agent produced on blasting agent mixing vehicle |
Non-Patent Citations (1)
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| 王小红等: "爆轰合成用的乳化***制备工艺与爆轰特性", 《工程***》 * |
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