CN104678073A - Manufacturing method of ion proportionality coefficient trajectory of seawater evaporation experiment - Google Patents

Manufacturing method of ion proportionality coefficient trajectory of seawater evaporation experiment Download PDF

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CN104678073A
CN104678073A CN201510059689.XA CN201510059689A CN104678073A CN 104678073 A CN104678073 A CN 104678073A CN 201510059689 A CN201510059689 A CN 201510059689A CN 104678073 A CN104678073 A CN 104678073A
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ion
coefficient
evaporation
seawater
trajectory
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周训
王晓翠
曹琴
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China University of Geosciences
China University of Geosciences Beijing
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China University of Geosciences Beijing
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Abstract

The invention discloses a manufacturing method of an ion proportionality coefficient trajectory of a seawater evaporation experiment. The ion proportionality coefficient trajectory is obtained by drawing a curve of the ion proportionality coefficient changing along with the content of Br<-> on a bilogarithmic graph by utilizing the values of ion proportionality coefficients, including gamma Na/gamma Cl, Br*10<3>/Cl, I*10<3>/Cl, Ca/Sr, gamma Mg/gamma Ca, K*10<3>/TDS, K*10<3>/Cl, K/Br, gamma Mg/gamma Cl and gamma Ca/ (gamma SO4+gamma HCO3) via taking the content of symbolic component Br<-> as an x-coordinate and the ion proportionality coefficient value as a y-coordinate in the seawater evaporation and concentration experiment process. In the process of seawater evaporation, before an ion is deposited as a salt, the ion proportionality coefficient trajectory is a horizontal line parallel to the x-coordinate; after the ion is deposited as the salt, the trajectory deviates from the horizontal line. The ion proportionality coefficient trajectory can be used for researching the formation and evolution principle of different brine chemical components.

Description

The method for making of evaporation of seawater experiment ion ratio coefficient locus line
1. technical field
The present invention relates to and utilize the variation relation of evaporation of seawater experimentation ions content to make ion ratio coefficient locus line, can be used for the Forming and evolution of Study of The Underground bittern, belong to sedimentary basin subsurface brine hydrogeochemistry technical field.
2. background technology
The earth is distributed with many large-scale sedimentary basins, the Michigan basin of the such as U.S., Illinois basin and Palo Duro basin, the Alberta basin of Jia He western provinces, the Murray basin of the Australian southeast, Paris France basin, the Sichuan Basin etc. of China.Sedimentary basin is in a metastable region in earth history period substantially, and the tectonic movement experienced is more weak, based on receive sediments, grows various sedimentary formation in basin.Sedimentary basin is often contained abundant oil, rock gas, salt deposit (halite, gypsum etc.) and some metalliferous deposit, is also distributed with subsurface brine simultaneously.In the Sichuan Basin, the place such as the depressed basin that underlies of Qaidam Basin, In Jianghan Basin, the North China Plain is all distributed with the higher bittern of salinity.
Sedimentary basin subsurface brine has following outstanding feature: 1. compose in the underground storage halogen layer being stored in low-porosity, low-permeability; 2., under being in buried (below ground hundreds of rice and even a few km) and high pressure (a hundreds of atmospheric pressure or tens MPas), the drilling well bittern that a part discloses storage halogen layer can flow out earth's surface certainly; 3. water temperature higher (mostly being 50 DEG C ~ 80 DEG C); 4. salinity (TDS) high (10 ~ > 400g/L, 35 ~ 330g/L are common); 5. lot of trace component (such as Br is rich in -, I -, Sr 2+, Ba 2+, B 3+, Li +deng).Bittern is a kind of underground water of specific type.Sedimentary basin subsurface brine has industrial utility value, can extract the multiple useful constituent such as halite and Br, I from bittern, because of but a kind of liquid mineral deposit.The production history of subsurface brine is extremely remote, before the history of adopting halogen in the area sinking shaft of Zi Gong, the Sichuan Basin can demand more than 2000 year.
The singularity of sedimentary basin subsurface brine, causes the interest of people, people to subsurface brine bury characteristic distributions, the aspect such as formation, RESERVE EVALUATION, exploitation of migration and seepage flow, Features of Hydrochemistry and bittern carried out large quantifier elimination.The origin of sedimentary basin subsurface brine and evolution problem are the problems that people are most interested in.High salinity and the water chemistry view being rich in this uniqueness of some microcomponent of subsurface brine, be both different from shallow underground fresh water, be also different from seawater.Can people propose such problem naturally: 1. why subsurface brine can have the so high salinity seen today? does bittern particularly in the sedimentary basin lacking evaporitic rock or sedimentary formation also have very high salinity? 2. once there is some chemical composition enrichment in the bittern which type of physics chemical action makes seen by today and other chemical composition is poor? the understanding of people to sedimentary basin subsurface brine formation mechenism reaches unanimity gradually, the dissolving mainly containing 1. evaporitic rock particularly rock salt forms dissolved salt bittern, 2. the remaining bittern in evaporite sediment process in sediment becomes evaporitic rock bittern, 3. the membrane filtration of mud stone, shale forms Union dyeing bittern, or above-mentioned mixed scenario.In fact, the forming process of subsurface brine should comprise 3 aspects: the 1. origin of water; 2. the formation of salinity; 3. the evolution of chemical composition.After certain water originated from enters sedimentary basin, or have an effect with sedimentary formation, or self change in sediment diagenetic environment, cause increasing of its salinity, and various physics, chemical action is participated in burying afterwards, diagenetic process, its chemical composition is changed further, thus forms subsurface brine seen now gradually.The forming process of subsurface brine is a very long process, experience deposition, buriedly to close and the period such as compaction, structure hydrothermal process, eluviation, has close contacting with environment residing in this process.
On the other hand, the existence of sedimentary basin subsurface brine and evolution, play an important role to the various physics occurred in sedimentary basin, chemical process.Subsurface brine is to the migration of the formation of mineral in sedimentary basin, structural deformation, metallics and petroleum and natural gas and assemble particular importance, also plays very large effect to the transmission of geothermal system heat in basin or migration.The speed of subsurface brine migration will have influence on the speed of the compacting of sediment in the process of burying; Mineral system complicated in sedimentary formation reaches chemical equilibrium always in burial diagenesis process, be that subsurface brine allows material composition to transfer to another kind of solid phase from a kind of solid phase, and the chemical composition of subsurface brine itself also there occurs evolution and changes.
Marine evaporite bittern is concentrated by ancient evaporation of seawater and is formed.People can expect carrying out the concentrated experiment of evaporation of seawater naturally, utilize experimental data, set up the relation between evaporation of seawater process ions content or between ion ratio coefficient, and contrast with actual bittern samples, are used for studying the formation of some subsurface brine.
The evaporation of seawater experiment material that foreign scholar carries out shows, seawater is along with evaporation and concentration, and various salt Precipitation in succession, the priority separated out according to salt, can be divided into gypsum, halite, epsomite, sylvine and bischofite 5 precipitate phases.Domestic scholars carries out evaporation and concentration experiment to Huanghai Sea water and Nan Haishui respectively, experiment is the spontaneous evaporation continuing at atmosheric pressure to have carried out under 25 DEG C of constant temperature 1 year, and result shows that salt deposit can be divided into 7 stages: aragonite, gypsum, halite, epsomite, sylvine, carnallite and bischofite.In evaporation of seawater concentration process, along with the precipitation of salt folds, in relict bittern there is regular change in various ion component content.Therefore, evaporation of seawater experimental data is utilized to set up the change of ion ratio coefficient relative to certain " mark " ion concentration, make the trajectory of ion ratio coefficient, be the important method of the Forming and evolution of research sedimentary basin subsurface brine, there is important theory significance and practical significance.
Evaporation of seawater trajectory has two classes.The first kind is ion trajectory line, and forefathers once made the ion trajectory line in evaporation of seawater concentration process, can be used for the Forming and evolution of Study of The Underground bittern.Carpenter (1978) utilizes log-log coordinate to establish Cl, Na, SO 4, Mg, K and Ca ion concentration and Br content relation curve---ion trajectory line; Week, instruction waited (1995) on the basis of the work of Carpenter (1978), and the further perfect trajectory of above-mentioned 6 ions, also establishes HCO 3, Li, Sr, B, Rb, Cs, I ion and TDS trajectory, these 14 ion trajectory lines characterize the content of each ion and the Changing Pattern of TDS in evaporation of seawater concentration process well.Equations of The Second Kind is ion ratio coefficient locus line.The positive equality of Song (1986) once made the trajectory of evaporation of seawater concentration process intermediate ion scale-up factor, had 6 scale-up factors, comprised γ Na/ γ Cl coefficient, Br × 10 3/ Cl coefficient, K × 10 3/ Cl coefficient, K/Br coefficient, (γ Ca+ γ Mg-γ SO 4-γ HCO 3)/γ Cl coefficient, horizontal ordinate Cl -mark component, ordinate is ion ratio coefficient value, and horizontal ordinate and ordinate are all adopt arithmetic coordinate.Its weak point is, due to Cl -reach the halite depositional phase in evaporation of seawater concentration process after, Cl -separate out from solution because forming halite, residual Cl in the solution -content just reduces, and uses Cl -increase the uncertainty of scale-up factor as mark component, be difficult to the effect as typical curve using this trajectory made.In addition, adopt arithmetic coordinate, be inconvenient to represent that numerical value differs the change of the ion ratio coefficient value of several order of magnitude.Difference of the present invention is (1) horizontal ordinate Br -mark component, because Br -any saline minerals deposition is not formed in evaporation of seawater concentration process, its stable content ground increases, thus play well with reference to effect, (2) horizontal ordinate and ordinate all use logarithmic coordinate, be convenient to express the change that numerical value differs the scalefactor value of several order of magnitude, (3) altogether make 10 ion ratio coefficient locus lines, wherein have 6 ion ratio coefficient forefathers not yet to relate to, (4) with regard to 10 ion ratio coefficients relative to Br -the trajectory of content, they occur all first.
3. summary of the invention
The invention discloses the method for making of evaporation of seawater concentration process intermediate ion scale-up factor trajectory.
In order to the geochemistry property history utilizing ion ratio coefficient locus line to study evaporitic rock bittern, need to determine " mark " component, such component neither forms precipitation of salts and separates out in evaporation of seawater process, also in diagenetic environment afterwards, water_rock interaction is not participated in, with the change of other component relative to the content of this " mark " component, set up the variation relation of evaporation of seawater process intermediate ion scale-up factor.
Evaporation of seawater experimental data shows to only have Br -in evaporation of seawater process, do not participate in diagenetic reaction precipitate.Br -the mineral of oneself are not formed in evaporation of seawater process, along with the increase of relict bittern salinity, Br -content linearly rises.Only after halite starts deposition, there is the Br of a seldom part -with Cl in sediment -form isomorphic mixture together, namely enter into solid salt with ion exchange form and replace Cl -.Even so, most Br -remain and be accumulated in bittern.Br in bittern -content is stable with evaporation and concentration to be increased, Br -the best mark component of seawater concentrating degree, with other ion ratio coefficient relative to Br -the chemical composition that the change of content carrys out spike marine evaporite bittern develops and becomes highly desirable.
Ion ratio coefficient is commonly used to the Forming and evolution studying sedimentary basin subsurface brine, comprises γ Na/ γ Cl coefficient, Br × 10 3/ Cl coefficient, I × 10 3/ Cl coefficient, Ca/Sr coefficient, γ Mg/ γ Ca coefficient, γ Ca/ (γ SO 4+ γ HCO 3) coefficient, be used for K × 10 of the enrichment of K in Study of The Underground bittern in addition 3/ TDS coefficient, K × 10 3/ Cl coefficient, K/Br coefficient, γ Mg/ γ Cl coefficient etc.Such as, the γ Na/ γ Cl coefficient with raw marine facies or nonmarine deposit bittern is less than 0.85 usually, and works as K × 10 of subsurface brine 3/ TDS coefficient is greater than 6, K × 10 3/ Cl coefficient is greater than 12, Br × 10 3when/Cl coefficient is greater than 0.4, K/Br coefficient is greater than 25, γ Mg/ γ Cl coefficient is greater than 0.13, just become rich K bittern.
Utilize above-mentioned 10 ion ratio coefficients in evaporation of seawater experimentation relative to Br -the change of content just can make ion ratio coefficient locus line (see photo).
4. accompanying drawing explanation
Accompanying drawing is that evaporation of seawater tests 10 ion ratio coefficient locus line charts.
In accompanying drawing, solid line is evaporation of seawater process intermediate ion scale-up factor trajectory, and the pattern table such as filled box, open squares, triangles, open triangles are shown in the subsurface brine sample number strong point that the Sichuan Basin gathers.
5. embodiment
Utilize evaporation of seawater experimental data, with Br -content is horizontal ordinate, and ion ratio coefficient value is ordinate, on bilogarithmic graph, can draw 10 kinds of ion ratio coefficients and Br -the graph of relation of content, is called the evaporation of seawater trajectory of often kind of ion ratio coefficient.Why select log-log coordinate, this is based on following two reasons.
(1) variation relation of various ion concentration in salt solusion dilution or evaporating concentration process is considered.If the salt solusion pure water dilution containing several different ions or an evaporation and concentration, then the proportionate relationship between various ion concentration will keep constant, although solution concentration can alter a great deal in dilution or evaporation and concentration.This relation can be expressed as:
B/A=k (1)
In formula, A, B are the content of two kinds of ions in solution, and k is constant.Formula (1) can be expressed as again:
log B=log A+logk (2)
Show that the relation of two kinds of ion concentrations on bilogarithmic graph is rendered as the linear relation that slope is 1.Now represent Br with A -, B represents other a certain ions, then the content of a certain ion and Br in evaporation of seawater process -content is rendered as the linear relation that slope is 1 on bilogarithmic graph.If this ion forms salt along with evaporation of seawater is concentrated and precipitates or other effects occur and enter into solid phase from solution, then the content of this ion in residual solution just reduces, and its trajectory just departs from the straight line that slope is 1.C represents another ion in solution again, then have:
log C=log A+logj (3)
J is constant.Formula (3) is substituted into formula (2):
log(B/C)=log(k/j) (4)
Show that the logarithm of ion ratio coefficient is a constant, thus the trajectory of ion ratio coefficient is the horizontal line being parallel to horizontal ordinate.If B, C ion forms salt along with evaporation of seawater is concentrated and precipitates or other effects occur and enter into solid phase from solution, then the scale-up factor trajectory of these two ions just departs from horizontal line.In formula (4), add another ion at the molecule of B/C or denominator or be multiplied by a constant, the trajectory after taking the logarithm remains the horizontal line being parallel to horizontal ordinate.So all proportions coefficient locus line is all the horizontal line being parallel to horizontal ordinate in the incipient stage.
(2) great variety of ion concentration is considered.In evaporation of seawater concentration process, the content of various ion differs several order of magnitude, and the change of the content of same ion also differs several order of magnitude, causes ion ratio coefficient value to differ huge.In this case, logarithmic coordinate are adopted can to represent the careful change of ion ratio coefficient value better.
In evaporation of seawater process before ion is with salt deposit, ion ratio coefficient locus line is in the horizontal line being parallel to horizontal ordinate, and after ion is with salt deposit, trajectory just departs from horizontal line.For scale-up factor γ Na/ γ Cl trajectory, in evaporation of seawater process before halite deposition, its trajectory is a horizontal line, after arriving halite deposition, due to Cl -and Na +particularly Na +the minimizing of content, its trajectory departs from horizontal line and reduces gradually.
Utilize the ion ratio coefficient locus line of evaporation of seawater, the Forming and evolution of Study of The Underground bittern can be contributed to.Such as, bittern samples is from the Sichuan Basin in the accompanying drawings, when the data point of actual bittern samples drops in evaporation of seawater trajectory or time neighbouring, illustrates that bittern is concentrated by evaporation of seawater and is formed.When above data point is positioned at evaporation of seawater trajectory, illustrate that bittern there occurs the water-rock effect of the ion enrichment causing being positioned at molecule in scale-up factor in the process of Forming and evolution.When data point is positioned at below evaporation of seawater trajectory, illustrate that bittern there occurs the poor water-rock effect of the ion that causes being positioned at denominator in scale-up factor in the process of Forming and evolution.
List of references
Carpenter AB.1978.Origin and chemical evolution of brines in sedimentary basins.Oklahoma Geological Survey Circular 79,60-77
Week instructs, Lee kind monarch .1995. evaporation of seawater trajectory and application thereof. geoscience, 20 (4): 409-414
Song Zhengping, Xu Tingliang, Xiao Zhangqi, bear refined monarch .1986. NE Sichuan Xuanhan area river 25 well potassium-rich brine hydrogeochemical characteristics and study on the genesis (internal report).

Claims (4)

1. a method for making for evaporation of seawater experiment ion ratio coefficient locus line, is characterized in that: utilize evaporation of seawater experimental data, with Br -content is horizontal ordinate, and ion ratio coefficient value is ordinate, draws 10 kinds of ion ratio coefficients and Br -the graph of relation of content, characterizes the Variation Features of ion ratio coefficient in evaporation of seawater concentration process.
2. ion ratio coefficient according to claim 1, is characterized in that: comprise γ Na/ γ Cl coefficient, Br × 10 altogether 3/ Cl coefficient, I × 10 3/ Cl coefficient, Ca/Sr coefficient, γ Mg/ γ Ca coefficient, γ Ca/ (γ SO 4+ γ HCO 3) coefficient, K × 10 3/ TDS coefficient, K × 10 3/ Cl coefficient, K/Br coefficient and γ Mg/ γ Cl coefficient 10.
3. coordinate according to claim 1, is characterized in that: represent Br with horizontal seat -content, ordinate represents ion ratio coefficient value, employing be log-log coordinate.
4. ion ratio coefficient locus line according to claim 1, it is characterized in that: in evaporation of seawater process before ion is with salt deposit, ion ratio coefficient locus line is in the horizontal line being parallel to horizontal ordinate, and after ion is with salt deposit, trajectory just departs from horizontal line.For γ Na/ γ Cl coefficient locus line, in evaporation of seawater process before halite deposition, its trajectory is a horizontal line, after arriving halite deposition, due to Cl -and Na +particularly Na +the minimizing of content, its trajectory departs from horizontal line and reduces gradually.
CN201510059689.XA 2015-02-05 2015-02-05 Manufacturing method of ion proportionality coefficient trajectory of seawater evaporation experiment Pending CN104678073A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105158426A (en) * 2015-07-22 2015-12-16 中国地质大学(北京) Making method for ion content trajectory in seawater evaporation
CN113281285A (en) * 2021-06-25 2021-08-20 中铁二院工程集团有限责任公司 Carbonate rich in Ca2+Balance determination method and tool for regional hydrothermal system

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CN101850991A (en) * 2010-01-14 2010-10-06 河北工业大学 Method for preparing potassium chloride from seawater
CN101928828A (en) * 2010-09-25 2010-12-29 西安蓝晓科技有限公司 Method for extracting lithium from salt lake brine by adsorption method

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JPS55157376A (en) * 1979-05-25 1980-12-08 Kinkai Kaisui Kogyo Kk Desulfurization of brine obtained by evaporation of seawater
CN1114288A (en) * 1994-06-28 1996-01-03 杨桂芳 Process for producing table salt by separating high-temp. salt using brine as carrier
CN101850991A (en) * 2010-01-14 2010-10-06 河北工业大学 Method for preparing potassium chloride from seawater
CN101928828A (en) * 2010-09-25 2010-12-29 西安蓝晓科技有限公司 Method for extracting lithium from salt lake brine by adsorption method

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105158426A (en) * 2015-07-22 2015-12-16 中国地质大学(北京) Making method for ion content trajectory in seawater evaporation
CN113281285A (en) * 2021-06-25 2021-08-20 中铁二院工程集团有限责任公司 Carbonate rich in Ca2+Balance determination method and tool for regional hydrothermal system
CN113281285B (en) * 2021-06-25 2023-02-21 中铁二院工程集团有限责任公司 Carbonate rich in Ca 2+ Balance determination method and tool for regional hydrothermal system

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