CN1839880A - Heavy metal removal method from mineral drug - Google Patents

Heavy metal removal method from mineral drug Download PDF

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CN1839880A
CN1839880A CNA2006102000675A CN200610200067A CN1839880A CN 1839880 A CN1839880 A CN 1839880A CN A2006102000675 A CNA2006102000675 A CN A2006102000675A CN 200610200067 A CN200610200067 A CN 200610200067A CN 1839880 A CN1839880 A CN 1839880A
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mineral
acidiphilium
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CN1839880B (en
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李红玉
张景红
支德娟
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Lanzhou University
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Lanzhou University
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Abstract

The invention discloses a process for processing mineral medicaments such as cinnabar, orpiment, native copper, magnetite, and reddle, especially the method for dissolving and removing hazardous materials in the medicaments, which comprises processing the minerals with bacteria, dissolving the minerals insoluble to water into aqueous solutions under the action of bacteria, then removing unwanted ions in the solution through chemical or physical methods.

Description

Heavy metal removal method in the mineral drug
Technical field
The present invention relates to a kind of to the Chinese medicine ore deposit medicine processing method of (referring to the mineral drug in Chinese medicine and the other nationality medicine), be that a kind of bacterial treatment method of utilizing is with undissolvable mineral medicine more exactly, as: Cinnabaris, Realgar, Pyritum, Magnetitum, Haematitum etc., become in the soluble composition pass into solution, and remove the method for harmful substance.
Background technology
Remove in the Chinese medicine pharmacopeia and record a large amount of medicinal plants, animal pharmaceuticals has also been recorded many mineral medicines outward, as: Cinnabaris, Realgar, Pyritum, Magnetitum, Haematitum etc.In the traditional Chinese medical science practice is with the peculiar effect of these medicines, is used for the treatment of multiple disease with other medicine is compatible.But owing to contain the heavy metal class oxious component of excess in the mineral medicine, make its use be subjected to some restrictions more, perhaps produce certain negative effect.Particularly since the eighties in last century, international community is to heavy metal strong reaction in the Chinese patent medicine of China's outlet, even some mineral medicines of Chinese medicine directly are considered as poisonous substance, as: (HgS) is considered as hydrargyrum with the Cinnabaris in the Chinese medicine, with the Realgar (As in the Chinese medicine 2S 2Or As 4S 4) be considered as arsenic (As) or arsenicum (As 2O 3), and formulate strict standard, the content of heavy metals such as the hydrargyrum in the restriction Chinese patent medicine, arsenic.But on the other hand, remove in the Chinese medicine production up to now and still adopt the traditional concocting method of the traditional Chinese medical science to handle the mineral drug beyond the region of objective existence, there is no better processing method.And the mineral Chinese medicine concocting method of Chinese medicine pharmacopeia regulation, for example: burn moxibustion, water fly, forge make, quench in vinegar, not only time-consuming, the effort, the power consumption, and produce pollution such as waste gas waste water, the more important thing is and adopt not only effective dissolution of minerals Chinese medicine of these class methods, more can't quantitatively control the content of active ingredient in the medicine, effective removal harmful heavy metal wherein.Theoretically, adopt the chemical method can dissolution of minerals Chinese medicine, but chemical method often require harsh conditions such as chloroazotic acid, is difficult to keep necessary effective ingredient in the mineral medicine, thereby loses the therapeutical effect of Chinese medicine; On the other hand, adopt the pure chemistry method to carry out the composition that drug treating also may not had medicine itself, even with in the poisonous and hypertoxic composition introducing medicine, for avoiding this phenomenon to take place, not only need the technological measure of being correlated with, cause the drug treating cost to improve, remove clean even be difficult to that so also these are added composition.
In addition, in medical practice, adopt these Chinese medicine mineral medicines itself, or with the compatible disease that is used for the treatment of of other medicine because the mineral medicine is insoluble in water, in application, have following defective, the first, effective ingredient can not play one's part to the full; The second, the use amount of mineral drug is bigger, heavy metal and arsenic content overproof thereof; The 3rd, mineral drug is insoluble in water, makes its use be subjected to some restrictions, as be difficult in the injectable drug prescription, use etc.The 4th, can't quantitatively control the content and the harmful substance contents of active ingredient in the medicine.
Summary of the invention
The invention provides a kind of method, this method can be dissolved the Chinese medicine mineral drug effectively, quantitatively controls wherein active ingredient and content of harmful, the active component in particularly can the stripping mineral Chinese medicine, increased the property of medicine, and content of beary metal in the mineral medicine has been control effectively.Because mineral Chinese medicine is effectively dissolved, can in various forms of pharmaceutical compositions, use easily, as with in the past greatly different be use the present invention with the mineral Chinese medicine dissolving after, can be applied to prepare in the medicinal composition for injections.Method provided by the present invention also has lower cost simultaneously, and the composition that Chinese medicine mineral medicine itself can not had is introduced wherein.
Method of the present invention is that Chinese medicine mineral medicine is handled with antibacterial, under the effect of antibacterial, make water-fast mineral Chinese medicine change soluble mineral Chinese medicine into and enter solution, guarantee the stripping of active substance in the mineral drug on the one hand, increase the property of medicine, on the other hand the special chemical precipitation reaction of reuse or and method such as film dialysis remove harmful substance in the solution.
The cardinal principle of method of the present invention institute foundation is effects such as the oxidation that utilizes antibacterial that mineral (being mainly sulfide mineral) are had, reduction, dissolving, molten process of soaking metal and other composition from mineral Chinese medicine.This bacterioid majority is had a liking for acid, and the optimum pH scope is 0.5~3.5; Can in 0~95 ℃ of scope, play a role; Culture medium commonly used has 9K culture medium, Leathen culture medium; Waksman culture medium and NA culture medium etc.
For the mineral medicine that causes certain difference owing to reasons such as source, the place of production and compositions, but also appropriate change strain or strain portfolio ratio.
The specific embodiment of the present invention be with Chinese medicine mineral drug fine powder according to breeze: treatment fluid is that 1: 5~50 ratio (weight ratio) adds bacterial treatment liquid, and treatment fluid wherein is the treatment fluid that contains bacteria culture media and bacteria culture, and inoculum concentration is 5~35%.Accent system pH value is 0.5~3.5 after stirring, system is placed on the shaking table again and under 15~95 ℃ of conditions, shake cultivation, replenish institute's moisture evaporated with deionized-distilled water therebetween, regularly carry out the detection of heavy metal and other composition stripping quantity in the treatment fluid, after the dissolution degree of mineral Chinese medicine reaches requirement, stop concussion and cultivate, carry out solid-liquid separation.After gained liquid removed harmful heavy metal ion and thalline with conventional chemical and/or physical method, carry out dried again, resultant solid uses as the mineral Chinese medicine raw material; Or the liquid of solid-liquid separation gained used as the mineral Chinese medicine raw material; Or will use as the mineral Chinese medicine raw material after resultant solid heat sterilization or the filtration sterilization after the solid-liquid separation; Or, use as the mineral Chinese medicine raw material after heat sterilization or the filtration sterilization gained solid and liquid merging after the solid-liquid separation.After perhaps stopping the concussion cultivation, do not carry out solid-liquid separation, use as the mineral Chinese medicine raw material after sterilization of culture fluid direct heating or the filtration sterilization.
Strain in the treatment fluid among the present invention can be any following form:
A, strain are thiobacillus ferrooxidant (Acidithiobacillus ferrooxidans, original name Thiobacillusferrooxidans), perhaps be thiobacillus thiooxidans (Acidithiobacillus thiooxidans, original name Thiobacillu thiooxidans), perhaps be Leptospirillum ferrooxidans (Chinese name: ferricoxidans); It perhaps is T.concretivorus (Chinese name: corrodecloacathiobacilli); It perhaps is T.thioparus (Chinese name: thiobacillus thioparus); It perhaps is T.denitrificans (Chinese name: thiobacillus denitrificans); It perhaps is T.novellus (Chinese name: new model thiobacilli); It perhaps is T.acidophilus (Chinese name: thiobacillus ferrooxidans); It perhaps is T.intermedius (Chinese name: intermediate thiobacilli); Perhaps be T.caldus; Perhaps be T.cuprinus; It perhaps is L.theroferrroxidans (Chinese name: thermoferricoxidans); It perhaps is Sulfobacillusthermosulfidooxidans (Chinese name: sulfobacillus thermosulfidooxidans); It perhaps is Moderate thermophiles (Chinese name: medium thermophilic bacteria); It perhaps is Ferrobacillus ferrooxidans (Chinese name: ferrobacillus ferrooxidans); It perhaps is Sulfolobus acidocaldarius (Chinese name: the sulpolobus acidocaldarius); It perhaps is Thermoacidophilic archaebacteria (Chinese name: the hyperthermoacidophilic crenarcheon); Perhaps for Acidianus spp. (Chinese name: have a liking for sour two sides Pseudomonas) have a liking for the ancient bacterium of high temperature, as Acidianus brierleyi, A.infernos, A.ambivalens; Perhaps be Metallosphaera; Perhaps be Sulferococcus; It perhaps is Bacillus (Chinese name: bacillus cereus); It perhaps is Pesudomonas (Chinese name: pseudomonas).
In biological wet method is soaked the document in ore deposit, also disclose following strain and also be generally used for soaking ore deposit research or production practices: Ferrimicrobium acidiphilum, Ferroplasma acidiphilum, F.Acidarmanus, Thiomonascuprina (Chinese name: coppersulfurmonad), Hydrogenobacter acidophilus, Sulfolobus spp. (Chinese name: sulfuration blade Pseudomonas): as Sulfolobus shibitae, S.Solfataricus, S.Hakonensis, S.Metallicus, Sulfolobus metallicus, Acidiphilium spp. (Chinese name: acidophilic bacteria belongs to heterotrophic bacteria): as Acidiphilium acidophilum, Acidiphilium aminilyticum, Acidiphilium angustum/Acidiphilium cryptum, Acidiphilium facile, Acidiphilium multivorum, Acidiphilium organovorum, Acidiphilium rubrum, Acidimicrobium ferrooxidans, Sulfobacillus spp. (Chinese name: the sulfuration Bacillus is had a liking for mesophilic bacteria), as: Sulfobacillus acidophilus, Sulfobacillus disulfidooxidans, Acidocella spp., Acidobacterium capsulatum, Acidisphaera rubrifaciens, Acidomonas methanolica, Alicyclobacillus spp., Picrophilus spp., Thermoplasma spp., Stygiolobus azoricus, Acidilobus aceticus etc., these strains equally also can be applicable to the present invention.Wherein having a liking for the ancient bacterium Acidianus of high temperature spp. can have high vigor during up to 95 ℃ in cultivation temperature, mineral Chinese medicine is dissolved or removes wherein harmful ion so this area research worker can be used disclosed method among the present invention in the condition of cultivation temperature up to 95 ℃.
B, strain are made up by at least two kinds of different strains in all strains in the A bar, as: any two kinds of differences
Plant combination; Or any three kinds of different strains combination; Or any four kinds of different strains combination; Make up until all any kind of different strains of planting in the strain, and the basic ratio between strain can be the geometric ratio relation in above each strain combination, also can be non-geometric ratio relation.When adopting different multiple strain combinations and multiple strain various combination ratio in the treatment fluid, can overcome because mineral Chinese medicine exists the difference of source, the place of production and composition to cause the different of treatment conditions and effect, can more easily handle the multiple Chinese medicine mineral medicine that is difficult to handle.
The present invention adopts the method for shaking bottle to carry out, if amplify production, can adopt that drill traverse, post soak, jar soaks, fermentation tank is handled and mode such as microbial immobilized processing is carried out the dissolution process of mineral Chinese medicine according to ultimate principle of the present invention, this is that the researcher in this field is to understand.
When adopting the present invention that Chinese medicine mineral drug thing is handled, it is effect by antibacterial, making former water-fast mineral Chinese medicine (comprising harmful heavy metal wherein) progressively change water-soluble water soluble ion into is dissolved in the solution, dissolving in mineral medicine part is still keeping its original composition in this course, not only do not influence effective ingredient and bring into play it effect should be arranged, and can increase the property of medicine; And then by chemistry or/physical method removes harmful substance.Because changing water miscible ion into by non-water-soluble composition is to finish gradually in the process with antibacterial culturing, therefore can be by the inversion quantity of heavy metal and other composition in the timing detection understanding mineral Chinese medicine, in time separate and remove to handle, so can control the heavy metal in the processed medicine and the effective content of other composition (comprising active component) at an easy rate.And unconverted part or the soluble part of removing harmful ion are keeping its original character in the mineral medicine in this course, therefore do not influence effective ingredient and bring into play it effect should be arranged.Obviously, the present invention provides a kind of new, valid approach for the release of the removal of the dissolving of mineral Chinese medicine, toxic heavy metal, active component.
The present invention be effect by antibacterial with mineral Chinese medicine by the water-insoluble water solublity that is converted into, after the entire process process finishes, just can remove or kill antibacterial in the system fully by simply centrifugal, filtration or heating process again, and remove harmful substance with simple physics, chemical method.Therefore can not introduce the component outside any former mineral in the whole conversion processing process, other composition of the mineral Chinese medicine except that harmful ion that yet can not run off.The removal of the removal of thalline and sterilizing methods and harmful substance also has method already, also no longer does many introductions at this.
In addition, the mineral drug in the ethnic drug of China, the mineral drug that wherein has even only be mineral medicine synonym medicine in the mineral Chinese medicine.Obviously, use method of the present invention can also to the ethnic drug mineral drug dissolve or remove harmful ion after use.
Operating process of the present invention is simple, can not produce pollution in the processing procedure, and processing cost is also lower, and one aspect of the present invention is soluble state with mineral Chinese medicine by not dissolving state-transition, increases the property of medicine; The animal acute toxicity test result shows that the present invention can obviously reduce the toxicity of Chinese medicine mineral drug on the other hand.
The specific embodiment
Below provide seven specific embodiments of the present invention, but this is not intended that the invention be limited to these concrete embodiments.
Embodiment one
Processed mineral Chinese medicine is Realgar, Cinnabaris and Pyritum.
Mineral drug is crushed to about 100 orders, then mineral medicated powder is carried out spectroscopic assay, to understand its concrete composition.
Again with finely-powdered minerals according to breeze: treatment fluid is that 1: 10 ratio (weight ratio) adds treatment fluid, and [the 9K culture medium basic composition is: per 1000 milliliters of culture fluid contain (NH to contain the basis of bacteria culture and 9K culture medium in the treatment fluid wherein 4) 2SO 43.0g, KCl 0.1g, K 2HPO 40.5g, MgSO 47H 2O 0.5g, Ca (NO 3) 20.01g, FeSO 47H 2O44.7g], wherein used strain is: thiobacillus ferrooxidant, thiobacillus thiooxidans and the combination of ferricoxidans equal proportion, inoculum concentration is 10%.
After breeze and treatment fluid stirred, transferring system pH with 25% dilute sulfuric acid solution is 1.5, system is placed on the shaking table again and under 30 ℃ of conditions, shake cultivation, replenish institute's moisture evaporated with deionized-distilled water therebetween, regularly carrying out the heavy metal ion amount of separating out detection in the treatment fluid, generally is that sampling in per 12 hours detects.Reaction in the system is as follows in this course:
After the dissolution degree of mineral Chinese medicine reaches requirement, stop concussion and cultivate, carry out solid-liquid separation.After gained liquid removed harmful heavy metal ion and thalline with conventional chemical and/or physical method, carry out dried again, resultant solid uses as the mineral Chinese medicine raw material; Or the liquid of solid-liquid separation gained used as the mineral Chinese medicine raw material; Or will use as the mineral Chinese medicine raw material after resultant solid heat sterilization or the filtration sterilization after the solid-liquid separation; Or, use as the mineral Chinese medicine raw material after heat sterilization or the filtration sterilization gained solid and liquid merging after the solid-liquid separation.After perhaps stopping the concussion cultivation, do not carry out solid-liquid separation, use as the mineral Chinese medicine raw material after sterilization of culture fluid direct heating or the filtration sterilization.
Test shows after hatching a couple of days (annotates: because the difference of mineral Chinese medicine sample type, the difference of inoculum concentration, it is different to hatch natural law) after, arsenic in the handled mineral Chinese medicine, the stripping quantity of hydrargyrum have bigger increase before handling, and its value added is also apparently higher than the stripping quantity that adopts prior art (process add water fly) to handle, and the animal acute toxicity test result shows that the present invention can obviously reduce the toxicity of Chinese medicine mineral drug.Table 1, table 2 provide test mineral Chinese medicine and stripping spectrum analysis result and animal acute toxicity test result thereof.
For these heavy metal ion soluble in water, can adopt special chemical precipitation reaction or film dialysis process to remove, also can adopt special chemical precipitation to add with film dialysis and remove.Remove metal ion has method in the prior art already in the aqueous solution more, no longer do many introductions at this; The place to go of thalline and sterilizing methods also have method already, no longer do many introductions at this.
Table 1. distinct methods is handled the stripping spectrum analysis result of back test with arsenic, hydrargyrum in the mineral Chinese medicine
Mineral drug Processing method Arsenic dissolution rate % Hydrargyrum dissolution rate % Plumbous dissolution rate % Cadmium dissolution rate % Ferrum dissolution rate %
Cinnabaris Former powder 0.015 0.0225 0.026 0.009
Cinnabaris Process and add water and fly 0.028 0.0427 0.039 0.028
Cinnabaris The present invention 78.13 90.13 68.96 83.96
Realgar Former powder 0.021 0.011 0.009 0.006
Realgar Process and add water and fly 0.261 0.023 0.015 0.015
Realgar The present invention 92.18 86.16 92.11 93.06
Pyritum Former powder 0.006
Pyritum Forge 0.093
Pyritum The present invention 83.06
Table 2. acute toxicity test in mice result
Mineral drug Various processing methods LD50 (95% average fiducial limit) i.g.
Cinnabaris Former powder 2.98g/kg±0.37g/kg
Cinnabaris Process and add water and fly 10.16g/kg±0.59g/kg
Cinnabaris The present invention 40.28g/kg±2.50g/kg
Realgar Former powder 3.86g/kg±0.61g/kg
Realgar Process and add water and fly 12.58g/kg±0.32g/kg
Realgar The present invention 70.68g/kg±2.80g/kg
Embodiment two
Processed mineral Chinese medicine is Realgar, Cinnabaris and Pyritum.
Mineral drug is crushed into different granule sizes, presses the disposal methods mineral drug of embodiment one, the results are shown in Table 3
The table 3. different grain size test stripping spectrum analysis result of arsenic, hydrargyrum in the mineral Chinese medicine
Mineral drug Granularity (order) Arsenic dissolution rate % Hydrargyrum dissolution rate % Plumbous dissolution rate % Cadmium dissolution rate % Ferrum dissolution rate %
Cinnabaris 50 36.98 69.38 46.86 56.98
Cinnabaris 150 91.39 92.39 93.18 92.51
Cinnabaris 250 92.16 92.96 93.86 92.96
Realgar 100 68.94 39.68 45.63 43.25
Realgar 200 92.68 93.18 90.36 89.56
Realgar 300 92.98 93.68 90.58 90.25
Pyritum 50 83.23
Pyritum 150 86.67
Pyritum 250 90.06
Embodiment three
Processed mineral Chinese medicine is Realgar, Cinnabaris and Pyritum.
Mineral drug is crushed into 80 orders, and breeze adds in different ratios with treatment fluid in the system, and disposal methods Realgar, Cinnabaris and Pyritum that other presses embodiment one the results are shown in Table 4.
Table 4. different proportion treatment fluid is handled the stripping spectrum analysis result of back test with arsenic, hydrargyrum in the mineral Chinese medicine
Mineral drug Breeze: treatment fluid Arsenic dissolution rate % Hydrargyrum dissolution rate % Plumbous dissolution rate % Cadmium dissolution rate % Ferrum dissolution rate %
Cinnabaris 1∶5 36.98 63.29 56.97 62.35
Cinnabaris 1∶15 91.32 92.39 93.06 92.18
Cinnabaris 1∶30 91.89 92.89 93.56 92.98
Realgar 1∶10 63.98 49.89 52.36 52.45
Realgar 1∶20 93.06 90.15 91.36 93.08
Realgar 1∶50 93.86 90.86 91.89 93.96
Pyritum 1∶5 58.67
Pyritum 1∶15 90.00
Pyritum 1∶30 92.89
Embodiment four
Processed mineral Chinese medicine is Realgar, Cinnabaris and Pyritum.
Mineral drug is crushed into 80 orders, regulates the pH value of treatment fluid, disposal methods Realgar, Cinnabaris and Pyritum that other presses embodiment one the results are shown in Table 5.
The different pH of table 5. handle the stripping spectrum analysis result of back test with arsenic, hydrargyrum in the mineral Chinese medicine
Mineral drug Treatment fluid pH Arsenic dissolution rate % Hydrargyrum dissolution rate % Plumbous dissolution rate % Cadmium dissolution rate % Ferrum dissolution rate %
Cinnabaris 0.5 42.36 35.96 46.98 52.15
Cinnabaris 1.5 89.36 90.68 91.36 90.89
Cinnabaris 2.5 84.35 83.65 83.68 83.89
Realgar 1.0 52.96 46.96 53.15 47.68
Realgar 2.0 89.38 90.18 89.65 85.15
Realgar 3.5 83.98 83.25 82.36 82.35
Pyritum 1.0 61.15
Pyritum 2.0 87.72
Pyritum 3.5 73.97
Embodiment five
Processed mineral Chinese medicine is Realgar, Cinnabaris and Pyritum.
Mineral drug is crushed into 80 orders, and with different treatment temperature Processing Test mineral Chinese medicines, disposal methods Realgar, Cinnabaris and Pyritum that other presses embodiment one the results are shown in Table 6.
The test stripping spectrum analysis result of arsenic, hydrargyrum in the mineral Chinese medicine after table 6. treatment of different temperature
Mineral drug Cultivation temperature ℃ Arsenic dissolution rate % Hydrargyrum dissolution rate % Plumbous dissolution rate % Cadmium dissolution rate % Ferrum dissolution rate %
Cinnabaris 15 42.35 56.35 45.36 40.15
Cinnabaris 30 92.35 91.68 90.18 88.96
Cinnabaris 45 72.35 69.23 69.35 72.38
Realgar 20 52.36 42.08 32.15 30.18
Realgar 40 92.75 86.93 90.18 87.36
Realgar 65 80.18 72.13 69.78 68.97
Pyritum 15 40.18
Pyritum 30 86.30
Pyritum 45 61.92
Embodiment six
Processed mineral Chinese medicine is a Realgar, and wherein: medicine a originates in Gansu, and medicine b originates in the Hunan.Contain different strain combinations in the used treatment fluid, other all uses mineral Chinese medicine by the disposal methods test of embodiment one, the results are shown in Table 7.
The test stripping spectrum analysis result of arsenic, hydrargyrum in the mineral Chinese medicine after the table 7. different strain combined treatment
The Chinese medicine mineral drug The combination of treatment fluid strain Arsenic dissolution rate % Hydrargyrum dissolution rate % Plumbous dissolution rate % Cadmium dissolution rate %
a X 79.36
a Y 54.31
a Z 60.36
a A 86.39
a B 63.56
a C 42.36
a D 40.98
a E 45.21
a F 46.35
a X∶Y=1∶1 85.41
a Z∶Y=3∶1 74.38
a X∶Z=10∶1 84.22
a X∶Y∶Z=1∶1∶1 92.17
a X∶A∶B=4∶3∶1 77.94
a Y∶D∶F=2∶3∶1 85.75
a Z∶E∶C=3∶3∶1 86.33
a M 93.52
b X 75.00
b Y 64.82
b Z 80.74
b A 80.12
b B 73.33
b C 44.25
b D 42.43
b E 58.91
b F 40.11
b X∶Y=1∶1 88.67
b Z∶Y=3∶1 85.29
b X∶Z=10∶1 74.31
b X∶Y∶Z=1∶1∶1 95.13
b X∶A∶B=4∶3∶1 89.24
b Y∶D∶F=2∶3∶1 80.54
b Z∶E∶C=3∶3∶1 89.82
b M 97.79
X is a thiobacillus ferrooxidant;
Y is a thiobacillus thiooxidans;
Z is a ferricoxidans;
The A thermoferricoxidans
The B sulfobacillus thermosulfidooxidans
The C medium thermophilic bacteria
The D ferrobacillus ferrooxidans
The E sulpolobus acidocaldarius
The F hyperthermoacidophilic crenarcheon
M is the equal proportion compositions of 22 kinds of bacterium, these 22 kinds of bacterium are thiobacillus ferrooxidant (Acidithiobacillusferrooxidans, original name Thiobacillus ferrooxidans), perhaps be thiobacillus thiooxidans (Acidithiobacillus thiooxidans, original name Thiobacillu thiooxidans), perhaps be Leptospirillum ferrooxidans (Chinese name: ferricoxidans); It perhaps is T.concretivorus (Chinese name: corrodecloacathiobacilli); It perhaps is T.thioparus (Chinese name: thiobacillus thioparus); It perhaps is T.denitrificans (Chinese name: thiobacillus denitrificans); It perhaps is T.novellus (Chinese name: new model thiobacilli); It perhaps is T.acidophilus (Chinese name: thiobacillus ferrooxidans); It perhaps is T.intermedius (Chinese name: intermediate thiobacilli); Perhaps be T.caldus; Perhaps be T.cuprinus; It perhaps is L.theroferrroxidans (Chinese name: thermoferricoxidans); It perhaps is Sulfobacillus thermosulfidooxidans (Chinese name: sulfobacillus thermosulfidooxidans); It perhaps is Moderate thermophiles (Chinese name: medium thermophilic bacteria); It perhaps is Ferrobacillus ferrooxidans (Chinese name: ferrobacillus ferrooxidans); It perhaps is Sulfolobusacidocaldarius (Chinese name: the sulpolobus acidocaldarius); It perhaps is Thermoacidophilicarchaebacteria (Chinese name: the hyperthermoacidophilic crenarcheon); Perhaps be Acidanus; Perhaps be Metallosphaera; Perhaps be Sulferococcus (not having Chinese name temporarily); It perhaps is Bacillus (Chinese name: bacillus cereus); It perhaps is Pesudomonas (Chinese name: pseudomonas).
Test shows that for the easy to handle mineral Chinese medicine, the strain in its treatment fluid can be a thiobacillus ferrooxidant, or thiobacillus thiooxidans, or the independent use of ferricoxidans, also can combine by two different strains, the basic ratio of strain is 1: 1.In addition, in biological wet method is soaked the document in ore deposit, also disclose following strain and also be generally used for soaking ore deposit research or production practices: Ferrimicrobium acidiphilum, Ferroplasma acidiphilum, F.Acidarmanus, Thiomonas cuprina (Chinese name: coppersulfurmonad), Hydrogenobacter acidophilus, Sulfolobusspp. (Chinese name: vulcanize the blade Pseudomonas): as Sulfolobus shibitae, S.Solfataricus, S.Hakonensis, S.Metallicus, Sulfolobus metallicus, Acidiphilium spp. (Chinese name: acidophilic bacteria belongs to heterotrophic bacteria): as Acidiphilium acidophilum, Acidiphilium aminilyticum, Acidiphilium angustum/Acidiphilium cryptum, Acidiphilium facile, Acidiphiliummultivorum, Acidiphilium organovorum, Acidiphilium rubrum, Acidimicrobiumferrooxidans, Sulfobacillus spp. (Chinese name: the sulfuration Bacillus is had a liking for mesophilic bacteria), as: Sulfobacillus acidophilus, Sulfobacillus disulfidooxidans, Acidocella spp., Acidobacterium capsulatum, Acidisphaera rubrifaciens, Acidomonas methanolica, Alicyclobacillus spp., Picrophilus spp., Thermoplasma spp., Stygiolobus azoricus, Acidilobus aceticus etc., these strains equally also can be applicable to the present invention.
The researcher in this field can adopt the combination of any or any strain of these strains, mineral Chinese medicine is dissolved or removes wherein harmful ion with disclosed method among the present invention.
Wherein having a liking for the ancient bacterium Acidianus of high temperature spp. can have high vigor during up to 95 ℃ in cultivation temperature, thus this area research worker can the condition of cultivation temperature up to 95 ℃ with the present invention in disclosed method mineral Chinese medicine dissolved or remove wherein harmful ion.
Embodiment seven
Processed mineral Chinese medicine is Realgar, Cinnabaris and Pyritum.
Be that mineral drug is crushed into 100 orders in the present embodiment, press the different vaccination amount and handle that disposal methods Realgar, Cinnabaris and Pyritum that other presses embodiment one the results are shown in Table 8.
Table 8. different vaccination amount is handled the stripping spectrum analysis result of back test with arsenic, hydrargyrum in the mineral Chinese medicine
Mineral drug Inoculum concentration % Arsenic dissolution rate % Hydrargyrum dissolution rate % Plumbous dissolution rate % Cadmium dissolution rate % Ferrum dissolution rate %
Cinnabaris 5 62.35 66.00 65.30 60.50
Cinnabaris 15 91.45 91.80 90.05 94.00
Cinnabaris 30 92.65 92.30 91.75 95.00
Realgar 10 91.25 90.87 88.45 94.32
Realgar 20 92.00 91.90 91.15 95.00
Realgar 35 93.00 92.90 92.38 95.20
Pyritum 5 67.50
Pyritum 15 94.23
Pyritum 30 94.80
This test shows that the strain in the treatment fluid of the present invention can be by thiobacillus ferrooxidant, and combining of thiobacillus thiooxidans and ferricoxidans perhaps adds (the Chinese name: corrodecloacathiobacilli) from T.concretivorus more within it; It perhaps is T.thioparus (Chinese name: thiobacillus thioparus); It perhaps is T.denitrificans (Chinese name: thiobacillus denitrificans); It perhaps is T.novellus (Chinese name: new model thiobacilli); It perhaps is T.acidophilus (Chinese name: thiobacillus ferrooxidans); It perhaps is T.intermedius (Chinese name: intermediate thiobacilli); Perhaps be T.caldus (not having Chinese name temporarily); Perhaps be T.cuprinus; It perhaps is L.theroferrroxidans (Chinese name: thermoferricoxidans); It perhaps is Sulfobacillus thermosulfidooxidans (Chinese name: sulfobacillus thermosulfidooxidans); It perhaps is Moderate thermophiles (Chinese name: medium thermophilic bacteria); It perhaps is Ferrobacillus ferrooxidans (Chinese name: ferrobacillus ferrooxidans); It perhaps is Sulfolobus acidocaldarius (Chinese name: the sulpolobus acidocaldarius); It perhaps is Thermoacidophilic archaebacteria (Chinese name: the hyperthermoacidophilic crenarcheon); Perhaps for Acidianus spp. (Chinese name: have a liking for sour two sides Pseudomonas) have a liking for the ancient bacterium of high temperature, as Acidianus brierleyi, A.infernos, A.ambivalens; Perhaps be Metallosphaera: perhaps be Sulferococcus; It perhaps is Bacillus (Chinese name: bacillus cereus); It perhaps is Pesudomonas (Chinese name: pseudomonas); Perhaps be Ferrimicrobium acidiphilum; Perhaps be Ferroplasma acidiphilum; Perhaps be F.Acidarmanus; It perhaps is Thiomonas cuprina (Chinese name: coppersulfurmonad); Perhaps be Hydrogenobacteracidophilus; Perhaps be Sulfolobus spp. (Chinese name: sulfuration blade Pseudomonas), as: Sulfolobusshibitae, S.Solfataricus, S.Hakonensis, S.Metallicus or be Sulfolobusmetallicus; Perhaps be the peculiar bacterium of Acidiphilium spp. (Chinese name: acidophilic bacteria belongs to) such as Acidiphiliumacidophilum, Acidiphilium aminilyticum, Acidiphilium angustum/Acidiphiliumcryptum, Acidiphilium facile, Acidiphilium multivorum, Acidiphilium organovorum, Acidiphilium rubrum; Perhaps be Acidimicrobium ferrooxidans; Perhaps be that Sulfobacillus.spp. (Chinese name: vulcanize Bacillus) has a liking for mesophilic bacteria, as: Sulfobacillus acidophilus, Sulfobacillus disulfidooxidans; Perhaps be Acidocella spp.; Perhaps be Acidobacteriumcapsulatum; Perhaps be Acidisphaera rubrifaciens; Perhaps be Acidomonas methanolica; Perhaps be Alicyclobacillus spp.; Perhaps be Picrophilus spp.; Perhaps be Thermoplasma spp.; Perhaps be Stygiolobus azoricus; Perhaps be the compound composition of antibacterial optional among the Acidilobus aceticus, each strain relative quantity can concern for equal proportion, also can be non-geometric ratio relation.Also can inoculate any single culture in above-mentioned each antibacterial in the treatment fluid of the present invention, but the effect that this class treatment fluid is handled to be lower than the embodiment with the different strain combination relatively.
For the Chinese medicine mineral medicine that causes certain difference owing to reasons such as source, the place of production and compositions, the strain in its treatment fluid also can be on the basis of above-mentioned equal proportion relation appropriate change strain portfolio ratio.
In addition, the mineral drug in the ethnic drug of China also can with method of the present invention dissolve or remove harmful ion after use.
Adopt culture medium in the treatment fluid among the present invention except that available 9K culture medium, can also adopt other culture medium that can be suitable for Thiobacillus bacterial growth and other bacterial growth, as: Leathen culture medium, or Mackintosh culture medium, or the Waksman culture medium, or the NA culture medium etc.These culture medium both can be used separately, use also capable of being combined.

Claims (6)

1. the dissolving of mineral drug and heavy metal removal method thereof is characterized in that the mineral medicine is handled with antibacterial, and insoluble mineral drug is dissolved in aqueous solution, and reuse chemistry or physical method are removed the harmful substance in the solution.
2. the dissolving method of mineral drug according to claim 1 and heavy metal removal method thereof, it is characterized in that mineral drug is pulverized is fine powder, with finely-powdered minerals according to breeze: treatment fluid is that 1: 5~50 ratio (weight ratio) adds treatment fluid, contain bacteria culture media and bacteria culture in the treatment fluid, bacterial load is 5~35%, transferring system pH after stirring is 0.5~3.5, system is placed on the shaking table again and under 15~95 ℃ of conditions, shake cultivation, add water during this time and replenish institute's moisture evaporated, regularly carry out that the amount of separating out of heavy metal ion and other material detects in the treatment fluid, after the dissolution degree of mineral drug reaches requirement, stopping concussion cultivating, after culture fluid is removed harmful substance with conventional chemical and/or physical method, use as the mineral drug crude drug after direct heating sterilization or the filtration sterilization.
3. the dissolving method of mineral drug according to claim 2 and heavy metal removal method thereof, it is characterized in that after stopping the concussion cultivation, carry out solid-liquid separation, after gained liquid removed harmful heavy metal ion and thalline with conventional chemical and/or physical method, carry out dried again, resultant solid uses as the mineral drug crude drug; Or the liquid of solid-liquid separation gained used as the mineral drug crude drug; Or will use as the mineral drug crude drug after resultant solid heat sterilization or the filtration sterilization after the solid-liquid separation; Or, use as the mineral drug crude drug after heat sterilization or the filtration sterilization gained solid and liquid merging after the solid-liquid separation.
4. according to the dissolving method and the heavy metal removal method thereof of the described mineral drug of claim 1 to 3, it is characterized in that in the treatment fluid bacteria culture can for following any one: thiobacillus ferrooxidant (Acidithiobacillusferrooxidans, original name Thiobacillus ferrooxidans), perhaps be thiobacillus thiooxidans (Acidithiobacillus thiooxidans, original name Thiobacillu thiooxidans), perhaps be Leptospirillum ferrooxidans (Chinese name: ferricoxidans); It perhaps is T.concretivorus (Chinese name: corrodecloacathiobacilli); It perhaps is T.thioparus (Chinese name: thiobacillus thioparus); It perhaps is T.denitrificans (Chinese name: thiobacillus denitrificans); It perhaps is T.novellus (Chinese name: new model thiobacilli); It perhaps is T.acidophilus (Chinese name: thiobacillus ferrooxidans); It perhaps is T.intermedius (Chinese name: intermediate thiobacilli); Perhaps be T.caldus; Perhaps be T.cuprinus; It perhaps is L.theroferrroxidans (Chinese name: thermoferricoxidans); It perhaps is Sulfobacillus thermosulfidooxidans (Chinese name: sulfobacillus thermosulfidooxidans); It perhaps is Moderate thermophiles (Chinese name: medium thermophilic bacteria); It perhaps is Ferrobacillus ferrooxidans (Chinese name: ferrobacillus ferrooxidans); It perhaps is Sulfolobusacidocaldarius (Chinese name: the sulpolobus acidocaldarius); It perhaps is Thermoacidophilicarchaebacteria (Chinese name: the hyperthermoacidophilic crenarcheon); Perhaps for Acidianus spp. (Chinese name: have a liking for sour two sides Pseudomonas) have a liking for the ancient bacterium of high temperature, as Acidianus brierleyi, A.infernos, A.ambivalens; Perhaps be Metallosphaera; Perhaps be Sulferococcus; It perhaps is Bacillus (Chinese name: bacillus cereus); It perhaps is Pesudomonas (Chinese name: pseudomonas); Perhaps be Ferrimicrobium acidiphilum; Perhaps be Ferroplasma acidiphilum; Perhaps be F.Acidarmanus; It perhaps is Thiomonas cuprina (Chinese name: coppersulfurmonad); Perhaps be Hydrogenobacter acidophilus; Perhaps be Sulfolobus spp. (Chinese name: sulfuration blade Pseudomonas), as: Sulfolobus shibitae, S.Solfataricus, S.Hakonensis, S.Metallicus or be Sulfolobus metallicus; Perhaps be that Acidiphilium spp. (Chinese name: acidophilic bacteria belongs to heterotrophic bacteria) is as Acidiphilium acidophilum, Acidiphilium aminilyticum, Acidiphiliumangustum/Acidiphilium cryptum, Acidiphilium facile, Acidiphilium multivorum, Acidiphilium organovorum, Acidiphilium rubrum; Perhaps be Acidimicrobiumferrooxidans; Perhaps be Sulfobacillus spp. (Chinese name: the sulfuration Bacillus is had a liking for mesophilic bacteria), as: Sulfobacillus acidophilus, Sulfobacillus disulfidooxidans; Perhaps be Acidocellaspp.; Perhaps be Acidobacterium capsulatum; Perhaps be Acidisphaera rubrifaciens; Perhaps be Acidomonas methanolica; Perhaps be Alicyclobacillus spp.; Perhaps be Picrophilus spp.; Perhaps be Thermoplasma spp.; Perhaps be Stygiolobus azoricus; Perhaps be Acidilobus aceticus.
5. according to the dissolving method and the heavy metal removal method thereof of the described mineral drug of claim 1 to 3, it is characterized in that the strain in the treatment fluid can also be any at least two kinds of different strains combination by following strain, and the portfolio ratio of strain amount is geometric ratio or non-geometric ratio in each strain combination, these strains are: thiobacillus ferrooxidant (Acidithiobacillusferrooxidans, original name Thiobacillus ferrooxidans), perhaps be thiobacillus thiooxidans (Acidithiobacillus thiooxidans, original name Thiobacillu thiooxidans), perhaps be Leptospirillum ferrooxidans (Chinese name: ferricoxidans); It perhaps is T.concretivorus (Chinese name: corrodecloacathiobacilli); It perhaps is T.thioparus (Chinese name: thiobacillus thioparus); It perhaps is T.denitrificans (Chinese name: thiobacillus denitrificans); It perhaps is T.novellus (Chinese name: new model thiobacilli); It perhaps is T.acidophilus (Chinese name: thiobacillus ferrooxidans); It perhaps is T.intermedius (Chinese name: intermediate thiobacilli); Perhaps be T.caldus; Perhaps be T.cuprinus; It perhaps is L.theroferrroxidans (Chinese name: thermoferricoxidans); It perhaps is Sulfobacillus thermosulfidooxidans (Chinese name: sulfobacillus thermosulfidooxidans); It perhaps is Moderate thermophiles (Chinese name: medium thermophilic bacteria); It perhaps is Ferrobacillus ferrooxidans (Chinese name: ferrobacillus ferrooxidans); It perhaps is Sulfolobusacidocaldarius (Chinese name: the sulpolobus acidocaldarius); It perhaps is Thermoacidophilicarchaebacteria (Chinese name: the hyperthermoacidophilic crenarcheon); Perhaps for Acidianus spp. (Chinese name: have a liking for sour two sides Pseudomonas) have a liking for the ancient bacterium of high temperature, as Acidianus brierleyi, A.infernos, A.ambivalens; Perhaps be Metallosphaera; Perhaps be Sulferococcus (not having Chinese name temporarily); It perhaps is Bacillus (Chinese name: bacillus cereus); It perhaps is Pesudomonas (Chinese name: pseudomonas); Perhaps be Ferrimicrobium acidiphilum; Perhaps be Ferroplasma acidiphilum; Perhaps be F.Acidarmanus; It perhaps is Thiomonas cuprina (Chinese name: coppersulfurmonad); Perhaps be Hydrogenobacter acidophilus; Perhaps be Sulfolobus spp. (Chinese name: sulfuration blade Pseudomonas), as: Sulfolobus shibitae, S.Solfataricus, S.Hakonensis, S.Metallicus or be Sulfolobus metallicus; Perhaps be that Acidiphilium spp. (Chinese name: acidophilic bacteria belongs to heterotrophic bacteria) is as Acidiphilium acidophilum, Acidiphilium aminilyticum, Acidiphilium angustum/Acidiphilium cryptum, Acidiphilium facile, Acidiphiliummultivorum, Acidiphilium organovorum, Acidiphilium rubrum; Perhaps be Acidimicrobiumferrooxidans; Perhaps be Sulfobacillus spp. (Chinese name: the sulfuration Bacillus is had a liking for mesophilic bacteria), as: Sulfobacillus acidophilus, Sulfobacillus disulfidooxidans; Perhaps be Acidocellaspp.; Perhaps be Acidobacterium capsulatum; Perhaps be Acidisphaera rubrifaciens; Perhaps be Acidomonas methanolica; Perhaps be Alicyclobacillus spp.; Perhaps be Picrophilus spp.; Perhaps be Thermoplasma spp.; Perhaps be Stygiolobus azoricus; Perhaps be Acidilobus aceticus.
6. the dissolving method of mineral drug according to claim 1 and 2 and heavy metal removal method thereof, it is characterized in that the present invention amplifies production, can adopt drill traverse, post soak according to substance of the present invention, jar soaks with fermentation tank handles and modes such as microbial immobilized processing are carried out the dissolution process of mineral drug, adopts conventional chemical and/or physical method to remove harmful substance then.
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CN106947720A (en) * 2017-04-17 2017-07-14 中南大学 A kind of energy high-performance bio converts the microbial bacterial agent of Cadium In Polluted Soil form
CN107052042A (en) * 2017-04-17 2017-08-18 湖南省农业生物技术研究中心 A kind of application of the microbial bacterial agent of energy high-performance bio conversion Cadium In Polluted Soil form
CN106947720B (en) * 2017-04-17 2020-04-24 中南大学 Microbial agent capable of efficiently biotransforming cadmium form in polluted soil
CN107052042B (en) * 2017-04-17 2020-04-28 湖南省农业生物技术研究中心 Application of microbial agent capable of efficiently biotransforming cadmium form in polluted soil
CN107020295A (en) * 2017-06-14 2017-08-08 中南大学 A kind of cadmium pollution arable land in-situ rapid renovation method based on microorganism conversion
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