CN102701620B - Method utilizing microwave technique to induce modified ardealite - Google Patents
Method utilizing microwave technique to induce modified ardealite Download PDFInfo
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- CN102701620B CN102701620B CN201210215133.1A CN201210215133A CN102701620B CN 102701620 B CN102701620 B CN 102701620B CN 201210215133 A CN201210215133 A CN 201210215133A CN 102701620 B CN102701620 B CN 102701620B
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- Prior art keywords
- microwave
- phosphogypsum
- ardealite
- modified ardealite
- dielectric material
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- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000003989 dielectric material Substances 0.000 claims abstract description 11
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 claims description 54
- 238000005516 engineering process Methods 0.000 claims description 16
- 230000006698 induction Effects 0.000 claims description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims description 9
- 150000004706 metal oxides Chemical class 0.000 claims description 9
- 239000011148 porous material Substances 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000012545 processing Methods 0.000 abstract description 6
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 3
- 238000000498 ball milling Methods 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 8
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000002699 waste material Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000002910 solid waste Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- -1 add 10g inorganic Chemical class 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 208000037656 Respiratory Sounds Diseases 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002686 phosphate fertilizer Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Inorganic materials [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011507 gypsum plaster Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a method utilizing a microwave technique to induce modified ardealite. The method comprises the following steps of: ball-milling the ardealite to 160-200meshes; according to the mass ratio of the ardealite and an amorphous dielectric material being 1-2: 0.05-0.1, adding the amorphous dielectric material to be mixed; putting the mixture under the conditions of 2350MHZ of microwave frequencies, 750-950w of power and 100-150 DEG C of temperature to carry out microwave processing for 10-15 minutes, and then naturally cooling to the room temperature; and finally obtaining microwave induced modified ardealite. According to the method, the surface free energy, the electric potential, the average pore size and the specific surface area of the ardealite can be significantly increased. The prepared microwave induced modified ardealite can be used for adsorption of heavy metal wastewater. The method has the advantages of simple operation, low cost and high efficiency, a lot of energy sources are saved, and the secondary pollution is avoided.
Description
Technical field
The present invention relates to phosphogypsum modification and utilize technical field, specifically a kind of method of utilizing microwave technology induction modified ardealite.
Background technology
Phosphogypsum is the solid waste producing in Wet-process phosphoric acid (WPPA) technological process, and its main component is CaSO
42H
2o, also contains part H simultaneously
3pO
4, Ca (H
2pO
4)
2h
2o, CaHPO
42H
2o, Ca
3(PO
4)
2and sulfide (NaF, Na
2siF
6, Na
3alF
6, Na
3feF
6, CaF
2).China's phosphogypsum comprehensive utilization ratio is only 15% at present.The whole nation has been piled up more than 100,000,000 ton, and annual also with the speed increase of 2,000 ten thousand tons, only more than 4,000 ten thousand tons of phosphogypsums have just been piled up in Yunnan Province.In May, 2006, State Environmental Protection Administration was with ring letter (2006) No. 176 civilian forms, by phosphogypsum qualitative be dangerous solid waste, classify the controlling object of national noxious waste pollution environment as.The recycling of phosphogypsum has become the key that phosphate fertilizer industry is realized Sustainable development.Therefore, how to fully utilize phosphogypsum, control pollution, the treatment of wastes with processes of wastes against one another that phosphogypsum produces, improve the utility value of phosphogypsum, create good social benefit and environmental benefit and just seem and be even more important.
The research of the microwave induced processing phosphogypsum of employing both at home and abroad mainly concentrates on and adopts microwave technology to carry out purifying treatment to phosphogypsum.The method of microwave treatment for the preparation of the modified activated carbon of hydrogen iodide catalytic decomposition disclosed in the application that is CN101811016A at publication number.The method comprising the steps of: gac is placed in to microwave oven, under the protection of protection gas, with the power of 100～800W,, the frequency of 2450MHz is carried out microwave treatment 5～30min, obtains modified activated carbon.The preparation method of the active sludge carbon that utilizes flue gas desulfurization is disclosed in patent CN200610130548.3.The method comprises the pre-treatment of (1) mud, (2) microwave treatment thousand mud, and (3) charing, (4) are physically activated, the step of (5) microwave modification.At microwave modification, prepare in gac and municipal sludge research direction, microwave technology is applied in the recycling of solid waste as a kind of comparatively ripe means, but in the less research of the means as modified ardealite.The methods such as ball milled, sudden strain of a muscle burning method, lime neutralisation that adopt are carried out modification to phosphogypsum more both at home and abroad, obviously these methods can be removed the impurity in phosphogypsum to a great extent, but for improving, phosphogypsum surface charge distributes, surface can, increase specific surface area without contribution.
For utilizing microwave technology modified ardealite to there is not yet breakthrough research at home and abroad.Be necessary to study and use microwave technology to induce processing to phosphogypsum, change its surface charge and distribute, improve surface energy, increase specific surface area.If can have on the basis of certain loading capacity at phosphogypsum, adopt microwave means, the inner vesicular structure of phosphogypsum is transformed into open hole, make phosphogypsum particle surface be polynuclear plane, increase its specific surface area and can greatly improve the practicality of phosphogypsum in processing heavy metal wastewater thereby, widen its recycling approach.
Summary of the invention
For improving the distribution of phosphogypsum surface charge, surface energy, increasing specific surface area, the invention provides a kind of method of utilizing microwave technology induction modified ardealite, phosphogypsum specific surface area after microwave modification is large, loading capacity is high, and the surface free energy of phosphogypsum and current potential are also improved and change.
The present invention realizes by following technical proposal: a kind of method of utilizing microwave technology induction modified ardealite, and following each step of process:
Phosphogypsum ball is milled to 160～200 orders, by the mass ratio of phosphogypsum and amorphous dielectric material, be 1～2 ︰ 0.05～0.1 again, after adding amorphous dielectric material to mix, be placed in microwave frequency and be 2350MHZ, power and be 750～950w, temperature and be under the condition of 100～150 ℃ and carry out microwave treatment 10～15 minutes, then naturally cool to room temperature, obtain microwave induced modified ardealite.
Described phosphogypsum is that the plaster of paris, desulfurated plaster, phosphate fertilizer plant are residue phosphogypsums.
Described amorphous dielectric material is inorganic, metal oxide, as Fe
2o
3, Al
2o
3deng.
Principle of the present invention is according to add strong absorption material by microwave application in weak absorption material by microwave application, thereby the weak material by microwave application that absorbs is heated rapidly.Its essence is: (one) utilizes the strong material absorbing microwave that absorbs microwave to heat up rapidly, a little less than being transmitted heat and microwave energy and inputted two kinds of modes and make by contact, the material temperature of absorption microwave raises rapidly; (2) in microwave heating process, due to the variation of the electric conductivity of dielectric loss factor and particle, changed the rate of heating of weak absorption material by microwave application.
In the present invention, amorphous dielectric material is as the material of strong absorption microwave, when himself heating up rapidly, variation releases heat due to the electric conductivity of its dielectric loss factor and particle, thereby strengthened this weak rate of heating of inhaling ripple material of phosphogypsum, make the rate of heating of phosphogypsum than the fast several times of existing conventional heating speed, and therefore make phosphogypsum produce following variation:
(1) the free state moisture in phosphogypsum and organism evaporate completely or decompose;
(2) linearity of heat increases and will cause that the weak water layer room of bonding force is to the migrations such as room, distortion, peritectoid, cleavage, crackle and impurity on phosphogypsum crystal;
(3) Void diffusing disappears thereupon and forms dew point and then form crackle behind the surface of phosphogypsum, efflorescence, then stablizes nucleus and forms, and growth diffusion, surface free energy and the current potential of phosphogypsum are improved, and the specific surface area of phosphogypsum and mean pore size increase.
Because the heating of phosphogypsum is in fact the heating to pure gypsum and its impurity, characteristic due to microwave, its heating feature is classification heating, whole heating, so heating phosphogypsum can be regarded as and heat respectively pure gypsum and phosphogypsum impurity, heating efficiency is higher than traditional type of heating, can save in a large number the energy, and what adopt is electric energy, avoided secondary pollution.
The present invention adopts microwave technology induction modified ardealite, has overcome the shortcoming of other physics of independent employing or chemical process modified ardealite, and other techniques exist secondary pollution, calcination processing modified ardealite speed slow; The amorphous dielectric material of inorganics class adds as modifying agent, has increased substantially the speed of microwave technology induction modified ardealite, has significantly improved the physico-chemical property of phosphogypsum.
The present invention adopts microwave technology to carry out radiation modification to phosphogypsum, makes specific inductivity, apparent activation energy and the microvoid structure of phosphogypsum under radiation environment, thereby improves porosity and the specific surface area of phosphogypsum.Specific surface area and the mean pore size of the phosphogypsum before and after modification see the following form 1.
Specific surface area and the mean pore size of the phosphogypsum before and after table 1 modification
Compared with prior art, the invention has the advantages that:
(1) the present invention carries out microwave induced processing to phosphogypsum, and directly using the amorphous dielectric material of inorganics class as modifying agent, can significantly improve phosphogypsum surface free energy, current potential, mean pore size and specific surface area;
(2) the microwave induced modified ardealite that the present invention makes can be for heavy metal wastewater thereby absorption aspect;
(3) the present invention is simple to operate, with low cost, efficiency is high, save in a large number the energy, avoided secondary pollution; When widening solid waste and utilizing approach, realize the treatment of wastes with processes of wastes against one another, create good economic benefit and environment social benefit.
Embodiment
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1
100g phosphogypsum ball is milled to 160 orders, then is 1 ︰ 0.1 by the mass ratio of phosphogypsum and inorganic, metal oxide, add 10g inorganic, metal oxide Fe
2after O mixes, be placed in microwave frequency and be 2350MHZ, power and be 750w, temperature and be under the condition of 100 ℃ and carry out microwave treatment 10 minutes, then naturally cool to room temperature, obtain microwave induced modified ardealite.
Embodiment 2
100g phosphogypsum ball is milled to 180 orders, then is 1 ︰ 0.05 by the mass ratio of phosphogypsum and inorganic, metal oxide, add 5g inorganic, metal oxide Al
2o
3after mixing, be placed in microwave frequency and be 2350MHZ, power and be 850w, temperature and be under the condition of 120 ℃ and carry out microwave treatment 12 minutes, then naturally cool to room temperature, obtain microwave induced modified ardealite.
Embodiment 3
100g phosphogypsum ball is milled to 200 orders, then is 2 ︰ 0.05 by the mass ratio of phosphogypsum and inorganic, metal oxide, add 2.5g inorganic, metal oxide Al
2o
3after mixing, be placed in microwave frequency and be 2350MHZ, power and be 950w, temperature and be under the condition of 150 ℃ and carry out microwave treatment 15 minutes, then naturally cool to room temperature, obtain microwave induced modified ardealite.
The present invention, to utilizing the prepared modified ardealite of embodiment of microwave technology induction modified ardealite to carry out the de-absorption representation analysis of BET nitrogen and contrast, the results are shown in Table 2:
Table 2 embodiment test result
As can be seen from Table 2, at high-temperature, under high-power early stage, suitably extend the microwave induced time and adopt the little phosphogypsum of particle diameter, specific surface area and the mean pore size of the phosphogypsum after microwave induced are significantly improved, this technology has improved surface free energy, current potential, mean pore size and the specific surface area of phosphogypsum significantly, avoid adding too much metal oxide, reduced cost.
What more than enumerate is only specific embodiments of the invention.Obviously the invention is not restricted to above embodiment, can also have many distortion.The all distortion that can directly derive or associate from content disclosed by the invention at the those of ordinary skill of microwave technical field, all should think protection scope of the present invention.
Claims (2)
1. a method of utilizing microwave technology induction modified ardealite, is characterized in that through following each step:
Phosphogypsum ball is milled to 160～200 orders, by the mass ratio of phosphogypsum and amorphous dielectric material, be 1～2 ︰ 0.05～0.1 again, after adding amorphous dielectric material to mix, be placed in microwave frequency and be 2350MHZ, power and be 750～950w, temperature and be under the condition of 100～150 ℃ and carry out microwave treatment 10～15 minutes, then naturally cool to room temperature, obtain microwave induced modified ardealite.
2. the method for utilizing microwave technology induction modified ardealite according to claim 1, is characterized in that: described amorphous dielectric material is inorganic, metal oxide.
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|---|---|---|---|
| CN201210215133.1A CN102701620B (en) | 2012-06-27 | 2012-06-27 | Method utilizing microwave technique to induce modified ardealite |
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| CN201210215133.1A CN102701620B (en) | 2012-06-27 | 2012-06-27 | Method utilizing microwave technique to induce modified ardealite |
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| CN102701620B true CN102701620B (en) | 2014-09-03 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105197977B (en) * | 2015-09-09 | 2018-03-06 | 昆明理工大学 | A kind of preparation method that β type phosphorus plaster of Paris is developed using microwave |
| CN106477529B (en) * | 2016-11-02 | 2018-07-20 | 昆明冶金研究院 | A kind of method of microwave method reducing and decomposing phosphogypsum |
| CN108147762A (en) * | 2017-12-28 | 2018-06-12 | 四川绵竹三佳饲料有限责任公司 | A kind of modified ardealite imitates wood plank and preparation method thereof |
| CN108314341B (en) * | 2018-03-12 | 2021-01-12 | 湘潭大学 | Production process method of gypsum powder with various strength properties |
| CN110038890B (en) * | 2019-05-15 | 2019-11-26 | 湖北同惠生物工程有限公司 | A kind of ecological, environmental protective soil remediation method |
| CN113860773B (en) * | 2021-11-04 | 2022-06-14 | 云南云天化环保科技有限公司 | Device and method for dehydrating microwave-enhanced fluidized phosphogypsum |
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2012
- 2012-06-27 CN CN201210215133.1A patent/CN102701620B/en not_active Expired - Fee Related
Non-Patent Citations (4)
| Title |
|---|
| 唐霜露.磷石膏介电性及其微波分解模拟仿真研究.《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》.2012,(第2期),第11-12页. |
| 微波场对晶体矿物质表面性能的影响;陈勤芹;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》;20080515(第5期);第30-37页 * |
| 磷石膏介电性及其微波分解模拟仿真研究;唐霜露;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20120215(第2期);第11-12页 * |
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