CN107328845B - Experimental method for element migration mechanism research in hydrothermal lead-zinc deposit - Google Patents
Experimental method for element migration mechanism research in hydrothermal lead-zinc deposit Download PDFInfo
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Abstract
the invention discloses an experimental method for element migration mechanism research in hydrothermal lead-zinc deposit, which comprises the steps of obtaining geological conditions and preparing a chlorine complex solution of metal elements; adjusting the solution to be hydrolyzed by HCl or NaCl, filtering and centrifugally separating, and carrying out ICP-Ms (inductively coupled plasma-mass spectrometry) on clear liquid to obtain the content of hydrolyzed metal elements; placing the solution into a plastic bottle according to an open system or a semi-closed system, adding the solution with the same volume into the bottle for 6-10 days every day by the open system, taking part of the solution from the bottle every day by the open system or the semi-closed system, filtering, centrifugally separating, drying precipitates, performing ICP-Ms (inductively coupled plasma-mass spectrometry) on the filtered clear solution, and performing EPMA (expanded polyethylene-maleic anhydride) on the surrounding rock and the precipitates; and comprehensively analyzing the element migration mechanism by combining the test result with geological conditions. The method of the invention is simple, can reach the equilibrium fast and can be calculated quantitatively, can reflect the basic properties of elements and the stability of complex compounds.
Description
Technical Field
The invention belongs to the technical field of geological mineral exploration, and particularly relates to an experimental method for researching an element migration mechanism in a hydrothermal lead-zinc deposit, which is simple in method, fast in balance, capable of being quantitatively calculated and capable of reflecting basic properties and complex stability of elements.
background
The migration of elements in the geological process in what form and how to migrate is always the most basic scientific problem in the geochemistry, and the problem that the fluid migration mechanism research cannot avoid, and the understanding of the cause of the deposit of the metal how to occur, migrate and pile up in the source plays an important role. In recent years, the testing technology is continuously perfected, the computer simulation function is gradually powerful, but the development of the diagenetic mineralization experiment is relatively lagged, and an effective experimental method is required to be found to simulate and reproduce the diagenetic action at different stages in the geological process, so that more basic data are provided for the research of element migration and precipitation mechanisms, and the visual angle for researching the problems is continuously expanded.
in fluid-dominated geological processes, it is generally considered that elements mainly exist and migrate as coordination type complexes and polyacid type complexes, the nature, activity, ligand field stability and other intrinsic factors as well as environmental factors such as temperature, pressure, pH, oxygen fugacity, sulfur fugacity influence the stability of the complexes, and the migration form and stability of the elements influence and restrict the precipitation mechanism of minerals, and the complexes are the most dominant form of element migration in hydrothermal fluid, and the research is always the focus of attention of miners and geochemists. In addition to theoretical calculation and computer simulation, most of domestic and foreign scholars determine the existence form of elements in hydrothermal solution by using a mineral solubility method, however, the mineral solubility is mainly measured by the amount of elements in a source region which can be dissolved out, the migration amount and migration scale of the elements in the fluid are determined by the stability of a stable migration form, namely a complex, and relevant and reliable basic experimental data are lacked for the stability of an element chlorine-containing complex in an ore-forming fluid. In fact, the solubility of metal sulfides is very low, the dissolution equilibrium time is long, and it is difficult to accurately obtain the solubility of minerals. Meanwhile, elements are dissolved into a fluid phase, stably migrate in the fluid and then precipitate out of the fluid, and the method is a dynamic and long process.
Lead and zinc are important dominant mineral species in China, but the reserves of lead and zinc resources are rapidly reduced by the large-scale development and utilization in recent decades, and the consumption in recent decades is the top of the world. At present, the guarantee period of lead and zinc available for planning and utilizing a mining area in China is only 8 years, nearly half of large and medium-sized mine resources are in crisis, and the year-by-year decline of the mining ratio is discovered, so that China gradually loses the global dominance of lead and zinc resources, the lead and zinc become the scarce resources in China, and the external dependency degree is up to more than 25%. Therefore, the search for large-ultra large lead-zinc-rich ore deposits (such as lead-zinc ore deposits in northeast Yunnan mine collection areas) is an urgent task in the field of lead-zinc geological exploration in China.
In hydrothermal mineralization unrelated to magma, Lead and zinc tend to be enriched to form ultra-large carbonate-bearing non-magma hydrothermal Lead-zinc deposits, such as the meetings of the Chuan-Dian-Qian Lead-zinc polymetallic mineralization field, Zhaotong workplace Lead-zinc deposits, girder Lead-zinc deposits, Jefferson City, Copper Ridge, Ozark, Old Lead Belt, Tristat, Upper Mississsippi, Australian KamargaAdmirals Bay, Sorby Hills, Coxco, Lennadshelf, Nanisivik, Pine Point, Polaris, Pobb Lake, Monarch-KickingHors, Gayna River, and other mineral deposits have obvious clustering properties, often dense grade distribution, region distribution, 2 km, significance, and significance for the research on the chemical mining mechanism, and the research on the chemical mining mechanism of the chemistry, and the research on the chemical mining mechanism of the world, and the research on the chemical mining mechanism of the origin, the research of the Lead deposit, the research of the mineral deposit, the research on the world, the research on the quality of the mineral deposit, the mining mechanism of the world, the research of the zinc, the research of the world, the research of the world, the research of the Lead deposit, the research of the world, the research of the.
the characteristics of large-scale intensive production in the same region reflect that non-magma post-production hydrothermal lead-zinc deposits of carbonate bearing ores may be the result of large-scale fluid transport. The cause of The lead-zinc deposit in MVT (The Mississippi Valley-type, Mississippi Valley type) was successfully explained by many foreign scholars, and many scholars in China considered that The formation of The lead-zinc deposit in Chuan-Dian-Qian region is related to large-scale fluid migration. Therefore, the hydrolysis experimental study of the lead-zinc migration mechanism is not only an important innovation in the research field of the front edge of the mineral fluid of the special mineral system in China, but also adds new contents to the research of the geochemistry and the mineral deposit science of the fluid of the mineral forming area of the lead-zinc from Chuanhui and Qian, and the achievement of the hydrolysis experimental study also has an important guiding function on the research of the hydrothermal alteration lithofacies of the mineral deposit and the prediction of the mineral finding.
Disclosure of Invention
The invention aims to provide an experimental method for researching element migration mechanism in hydrothermal lead-zinc deposit, which is simple in method, fast in reaching balance, capable of being quantitatively calculated and capable of reflecting basic properties and complex stability of elements.
The purpose of the invention is realized as follows: the method comprises the steps of solution preparation, complex hydrolysis under different pH values, complex hydrolysis under water-rock interaction and comprehensive analysis, and specifically comprises the following steps:
A. solution preparation: obtaining geological conditions of the hydrothermal lead-zinc deposit in advance, and preparing a chlorine-containing complex solution containing Pb and Zn metal elements at a certain concentration according to the geological conditions;
B. the complex was hydrolyzed at different pH as follows:
b1, complex hydrolysis: adjusting the chlorine-containing complex solution of the Pb and Zn metal elements by using HCl or NaCl to hydrolyze the metal elements;
B2, solid-liquid separation: filtering the hydrolyzed chlorine-containing complex solution, then performing centrifugal separation, and collecting the separated clear liquid;
b3, ICP-Ms analysis: performing ICP-Ms analysis on the clear liquid after the solid-liquid separation of B2 to obtain the content of metal elements after hydrolysis;
C. complex hydrolysis under water-rock interaction, the method is as follows:
C1, assuming an open system, putting a certain amount of the Pb and Zn-containing metal element solution prepared in the step A into a plastic bottle on day 1, adding surrounding rock, then adding the same metal element-containing solution with the same concentration and volume into the plastic bottle every day until day 6-10, filtering part of the solution in the plastic bottle every day, centrifugally separating a sample, drying the precipitate, and separately storing clear liquid and the precipitate to be tested;
c2, supposing a semi-closed system, putting a certain amount of the Pb and Zn-containing metal element solution prepared in the step A into a plastic bottle on day 1, adding surrounding rock, then taking part of the solution in the plastic bottle every day, filtering and centrifugally separating a sample until day 6-10, drying the separated sample precipitate every day, and separately storing clear liquid and precipitate to be tested;
c3, ICP-Ms test: performing ICP-Ms test on the filtered clear liquid in the C1 or C2;
C4, EPMA test: carrying out EPMA test on the surrounding rock and the sediment in C1 or C2;
D. and (3) comprehensive analysis: the element migration mechanism is comprehensively analyzed according to the test results of B3, C3 and C4 in combination with the geological conditions of the hydrothermal lead-zinc deposit obtained in advance.
compared with the prior art, the invention has the following beneficial effects:
1. The method is suitable for the research on the migration mechanism of the elements of lead and zinc in the hydrothermal lead-zinc ore deposit at normal temperature (25 ℃) and normal pressure (1 atm), and is also suitable for the research on the migration mechanism of the elements of high-valence elements such as niobium, tantalum, zirconium, hafnium, molybdenum, tungsten, tin, aluminum and the like and multi-metal ore deposits of divalent elements such as copper, lead, zinc, iron and the like;
2. The hydrolysis characteristics of the element complex in the hydrothermal lead-zinc deposit are related to factors such as the ionic polarizability of the center of the ligand, the temperature, the pressure medium condition, the water property and the like, so that the complex hydrolysis method is adopted, the balance is fast, the quantitative calculation can be realized, and the basic properties of the element and the stability of the complex can be reflected better;
3. The invention solves the problems of long dissolution equilibrium time, difficult accurate acquisition of mineral solubility and the like in the traditional solubility method.
drawings
FIG. 1 is a graph of pH-Zn content of ICP-Ms in hydrolysis experiments according to examples of the present invention;
FIG. 2 is a graph of pH-Pb content of ICP-Ms for hydrolysis experiments in accordance with an embodiment of the present invention;
FIG. 3 is a graph of pH-Pb (Zn) content by ICP-Ms for hydrolysis experiments according to an embodiment of the present invention;
FIG. 4 is a graph of pH versus precipitation rate for ICP-Ms analysis for hydrolysis experiments in accordance with an embodiment of the present invention;
FIG. 5 is a graph showing the kinetics of the hydrolysis reaction of lead and zinc in accordance with an embodiment of the present invention;
FIG. 6-1 is a TD-0 electron probe spectrum of an embodiment of the present invention;
FIG. 6-2 shows a TD-1 electron probe spectrum of an embodiment of the present invention;
FIGS. 6-3 are TD-2 electron probe spectra of examples of the present invention;
FIGS. 6-4 are TD-3 electron probe spectra of examples of the present invention;
FIGS. 6-5 are TD-4 electron probe spectra of examples of the present invention;
FIGS. 6-6 are TD-5 electron probe spectra of examples of the present invention;
FIGS. 6-7 are TD-6 electron probe spectra of examples of the present invention;
FIGS. 6-8 are TD-7 electron probe spectra of examples of the present invention;
FIGS. 6-9 are TD-8 electron probe spectra of examples of the present invention;
FIGS. 6-10 are TD-9 electron probe spectra of examples of the present invention;
FIGS. 6-11 are TD-10 electron probe spectra of examples of the present invention.
Detailed Description
The invention is further illustrated by the following figures and examples, which are not intended to limit the invention in any way, and any variations or modifications which are based on the teachings of the invention are intended to be within the scope of the invention.
as shown in fig. 1 to 6, the method comprises the steps of solution preparation, complex hydrolysis under different pH, complex hydrolysis under water-rock interaction, and comprehensive analysis, and specifically comprises the following steps:
A. solution preparation: obtaining geological conditions of the hydrothermal lead-zinc deposit in advance, and preparing a chlorine-containing complex solution containing Pb and Zn metal elements at a certain concentration according to the geological conditions;
B. the complex was hydrolyzed at different pH as follows:
b1, complex hydrolysis: adjusting the chlorine-containing complex solution of the Pb and Zn metal elements by using HCl or NaCl to hydrolyze the metal elements;
B2, solid-liquid separation: filtering the hydrolyzed chlorine-containing complex solution, then performing centrifugal separation, and collecting the separated clear liquid;
b3, ICP-Ms analysis: performing ICP-Ms (Inductively coupled plasma mass spectrometry) analysis on the clear liquid obtained after the solid-liquid separation of B2 to obtain the content of the hydrolyzed metal elements;
C. complex hydrolysis under water-rock interaction, the method is as follows:
in the geological process, fluid is stressed to migrate in fractures and fissures among rocks, the migration rate and the residence time in holes are different due to different porosities, permeabilities and stress sizes, and the fluid is always in contact with surrounding rocks and reacts with the surrounding rocks to change the property and the components of the fluid no matter the fluid stays in the migration process or the holes, so that the research of the dynamics of the element is emphasized when the migration mechanism of the element is researched; therefore, the C step is to study the element migration mechanism by utilizing the hydrolysis kinetics when contacting with the surrounding rock.
c1, assuming an open system, putting a certain amount of the Pb and Zn-containing metal element solution prepared in the step A into a plastic bottle on day 1, adding surrounding rock, then adding the same metal element-containing solution with the same concentration and volume into the plastic bottle every day until day 6-10, filtering part of the solution in the plastic bottle every day, centrifugally separating a sample, drying the precipitate, and separately storing clear liquid and the precipitate to be tested;
C2, supposing a semi-closed system, putting a certain amount of the Pb and Zn-containing metal element solution prepared in the step A into a plastic bottle on day 1, adding surrounding rock, then taking part of the solution in the plastic bottle every day, filtering and centrifugally separating a sample until day 6-10, drying the separated sample precipitate every day, and separately storing clear liquid and precipitate to be tested;
c3, ICP-Ms test: performing ICP-Ms test on the filtered clear liquid in the C1 or C2;
c4, EPMA test: carrying out EPMA (Electron Microprobe) test on the surrounding rock and the sediment in C1 or C2;
D. And (3) comprehensive analysis: the element migration mechanism is comprehensively analyzed according to the test results of B3, C3 and C4 in combination with the geological conditions of the hydrothermal lead-zinc deposit obtained in advance.
the step A is to determine the conditions of solution concentration, medium and the like according to the geological conditions of the researched ore deposit, the fluid inclusion composition in the non-magma hydrothermal ore deposit shows that the metal ions in the fluid mainly comprise Na +, Ca2 +, Mg 2+ and the like besides the mineral forming metal, wherein the Na content is the maximum, the in-situ test of a single fluid inclusion can reveal the content of the mineral forming metal, and the chlorine-containing complex solution with a certain concentration of metal elements is prepared according to the conditions.
and the step A is to test the inclusion components and the metal ion activity of the ore-forming fluid of the hydrothermal lead-zinc ore deposit in advance, obtain the content of the ore-forming metal elements of the ore-forming fluid of the ore deposit according to the test, and then prepare the chlorine-containing complex solution containing the ore-forming metal elements with a certain concentration according to the content of the ore-forming metal elements.
the B1 step is that high valence metal ions such as Nb 4+, Ta 4+, Sn 4+, Ti 4+, Fe 3+, Al 3+ and the like in aqueous solution can be hydrolyzed strongly, divalent metal ions such as Fe 2+, Cu 2+, Pb 2+, Zn 2+ and the like can also be hydrolyzed in a certain range, and the hydrolysis degree is mainly controlled by pH and ionic activity under certain temperature and pressure, wherein the ionic activity is determined according to geological conditions, so that HCl or NaCl is used for adjusting the chlorine-containing complex solution of the mineral forming metal elements to be hydrolyzed so as to research the hydrolysis degree of the mineral forming metal elements under different pH conditions.
The chlorine complex solution containing the mineral-forming metal elements and prepared according to the content of the mineral-forming metal elements is a single-metal-element chlorine complex solution and a chlorine complex mixed solution containing all the mineral-forming metal elements, which are respectively prepared.
in the step B1, HCl or NaCl is added in different amounts to adjust the pH of the chlorine complex solution of the single metal element and the mixed solution of the chlorine complexes containing all the mineral-forming metal elements to hydrolyze the chlorine complex solution of the single metal element and the mixed solution of the chlorine complexes containing all the mineral-forming metal elements, respectively, so as to obtain a plurality of hydrolysates of the chlorine complex solution of the single metal element and the mixed solution of the chlorine complexes containing all the mineral-forming metal elements at different pH values.
And the certain amount of the solution containing the metal elements prepared in the step A in the steps C1 and C2 is the mixed solution containing the chlorine complexes and containing all the mineral-forming metal elements, which is prepared in the step A.
the analysis result of the inclusion composition of the mineral-forming fluid in the step A shows that the mineral-forming fluid of the ore deposit is Ca 2+ -Mg 2+ -Na + -Cl - -HCO 3 - -SO 4 2- type containing metal elements of Pb and Zn, and the following chlorine-containing complex solution is prepared according to the content of the mineral-forming elements:
Solution of A1 and Na 2 ZnCl 4
respectively weighing a certain amount of analytically pure ZnCl 2 and NaCl, putting the analytically pure ZnCl 2 and NaCl into a beaker cleaned by deionized water, adding the deionized water, stirring and dissolving, transferring the beaker and a glass rod into a 250ml volumetric flask, washing the beaker and the glass rod by the deionized water, transferring the beaker and the glass rod into the volumetric flask, and shaking the beaker and the glass rod uniformly after constant volume to obtain a NaCl solution containing 0.01mol/kg of ZnCl 2 and 1mol/kg of NaCl for later use;
a2, Na 2 PbCl 4 solution
Respectively weighing a certain amount of analytically pure PbCl 2 and NaCl, putting into a beaker cleaned by deionized water, adding deionized water, stirring and dissolving, transferring into a 250ml volumetric flask, washing the beaker and a glass rod by the deionized water, transferring into the volumetric flask, and shaking uniformly after constant volume to obtain a NaCl solution containing 0.005mol/kg of PbCl 2 and 1mol/kg for later use;
mixed solution of A3, Pb and Zn
Respectively weighing a certain amount of analytically pure NaCl, CaCl 2 and MgCl 2, putting the analytically pure NaCl, CaCl 2 and MgCl 2 into a beaker cleaned by deionized water, adding deionized water, stirring and dissolving the mixture in about 100ml of water, then adding a certain amount of ZnCl 2 and PbCl 2 into the salt solution one by one, dripping hydrochloric acid to ensure that the pH is less than 4, transferring the solution into a 250ml volumetric flask, flushing the beaker and a glass rod by deionized water, transferring the flask into the volumetric flask, and shaking the flask uniformly after constant volume to obtain a mixed solution containing 0.0005mol/kg of PbCl 2, 0.01mol/kg of ZnCl 2, 2mol/kg of NaCl, 0.002mol/kg of CaCl 2 and 0.002mol/kg of MgCl 2 for later use.
and in the step C1, 10ml of the Pb and Zn mixed solution obtained in the step A3 is taken on day 1 and added into a 200ml plastic bottle, 2g of 40-mesh fine-grained dolomite is added, then 10ml of the Pb and Zn mixed solution with the same concentration is added into the plastic bottle every day until day 6-10, the solution with the same volume in the plastic bottle is taken every day during the period, the solution is filtered and centrifugally separated to obtain a sample, the precipitate is dried in a 75 ℃ oven, and clear liquid and the precipitate are separately stored for testing.
And in the step C2, adding 80ml of the Pb and Zn mixed solution obtained in the step A3 into a 200ml plastic bottle on day 1, adding 2g of 40-mesh fine-grained dolomite, filtering and centrifugally separating the solution with the same volume in the plastic bottle every day to obtain a sample, drying the precipitate in an oven at 75 ℃, and separately storing clear liquid and the precipitate to be tested.
In the step B1, HCl or NaCl is added in different amounts to adjust the pH of the chlorine-containing complex solution of the metal element, so that the solution is hydrolyzed, and a plurality of hydrolysates of the chlorine-containing complex solution of the metal element at different pH values are obtained.
step D, analyzing the relation between the large amount of metal carried and the pH value of the ore forming fluid during the transportation of the ore forming fluid of the ore deposit according to the test result of the step B3, namely the relation between the ore forming grade of the ore deposit and the acidity of the ore forming fluid; analyzing the relationship between the precipitation of the ore deposit mineralizing metallic elements and the change rate of the pH value of the mineralizing fluid according to the test results of the steps B3 and C3; and analyzing the relation between the change of the surrounding rock and the system, the pH and the action time after the interaction of the deposit mineralization fluid and the surrounding rock and the relation between the amount of hydrolysis products under the action of the water rock and the system, the pH and the action time according to the test result of the C4 step.
and the step D is to comprehensively consider the test results of the B3, the C3 and the C4 with the mineralogy, the petrology and the fluid inclusion geochemistry of the hot liquid lead-zinc deposit, the trace element geochemistry, the isotope geochemistry, the geological thermodynamics and/or the geological characteristics, so that a mechanism which can be mutually verified and is reasonable is obtained.
example 1
Take the lead-zinc ore deposit in the area of multi-metal mineral formation of Chuan-Dian-Qian lead-zinc as an example.
S100, preparation of solution
according to geological conditions of the researched ore deposit, conditions such as solution concentration, medium and the like are determined, and fluid inclusion composition test results show that the ore deposit forming fluid is Ca 2+ -Mg 2+ -Na + -Cl - -HCO 3 - -SO 4 2- type containing metal elements such as Pb, Zn and the like, and the following solution is prepared by the content of the ore forming elements:
S110, Na 2 ZnCl 4 solution
respectively weighing 0.3408g and 14.61g of analytically pure ZnCl 2 and NaCl, putting the analytically pure ZnCl 2 and NaCl into a beaker washed by deionized water, adding the deionized water, stirring to dissolve the analytically pure ZnCl 2 and NaCl, transferring the mixture into a 250ml volumetric flask, washing the beaker and a glass rod by the deionized water, transferring the beaker and the glass rod into the volumetric flask, and shaking uniformly after constant volume to obtain a solution containing 0.01mol/kg of ZnCl 2 and 1mol/kg of NaCl for later use;
S120 and Na 2 PbCl 4 solution
respectively weighing 0.03476g and 14.61g of analytically pure PbCl 2 and NaCl, putting the analytically pure PbCl 2 and NaCl into a beaker washed by deionized water, adding the deionized water, stirring to dissolve the analytically pure PbCl 2 and NaCl, transferring the mixture into a 250ml volumetric flask, washing the beaker and a glass rod by the deionized water, transferring the beaker and the glass rod into the volumetric flask, and shaking uniformly after constant volume to obtain a solution containing 0.005mol/kg of PbCl 2 and 1mol/kg of NaCl for later use;
S130, Pb and Zn mixed solution
Respectively weighing 29.22g, 0.0277g and 0.0508g of analytically pure NaCl, CaCl 2 and MgCl 2, putting the analytically pure NaCl, CaCl 2 and MgCl 2 into a beaker cleaned by deionized water, adding deionized water, stirring to dissolve the analytically pure NaCl, CaCl 2 and MgCl 2 into about 100ml of water to obtain a salt solution, respectively adding 0.3408g of ZnCl 2 and 0.0348g of PbCl 2 into the salt solution, adding a few drops of hydrochloric acid to enable the pH of the solution to be less than 4 due to easy hydrolysis of Pb and Zn, then transferring the solution into a 250ml volumetric flask, washing the beaker and a glass rod by deionized water, transferring the beaker and the glass rod into the volumetric flask, and shaking uniformly after constant volume to obtain a mixed solution containing 0.0005mol/kg of PbCl 2, 0.01mol/kg of ZnCl 2, 2mol/kg of NaCl, 0.002mol/kg of CaCl 35;
s200, hydrolysis of Complex at different pH
S210, complex hydrolysis: respectively adding HCl or NaCl with different dosages to adjust the pH values of the chlorine-containing complex solutions of the single metal elements obtained in S110 and S120 and the chlorine-containing complex mixed solutions containing all the mineral-forming metal elements obtained in S130 to respectively hydrolyze the chlorine-containing complex solutions of the single metal elements and the chlorine-containing complex mixed solutions containing all the mineral-forming metal elements under different pH values to obtain a plurality of hydrolysates;
s220, solid-liquid separation: filtering the hydrolysate of S210 by using a funnel respectively, then carrying out centrifugal separation, and collecting the separated clear liquid to be tested;
S230, ICP-Ms test: and (5) carrying out ICP-Ms analysis on the clear liquid after the solid-liquid separation in the step (S220) to obtain the content of the metal elements after the hydrolysis. The test results are shown in table 1 and fig. 1, fig. 2, fig. 3 and fig. 4;
TABLE 1 hydrolysis experiment ICP-Ms test results 1
S300, hydrolysis of complex under interaction of water and rock
in order to simulate the migration process of elements more truly and to observe the precipitate generated in the hydrolysis reaction more intuitively and research the importance of the surrounding rock in the mineralization process, the S300 step of the method is the hydrolysis kinetic study when the surrounding rock is contacted.
S310, considering two systems of opening and closing:
Assuming an open system, namely a certain amount of Pb and Zn fluid enters NE direction torsion fracture every day, and after a certain time (7 days in the experiment), the Pb and Zn fluid is moved away or still remained in the fracture;
Assuming a semi-closed system, a certain amount of Pb and Zn fluid enters NE direction pressure torsion fracture, and after a certain time (7 days in the experiment), the Pb and Zn fluid is moved away or still remained in the fracture;
s311, an open system: taking 10ml of Pb-Zn mixed solution obtained in S130 in a 200ml plastic bottle on the first day, adding 2g of 40-mesh fine-grained dolomite, then adding 10ml of Pb-Zn mixed solution with the same concentration into the plastic bottle every day until the 8 th day, taking the solution with the same volume in the plastic bottle every day during the period, filtering and centrifugally separating to obtain a sample, drying the precipitate in a 75 ℃ oven, and separately storing clear liquid and the precipitate to be tested;
s312, a semi-closed system: taking 80ml of Pb and Zn mixed solution obtained in S130 in a 200ml plastic bottle, adding 2g of 40-mesh fine-grained dolomite, then taking the solution with the same volume in the plastic bottle every day, filtering and centrifugally separating to obtain a sample, drying the precipitate in a 75 ℃ oven, and separately storing clear liquid and the precipitate to be tested;
s320, ICP-Ms test: the supernatant after filtration in S311 or S312 was subjected to ICP-Ms test, and the results are shown in Table 2 and FIG. 5;
S330, EPMA testing: EPMA test of the above-mentioned surrounding rock and the sediment in S311 or S312, the results are shown in Table 3 and FIGS. 6-1 to 6-11;
TABLE 2 hydrolysis kinetics experiment ICP-Ms test results 2
In the table: TD-18 is a blank control sample, and TD-0 to TD-10 are open system samples; TD-11 to TD-17 are semi-open system samples.
TABLE 3 EPMA test results (%)
S400, comprehensive analysis
Carrying out comprehensive analysis research on the migration mechanism of the elements according to the test result and combining geological facts:
figures 1 to 4 show that a lower pH ensures that a large amount of metal is handled during fluid transport, a pH < 4 is an advantageous condition for handling large amounts of metal, and the lower the pH, the greater the amount of metal that can be handled. The pH value of the ore forming fluid of the MVT type ore deposit is generally between 5 and 6, and in such a pH range (shown in figures 1 to 4), the precipitation rate of Zn reaches 30 to 50 percent, and Pb reaches 50 to 80 percent, namely hydrolysis of lead and zinc can cause that the ore forming fluid of the MVT type ore deposit can not carry a large amount of metal, which is the main reason that the general grade of MVT is low; the main reason why this lead-zinc deposit in northeast Yunnan is so rich is that the ore-forming fluid is highly acidic and can carry a large amount of metal for a long distance.
table 3 and FIG. 6 show that lead and zinc hydrolysis under the action of the water rock can generate hydroxide precipitate of lead and zinc, the amount of the precipitate has a relationship with the reaction time and the system, and the surrounding rock after the reaction is altered to different degrees due to different action times. Comparing the experiment of directly adjusting the pH value of the solution (figures 1 to 4) and the experiment of water rock reaction (figure 5) to cause the pH value to rise so as to hydrolyze lead and zinc, the former has a much higher precipitation rate than the latter, which is probably caused by different precipitation rates due to different pH rise rates (the former rises slowly in a few seconds and the latter rises slowly in a few days), and the dissolved metal cations such as Ca, Mg and the like also undergo different degrees of hydrolysis, which inhibits the hydrolysis of lead and zinc to a certain extent, and finally causes a large difference in precipitation rate.
Claims (5)
1. an experimental method for element migration mechanism research in hydrothermal lead-zinc ore deposit is characterized by comprising the steps of solution preparation, complex hydrolysis under different pH values, complex hydrolysis under water-rock interaction and comprehensive analysis, and specifically comprises the following steps:
A. Solution preparation: testing the inclusion components and the metal ion activity of the mineral-forming fluid of the hydrothermal lead-zinc deposit in advance, obtaining the mineral-forming metal element content of the mineral-forming fluid of the deposit according to the test, and then preparing a single-metal-element chlorine-containing complex solution containing Pb and Zn metal elements at a certain concentration and a chlorine complex mixed solution containing the Pb and Zn metal elements according to the mineral-forming metal element content;
B. The complex was hydrolyzed at different pH as follows:
B1, complex hydrolysis: adjusting the chlorine-containing complex solution of the Pb and Zn metal elements by using HCl or NaCl to hydrolyze the metal elements;
b2, solid-liquid separation: filtering the hydrolyzed chlorine-containing complex solution, then performing centrifugal separation, and collecting the separated clear liquid;
B3, ICP-Ms analysis: performing ICP-Ms analysis on the clear liquid after the solid-liquid separation of B2 to obtain the content of metal elements after hydrolysis;
C. Complex hydrolysis under water-rock interaction, the method is as follows:
c1, assuming an open system, taking a certain amount of the chlorine complex mixed solution containing Pb and Zn metal elements prepared in the step A on the 1 st day, adding surrounding rock, then adding the same solution containing the metal elements with the same concentration and volume into the plastic bottle every day until the 6 th 6 ~ 10 th day, taking part of the solution in the plastic bottle every day, filtering and centrifugally separating a sample, drying the precipitate, and separately storing the clear solution and the precipitate to be tested;
C2, assuming a semi-closed system, putting a certain amount of the chlorine complex mixed solution containing Pb and Zn metal elements prepared in the step A into a plastic bottle on day 1, adding surrounding rock, then taking part of the solution in the plastic bottle every day, filtering and centrifugally separating a sample till day 6 ~ 10, drying the separated sample precipitate every day, and separately storing clear liquid and the precipitate to be tested;
C3, ICP-Ms test: performing ICP-Ms test on the filtered clear liquid in the C1 or C2;
C4, EPMA test: carrying out EPMA test on the surrounding rock and the sediment in C1 or C2;
D. and (3) comprehensive analysis: the element migration mechanism is comprehensively analyzed according to the test results of B3, C3 and C4 in combination with the geological conditions of hydrothermal lead-zinc ore deposits acquired in advance: analyzing the relationship between the handling of a large amount of metal and the pH value of the ore forming fluid during the transportation of the ore forming fluid, namely the relationship between the ore forming grade of the ore deposit and the acidity of the ore forming fluid according to the test result of the step B3; analyzing the relationship between the precipitation of the ore deposit mineralizing metallic elements and the change rate of the pH value of the mineralizing fluid according to the test results of the steps B3 and C3; and analyzing the relation between the change of the surrounding rock and the system, the pH and the action time after the interaction of the deposit mineralization fluid and the surrounding rock and the relation between the amount of hydrolysis products under the action of the water rock and the system, the pH and the action time according to the test result of the C4 step.
2. The experimental method according to claim 1, wherein in the step B1, the solutions of the chlorine-containing complex of the monometallic element and the mixed solution of the chlorine-containing complex of all the mineralizing metallic elements are hydrolyzed by adjusting the pH values of the solutions of the chlorine-containing complex of the monometallic element and the mixed solution of the chlorine-containing complex of all the mineralizing metallic elements by adding different amounts of HCl or NaCl respectively, so as to obtain a plurality of hydrolysates of the solutions of the chlorine-containing complex of the monometallic element and the mixed solution of the chlorine-containing complex of all the mineralizing metallic elements.
3. the experimental method according to claim 1, characterized in that the analysis of the inclusion composition of the mineral-forming fluid in step a shows that the mineral-forming fluid of the deposit is of the Ca 2+ -Mg 2+ -Na + -Cl - -HCO 3 - -SO 4 2- type containing metallic elements of Pb and Zn, from which the following chlorine-containing complex solutions are prepared:
Solution of A1 and Na 2 ZnCl 4
respectively weighing a certain amount of analytically pure ZnCl 2 and NaCl, putting the analytically pure ZnCl 2 and NaCl into a beaker cleaned by deionized water, adding the deionized water, stirring and dissolving, transferring the beaker and a glass rod into a 250mL volumetric flask, washing the beaker and the glass rod by the deionized water, transferring the beaker and the glass rod into the volumetric flask, and shaking the beaker and the glass rod uniformly after constant volume to obtain a NaCl solution containing 0.01mol/kg of ZnCl 2 and 1mol/kg of NaCl for later use;
A2, Na 2 PbCl 4 solution
Respectively weighing a certain amount of analytically pure PbCl 2 and NaCl, putting into a beaker cleaned by deionized water, adding deionized water, stirring and dissolving, transferring into a 250mL volumetric flask, washing the beaker and a glass rod by the deionized water, transferring into the volumetric flask, and shaking uniformly after constant volume to obtain a NaCl solution containing 0.005mol/kg of PbCl 2 and 1mol/kg for later use;
mixed solution of A3, Pb and Zn
Respectively weighing a certain amount of analytically pure NaCl, CaCl 2 and MgCl 2, putting the analytically pure NaCl, CaCl 2 and MgCl 2 into a beaker cleaned by deionized water, adding deionized water, stirring and dissolving the mixture in 100mL of water, then adding a certain amount of ZnCl 2 and PbCl 2 into the salt solution one by one, dripping hydrochloric acid to ensure that the pH is less than 4, transferring the solution into a 250mL volumetric flask, flushing the beaker and a glass rod with deionized water, transferring the flask into the volumetric flask, and shaking the flask uniformly after constant volume to obtain a mixed solution containing 0.0005mol/kg of PbCl 2, 0.01mol/kg of ZnCl 2, 2mol/kg of NaCl, 0.002mol/kg of CaCl 2 and 0.002mol/kg of MgCl 2 for later use.
4. The experimental method according to claim 3, wherein in the step C1, 10mL of the Pb-Zn mixed solution obtained in the step A3 is taken at day 1 and added into a 200mL plastic bottle, 2g of fine-grained dolomite of 40 meshes is added, 10mL of the Pb-Zn mixed solution with the same concentration is added into the plastic bottle every day till day 6 ~ 10, during which the same volume of the solution in the plastic bottle is taken every day, filtered and centrifuged to obtain a sample, the precipitate is dried in an oven at 75 ℃, and the clear solution and the precipitate are separately stored for testing.
5. The experimental method according to claim 3, wherein in the step C2, 80mL of the mixed solution of Pb and Zn obtained in the step A3 is taken at day 1, added into a 200mL plastic bottle, added with 2g of 40-mesh fine-grained dolomite, and then the solution with the same volume in the plastic bottle is taken every day, filtered and centrifuged to obtain a sample, the precipitate is dried in an oven at 75 ℃, and the clear solution and the precipitate are separately stored for testing.
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| CN105181783A (en) * | 2015-10-10 | 2015-12-23 | 河南省岩石矿物测试中心 | Platinum-palladium metallographic analysis method in dolomite and quartzite type platinum group ore deposit |
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| CN105181783A (en) * | 2015-10-10 | 2015-12-23 | 河南省岩石矿物测试中心 | Platinum-palladium metallographic analysis method in dolomite and quartzite type platinum group ore deposit |
Non-Patent Citations (3)
| Title |
|---|
| 云南昭通铅锌矿pH-logfo2和pH-loga 相图对铅锌共生分异的制约;张艳等;《中国地质》;20150430;第42卷(第2期);第607-619页 * |
| 滇东北矿集区会泽超大型铅锌矿床流体混合成矿机制;张艳;《中国博士学位论文全文数据库基础科学辑》;20170115;正文第54、102-142页 * |
| 碳酸盐岩型铅锌矿床成矿流体中铅锌元素运移与沉淀机制研究综述;张艳等;《地质论评》;20160131;第62卷(第1期);第187-197页 * |
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