CN103864083A - Process for manufacturing tourmaline from limestone - Google Patents
Process for manufacturing tourmaline from limestone Download PDFInfo
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- CN103864083A CN103864083A CN201410037207.6A CN201410037207A CN103864083A CN 103864083 A CN103864083 A CN 103864083A CN 201410037207 A CN201410037207 A CN 201410037207A CN 103864083 A CN103864083 A CN 103864083A
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- wingdale
- tourmalinite
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Abstract
The invention provides a process for manufacturing tourmaline from limestone. The process comprises the following steps: (1) grinding, namely mixing selected mineral substances in parts by weight, and grinding the mineral substances into powder, wherein the grain diameter of the powder is 2-5nm; (2) dissolving, namely dissolving the ground mineral substance mixture into a selected acid solvent in parts by weight, and controlling the temperature at 25 DEG C; (3) reaction, namely heating a mixture solution in the step (2) to 90 DEG C, and controlling the pressure at 25 MPa to carry out a synthetic reaction for 20 hours; (4) crystallization, namely evaporating to separate crystals out, wherein the crystallization temperature is 60 DEG C; and (5) regrinding, namely grinding the crystals into the powder, so as to obtain the tourmaline, wherein the grain diameter of the powder is 10-15nm.
Description
Technical field
The present invention relates to a kind of technique of artificial synthetic tourmaline, relate in particular to a kind of technique of manufacturing tourmalinite with Wingdale.
Background technology
Tourmalinite is called tourmaline in ancient times, English name Tourmaline, be a kind of take boracic as feature, the silicate minerals of the aluminium of chemical constitution complexity, sodium, iron, lithium ring texture.Crude tourmaline, its chemical formula generally can be expressed as XY
3z
6(T
6o
18) (BO
3)
3v
3w, variant according to the different chemical formula in the place of production and mining area: X position is mostly Na and Ca, or a small amount of K, even can vacancy; Can there be many valencys positively charged ion widely Y position, is generally mostly Li
+, Mg
2+, Fe
2+, Mn
2+, Al
3+, Cr
3+, V
3+, Fe
3+and Ti
4+deng; Z position is mainly trivalent positive ion, as Al
3+, Cr
3+, V
3+, Fe
3+, can comprise divalent cation Mg
2+, Fe
2+; T position is generally Si, contains a small amount of Al or B in the crude tourmaline in some place of production.
Tourmalinite is mainly column, is secondly fibrous agrregate.Generally present the different gorgeous colors such as black, brown, green, blueness, redness, wherein common with black.Tourmalinite generally has vitreous luster, and specific refractory power is 1.624-1.644, and mohs hardness is 7.0-7.5, and density is 2.9-3.25g/cm
3.
Tourmalinite belongs to trigonal system, space group is R3m system, for the typical polarity crystallization of one, in crystal R3m point group without symmetry centre, the axial positive and negative charge of its C cannot overlap, and crystal structure two ends form positive pole and negative pole, in without extra electric field situation, two ends positive and negative electrode is not also withered away, therefore claim again permanent electrode.
Tourmalinite has piezoelectricity and pyroelectricity.The in the situation that of temperature, pressure change, the potential difference producing between crystal can make ambient air ionize, and the electron attachment of being hit is in close water molecules and oxygen molecule, and makes them be converted into negative aeroion.Negative ion moves after occurring in air, can be by negative charge transport to harmful molecule in bacterium, dust, smoke particles, water droplet or even air as formaldehyde etc., electric charge is combined with these particulates, can reach the object purifying air.Therefore, tourmalinite, as the good environment functional material of one, can produce negative ion for the coated material of indoor paint and furniture, electrical equipment etc., purifies the air of a room.Again because it has pyroelectricity, therefore along with the variation of temperature, crystallizable mineral body two ends can produce voltage, its polarity ion causes that in equilibrium theory of tide vibration moment of dipole changes, the electromagnetic radiation that can produce far infrared band, and this ir radiation has health-care effect to human body.
Tourmalinite is main or take crude tourmaline as main, this present situation is limited by output greatly in the market, and crude tourmaline belongs to a kind of non-renewable natural resource, is faced with problem in great short.Therefore, the domestic research that has started to attempt artificial synthetic tourmaline.
CN1800014A discloses a kind of artificially-synthesized tourmaline crystalline substance and preparation method thereof, wherein comprise the tourmalinite of 2-10%, the mineral substance of 90-98%, above-mentioned mineral substance is the one in clay, medical stone, serpentine or leaf gneiss, and its preparation method comprises the steps: a) above-mentioned tourmalinite and above-mentioned mineral substance to be ground to form to the ultra-fine grain diameter powder below particle diameter 15nm; B) tourmalinite ultra-fine grain diameter powder above-mentioned 2-10 part dropped into the mineral substance ultra-fine grain diameter powder that 90-98 part is above-mentioned and be fully mixed into mixture; C) by above-mentioned mixture with 1600
othe above high temperature of C makes it completely molten molten; D) after cooling the mixture after above-mentioned molten melting, grind, be ground to the artificially-synthesized tourmaline crystalline substance below particle diameter 15nm.The advantage of this patent is that the artificial synthetic tourmaline that described method obtains can produce a large amount of negative ions in actual applications, has even better effect identical with crude tourmaline.And provided a technological line that synthesizes tourmalinite by mineral substance, there is certain directive significance for artificial synthetic tourmaline.On the other hand, the shortcoming of this patent is mainly 1600
othe high temperature of C is comparatively harsh to the requirement of equipment, and fund input is larger, and process conditions also has certain restriction and impact, also has higher requirement for the add-on of crude tourmaline, can not be completely free of the problem of natural matter shortage.Further, it does not provide the effect comparison example of artificial synthetic tourmaline and crude tourmaline.
CN101654254A discloses a kind of synthetic method of tourmalinite thing phase, is made up of following step: (1) is n(Mg in molar ratio): n(Al): n(Si): n(B): the proportional of=1:2:2:1 takes respectively magnesium chloride (MgCl
26H
2o), aluminum chloride (AlCl
3), water glass (Na
2siO
39H
2o), boric acid (H
3bO
3); Then the boric acid taking and water glass are dissolved in to wiring solution-forming a in deionized water, the aluminum chloride taking and magnesium chloride are dissolved in to wiring solution-forming b in the HCl solution of 1mol/l; 60 ± 5
ounder C condition, difference thermostatically heating stirred solution a and solution b, be then added drop-wise to solution a in solution b, and 60 ± 5
ounder C constant temperature, stir 10-15min, obtain homogeneous phase solution c, wherein the amount of magnesium ion is 0.01-0.04g/ml; (2) be that 1-5mol/L, temperature are 60 ± 10 with base buret to dripping concentration in homogeneous phase solution c
othe sodium hydroxide solution of C detects pH value simultaneously, is 9 ± 0.5 until be added drop-wise to pH value, produces white flocks and stop dripping and continue stirring 0.5-2h in solution; In dropping process, must note keeping homo(io)thermism, should in the time that temperature reaches design temperature, carry out again titration if larger fluctuation appears in temperature.(3) step (2) is reacted to the still aging 12-48h of slip obtaining, make the abundant crystallization of product; To outwell after supernatant liquid through the slip of ageing, use deionized water wash 3-4 time, remove the Cl containing in precipitation solution
-with unnecessary Na
+, then filter, obtain paste slip; (4) paste slip is placed in to loft drier, 80-120
oc constant temperature drying, obtains white blocks, is ground in a usual manner even-grained nano-powder; (5) nano-powder making is placed in to resistance furnace, take temperature as 500-900
othe condition of C is calcined, and calcination time is 1-8h, generates tourmalinite thing phase.The advantage of the method is that the condition of reaction relaxes relatively, easily implements.Weak point is to exist the problem of production cost, and what all use as the selection of raw material is the pure material of sodium, magnesium, aluminium, silicon, boron etc., and processing step is more, needs repeatedly titration to be precipitated slurry, controls the consumption of strict material proportion and each ion.
CN102328934A discloses the artificial tourmalinite synthetic method of carrying out under a kind of cold condition, this tourmalinite is the crystalline nanoparticles being prepared through hydrothermal synthesis method in acid solvent by mineral substance, comprises the steps: that (1) mix the described mineral substance of selected weight part and grind to form the powder that particle diameter is 2-5nm; (2) mineral mixture after grinding is dissolved in the described acid solvent of selected weight part, controls temperature 20-30
oc, carries out building-up reactions 20-30h under pressure 1-10MPa; (3) crystallization; (4) crystal is ground to the powder that particle diameter is 5-15nm, obtains final product.The advantage of this patent has been to select common mineral substance and acidic solution to prepare tourmalinite, says, without adding any crude tourmaline from material choice; Say from preparation technology, cold condition operation, comparatively relaxes equipment requirements; From the technique effect of product, its negative ion burst size is up to 12000/cm
3, effect is similar compared with crude tourmaline.Weak point is that mineral substance is defined to be in clay, medical stone, zeolite, serpentine or leaf gneiss the mixture of at least two kinds, becomes component selections narrower, and compared with crude tourmaline, element coverage rate is limited, is difficult to reach the result of use of crude tourmaline.
Summary of the invention
In sum, the object of the present invention is to provide a kind of technique of manufacturing tourmalinite with Wingdale.The tourmalinite that the present invention will prepare is not and the duplicate structure and composition of crude tourmaline, but adopts the method for synthetic to prepare the artificial synthetic tourmaline product similar to crude tourmaline structure and composition.Substitute existing crude tourmaline with this, save non-renewable natural resource, reach substantially similar result of use.
A kind of technique of manufacturing tourmalinite with Wingdale of the present invention, comprises the steps:
(1) grind: the mineral substance of selected weight part is mixed and grind to form the powder that particle diameter is 2-5nm;
(2) dissolve: the mineral mixture after grinding is dissolved in the acid solvent of selected weight part, controls temperature 20-30
oc;
(3) reaction: by the mixture solution rising temperature of step (2) to 80-100
oc, control pressure 20-30MPa, carries out building-up reactions 15-20h;
(4) crystallization: evaporation crystallization, Tc is 60-65
oc; Preferably add the crude tourmaline powder of solution quality 0.1-1wt% to be evaporated as crystal seed, be more preferably 0.1-0.5wt%;
(5) grind again: by mechanical mill, crystal is ground to the powder that particle diameter is 5-15nm, obtains final product.
Its mineral is the mixture of Wingdale, clay and zeolite, also comprises at least one in medical stone, serpentine, leaf gneiss.The mixture of Wingdale, clay and zeolite accounts for the 30-50% of described mineral substance gross weight; Take the mixture total weight amount of Wingdale, clay and zeolite as 100 parts, the content of Wingdale is 20-40 part.
Described acid solvent is one or more the mixing solutions in hydrofluoric acid, sulfuric acid or perchloric acid.The weight ratio of mineral substance and acidic solution is 2-5:1.
Make after finished product, detect negative ion burst size, and compare with prior art products.
The present invention compared with prior art has the following advantages: on the one hand, from a large amount of existing mineral substance, choose Wingdale as neccessary composition raw material, on the other hand, by optimizing temperature of reaction and pressure, shorten the reaction times, by adding a small amount of crude tourmaline powder as crystal seed, reduce Tc; By the joint efforts of above-mentioned several respects, the artificial tourmalinite sustained release negative ion in a large number that the present invention is made, negative ion burst size remains on 12500/cm after testing
3above, be up to 14000/cm
3, successful improves.
Embodiment
Embodiment of the present invention acid solvent used is hydrofluoric acid, and pH value is 3.
Embodiment 1:
Described in the present embodiment, the preparation method of artificial synthetic tourmaline, comprises the steps:
(1) grind: the mineral substance of selected weight part is mixed and grind to form the powder that particle diameter is 2-5nm;
(2) dissolve: the mineral mixture after grinding is dissolved in the acid solvent of selected weight part, controls temperature 25
oc;
(3) reaction: by the mixture solution rising temperature to 90 of step (2)
oc, control pressure 25MPa, carries out building-up reactions 20h;
(4) crystallization: evaporation crystallization, Tc is 60
oc;
(5) grind again: by mechanical mill, crystal is ground to the powder that particle diameter is 10-15nm, obtains final product.
Its mineral is 300 weight parts, and acid solvent is 100 weight parts; Mineral substance is selected 40 weight part Wingdales, 40 weight part clays, 40 weight part zeolites, 180 weight part medical stones.
After 150g tourmalinite sample is coated on cardboard, be placed in 60L watertight chest, use direct-reading negative ion determinator to measure negative ion concentration in case after 24 hours, negative ion burst size reaches 12500/cm after testing
3above.
Embodiment 2:
In the time of evaporative crystallization, add the crude tourmaline powder of solution quality 0.1wt% to be evaporated as crystal seed, the particle diameter of crude tourmaline powder used is below 1nm, and other is identical with embodiment 1.Negative ion burst size reaches 13500/cm after testing
3above
Embodiment 3:
In the time of evaporative crystallization, add the crude tourmaline powder of solution quality 0.5wt% to be evaporated as crystal seed, the particle diameter of crude tourmaline powder used is below 1nm, and other is identical with embodiment 1.Negative ion burst size reaches 14000/cm after testing
3above.
Embodiment 4:
In the time of evaporative crystallization, add the crude tourmaline powder of solution quality 1wt% to be evaporated as crystal seed, the particle diameter of crude tourmaline powder used is below 1nm, and other is identical with embodiment 1.Negative ion burst size reaches 14000/cm after testing
3above.
Embodiment 5:
Reaction times is 15h, and other is identical with embodiment 1.Negative ion burst size reaches 12500/cm after testing
3above.
Embodiment 6:
Tc is 70
oc, other is identical with embodiment 1.Negative ion burst size reaches 12500/cm after testing
3above.
Comparative example 1:
Temperature of reaction is 25
oc, reaction pressure is 10MPa, other is identical with embodiment 1.Negative ion burst size reaches 12000/cm after testing
3.
Comparative example 2:
Use 80 parts of zeolites, 40 parts of clays, 180 parts of medical stones are as mineral substance, and other is identical with embodiment 1.Negative ion burst size reaches 11000/cm after testing
3.
Comparative example 3:
Use 80 parts of zeolites, 40 parts of clays, 180 parts of medical stones are as mineral substance, and temperature of reaction is 25
oc, reaction pressure is 10MPa, the reaction times is 25h, Tc 70
oc; Other is identical with embodiment 1.Negative ion burst size reaches 10000/cm after testing
3.
Found through experiments, embodiment 1 is more visible with comparative example 1, improves temperature of reaction and pressure, can obviously improve the negative ion burst size of the finished product.
Embodiment 1 is more visible with comparative example 2, and the present invention compared with prior art, adopts the Wingdale of proper content can obviously improve the negative ion burst size of the finished product as mineral substance.
Embodiment 1 and comparative example 3(CN102328934A) more visible, compared with prior art, product technology effect of the present invention is improved significantly.
Embodiment 1 is more visible with embodiment 2-4's, adds appropriate crude tourmaline powder can effectively improve the negative ion burst size of the finished product at crystallisation step.Wherein take solution quality to be evaporated as benchmark, the crude tourmaline powder that adds 0.1-0.5wt% is for well, and add-on exceedes 0.5wt%, from the angle of negative ion burst size, there is no further raising.
Embodiment 1 is more visible with embodiment's 5, and the reaction times is that 15h can reach identical negative ion burst size, therefore, considers from cost-saving angle, the reaction times can be shortened to 15h, and not affect final product negative ion burst size.
Claims (10)
1. a technique of manufacturing tourmalinite with Wingdale, comprises the steps:
(1) grind: the mineral substance of selected weight part is mixed and grind to form the powder that particle diameter is 2-5nm;
(2) dissolve: the mineral mixture after grinding is dissolved in the acid solvent of selected weight part, controls temperature 20-30
oc;
(3) reaction: by the mixture solution rising temperature of step (2) to 80-100
oc, control pressure, carries out building-up reactions 15-20h;
(4) crystallization: evaporation crystallization;
(5) grind again: by mechanical mill, crystal is ground to the powder that particle diameter is 5-15nm, obtains final product;
Its mineral is the mixture of Wingdale, clay and zeolite, also comprises at least one in medical stone, serpentine, leaf gneiss.
2. the technique of manufacturing tourmalinite with Wingdale according to claim 1, is characterized in that: the pressure of step (3) is 20-30MPa.
3. the technique of manufacturing tourmalinite with Wingdale according to claim 1, is characterized in that: step (4) Tc is 60-65
oc.
4. the technique of manufacturing tourmalinite with Wingdale according to claim 1, is characterized in that: the mixture of Wingdale, clay and zeolite accounts for the 30-50% of described mineral substance gross weight.
5. according to claim 1ly manufacture the technique of tourmalinite with Wingdale, it is characterized in that: take the mixture total weight amount of Wingdale, clay and zeolite as 100 parts, the content of Wingdale is 20-40 part.
6. according to manufacturing the technique of tourmalinite with Wingdale described in claim 1-5 any one, it is characterized in that: described acid solvent is one or more the mixing solutions in hydrofluoric acid, sulfuric acid or perchloric acid.
7. according to the technique with Wingdale manufacture tourmalinite described in claim 1 any one, it is characterized in that: the weight ratio of mineral substance and acidic solution is 2-5:1.
8. according to the technique with Wingdale manufacture tourmalinite described in claim 1 any one, it is characterized in that: in step (4), add the crude tourmaline powder of solution quality 0.1-1wt% to be evaporated as crystal seed.
9. the technique of manufacturing tourmalinite with Wingdale according to claim 8, is characterized in that: the particle diameter of crude tourmaline powder used is below 1nm.
10. the technique of manufacturing tourmalinite with Wingdale according to claim 8, is characterized in that: in step (4), add the crude tourmaline powder of solution quality 0.1-0.5wt% to be evaporated as crystal seed.
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|---|---|---|---|
| CN201410037207.6A CN103864083B (en) | 2014-01-26 | 2014-01-26 | A kind of Wingdale manufactures the technique of tourmalinite |
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|---|---|---|---|
| CN201410037207.6A CN103864083B (en) | 2014-01-26 | 2014-01-26 | A kind of Wingdale manufactures the technique of tourmalinite |
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|---|---|
| CN103864083A true CN103864083A (en) | 2014-06-18 |
| CN103864083B CN103864083B (en) | 2015-09-16 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1800014A (en) * | 2005-12-08 | 2006-07-12 | 深圳市方浩实业有限公司 | Artificially-synthesized tourmaline crystalline substance and its preparation method |
| JP2007169092A (en) * | 2005-12-20 | 2007-07-05 | Hitachi Zosen Corp | Method of recycling chromium-containing refractory |
| CN102328934A (en) * | 2011-06-22 | 2012-01-25 | 北京方浩赛阳科技有限公司 | Artificially synthesized tourmaline and preparation method thereof |
| CN102491354A (en) * | 2011-12-05 | 2012-06-13 | 河北工业大学 | Preparation method of nano-scale tourmaline powder |
-
2014
- 2014-01-26 CN CN201410037207.6A patent/CN103864083B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1800014A (en) * | 2005-12-08 | 2006-07-12 | 深圳市方浩实业有限公司 | Artificially-synthesized tourmaline crystalline substance and its preparation method |
| JP2007169092A (en) * | 2005-12-20 | 2007-07-05 | Hitachi Zosen Corp | Method of recycling chromium-containing refractory |
| CN102328934A (en) * | 2011-06-22 | 2012-01-25 | 北京方浩赛阳科技有限公司 | Artificially synthesized tourmaline and preparation method thereof |
| CN102491354A (en) * | 2011-12-05 | 2012-06-13 | 河北工业大学 | Preparation method of nano-scale tourmaline powder |
Non-Patent Citations (1)
| Title |
|---|
| 张雪荣: "《药物分离与纯化技术》", 31 January 2011, article "结晶工艺过程" * |
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Effective date of registration: 20181130 Address after: 830000 High-tech Industrial Development in Urumqi, Xinjiang Uygur Autonomous Region (New Urban Area) Room A22, Yingke Plaza, 416 Beijing South Road Patentee after: Xinjiang Shiquan Gold Mining Co.,Ltd. Address before: 830000 22A tower 1, Diamond City, hi tech Zone, Urumqi, the Xinjiang Uygur Autonomous Region. Patentee before: URUMQI JINSHI WEILONG MINING INDUSTRY CO., LTD. |
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