CN1066049A - Maifanshi sintered material and preparation method thereof - Google Patents
Maifanshi sintered material and preparation method thereof Download PDFInfo
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- CN1066049A CN1066049A CN 91102468 CN91102468A CN1066049A CN 1066049 A CN1066049 A CN 1066049A CN 91102468 CN91102468 CN 91102468 CN 91102468 A CN91102468 A CN 91102468A CN 1066049 A CN1066049 A CN 1066049A
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Abstract
The present invention relates to a kind of Maifanshi sintered material and preparation method thereof.Described sinter contains the natural medical stone of 70-95% (weight), at least a other the natural rock or the mineral as mineral medicinal material of 5-30% (weight).Maifanshi sintered material of the present invention is by with natural medical stone and at least a other make through pulverizing grinding, moulding, drying and sintering as the natural rock of mineral medicinal material or mineral.
Description
The present invention relates to a kind of trace element and rare earth element additive, particularly a kind of Maifanshi sintered material and preparation method thereof.
Trace element and some rare earth element are the people, though biological intravital content such as animal and plant is very low, but its action and function is irreplaceable, concerning the human or animal, the integral part of they or enzyme and hormone and VITAMIN for example, or enzyme is activated, promote the synthetic and prolongation functions of hormones usefulness of hormone or play compensation and coordinative role with VITAMIN, concerning plant, they are the photosynthesis of involved in plant then, the biological nitrogen fixation process, and promote the growth of plant in that synergy or antagonistic action take place between the trace element or between trace element and the major element.In view of trace element and rare earth element to the vital role of organism, present many countries are carrying out the development work of trace element and major element additive, but mainly are mineral or the bigger inorganic salts of solubleness that employing has commercial mining value.But concerning the former, on the one hand, it is few to have a mineral species that commercial mining is worth, consider from the angle of economy not ideal, low to the stripping quantity of organism beneficial trace elements and rare earth element on the other hand, some in addition can not stripping; Concerning the latter, because its solubleness is bigger, and organism is more approaching with the poisoning level of trace element to the top requirement quantity of trace element, so its safety in utilization is lower; In addition, the micro-ionic stripping equilibrium concentration height in the inorganic salts runs off easily, causes micro-effective rate of utilization low, and validity period is shorter.
Medical stone is a kind of natural mineral of finding very early and being used as medicinal stone, belong to quartz porphyry or quartzy long rock in the igneous rock, the multiple constant, trace and the trace elements that wherein contain the organism needs, and some heavy metal ion and ionic group (comprising some organism ionic groups) are had the function of absorption or selective adsorption.Therefore the development and use of medical stone have caused attention more and more widely.But the solubleness of natural medical stone extremely low (be about ten thousand/several), the various elements useful to organism are in different locations of structures again in the various mineral of medical stone, therefore various elements can not be by its component consistence stripping, especially the stripping quantity to useful transition metal of organism and rare earth element is lower, and its absorption property is subjected to the influence of mineral composition bigger.
For improving each ionic stripping capacity in the medical stone, a kind of method is that medical stone is levigate, increases to be in the metallic cation polyhedron of solid surface and the number of metallic cation, thereby increases the ionic stripping quantity, but by this method, the increase of ion stripping quantity is very limited; Another kind method is with the medical stone heating and uses the vinegar quenching, adopt this method can change or destroy the structure of each mineral in the medical stone, the bonding state of metallic cation polyhedron or metallic cation is weakened, thereby increase its stripping capacity greatly, but simultaneously to deleterious metallic element ion of organism such as Pb
2+, Hg
2+, Cd
2+, Ag
+Also heighten Deng stripping quantity.
The objective of the invention is provides a kind of released ion concentration height in order to overcome the deficiencies in the prior art part, and dissolution rate is fast, the released ion kind is many and the good Maifanshi sintered material of absorption property.
Another object of the present invention provides the Maifanshi sintered material under the malicious therein level of a kind of released ion concentration.
A further object of the present invention provides a kind of method for preparing described Maifanshi sintered material.
The present invention relates to a kind of Maifanshi sintered material and preparation method thereof.It is heavy that described Maifanshi sintered material contains 70-95%() medical stone, 5-30%(is heavy) at least a other natural rock or mineral as mineral medicinal material, the ion dissolution rate of this sinter is natural medical stone or other natural rocks or mineral 20-60 a times, the kind analogy natural medical stone of released ion increases, and the concentration of released ion is malicious therein below horizontal; The mineral structure of sinter and the mineral structure of natural medical stone are basic identical; Contain a large amount of micropores in the sinter of the present invention, its pore diameter range is between 0.01-8.0 μ, and mean pore size is in the scope of 1.5-3 μ, and the inner ratio surface area of micropore is 15,000-35,000cm
2Between/the g; Described sinter to some to the deleterious heavy metal element ion of biology, as Pb
2+, Hg
2+, Ag
+, Cd
2+Deng stronger selective adsorption effect is arranged.
The preparation method of Maifanshi sintered material of the present invention may further comprise the steps:
A. with pulverizer with natural medical stone and at least a particle that other become the 0.10-15mm size as the natural rock or the mineral separated pulverizing of mineral medicinal material;
The broken particle that b. will obtain mixes according to the proportion requirement of sinter, grinds 10-40 hour in ultra-fine grinding mill then, obtains 80-500 purpose mix powder;
C. with the mix powder and the evenly back moulding in shaper of a certain amount of water concocting that obtain, make the particle of particle diameter in the 3-12mm magnitude range;
D. the particle that will be obtained by step c was 80-200 ℃ temperature range inner drying 5-10 hour;
E. dried particle makes Maifanshi sintered material 800-1200 ℃ temperature range inner drying 0.5-3 hour.
In the sintering process, the fluctuation range of sintering temperature is controlled at ± 10 ℃ between.
Brief Description Of Drawings
Fig. 1 is the x-ray diffraction pattern of natural medical stone;
Fig. 2 is the x-ray diffraction pattern of Maifanshi sintered material of the present invention;
Fig. 3 is the SEM photo of Maifanshi sintered material of the present invention.
As previously mentioned, natural medical stone is a kind of mineral drug of being used by the people for a long time, the quartz porphyry that it belongs in the igneous rock becomes quartz monzonite, essential mineral is plagioclase, potassic feldspar, albite, quartz, hornblend, biotite, andradite etc., accessory mineral has zircon, apatite, magnetic iron ore, ilmenite etc., wherein alteration has in various degree taken place in some mineral (such as hornblend, biotite etc.), on its chemical composition, mainly contains SiO2、Na
2O、K
2O、CaO、MgO、Fe
2O
3With FeO etc., contain in addition Determination of multiple metal elements and transition metal, such as Li, Sr, Ba, Ga, Ge, Sn, Pb, As, Sb, Bi, Se, Sc, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Co, Ni, Cu, Zn, Cd, Hg and multiple rare earth element and nonmetalloid, such as La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Ho, Er, Tm, Yb, Lu, Y, P, S, I, F, B etc.
Maifanshi sintered material of the present invention is take natural medical stone as Main Ingredients and Appearance, its content is the 70-95% of sinter gross weight, also contain at least a other natural rock or mineral as mineral medicinal material in the described sinter, its content is in the gross weight of sinter, be 5-30%, described natural rock or mineral comprise aspidelite, magnetic iron ore, calcite, diopside, gypsum, hornblend, talcum, pyrophyllite, kaolinite, imvite, zeolite, sepiolite, fluorite, avasite etc.
Maifanshi sintered material of the present invention contains:
SiO
262-74%
Al
2O
314-18%
CaO 2-4%
MgO 1-3%
Na
2O 2-5%
K
2O 2-4%
Fe
2O
31-3%
FeO 1-3%
And Ti, Mn, P, Ba, Co, Cu, Zn, Li, Sr, V, Mo, Nb, Ta, Ga, Ni, La, Ce, Pr, Nd, Gd, Yb, Y, Sc, Bi, Eu, Tb, Er, Ho, Lu, Se, Ge, Sn, W, Sm, Dy, Tm and Sb be respectively 1-1000ppm, and described per-cent is weight percentage.
Fig. 1 and Fig. 2 are respectively the x-ray diffraction patterns of natural medical stone and Maifanshi sintered material of the present invention.As shown in the figure, the mineral structure feature basically identical of the mineral structure feature of sinter of the present invention and natural medical stone, this shows the mineral structure of Maifanshi sintered material of the present invention and the mineral structure basically identical of natural medical stone.
Contain at least a other natural rock or mineral in the Maifanshi sintered material of the present invention as mineral medicinal material, ion in these natural rocks or the mineral weakens the medical stone ionic bonding strength useful to organism by factors such as solid solution, doping, manufacturing omission and lattice are twisted when high temperature, thereby strengthen its stripping capacity, realize simultaneously strengthening the combination of medical stone, thereby maximum strength ground reduces its stripping capacity to the organism harmful ion.It is generally acknowledged that the trace element of needed by human has following 14 kinds (World Health Organization announced in 1979): Fe, Zn, Cu, Cr, Mn, Co, F, I, Se, V, Ni, Mo, Sr, Sn.In recent years, people find also and have confirmed that Li, Ge, Si, Br, B, Nb, Rb and some rare earth element such as La, Pr, Yb, Y etc. are useful to HUMAN HEALTH; And the obvious deleterious unit of HUMAN HEALTH is have Be, Cd, Hg, Pb, Al, Tl, Sb and Te etc.; For plant, essential trace element has Fe, Zn, Mn, Cu, B, Mo, Cl etc.
In natural medical stone, some are to the useful element of organism such as Li, Zn, Mo, Mg etc., or because content seldom, or can not stripping because bonding force is very strong or stripping quantity very little, the stripping quantity of other beneficial elements is also very little, and dissolution rate is also very low, Maifanshi sintered material of the present invention, be formed with a large amount of micropores, as shown in Figure 3, its aperture is between 0.01-8.0 μ, and its inner ratio surface area is 15,000-35,000cm
2Between/the g, the aperture, mean pore size and the hole inner ratio surface area that are much higher than natural medical stone (are respectively 0.01-0.75 μ, 0.30-0.45 μ, 5,000-8,000cm
2/ g).
In the sinter of the present invention, owing to contain the big micropore in a large amount of apertures, so the speed of its released ion can improve greatly.
1 gram sample is soaked in the 500ml distilled water,, comes the ion dissolution rate of judgement sample according to the changing value of specific conductivity by the conductivity value of certain time interval mensuration solution.Measurement result sees Table 1.
The ionic dissolution rate of table 1 natural medical stone and Maifanshi sintered material
Time (branch) electrical conductivity of solution (μ S/cm)
The natural medical stone Maifanshi sintered material increases multiplying power
1 2.6 63.5 24.4
5 2.7 124 45.7
10 3.05 124 40.7
20 3.3 187 56.7
30 3.5 186 52.8
60 4.8 190 39.6
120 4.3 221 51.4
As shown in table 1, the ionic dissolution rate in the Maifanshi sintered material of the present invention will be much higher than the ionic dissolution rate in the natural medical stone, the former be the latter 20-60 doubly.
Table 2 has been listed the kind of the ion stripping concentration and the released ion of natural medical stone and Maifanshi sintered material of the present invention.
As shown in table 2, in the Maifanshi sintered material of the present invention, the for example isoionic stripping concentration increase of Mn, Cu, Ni, V, Y, Ni, Yb and Cl of ion to the useful element of organism, and some trace elements that can not stripping in the natural medical stone, as Zn, Mg, Mo, Li etc., sinter of the present invention can stripping.And some trace elements and the rare earth element useful to organism, bigger as the ionic stripping quantity increase of elements such as Mn, Ni, V, Y, Yb.On the other hand, as can be seen from Table 2, the stripping concentration of Maifanshi sintered material intermediate ion of the present invention does not all exceed its poisoning concentration level.
The microtexture of sinter of the present invention is to have wide aperture and the high sinter of pore specific surface area.The micropore of described wide aperture, high pore specific surface area, can increase kind on the one hand to the useful ionic dissolution rate of organism and stripping quantity and increase released ion, on the other hand, the micropore capillary action can play adsorption to ion, the selective adsorption effect of especially harmful heavy metal ion is for example to Pb
2+, Hg
2+, Ag
+Deng absorption, controlled their dissolution rate and stripping quantity, it is below horizontal to make the stripping concentration of harmful ion in the sinter be controlled at its poisoning.
Be the Pb of 10ppm with 1g Maifanshi sintered material adding of the present invention 100ml, concentration respectively
2+, Cd
2+, Hg
2+, Ag
+In the solution, measure the adsorptive capacity of the Maifanshi sintered material of immersion after 1 hour to different harmful ions, the result is as shown in table 3.
Table 3 Maifanshi sintered material is to the adsorption of heavy metal ion
Adion Ag
+Pb
2+Hg
2+Cd
2+
The unit adsorptive capacity
（μg/g） 32.08 32.68 31.30 22.49
The result shows that Maifanshi sintered material of the present invention has some harmful heavy metal ion selects adsorption preferably.
Maifanshi sintered material of the present invention can be widely used in drinking water purification, improver of water quality, fertilizer additive, fodder additives, medicated premix, soil improvement agent etc., also can be used as preparation tea set, tableware, mess kit or container.
For the Application Areas at tap water, on the one hand, Maifanshi sintered material of the present invention can make the tap water stripping contain more trace element and rare earth element ion to the human body beneficial, thereby can improve water quality; On the other hand, its some objectionable impurities in can also planar water.
Respectively 1g Maifanshi sintered material of the present invention is soaked in the 100ml water of different PH, after the different soak times, the pH value of water changes lists in the table 4.
Table 4 wheat after meal sinter to the influence of the pH value of water quality
| Soak time (hr) | PH value changes |
| 0 1/12 1/4 1/2 1 2 2.5 4 5 19 | 3.41 3.96 4.96 5.64 8.32 8.80 10.80 3.68 4.06 5.16 5.68 7.68 8.08 9.80 3.70 4.12 5.22 5.72 7.06 7.22 9.70 3.94 4.17 5.22 5.66 － 7.20 9.70 3.92 4.16 5.41 6.12 7.20 6.92 9.30 4.30 6.30 6.40 7.17 5.78 7.04 |
As shown in table 4, Maifanshi sintered material of the present invention has stronger adjustment water quality function, slightly acidic or weakly alkaline water quality can be adjusted into neutrality or subacidity water quality.
High pore specific surface area that Maifanshi sintered material of the present invention has and wide-aperture micropore increase the quantity that is in surperficial metallic cation polyhedron and metallic cation, and therefore the amount of leachable metallic cation increases, thereby can prolong its work-ing life.
Adopt 1 gram Maifanshi sintered material of the present invention and natural medical stone to be soaked in the 500ml distilled water respectively, every immersion was measured electrical conductivity of water in 2 hours, changed distilled water then again, measured repeatedly 28 times, and conductivity value (ionic stripping concentration) is listed in the table 5.
The different specific conductivity (μ S/cm) of soaking the aqueous solution of number of times of table 5
| Number of times natural medical stone Maifanshi sintered material | Number of times natural medical stone table meal stone sinter | ||||
| 1 1.8 19 2 1.6 12.5 3 1.2 8.2 4 1.2 5.5 5 1.2 4.6 6 1.2 4.1 7 1.2 4.6 8 1.15 4.0 9 1.15 4.1 10 1.05 3.2 11 1.15 3.0 12 1.2 3.2 13 1.1 3.6 14 1.05 3.6 | 15 1.2 4.4 16 1.2 3.9 17 1.2 4.0 18 1.2 3.6 19 1.2 6.6(4h) 20 1.05 12.5(12h) 21 1.25 3.0 22 1.2 3.8 23 1.1 3.0 24 2.5 4.8 25 2.5 4.95 26 2.8 3.8 27 2.8 4.1 28 2.6 4.2 |
As shown in table 5, after each the immersion, use Maifanshi sintered material of the present invention, the specific conductivity of the aqueous solution all is higher than natural medical stone, and this shows that the work-ing life of Maifanshi sintered material of the present invention and effect all are better than natural medical stone.
Maifanshi sintered material of the present invention can be made different shape, for example, as the case may be, can make Powdered, spherical, sheet or shapes such as rectangular parallelepiped, square, is preferably spherical.
The preparation method of Maifanshi sintered material of the present invention may further comprise the steps:
A. natural medical stone and at least a other natural rock or mineral as mineral medicinal material are ground into the 0.1-15.0 size respectively in pulverizer particle;
B. the particle after pulverizing is mixing in mixing tank by a certain percentage, grinds 10-40 hour in ultra-fine grinding mill then, obtains 80-500 purpose powder;
C. after the powder that obtains and a certain proportion of water being mixed thoroughly, moulding in general shaper makes the particle of granularity in the 3-12mm scope;
D. the particle that will be obtained by step c was 80-200 ℃ temperature range inner drying 5-10 hour;
E. dried particle was calcined 0.5-3 hour in 800-1200 ℃ temperature range, obtained Maifanshi sintered material of the present invention.
According to method of the present invention, natural medical stone and other are respectively 70-95% and 5-30% as the content of the natural rock of mineral medicinal material or the mineral gross weight in sinter; Described natural rock or mineral as mineral medicinal material comprise aspidelite, magnetite, calcite, diopside, gypsum, hornblende, talcum, pyrophyllite, kaolinite, polynite, zeolite, sepiolite, fluorite and avasite etc.
According to method of the present invention, as required, the mix powder after levigate also can be without moulding and dry and directly make pulverous sinter through sintering.
In the forming step of the inventive method, also can add other tackiness agents and mix powder and mix thoroughly, be beneficial to its moulding.Described tackiness agent comprises glycerine, water glass, clay, dextrin, polyvinyl alcohol, polystyrene, ethyl oxalic acid, carboxymethyl cellulose, polyvinyl acetate (PVA) etc.
In sinter of the present invention and preparation method thereof, other are as the adding of the natural rock or the mineral of mineral medicinal material, on the one hand, in sintering process, can change the microtexture of medical stone by effects such as solid solution, doping, manufacturing omission and lattice are twisted, and the wide aperture that has by Maifanshi sintered material, the micropore of high hole inner ratio surface area increase ionic dissolution rate and stripping quantity; On the other hand, can increase some content of elements in the natural medical stone, help to adjust the speed and the concentration of released ion.
According to method of the present invention, powder diameter is controlled at the 80-500 order, preferably the 300-450 order.Because powder diameter is little, its specific surface area is bigger, and the atom or the ionic quantity that are in solid surface are many, and ionic dissolution rate and stripping quantity increase.
According to method of the present invention, the sintering temperature in the sintering process is very big to the Effect on Performance of Maifanshi sintered material: temperature is low excessively, and sintering strength is not enough, and temperature is too high, then influences the formation of the micropore of sinter.In addition, the performance of sinter is very responsive to temperature variation, must control the fluctuation range of sintering temperature in the sintering process in ± 10 ℃.Sintering temperature is adjusted according to the composition of sinter.
In the preferred embodiment of the inventive method, natural medical stone with as the content of the natural rock of mineral medicinal material or mineral gross weight in sinter, be respectively 85-90% and 10-15%, powder diameter is in 350-400 purpose scope, select polyvinyl alcohol as binding agent in the moulding process, drying temperature between 100-150 ℃, dry 7-8 hour, sintering temperature is between 1000-1100 ℃, and sintering time is 40-150 minute.
Below in conjunction with embodiment the present invention is carried out further detailed elaboration.
Embodiment 1
Present embodiment adopts the Shengxian County, Zhejiang to produce medical stone, and being aided with gypsum and zeolite is that additive prepares Maifanshi sintered material.
Proportion scale is a medical stone 90%(weight)
Gypsum 6%(weight)
Zeolite 4%(weight)
Described medical stone, gypsum and zeolite are ground into the particle of 6mm size respectively in pulverizer, then with its mixing in mixing tank according to the above ratio, and in ultra-fine grinding mill, grind the mixed powder obtained 320 order sizes in 10 hours, adding a certain amount of water then in mix powder mixes well, and in shaper, make the ball that radius is 5mm, and be 150 ℃ of following dryings 5 hours in temperature then, calcined 1.5 hours down at 1000 ℃ ± 10 ℃ at last, make the medical stone sintering ball, its performance is as follows:
(1) released ion speed: represent (μ S/cm) with specific conductivity
25 ℃ of water temperatures, PH=6.9
The results are shown in Table 6
Table 6 ion dissolution rate
(2) released ion concentration sees Table 7
Why table 7 released ion concentration table
Preface item released ion concentration table ppm
Number order natural medical stone Maifanshi sintered material
1 Li ＜0.005 0.286
2 Na 0.185 340.47
3 K 0.189 62.559
4 Fe 0.078 0.012
5 Mn 0.015 0.065
6 Cu 0.02 0.05
7 Zn ＜0.001 0.017
8 Ca 0.53 90.3
9 Mg ＜0.00005 2.69
10 Co ＜0.003 ＜0.003
11 Ni 0.0097 0.027
12 V 0.009 0.108
13 Mo ＜0.001 0.03
14 Ce 0.364 0.434
15 Pr 0.221 0.169
16 Nd 0.365 0.611
17 Yb 0.0004 0.421
18 Y 0.0054 0.0146
19 Ag ＜0.002 ＜0.002
20 Se ＜0.0005 ＜0.0005
21 Pb 0.005 ＜0.005
22 Cd ＜0.003 ＜0.003
23 Hg 0.0015 ＜0.0005
24 Cr 0.03 0.04
25 As ＜0.0005 ＜0.0005
(3) absorption property:
Natural medical stone and Maifanshi sintered material are to Ag
+, Pb
2+, Cd
2+, Hg
2+Adsorptive capacity Deng harmful ion sees Table 8:
The adsorption of table 8 pair harmful ion
Unit adsorptive capacity (μ g/g)
Adion natural medical stone Maifanshi sintered material
Ag
+25.06 32.08
Pb
2+20.39 32.68
Cd
2+15.68 22.49
Hg
2+19.36 31.30
It is raw material that present embodiment adopts the Jinhua, Zhejiang medical stone, and being aided with gypsum and rhombspar is additive, the preparation Maifanshi sintered material.
(1) proportion scale medical stone 85%(weight)
Gypsum 5%(weight)
Rhombspar 10%(weight)
Step of preparation process is with embodiment 1, and the processing parameter of each step is as follows:
Batch mixing milling time 12 hours
Abrasive material fineness 180 orders
The balling-up condition adds water
150 ℃ of drying temperatures
7 hours time of drying
1100 ℃ ± 10 ℃ of calcining temperatures
Calcination time 1 hour
The sinter performance that makes is as follows:
(1) released ion speed: represent (μ S/cm) with specific conductivity
Water temperature: 23 ℃ of PH=7.2
Table 9 ion dissolution rate
(2) released ion concentration sees Table 10
Table 10 released ion concentration table
Preface item released ion concentration ppm
Number order natural medical stone Maifanshi sintered material
1 Li ＜0.005 ＜0.005
2 Na 0.867 2.23
3 K 0.207 0.36
4 Fe 0.0168 0.0399
5 Mn 0.0192 0.0314
6 Cu 0.0126 0.0007
7 Zn 0.1029 1.8666
8 Ca 1.8037 341.69
9 Mg ＜0.00005 0.25
10 Co ＜0.003 ＜0.003
11 Ni 0.0337 0.1334
12 V 0.1630 0.5736
13 Mo 0.0285 0.0529
14 Ce ＜0.03 0.089
15 Pr ＜0.02 0.0513
16 Nd ＜0.06 ＜0.006
17 Yb ＜0.006 ＜0.006
18 Y ＜0.005 ＜0.005
19 Ag ＜0.002 0.0034
20 Se 0.0015 0.0001
21 Pb 0.0021 0.0018
22 Cd ＜0.003 0.0046
23 Hg ＜0.000033 ＜0.000033
24 Cr 0.0194 0.0242
25 As ＜0.0008 0.00207
(3) absorption property:
Jinhua, Zhejiang medical stone raw ore and Maifanshi sintered material are to Ag
+, Pb
2+, Cd
2+, Hg
2+See Table 11 Deng the harmful ion adsorptive capacity
The adsorption of table 11 pair harmful ion
Unit adsorptive capacity (μ g/g)
Adion natural medical stone Maifanshi sintered material
Ag
+27.36 35.29
Pb
2+23.53 31.04
Cd
2+17.08 24.36
Hg
2+21.83 33.46
Embodiment 3
It is raw material that present embodiment adopts the Central Mountain, Henan medical stone, and being aided with rhombspar and sepiolite is additive, the preparation Maifanshi sintered material.
Step of preparation process is with embodiment 1, and the processing parameter of each step is as follows:
Proportion scale: medical stone 75%(weight)
Rhombspar 15%(weight)
Sepiolite 10%(weight)
Batch mixing milling time 10.5 hours
Abrasive material fineness 200 orders
The balling-up condition adds water and polyvinyl alcohol
150 ℃ of drying temperatures
5.5 hours time of drying
850 ℃ ± 10 ℃ of calcining temperatures
Calcination time 1 hour
The sinter performance is as described below:
(1) released ion speed: represent (μ S/cm) with specific conductivity
20 ℃ of PH=7.1 of water temperature
The results are shown in Table 12
Table 12 released ion concentration
(2) released ion concentration sees Table 13
Table 13 released ion concentration table
Preface item released ion concentration ppm
Number order natural medical stone Maifanshi sintered material
1 Li ＜0.025 ＜0.5
2 Na 0.198 62.6
3 K ＜0.025 13.37
4 Fe 0.1345 0.0245
5 Mn 0.0025 0.3475
6 Cu ＜0.0010 ＜0.0010
7 Zn 0.0083 0.0251
8 Ca 2.1760 330.89
9 Mg ＜0.00005 0.5833
10 Co ＜0.003 ＜0.003
11 Ni ＜0.001 ＜0.001
12 V 0.2677 0.3132
13 Mo 0.0362 0.0204
14 Ce ＜0.03 0.0879
15 Pr 0.02 0.0427
16 Nd ＜0.06 ＜0.06
17 Yb ＜0.006 ＜0.006
18 Y ＜0.005 ＜0.005
19 Ag ＜0.002 ＜0.002
20 Se 0.0004 0.0001
21 Pb 0.001 0.0028
22 Cd ＜0.003 ＜0.003
23 Hg 0.000033 0.000033
24 Cr 0.0256 0.0059
25 As 0.0001 0.00081
(3) absorption property the results are shown in Table 14
The Central Mountain, Henan medical stone raw ore and Maifanshi sintered material are to Ag
+, Pb
2+, Cd
2+, Hg
2+Adsorptive capacity Deng harmful ion is as follows:
The adsorption of table 14 pair harmful ion
Unit adsorptive capacity (μ g/g)
Adion medical stone raw ore Maifanshi sintered material
Ag
+28.36 42.69
Pb
2+24.67 39.82
Cd
2+26.53 33.74
Hg
2+27.46 40.58
Table 2 released ion concentration table
| Sequence number | Project | Released ion concentration ppm | Sequence number | Project | Released ion concentration ppm | ||
| Natural medical stone | Maifanshi sintered material | Natural medical stone | Maifanshi sintered material | ||||
| 1 | Na | 0.185 | 18 | Ge | -- | -- | |
| 2 | K | 0.189 | 62.559 | 19 | Li | -- | 0.286 |
| 3 | Mn | 0.015 | 0.065 | 20 | V | 0.009 | 0.108 |
| 4 | Cu | 0.02 | 0.05 | 21 | Y | 0.0054 | 0.0146 |
| 5 | Zn | -- | 0.017 | 22 | Ge | 0.364 | 0.434 |
| 6 | Fe | 0.078 | 0.042 | 23 | Pr | 0.221 | 0.169 |
| 7 | Ca | 0.53 | 90.3 | 24 | Nd | 0.365 | 0.611 |
| 8 | Mg | —— | 2.69 | 25 | Yb | 0.0004 | 0.0421 |
| 9 | Mo | —— | 0.03 | 26 | Ag | —— | ＜0.062 |
| 10 | Co | ＜0.003 | ＜0.003 | 27 | NO 3 － | 0.519 | ＜0.19 |
| 11 | Ni | 0.0097 | 0.027 | 28 | SO 4 2－ | 0.462 | 293.18 |
| 12 | Cr | 0.03 | 0.04 | 29 | F － | ＜0.364 | ＜0.364 |
| 13 | Cd | ＜0.003 | ＜0.003 | 30 | HCO 2 － | ＜2 | ＜2 |
| 14 | Hg | 0.0015 | ＜0.0005 | 31 | Cl － | ＜0.052 | ＜0.052 |
| 15 | Pb | -- | ＜0.05 | 32 | NO 2 － | ＜0.078 | ＜0.078 |
| 16 | As | ＜0.0005 | ＜0.0005 | 33 | NH 4 ＋ | ＜0.0385 | ＜0.0385 |
| 17 | Se | ＜0.0005 | ＜0.0005 | ||||
Claims (20)
1, a kind of Maifanshi sintered material is characterized in that described sinter contains the natural medical stone of 70-95% (weight), at least a natural rock or the mineral that are selected from as mineral medicinal material of 5-30% (weight).
2,, it is characterized in that described sinter contains according to the described sinter of claim 1
SiO
262-74%
Al
2O
314-18%
CaO 2-4%
MgO 1-3%
Na
2O 2-5%
K
2O 2-4%
Fe
2O
31-3%
FeO 1-3%
And Ti, Mi, P, Ba, Co, Cu, Zn, Li! Sr, V, Mo, Nb, Ta, Ga, Ni, La, Ce, Pr, Nd, Gd, Yb, Y, Sc, Bi, Eu, Tb, Er, No, Lu, Se, Ge, Sn, W, Sm, Dy, Tm, Sb are respectively 1-1000ppm, and described per-cent is weight ratio.
3,, it is characterized in that the mineral structure of the mineral structure of described sinter and natural medical stone is basic identical according to the described sinter of claim 1.
4,, it is characterized in that described sinter contains the micropore as ion stripping passage and ionic adsorption surface according to the described sinter of claim 1.
5, according to the described sinter of claim 4, the aperture that it is characterized in that described micropore is between 0.01-8.0 μ, and mean pore size is between 1.0-3.0 μ, and the inner ratio surface area of micropore is 15,000-35,000cm
2Between/the g.
6, according to claim 1 or 2 described sinters, the ion dissolution rate that it is characterized in that described sinter be natural medical stone the ion dissolution rate 20-60 doubly.
7,, it is characterized in that the equilibrium concentration of released ion of described sinter is malicious therein below horizontal according to claim 1 or 2 described sinters.
8,, it is characterized in that described sinter has stronger selection adsorptivity to some to the deleterious element ion of organism according to claim 1 or 2 described sinters.
9,, it is characterized in that described natural rock or mineral as mineral medicinal material comprise aspidelite, magnetite, calcite, diopside, gypsum, hornblende, talcum, pyrophyllite, kaolinite, polynite, zeolite, sepiolite, fluorite, avasite according to the described sinter of claim 1.
10,, it is characterized in that described released ion comprises Zn, Mg, Mo, Li ion according to the described sinter of claim 6.
11, a kind of method for preparing Maifanshi sintered material may further comprise the steps:
A. with natural medical stone and other at least a as mineral medicinal material natural rock or mineral separated pulverizing in pulverizer to become granularity be the particle of 0.01-15mm;
B. the natural medical stone after will pulverizing and other at least a natural rock or mineral as mineral medicinal material proportionally mix, and mixture ground in ultra-fine grinding mill 10-40 hour, obtained 80-500 purpose mix powder;
C. the mix powder that obtains add water concocting evenly after, moulding in shaper makes the particle of granularity in the 3-12mm scope;
D. the particle after the moulding was 80-200 ℃ temperature range inner drying 5-10 hour;
E. dried particle in 800-1200 ℃ temperature range sintering 0.5-3 hour obtains Maifanshi sintered material.
12, in accordance with the method for claim 11, it is characterized in that in described moulding process, adding tackiness agent.
13, in accordance with the method for claim 12, it is characterized in that described tackiness agent comprises glycerine, water glass, clay, dextrin, polyvinyl alcohol, polystyrene, ethyl oxalic acid, carboxymethyl cellulose, polyvinyl acetate (PVA).
14, in accordance with the method for claim 11, it is characterized in that described natural medical stone be respectively 70-95%(weight as the natural rock of mineral medicinal material or the content of mineral), 5-30%(weight).
15, in accordance with the method for claim 11, it is characterized in that described natural rock or mineral as mineral medicinal material comprise aspidelite, magnetite, calcite, saturating muddy stone, gypsum, hornblende, talcum, pyrophyllite, kaolinite, polynite, zeolite, sepiolite, fluorite and avasite.
16, in accordance with the method for claim 11, the fluctuation range that it is characterized in that described sintering temperature must be controlled at ± 10 ℃ in.
17, in accordance with the method for claim 11, it is characterized in that the powder after levigate directly carries out sintering, obtain the Maifanshi sintered material powder.
18, the described sinter of claim 1 to the concentration of organism beneficial trace elements, reduces the concentration of harmful ion as improving water quality in the increase water.
19, the described sinter of claim 1 is as fertilizer additive, fodder additives or medicated premix.
20, the described sinter of claim 1 is as preparation tea set, tableware, mess kit or container.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91102468 CN1066049A (en) | 1991-04-22 | 1991-04-22 | Maifanshi sintered material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91102468 CN1066049A (en) | 1991-04-22 | 1991-04-22 | Maifanshi sintered material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1066049A true CN1066049A (en) | 1992-11-11 |
Family
ID=4905625
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91102468 Pending CN1066049A (en) | 1991-04-22 | 1991-04-22 | Maifanshi sintered material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1066049A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101348365B (en) * | 2008-09-04 | 2011-05-11 | 浙江苏泊尔家电制造有限公司 | Medical stone ceramic material and use thereof |
| CN104759035A (en) * | 2015-04-14 | 2015-07-08 | 伍建柏 | Method for manufacturing health products by means of actinolite |
| CN105753462A (en) * | 2016-02-04 | 2016-07-13 | 浙江醒缘生物科技有限公司 | Turtle type activated energy magnet therapy plate and preparation method thereof |
| CN107930613A (en) * | 2017-11-09 | 2018-04-20 | 南京大学（苏州）高新技术研究院 | The preparation and application of a kind of powder catalytic material, the compound porous nano catalytic material containing na-montmorillonite |
| CN108975889A (en) * | 2018-08-07 | 2018-12-11 | 奈曼旗中华麦饭石开发有限公司 | It is a kind of to dissolve out the ceramic materials of minerals, ceramic component and preparation method thereof |
| CN109133314A (en) * | 2018-08-30 | 2019-01-04 | 优高雅健康科技(深圳)有限公司 | A kind of continuous extract equipment and the method using equipment extraction medical stone |
| CN110217874A (en) * | 2019-07-15 | 2019-09-10 | 韩宝音代来 | A kind of Maifanitum minerals dry powder and its modified technique |
| CN112194477A (en) * | 2019-06-20 | 2021-01-08 | 深圳市合元科技有限公司 | Preparation method of porous ceramic material and porous material obtained by same |
| CN113880554A (en) * | 2021-10-19 | 2022-01-04 | 北京科技大学 | Method for preparing black ceramic material |
-
1991
- 1991-04-22 CN CN 91102468 patent/CN1066049A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101348365B (en) * | 2008-09-04 | 2011-05-11 | 浙江苏泊尔家电制造有限公司 | Medical stone ceramic material and use thereof |
| CN104759035A (en) * | 2015-04-14 | 2015-07-08 | 伍建柏 | Method for manufacturing health products by means of actinolite |
| CN105753462A (en) * | 2016-02-04 | 2016-07-13 | 浙江醒缘生物科技有限公司 | Turtle type activated energy magnet therapy plate and preparation method thereof |
| CN107930613A (en) * | 2017-11-09 | 2018-04-20 | 南京大学（苏州）高新技术研究院 | The preparation and application of a kind of powder catalytic material, the compound porous nano catalytic material containing na-montmorillonite |
| CN108975889A (en) * | 2018-08-07 | 2018-12-11 | 奈曼旗中华麦饭石开发有限公司 | It is a kind of to dissolve out the ceramic materials of minerals, ceramic component and preparation method thereof |
| CN109133314A (en) * | 2018-08-30 | 2019-01-04 | 优高雅健康科技(深圳)有限公司 | A kind of continuous extract equipment and the method using equipment extraction medical stone |
| CN112194477A (en) * | 2019-06-20 | 2021-01-08 | 深圳市合元科技有限公司 | Preparation method of porous ceramic material and porous material obtained by same |
| CN110217874A (en) * | 2019-07-15 | 2019-09-10 | 韩宝音代来 | A kind of Maifanitum minerals dry powder and its modified technique |
| CN113880554A (en) * | 2021-10-19 | 2022-01-04 | 北京科技大学 | Method for preparing black ceramic material |
| CN113880554B (en) * | 2021-10-19 | 2022-07-22 | 北京科技大学 | Method for preparing black ceramic material |
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