CN103194696B - Improve ocean depositing technology and the iron based mixture of metal anti-radiation - Google Patents
Improve ocean depositing technology and the iron based mixture of metal anti-radiation Download PDFInfo
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Abstract
The present invention proposes and a kind ofly improve the ocean depositing technology of metal anti-radiation and radiation-resistant iron based mixture.Iron-based, as matrix, bears deep sea static pressure, improves physical properties.Noncrystal protective membrane stable in properties, protection iron-based is not corroded, and for adsorbing multi-nuclear metal.At a predetermined temperature, protective membrane softens, and modified iron-based and multi-nuclear metal are preserved.Mixing iron-based and multi-nuclear metal, obtain steel fiber.Described iron based mixture comprises: iron, germanium, tin, lead and nickel, by weight, and described germanium: tin: plumbous: nickel=1:1.8-2.1:0.8-1.3:1.2-1.5, the density of this mixture is not less than 8.1g/cm
3.This iron based mixture of the present invention containing various metals, there is good electroconductibility and ferromegnetism, improve the protection to electromagnetic radiation.
Description
Technical field
The present invention relates to the technology being improved metal matrix magnetic and electroconductibility by ocean current static pressure and heavy metal adsorption, particularly relate to the iron based mixture that the ocean depositing technology that improves metal anti-radiation and this technique are made.
Background technology
Radioprotective mainly produces induced current by electro-conductive fiber under the effect of electromagnetic radiation, and this induced current generates electromagnetic waves, opposing source of radiation, and then stops radiation to penetrate conductive fiber layer.The induced current that the nano silver fibre of prior art produces under the effect of electromagnetic radiation is limited, and this silver-colored fiber is oxidizable, and the shielding property of the silver-colored fiber after oxidation reduces gradually.Therefore, be necessary to study other schemes to replace nano silver fibre.
Point out in " the magnetic research of multinuclear transition metal title complex " and " theoretical investigation of multi-nuclear metal and a metallising radical complex molecule magnetic ", multi-nuclear metal can show ferromegnetism.This multi-nuclear metal can improve comprehensive ferromegnetism with coordinating of a metallising radical, strengthens the sensitivity to electromagnetism.
The metal enrichment technology of prior art gives us some enlightenments, and these technical schemes can realize multi-nuclear metal, the enrichment of a metallising radical and modification.Such as, CN200910130485.5 discloses the sorbent material of a heavy metal species, and this sorbent material refers to sulphur carbon nano-composite material sorbent material, and this sorbent material can improve the speed of Adsorption of Heavy Metals from liquid and gas.
Prior art also provides the sorbent material that some take heavy metal as matrix, as that metal oxide sorbents of the US2004039706 that A Er Petter A Fei Erhaili provides.This case take magnesium aluminum oxide as sorbent material, the SO in absorption environment
x, NO
xdeng material.This case tells us metal oxide can become activated carbon, becomes the sorbent material of gas.
From the ocean of enrichment nonferrous metal ion, the technique of sorb non-ferrous metals is also known, the technique of such as, polymetallic nodule in that extraction deep-sea of patent CN200510134512.8.This technique is pointed out, wet reducing polymetallic nodule can realize.
In addition, CN200710305935.0 discloses metal adsorption device, passes into metal fluid at the entrance of this metal adsorption device, the metal in the uncrystalline silicon fluid-absorbent in this device.This case enlightens our the noncrystal effect to metal adsorption.
Cooling static pressure on the impact of physics of metals character by just slightly research, such as the analysis of densification process " under the metal-powder isostatic cool pressing ".
Although prior art discloses the technique of some adsorbing metals in a fluid, the impact of fluid on sorbent material itself is unknown, is necessary this to be done to careful research, to obtain the better steel fiber of radiation-proof effect.
Summary of the invention
The present invention proposes a kind of ocean depositing technology improving metal anti-radiation, solves the defect of silver-colored fiber radiation-proof in prior art.
Technical scheme of the present invention is achieved in that
Improve an ocean depositing technology for metal anti-radiation, it is characterized in that comprising the following steps:
Fe-based surface process
By melting sources, make melting viscous fluid, keep temperature 900 DEG C to 1200 DEG C;
Keep the oxygen level of Working environment below 0.1%, iron is added melting viscous fluid;
Cool extraction gradually, every 5mm, envrionment temperature reduction is not more than 10 DEG C;
The iron-based adhering to described viscous fluid is extracted out, scrapes off viscous fluid gradually, make viscous fluid wrap up described iron-based, finally make the sorbent material be made up of noncrystal protective membrane and iron-based;
Wherein, described raw material is made up of sodium oxide, aluminum oxide, silicon oxide, magnesium oxide, calcium oxide and boron oxide, it is sodium oxide by percent mass: aluminum oxide: silicon oxide: magnesium oxide: calcium oxide: boron oxide=1:1.3-1.8:3-4.6:1.6-2:0.8-2.1:0.2-0.5
The purity of described iron-based is not less than 99%, and the surface-area S of this iron-based and volume V meets: S
3/ V
2>=401,
The thickness H of described noncrystal protective membrane meets: S/H
2>=251,
Precipitation adsorption
Sorbent material is placed in the region from earth's surface at below 300m, leaves standstill 2 to 5 years;
The refinement of mixture
Take out sorbent material, melt under 1100 DEG C to 1400 DEG C conditions, filtration is precipitated, and precipitation reduction is obtained iron based mixture.
In the depositing technology of this deep-sea of the present invention, in the refining step of mixture, filter the depositing abrasive obtained and become particle at below 0.1mm, wherein more than 50% is less than 0.027mm,
Joined in ammonia-ammonium chloride solution by mixture after grinding, pass into carbon monoxide, controlling ore pulp solid-liquid concentration ratio is 18-40:1, control temperature 25 DEG C-65 DEG C, and time 30min-50min, is precipitated,
Use ammonium chloride solution washing and precipitating, in scavenging solution, the concentration of ammonium at 10-13g/l, the concentration of chlorion at 10-17g/l,
Fusing precipitation, temperature of fusion is at 1535 DEG C-1700 DEG C, and annealing is reeled off raw silk from cocoons and obtained iron based mixture fiber.
In the depositing technology of this deep-sea of the present invention, each composition of the noncrystal protective membrane of described manufacture meets: by percent mass, sodium oxide: aluminum oxide: silicon oxide: magnesium oxide: calcium oxide: boron oxide=1:1.6:4.0:1.7:1.6:0.33.
In the depositing technology of this deep-sea of the present invention, the surface-area S of this iron-based and volume V meets: S
3/ V
2>=1013.
In the depositing technology of this deep-sea of the present invention, the thickness H of described noncrystal protective membrane meets: S/H
2>=827, and H>=10mm.
In the deep-sea depositing technology of this metal of the present invention, sorbent material is placed in the region from earth's surface at below 800m, leaves standstill 4 years.
In the depositing technology of this deep-sea of the present invention, described iron-based is spheroidal graphite cast iron.
A kind of radiation-resistant iron based mixture, it is characterized in that comprising: iron, germanium, tin, lead and nickel, by weight, the content of described iron is more than 99%, described germanium: tin: plumbous: nickel=1:1.8-2.1:0.8-1.3:1.2-1.5, the density of this mixture is not less than 8.1g/cm
3.
In this iron based mixture of the present invention, this iron based mixture is made up of iron, germanium, tin, lead, nickel, copper, cobalt, by weight, the content of described iron is more than 99%, the gross weight of described germanium, tin, lead, nickel is 0.4%-0.6%, and carbon, nitrogen sum are 0.2%-0.3%, the copper of surplus, cobalt.
Ocean depositing technology and the iron based mixture of implementing this raising metal anti-radiation of the present invention have following beneficial effect: iron-based, as matrix, bears deep sea static pressure, improves physical properties.Noncrystal protective membrane stable in properties, protection iron-based is not corroded, and for adsorbing multi-nuclear metal.At a predetermined temperature, protective membrane softens, and modified iron-based and multi-nuclear metal are preserved.Mixing iron-based and multi-nuclear metal, obtain steel fiber.This iron based mixture of the present invention containing various metals, there is good electroconductibility and ferromegnetism, improve the protection to electromagnetic radiation.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the radiation-resistant schematic diagram of iron based mixture of the present invention;
Fig. 2 is the schema of deep-sea of the present invention depositing technology;
Fig. 3 is the schematic diagram of iron-based deep-sea precipitation process;
Fig. 4 illustrates the curve of approximation of the ratio of the time of shelving and metal content;
Fig. 5 illustrates the content of iron-based and the relation of radiation-proof effect;
Fig. 6 illustrates the relation of K value and radiation-proof effect.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, be clearly and completely described the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
This radiation-resistant iron based mixture of the present invention, is made up of iron, germanium, tin, lead, nickel, copper, cobalt, by weight, the content of described iron is more than 99%, the gross weight of described germanium, tin, lead, nickel is 0.4%-0.6%, and carbon, nitrogen sum are 0.2%-0.3%, the copper of surplus, cobalt.Described germanium: tin: plumbous: nickel=1:1.8-2.1:0.8-1.3:1.2-1.5, the density of this mixture is not less than 8.1g/cm
3.
As shown in Figure 1, the radioprotective principle of the steel fiber grid that iron based mixture is made, produces induced current between fiber 11, and then produces induction field, the high frequency radiation 13 of opposing source of radiation 12.Fig. 3 shows the schematic diagram that multi-nuclear metal 31 adsorbs on noncrystal protective membrane 32, and protective membrane covers 32 on iron-based 33.This, the steel fiber grid that iron based mixture is made has good radiation-proof effect, and relative to Stainless Steel Fibre, the strength of electric field in shield ranges reduces by 40%, and relative to nano silver fibre, strength of electric field reduces about 18%.The content of iron-based and the relation of radiation-proof effect, as Fig. 5.
With reference to Fig. 2, to the different step of this ocean of the present invention depositing technology, can carefully state, to obtain preferably result of use in actual use.
In the raw material preparing sorbent material, the content of boron oxide is conducive to improving thermal expansivity, so that protective membrane is attached on iron-based after cooling gradually.But boron oxide easily volatilizees, corrosion, even produces toxic gas.So boron oxide is limited to the 0.2-0.5 of sodium oxide doubly by the present invention.Other metallic elements in raw material show good wetting ability when the chloropexia with reduction-state.The composition of these oxidized metals forms the composition of amorphous state, may be used for adsorbing multi-nuclear metal, and has good normality stability.
Higher temperature, raw material mobility is larger, but high temperature is unfavorable for the existence of iron-based spheroidal graphite body, therefore selective temperature 900 DEG C to 1200 DEG C, when the apparatus processing time allows, preferably 930 DEG C.
Speed of cooling is slower, is more beneficial to the shaping of protective membrane, and in the present invention, every 5mm, envrionment temperature reduction is not more than 10 DEG C.It can be mechanical for scraping off non-crystal mode, carries out with the reduction of envrionment temperature simultaneously.
Due to the effect of protective membrane primary attachment, so surface-area is more greatly favourable, in the present invention, the thickness H limiting noncrystal protective membrane meets: S/H
2>=251, more excellent: S/H
2>=827.On the other hand, thickness is too small is unfavorable for the protection to iron-based and the enrichment to multi-nuclear metal, therefore H >=10mm.
The purity of iron-based is not less than 99%, preferably, exists with the form of spheroidal graphite cast iron.The surface-area S of this iron-based and volume V meets: S
3/ V
2>=401, more excellent: S
3/ V
2> > 1013.The surface-area of laminal iron-based can do large very large, and volume is very little, restriction K=S
3/ V
2maximum value be nonsensical.Such as, solid sphere and solid cubical K value are respectively 36 π, 216.The K>401 of the spheroid of semi-hollow, satisfies condition.K value and radiation-proof effect, as Fig. 6.It should be noted that, seabed static pressure is relevant with the degree of depth, and K value is too small can affect overall withstand voltage effect.
Yes with more dark better for the degree of depth of sorbent material, but also will consider the anti-pressure ability of equipment and benthic impact, general, sorbent material is placed in the region from earth's surface at below 300m, preferred below 800m, leaves standstill 2 to 5 years.Shelve the curve of approximation of the ratio of time and metal content, see Fig. 4.
Similar with the coated process of noncrystal protective membrane, the mode unloaded by this protective membrane is also high temperature melting, and in order to reduce the impact of high temperature on iron-based and multi-nuclear metal, preferred Heating temperature is 1100 DEG C to 1400 DEG C.
At these temperatures, iron-based and multi-nuclear metal can keep physical aspect.In order to improve reduction efficiency, the mixture after grinding being joined in ammonia-ammonium chloride solution, passes into carbon monoxide, reduce.Controlling ore pulp solid-liquid concentration ratio is 18-40:1, and control temperature 25 DEG C-65 DEG C, time 30min-50min, is precipitated.Use ammonium chloride solution washing and precipitating, in scavenging solution, the concentration of ammonium is at 20-30g/l, and the concentration of chlorion is at 20-45g/l.
Fusing precipitation, temperature of fusion is at 1535 DEG C-1700 DEG C, and annealing is reeled off raw silk from cocoons and obtained iron based mixture fiber.
In order to understand deep-sea of the present invention depositing technology further, now provide following embodiment.
Embodiment one
S101: by percent mass, sodium oxide: aluminum oxide: silicon oxide: magnesium oxide: calcium oxide: boron oxide=1:1.3:3:1.6:0.8:0.2, gets raw material.Keep temperature 900 DEG C, make melting viscous fluid.
S102: make iron-based, about 99.3% of described iron-based, the aluminium of surplus, S
3/ V
2about=1433.Keep the oxygen level of Working environment below 0.1%, iron is added melting viscous fluid.
S103: cool extraction gradually, every 5mm, envrionment temperature reduces by 10 DEG C, scrapes off viscous fluid gradually, makes viscous fluid wrap up described iron-based, finally makes the sorbent material be made up of noncrystal protective membrane and iron-based.The thickness H of noncrystal protective membrane meets: S/H
2>=269.
S104: sorbent material is placed in the region from earth's surface at below 300m, leaves standstill 2 years.
S105: take out sorbent material, melt under 1100 DEG C of conditions, filter the depositing abrasive obtained and become particle at below 0.1mm, wherein more than 50% is less than 0.027mm.
S106: joined in ammonia-ammonium chloride solution by the mixture after grinding, pass into carbon monoxide, controlling ore pulp solid-liquid concentration ratio is 18:1, and control temperature 25 DEG C, time 30min, is precipitated.
S107: use ammonium chloride solution washing and precipitating, in scavenging solution, the concentration of ammonium is at 10g/l, and the concentration of chlorion is at 10g/l.Fusing precipitation, temperature of fusion is at 1535 DEG C, and annealing is reeled off raw silk from cocoons and obtained iron based mixture fiber.
In the iron based mixture fiber made, containing various metals, there is good electroconductibility, ferromegnetism and plasticity.Relative to Stainless Steel Fibre, the strength of electric field in shield ranges reduces by 43%.This mixture of fibers is made up of iron, germanium, tin, lead, nickel, copper, cobalt.By weight, the gross weight of germanium, tin, lead, nickel is 0.41%, and carbon, nitrogen sum are 0.27%, the copper of surplus, cobalt.Described germanium: tin: plumbous: nickel=1:2.0:1.1:1.5, the density of this mixture is about 8.2g/cm
3.
Embodiment two
S201: by percent mass, sodium oxide: aluminum oxide: silicon oxide: magnesium oxide: calcium oxide: boron oxide=1:1.8:4.6:2:2.1:0.5, gets raw material.Keep temperature 1200 DEG C, make melting viscous fluid.
S202: make iron-based, the purity about 99.89%, S of described iron-based
3/ V
2=487.Keep the oxygen level of Working environment below 0.1%, iron is added melting viscous fluid.
S203: cool extraction gradually, every 5mm, envrionment temperature reduction is not more than 5 DEG C, scrapes off viscous fluid gradually, makes viscous fluid wrap up described iron-based, finally make the sorbent material be made up of noncrystal protective membrane and iron-based.The thickness H of noncrystal protective membrane meets: S/H
2>=857.
S204: sorbent material is placed in the region from earth's surface at below 900m, leaves standstill 5 years.
S205: take out sorbent material, melt under 1400 DEG C of conditions, filter the depositing abrasive obtained and become particle at below 0.07mm, wherein more than 50% is less than 0.013mm.
S206: joined in ammonia-ammonium chloride solution by the mixture after grinding, pass into carbon monoxide, controlling ore pulp solid-liquid concentration ratio is 40:1, and control temperature 65 DEG C, time 50min, is precipitated.
S207: use ammonium chloride solution washing and precipitating, in scavenging solution, the concentration of ammonium is at 13g/l, and the concentration of chlorion is at 17g/l.Fusing precipitation, temperature of fusion is at 1700 DEG C, and annealing is reeled off raw silk from cocoons and obtained iron based mixture fiber.
In the iron based mixture fiber made, containing various metals, there is good electroconductibility, ferromegnetism and plasticity.Relative to Stainless Steel Fibre, the strength of electric field in shield ranges reduces by 41%.This mixture of fibers is made up of iron, germanium, tin, lead, nickel, copper, cobalt.By weight, the gross weight of described germanium, tin, lead, nickel is 0.4%-0.6%, and carbon, nitrogen sum are 0.2%-0.3%, the copper of surplus, cobalt.By weight, the gross weight of germanium, tin, lead, nickel is 0.56%, and carbon, nitrogen sum are 0.23%, the copper of surplus, cobalt.Described germanium: tin: plumbous: nickel=1:1.8:1.3:1.4, the density of this mixture is about 8.4g/cm
3.
Implement three
S301: by percent mass, sodium oxide: aluminum oxide: silicon oxide: magnesium oxide: calcium oxide: boron oxide=1:1.5:4.0:1.8:2.0:0.3, gets raw material.Keep temperature 1100 DEG C, make melting viscous fluid.
S302: make iron-based, the purity about 99.7%, S of described iron-based
3/ V
2=865.Keep the oxygen level of Working environment below 0.1%, iron is added melting viscous fluid.
S303: cool extraction gradually, every 5mm, envrionment temperature reduction is not more than 13 DEG C, scrapes off viscous fluid gradually, makes viscous fluid wrap up described iron-based, finally make the sorbent material be made up of noncrystal protective membrane and iron-based.The thickness H of noncrystal protective membrane meets: S/H
2>=347.
S304: sorbent material is placed in the region from earth's surface at below 800m, leaves standstill 4 years.
S305: take out sorbent material, melt under 1300 DEG C of conditions, filter the depositing abrasive obtained and become particle at below 0.07mm, wherein more than 50% is less than 0.017mm.
S306: joined in ammonia-ammonium chloride solution by the mixture after grinding, pass into carbon monoxide, controlling ore pulp solid-liquid concentration ratio is 30:1, and control temperature 30 DEG C, time 45min, is precipitated.
S307: use ammonium chloride solution washing and precipitating, in scavenging solution, the concentration of ammonium is at 11g/l, and the concentration of chlorion is at 13g/l.Fusing precipitation, temperature of fusion is at about 1665 DEG C, and annealing is reeled off raw silk from cocoons and obtained iron based mixture fiber.
In the iron based mixture fiber made, containing various metals, there is good electroconductibility, ferromegnetism and plasticity.Relative to Stainless Steel Fibre, the strength of electric field in shield ranges reduces by 47%.This mixture of fibers is made up of iron, germanium, tin, lead, nickel, copper, cobalt.The gross weight of germanium, tin, lead, nickel is 0.55%, and carbon, nitrogen sum are 0.3%, the copper of surplus, cobalt.Described germanium: tin: plumbous: nickel=1:2.0:0.9:1.5, the density of this mixture is about 8.1g/cm
3.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. improve an ocean depositing technology for metal anti-radiation, it is characterized in that comprising the following steps:
Fe-based surface process
By melting sources, make melting viscous fluid, keep temperature 900 DEG C to 1200 DEG C;
Keep the oxygen level of Working environment below 0.1%, iron is added melting viscous fluid;
Cool extraction gradually, every 5mm, envrionment temperature reduction is not more than 10 DEG C;
The iron-based adhering to described viscous fluid is extracted out, scrapes off viscous fluid gradually, make viscous fluid wrap up described iron-based, finally make the sorbent material be made up of noncrystal protective membrane and iron-based;
Wherein, described raw material is made up of sodium oxide, aluminum oxide, silicon oxide, magnesium oxide, calcium oxide and boron oxide, it is sodium oxide by percent mass: aluminum oxide: silicon oxide: magnesium oxide: calcium oxide: boron oxide=1:1.3-1.8:3-4.6:1.6-2:0.8-2.1:0.2-0.5
The purity of described iron-based is not less than 99%, and the surface-area S of this iron-based and volume V meets: S
3/ V
2>=401,
The thickness H of described noncrystal protective membrane meets: S/H
2>=251,
Precipitation adsorption
Sorbent material is placed in the region from earth's surface at below 300m, leaves standstill 2 to 5 years;
The refinement of mixture
Take out sorbent material, melt under 1100 DEG C to 1400 DEG C conditions, filtration is precipitated, and precipitation reduction is obtained iron based mixture.
2. deep-sea as claimed in claim 1 depositing technology, is characterized in that, in the refining step of mixture, filter the depositing abrasive obtained and become particle at below 0.1mm, wherein more than 50% is less than 0.027mm,
Joined in ammonia-ammonium chloride solution by mixture after grinding, pass into carbon monoxide, controlling ore pulp solid-liquid concentration ratio is 18-40:1, control temperature 25 DEG C-65 DEG C, and time 30min-50min, is precipitated,
Use ammonium chloride solution washing and precipitating, in scavenging solution, the concentration of ammonium at 10-13g/l, the concentration of chlorion at 10-17g/l,
Fusing precipitation, temperature of fusion is at 1535 DEG C-1700 DEG C, and annealing is reeled off raw silk from cocoons and obtained iron based mixture fiber.
3. deep-sea as claimed in claim 1 or 2 depositing technology; it is characterized in that; each composition of the noncrystal protective membrane of described manufacture meets: by percent mass, sodium oxide: aluminum oxide: silicon oxide: magnesium oxide: calcium oxide: boron oxide=1:1.6:4.0:1.7:1.6:0.33.
4. deep-sea as claimed in claim 1 or 2 depositing technology, is characterized in that, the surface-area S of this iron-based and volume V meets: S
3/ V
2>=1013.
5. deep-sea as claimed in claim 1 or 2 depositing technology, is characterized in that, the thickness H of described noncrystal protective membrane meets: S/H
2>=827, and H>=10mm.
6. deep-sea as claimed in claim 1 or 2 depositing technology, is characterized in that, sorbent material is placed in the region from earth's surface at below 800m, leaves standstill 4 years.
7. deep-sea as claimed in claim 1 depositing technology, it is characterized in that, described iron-based is spheroidal graphite cast iron.
8. a radiation-resistant iron based mixture, it is characterized in that comprising: iron, germanium, tin, lead and nickel, by weight, the content of described iron is more than 99%, described germanium: tin: plumbous: nickel=1:1.8-2.1:0.8-1.3:1.2-1.5, the density of this mixture is not less than 8.1g/cm
3.
9. iron based mixture as claimed in claim 8, it is characterized in that, this iron based mixture is made up of iron, germanium, tin, lead, nickel, copper, cobalt, by weight, the content of described iron is more than 99%, the gross weight of described germanium, tin, lead, nickel is 0.4%-0.6%, and carbon, nitrogen sum are 0.2%-0.3%, the copper of surplus, cobalt.
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US20040039706A1 (en) * | 2002-06-19 | 2004-02-26 | Skowron John M. | System and method for digitally authenticating facility management reports |
CN1775966A (en) * | 2005-12-15 | 2006-05-24 | 北京矿冶研究总院 | Deep sea polymetallic nodule autocatalytic reduction ammonia leaching method |
CN101862645A (en) * | 2009-04-16 | 2010-10-20 | 纪秀磊 | Novel heavy metal absorbent |
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US20040039706A1 (en) * | 2002-06-19 | 2004-02-26 | Skowron John M. | System and method for digitally authenticating facility management reports |
CN1775966A (en) * | 2005-12-15 | 2006-05-24 | 北京矿冶研究总院 | Deep sea polymetallic nodule autocatalytic reduction ammonia leaching method |
CN101862645A (en) * | 2009-04-16 | 2010-10-20 | 纪秀磊 | Novel heavy metal absorbent |
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