CN100467387C - Preparing process of spherical ammonium metatungstate particle - Google Patents
Preparing process of spherical ammonium metatungstate particle Download PDFInfo
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- CN100467387C CN100467387C CNB2006101554819A CN200610155481A CN100467387C CN 100467387 C CN100467387 C CN 100467387C CN B2006101554819 A CNB2006101554819 A CN B2006101554819A CN 200610155481 A CN200610155481 A CN 200610155481A CN 100467387 C CN100467387 C CN 100467387C
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- Prior art keywords
- ammonium metawolframate
- particulate
- active agent
- spherical
- metawolframate
- Prior art date
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims description 27
- 239000002245 particle Substances 0.000 title abstract description 18
- 230000008569 process Effects 0.000 title description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 23
- 238000001694 spray drying Methods 0.000 claims abstract description 22
- 239000004094 surface-active agent Substances 0.000 claims abstract description 4
- 239000013543 active substance Substances 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
- 238000005507 spraying Methods 0.000 claims description 15
- 230000010355 oscillation Effects 0.000 claims description 12
- 230000008676 import Effects 0.000 claims description 10
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000007921 spray Substances 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920004890 Triton X-100 Polymers 0.000 description 1
- 239000013504 Triton X-100 Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- -1 polyethylene octyl phenyl ether Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
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Abstract
The preparation process of spherical ammonium metatungstate particle includes: compounding 2.5-50 wt% concentration water solution of ammonium metatungstate, adding surfactant and ultrasonic vibrating for 20-50 min, and spray drying in a spray drier with hot air nozzle temperature of 100-250 deg.c and tail gas exit temperature of 60-130 deg.c to obtain spherical ammonium metatungstate particle. The present invention combines ultrasonic technology and spray drying technology to obtain spherical ammonium metatungstate particle with reduced size.
Description
(1) technical field
The present invention relates to a kind of preparation method of spherical ammonium metawolframate particulate, particularly relate to the method for preparing solid spherical and hollow ball-shape ammonium metawolframate particulate with spray drying process.
(2) background technology
Ammonium metawolframate is the compound that arouses attention especially in the Tungstenic compound in recent years, and its consumption increases very fast.Be mainly used in cracking of oil, organic synthesis, nitration reactions etc. are made catalyzer; Ammonium metawolframate also is to have the of paramount importance presoma of eka-platinium active carbide tungsten catalyst, because the particle diameter of presoma and structure will prepare the wolfram varbide process and the tungsten carbide catalyst performance produces considerable influence to the later stage, seem particularly important in preparation process so the structure of ammonium metawolframate presoma and pattern controlled.
Spray-drying process be with single operation with solution, emulsion, suspension and pasty material through being processed to form a kind of drying means of powdery dried product.This method major advantage is that drying rate is fast, the time short, temperature of charge is lower.Be characterized in that liquid starting material can be formed directly in the powdered product, can serialization produce in enormous quantities, need not the disintegrating process process and can directly obtain even particle size, solvability and dispersed extremely excellent goods.The shortcoming that existing bibliographical information utilizes spray drying process that the ammonium metawolframate raw material is handled is that prepared ammonium metawolframate grain graininess is big, uncontrollable and related between the pattern of spray-dired preparation process condition and ammonium metawolframate and the granularity, what particularly the present invention relates to utilizes spray drying method for preparation ammonium metawolframate microballoon and this method to the control of ammonium metawolframate microballoon pattern and granularity, does not see document and application report so far as yet.
(3) summary of the invention
The preparation method who the purpose of this invention is to provide a kind of spherical ammonium metawolframate particulate, particulate form and particle diameter are controlled, and granularity is little, and spray-dired processing parameter is controlled, and easy handling can well be applied to catalytic field.
The technical solution used in the present invention is as follows:
Earlier ammonium metawolframate is mixed with the aqueous solution of 2.5～50wt%, imports spray-dryer then, the temperature in of control hot air nozzle is 100～250 ℃, and tail gas exit temperature is 60～130 ℃, and is spray-dried, promptly gets described spherical ammonium metawolframate particulate.
Spherical ammonium metawolframate particulate with present method preparation can select different spray-dryers to be prepared as required, and when using the pneumatic spray drying device, the ammonium metawolframate particulate of preparing mostly is the hollow ball-shape particulate; When using centrifugal spray-dryer, for preparing mostly is solid spheroidal particle.The diameter of particle that a process for preparing is less than the particulate of general spray drying method for preparation, usually between 1～20 μ m, and controlled to particle diameter.
When being the pneumatic spray drying device according to above-described spray-dryer, the pilot-gas flow velocity is 400～1500L/h, feed rate is 5～50mL/min, tail gas exit temperature is 70～130 ℃, spray-dried, get final product spherical ammonium metawolframate particulate, be hollow ball-shape more than 95% in these particulates.
And when described spray-dryer was centrifugal spray-dryer, the control feed rate was 3～8L/h, and tail gas exit temperature is 60～120 ℃, carries out spraying drying, get final product spherical ammonium metawolframate particulate, the particulate that obtains more than 95% for solid spherical.
Preferably, import spray-dryer again after in the aqueous solution of ammonium metawolframate, adding tensio-active agent, described tensio-active agent is a kind of or combination in anionic, cationic, both sexes or the nonionic surface active agent, concrete, described tensio-active agent is Triton X-100, polyvinyl alcohol or cetyl trimethylammonium bromide.The consumption of described tensio-active agent be in the ammonium metatungstate aqueous solution ammonium metawolframate quality 1～10%, be preferably 5～7%, most preferably be 6%.
Further again, in the aqueous solution of ammonium metawolframate, add tensio-active agent after, sonic oscillation 20～50min under the room temperature, 30min preferably vibrates.
The purpose that adds tensio-active agent and sonic oscillation above all is for the solute in the ammonium metatungstate solution is better disperseed, thereby the diameter of particle that obtains after the spraying drying is more evenly distributed.
Concrete, described method is for being mixed with ammonium metawolframate the aqueous solution of 5～30wt% earlier, add quality again and be 5～7% tensio-active agent of ammonium metawolframate quality, behind the sonic oscillation 30min, import the pneumatic spray drying device, the pilot-gas flow velocity is 600～1000L/h, feed rate is 10～50mL/min, the temperature in of hot air nozzle is 150～220 ℃, and tail gas exit temperature is 90～110 ℃ and carries out spraying drying, promptly gets described hollow ball-shape ammonium metawolframate particulate.
More specifically, described method is for being formulated as ammonium metawolframate the aqueous solution of 10wt% earlier, add tensio-active agent again, import the pneumatic spray drying device behind the sonic oscillation 30min, the pilot-gas flow velocity is 800L/h, and feed rate is 20mL/min, and the temperature in of hot air nozzle is 200 ℃, tail gas exit temperature is 100 ℃ and carries out spraying drying, promptly gets described hollow ball-shape ammonium metawolframate particulate.
Perhaps carry out: the aqueous solution that earlier ammonium metawolframate is formulated as 10～30wt% according to following steps, add tensio-active agent again, import centrifugal spray-dryer behind the sonic oscillation 30min, the control feed rate is 4～6L/h, the temperature in of hot air nozzle is 150～220 ℃, tail gas exit temperature is 70～110 ℃ and carries out spraying drying, promptly gets described solid spherical ammonium metawolframate particulate.
Concrete, described method is for being formulated as ammonium metawolframate the aqueous solution of 20wt% earlier, add tensio-active agent sonic oscillation 30min again, import centrifugal spray-dryer then, the control feed rate is 5L/h, the temperature in of hot air nozzle is 200 ℃, and tail gas exit temperature is 90 ℃ and carries out spraying drying, promptly gets described solid spherical ammonium metawolframate particulate.
The present invention compared with prior art, its beneficial effect is embodied in:
(1) makes full use of the advantage of ultrasonic technology and spray drying technology, both are organically combined, and be applied to the preparation of hollow ball-shape and solid spherical ammonium metawolframate.
(2) structure and the pattern of the related ammonium metawolframate microballoon of spray drying preparation technology, and realization is to the control of micro-sphere structure and granularity.
(3) make full use of the advantage of tensio-active agent, significantly reduce the surface tension of particulate in the solution, prevent the growth of particle aggregation and restriction particle, reach the purpose that reduces ammonium metawolframate microballoon granularity.
(4) description of drawings
Fig. 1 is the preparation technology flow process trend of embodiment 1 in conjunction with the pneumatic spray drying device;
Fig. 2 is the preparation technology flow process trend of embodiment 2 in conjunction with centrifugal spray-dryer;
Fig. 3 is the SEM figure of the hollow ball-shape ammonium metawolframate particulate of embodiment 1 preparation;
Fig. 4 is the SEM enlarged view of the hollow ball-shape ammonium metawolframate particulate of embodiment 1 preparation;
Fig. 5 is the SEM figure of the solid spherical ammonium metawolframate particulate of embodiment 2 preparations;
Fig. 6 is the SEM enlarged view of the solid spherical ammonium metawolframate particulate of embodiment 2 preparations;
Fig. 7 is the SEM figure of the ammonium metawolframate particulate of embodiment 4.
(5) embodiment:
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto:
Embodiment 1
With reference to Fig. 1, a kind of pneumatic spray drying device, the shower nozzle of this equipment belong to two streaming structures, and two fluid streams are respectively feed liquid and heated air.Wherein the flow direction of whole process fluid 1 enters from entering the mouth for adding warm air, after process furnace 2 heating, with and stream mode contact with the feed liquid that flows in the same way, dry in experiencing cannon spray head 4 successively, separate in the cyclonic separator 5, obtain powder at last in collector 6, tail gas filters the back through strainer 7 and extracts emptying out by suction filtration machine 8.
5g ammonium metawolframate raw material is dissolved in the 95mL water, abundant mixing, be mixed with 5% the aqueous solution, at room temperature ultra-sonic oscillation are 30 minutes, are 800L/h at air velocity then, and feed rate is 20mL/min, inlet temperature is 200 ℃, temperature out is under 100 ℃ the condition, more described solution to be imported the pneumatic spray drying device under the stirring of magnetic stirring apparatus and carry out spraying drying, and obtain hollow ball-shape ammonium metawolframate particle in cyclonic separator.The ammonium metawolframate powder that makes is made scanning electron microscope analysis, and by Fig. 3 and Fig. 4 as can be seen, the ammonium metawolframate particle of gained is a hollow ball-shape.Its granularity sees Table 1.
With reference to Fig. 2, a kind of centrifugal spray-dryer, this equipment belong to two streaming structures.Certain density feed liquid is subjected to high pressure air drives and on the spraying gun 4 of high speed rotating flowing under the action of gravity in the feed bin 3 at moisture eliminator top, owing to be subjected to powerful action of centrifugal force, feed liquid is very fast to be thrown away from the spraying gun edge and atomizes, and the drop after the atomizing moves with parabolic in moisture eliminator.Another fluid streams air is after process hotblast stove 1 heating under the suction function of induced draft fan 9, enter moisture eliminator from the moisture eliminator top with tangential direction, the warm air that moves in drying cylinder 5 internal screw modes fully contacts with drop, after the process heat exchange, both enter cyclonic separator 8 jointly and separate, wherein powder falls in the collector 7 in the effect of centrifugal force and gravity and reclaims, and tail gas is the suction evacuation by induced draft fan then.
The ammonium metawolframate raw material is soluble in water, abundant mixing, be mixed with 5% the aqueous solution, at room temperature ultra-sonic oscillation are 30 minutes, be 5L/h in feed rate then, inlet temperature is 200 ℃, and temperature out is under 90 ℃ the condition, again described solution is imported centrifugal spray-dryer and carry out spraying drying, and in cyclonic separator, obtain solid spherical ammonium metawolframate particle.The ammonium metawolframate powder that makes is made scanning electron microscope analysis, and by Fig. 5 and Fig. 6 as can be seen, the ammonium metawolframate particle of gained is solid spherical.
Pneumatic spray drying working conditions with reference to embodiment 1,5g ammonium metawolframate raw material is dissolved in the 95mL water, abundant mixing, be mixed with 5% the aqueous solution, at room temperature ultra-sonic oscillation are 30 minutes, add surfactant polyethylene octyl phenyl ether 0.3g, be 800L/h at air velocity then, feed rate is 20mL/min, inlet temperature is 200 ℃, temperature out is under 100 ℃ the condition, more described solution to be imported the pneumatic spray drying device under the stirring of magnetic stirring apparatus and carry out spraying drying, and obtain hollow ball-shape ammonium metawolframate particle in cyclonic separator.Its granularity sees Table 1.
Embodiment 4: the comparative example
The ammonium metawolframate raw material is made scanning electron microscope analysis, and as seen from Figure 7, the ammonium metawolframate raw material is irregular block structure.Its granularity sees Table 1.
As can be found from Table 1, the granularity of the spherical ammonium metawolframate particulate of handling through pneumatic spray drying is much smaller than the ammonium metawolframate raw material; Compare with embodiment 1, under identical processing condition, add the prepared ammonium metawolframate particulate of tensio-active agent among the embodiment 3 and have littler granularity.
The granularity of the different samples of table 1
Claims (6)
1. the preparation method of a spherical ammonium metawolframate particulate, it is characterized in that method is the aqueous solution that ammonium metawolframate is mixed with 2.5～50wt%, import spray-dryer, the temperature in of control hot air nozzle is 100～250 ℃, tail gas exit temperature is 60～130 ℃ and carries out spraying drying, promptly get described spherical ammonium metawolframate particulate, described spray-dryer is the pneumatic spray drying device, the pilot-gas flow velocity is 400～1500L/h, feed rate is 5～50mL/min, tail gas exit temperature is 70～130 ℃ and carries out spraying drying, promptly gets spherical ammonium metawolframate particulate.
2. the preparation method of spherical ammonium metawolframate particulate as claimed in claim 1, it is characterized in that described method imports spray-dryer again for add tensio-active agent in the aqueous solution of ammonium metawolframate after, described tensio-active agent is a kind of or combination in anionic, cationic, both sexes or the nonionic surface active agent.
3. the preparation method of spherical ammonium metawolframate particulate as claimed in claim 2, the consumption that it is characterized in that described tensio-active agent be in the ammonium metatungstate aqueous solution ammonium metawolframate quality 1～10%.
4. the preparation method of spherical ammonium metawolframate particulate as claimed in claim 2 is characterized in that described method for add tensio-active agent in the aqueous solution of ammonium metawolframate after, sonic oscillation 20～50min under the room temperature.
5. the preparation method of spherical ammonium metawolframate particulate as claimed in claim 1, described ammonium metawolframate particulate is a hollow ball-shape, it is characterized in that described method is for being formulated as ammonium metawolframate the aqueous solution of 5～30wt% earlier, add quality again and be 1～10% tensio-active agent of ammonium metawolframate quality, behind the sonic oscillation 30min, import the pneumatic spray drying device, the pilot-gas flow velocity is 600～1000L/h, feed rate is 10～50mL/min, the temperature in of hot air nozzle is 150～220 ℃, tail gas exit temperature is 90～110 ℃ and carries out spraying drying, promptly gets described hollow ball-shape ammonium metawolframate particulate.
6. the preparation method of spherical ammonium metawolframate particulate as claimed in claim 5, it is characterized in that described method is for being formulated as ammonium metawolframate the aqueous solution of 10wt% earlier, add tensio-active agent again, import the pneumatic spray drying device behind the sonic oscillation 30min, the pilot-gas flow velocity is 800L/h, and feed rate is 20mL/min, and the temperature in of hot air nozzle is 200 ℃, tail gas exit temperature is 100 ℃ and carries out spraying drying, promptly gets described hollow ball-shape ammonium metawolframate particulate.
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| CNB2006101554819A CN100467387C (en) | 2006-12-26 | 2006-12-26 | Preparing process of spherical ammonium metatungstate particle |
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| CNB2006101554819A CN100467387C (en) | 2006-12-26 | 2006-12-26 | Preparing process of spherical ammonium metatungstate particle |
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| CN100467387C true CN100467387C (en) | 2009-03-11 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101618893B (en) * | 2009-08-05 | 2011-04-13 | 江西稀有稀土金属钨业集团有限公司 | Method for preparing ammonium metawolframate |
| CN101948136B (en) * | 2010-09-13 | 2012-11-14 | 浙江工业大学 | Preparation method of laminated ammonium metatungstate with high dispersity |
| CN110517808B (en) * | 2019-08-05 | 2021-06-18 | 中国民用航空飞行学院 | Composite conductive film based on silver nanowires and preparation method thereof |
| CN110817963A (en) * | 2019-10-23 | 2020-02-21 | 江西铜鼓有色冶金化工有限责任公司 | Method and system for preparing ammonium metatungstate from acid-soluble slag waste |
| CN111333114A (en) * | 2020-03-17 | 2020-06-26 | 厦门钨业股份有限公司 | Method for preparing spherical ammonium paratungstate |
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Non-Patent Citations (4)
| Title |
|---|
| 喷雾干燥－固定床法制备碳化钨粉末. 甘永平，黄辉，张文魁.化学世界，第2期. 2006 |
| 喷雾干燥－固定床法制备碳化钨粉末. 甘永平，黄辉，张文魁.化学世界，第2期. 2006 * |
| 超细***粉体团聚－分散机理研究. 袁凤英，秦清风.火工品，第2期. 2003 |
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