CN108525642A - A kind of modified glauconite and its preparation method and application - Google Patents
A kind of modified glauconite and its preparation method and application Download PDFInfo
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- CN108525642A CN108525642A CN201810594957.1A CN201810594957A CN108525642A CN 108525642 A CN108525642 A CN 108525642A CN 201810594957 A CN201810594957 A CN 201810594957A CN 108525642 A CN108525642 A CN 108525642A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/165—Natural alumino-silicates, e.g. zeolites
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
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Abstract
The present invention relates to a kind of modified glauconites and its preparation method and application.The modified glauconite roughing sand is obtained by heating, crushing, dedusting and magnetic separation.Using obtained modified glauconite as main component, glauconite roughing sand is better than to wastewater treatment efficiency.
Description
Technical field
The present invention relates to a kind of water treatment agents of heavy metal contaminants, and glauconite and catalysis are modified more particularly, to containing
The heavy metal contaminants inorganic agent of its suction-operated compound.
Background technology
The increasingly deterioration of social environment, larger pressure is brought to city.In order to realize the sustainable development in city,
The strategy of sustainable development is proposed out.Especially in the processing of city domestic sewage, strengthen the technical office of city domestic sewage
Reason, improves the utilization ratio of water resource.Sewage disposal cause become city water resource administer emphasis, while be also urbanization into
The important content of journey, it is not only directly related to people’s lives problem of water consumption, more with The Surroundings in Cities improvement have it is close can not
The relationship divided.
From the 1960s, the former Soviet Union, the U.S., Japan and other countries have successively started magnetic treatment technique research heat, but
Never what breakthrough progress is also in the delay stage to its research.Since the 1980s, due to the skill
Art has certain achievement in terms of physical therapy, causes the concern of scientist again, to magnetic treatment technique at the beginning of the nineties big rule
It is applied to petroleum industry to mould, and achieves good benefit.Expanding rapidly with magnetic treatment application field in recent years, at magnetic
Reason technology is also focused on by ore dressing professional in mineral manufacture field, they pay close attention to the magnetic treatment mechanism of action in terms of ore dressing
Research starts to develop to the research direction for effectively utilizing magnetic field energy and magnetic field-intensification ore dressing mechanism.Mineral resources are can not be again
Production-goods source increases into the refractory ore quantity in ore dressing plant as the easy ore dressing of high-grade is gradually decreased, how to develop profit year by year
Become the important topic for selecting smelting now with these refractory ores.In order to recycle valuable constituent from refractory ore, need using multiple
Miscellaneous technique.Magnetic treatment technique integrates physics chemical action, need not generally add medicament in processing procedure, therefore do not deposit
In toxic and secondary pollution problems, and magnetic treatment technique using convenient, small investment and is easy shielding.By magnetic treatment technique with
Technique of preparing interpenetrates, collective effect is to strengthen aeneficiation effect, and carries out systematic research to these technologies, can make the best use of the advantages and keep away
It is short, play the advantage of multidisciplinary, more technologies.Magnetic treatment technique is introduced into mineral process and will be helpful to Mineral Resources in China
Comprehensive utilization and effectively recycling.
The basic theories of magnetic treatment technique：Scientific research personnel is from various micromodels are established, to magnetic from molecular level
The mechanism of processing effect has carried out a large amount of research with effect, makes great progress.Recent domestic is to magnetic field effect
The mechanism for acting on flotation has carried out a large amount of research.Currently mainly there are several hypothesis below and deduction.
Lorentz force action：Being mutually shifted for water and magnetic current, can generate induced current, under the action of Lorentz force,
The hydrone of low pole and the charged ion of other impurities make counter motion.During being somebody's turn to do, negative ions or particle mutually collide
It is formed a certain number of " ion association bodies ", this association body has enough stability, forms a large amount of crystallization in water
Core is present in using these crystal as what the suspended particulate of core can be stablized in water.
Polarization：The polarization in magnetic field makes the crystallised component of salt be changed.Particulate polarity enhances, cohesion
Power weakens, and so that original longer associated molecule chain is truncated for the deformation of shorter associated molecule chain and charged ion, breaks
It is broken interionic electrostatic attraction, changes crystallization condition, forms the stabilization small crystals of dispersion.
Hysteresis effect：Magnetic field causes the hysteresis effect of the magnetic couple of salt molecule or ion in water, changes salt and exists
The mutual compatibility (crystallinity) of dissolubility and salt molecule in water, prevents big crystal structure.
Magnetic torque reorientation：In the reaction of certain group, magnetic field influences magnetic torque reorientation pairs of in group,
Intermediate mechanism in this way and influence other chemical reactions.Kinetics is changed, and is newly obtained in reaction result
Proportionate relationship between product is also changed.
Hydrogen bond deforms：After dipole polarization effect occurs for the dipole molecule of Magnetic Field on Water, electron cloud can change, and cause hydrogen
The bending of key and local fracture make the quantity of single hydrone increase.These hydrones occupy each gap of solution, can press down
The formation of combinations body, and the overall performance of water is made to change.
Activation energy changes：The influence in magnetic field and the conversion of system are related.Although the energy that water is obtained in magnetization is seldom,
But there are one " energy barriers " between starting and terminate in systems, to overcome this energy barrier that must convey corresponding energy to system
To trigger activation energy.The effect of magnetic field short time plays a part of " being catalyzed " change of water system activation energy, eventually leads to whole system
The variation of property.
Above-mentioned several theories explain the mechanism of magnetic treatment technique from different aspect, but due to the reason of magnetic treatment technique
It is for a long time, either domestic or external by the not perfect property with laboratory study, also to the mechanism study of magnetic treatment technique
Be in the continuous alternate stage of demonstration and hypothesis, do not formed complete set, effective magnetic treatment technique rule with it is theoretical.
With magnetism, chemical analysis is closely related with the structure of matter, and magnetization effect can all occur in magnetic field for any substance
It answers.Certainly, it refers to that the substance interior energy being magnetized is changed that substance, which is magnetized, and magnetization can not make substance become magnetic material
Matter.Flotation and chemistry leaching mine are to recycle the most basic method of mineral, if introducing magnetic field in flotation and in leaching, we just have
It hopes and sorts effect in strengthen mineral using magnetic treatment technique.Just had to be combined magnetic method with other isolation technics in the past and answer
With especially being combined the appearance for resulting in magnetic gravity treatment with gravity separation method.As its name suggests, magnetic flotation is a kind of mutually to tie flotation with magnetic separation
The process integration of conjunction.Magnetic treatment technique is applied to flotation, and the object of main function is exactly flotation water, ore pulp and liquid medicine body
System.Some researches show that water can generate apparent physicochemical change after magnetization, and the conductivity of water improves 2%；PH improves 0.4
~1.0；Reduction in surface tension 1%~2%,
The infiltration angle of solid matter is increased, wetting capacity enhancing, evaporation rate improves；The solubility of some salts is carried
It is high by 20%~70%；Water penetration pressure improves 1.34 times；Dissolved oxygen amount increases by 3~6mg/L, it is seen that water system environment is changed after magnetic water
.According to Faraday's electromagnetic theory, when conductor makees cutting magnetic line movement by magnetic field under external force, charge will produce
With the electromotive force for making charge movement, the physical changes such as electric current, potential difference are then just produced in conductor, then produce electric energy.
When the conductor of cutting magnetic line is a branch of aqueous solution for having certain speed to flow, having certain electric conductivity, in flow
Also it is bound to that above-mentioned variation occurs, at this moment it may be said that water system is magnetized.But the complicated mechanism of magnetization treatment, influence magnetic
The factor for changing effect is also very much, so carrying out mechanism study to magnetization treatment, there is also many difficulties.
The many professionals of recent domestic have carried out a large amount of experimental study, have accumulated a large amount of test data and reality
Border experience provides some valuable models.It summarizes below to some achievements in research.
Magnetization floatation metallic ore：Magnetic treatment flotation refers to that water system changes the electrical of mineral surfaces after magnetic fields, is promoted
Into the interaction of medicament and target minreal, desired change is reached to target minreal and non-target minreal, to carry
Recycling of the height to mineral.The T Yales of Canadian Lao Lunqin are pungent, using a kind of test-type weak magnetic concentration equipment, to magnet
The synthetic sample of mine-quartz composite ore and a kind of typical magnetic iron ore have carried out conventional flotation, conventional magnetic separation and magnetic flotation
Contrast test (flotation at this use be reverse flotation process).Test result shows that magnetic flotation technique is floating better than conventional
Choosing and conventional magnetic separation process.He also proposes that the essential condition to take effect to certain ore magnetic flotation techniques is intended in the ore of separation
Mineral should be variant in magnetic and flotation, and magnetic mineral is preferably provided with lower flotation speed.Also studies have shown that floating
Choose the surface tension that application magnetic field can make liquid that significant change, under the conditions of certain magnetic field, the surface tension of liquid occurs
It is increased.The increase of the mineral wettability energy of flotability difference is less than the increase of the good mineral wettability energy of floatability energy
Amount.By the floatability research to pyrite and chalcopyrite it is found that magnetic treatment can increase the difference of chalcopyrite and pyrite floatability
It is different, increase the surface tension of solution, increase the wetability of mineral, to expand the hydrophobic difference of chalcopyrite, pyrite.And
And magnetic treatment can increase absorption of the inhibitor on Pyrite Mineral surface, substantially reduce the absorption of Pyrite Mineral surface xanthate
Amount.Promote the formation of hydrophilic component, expands the difference of copper two kinds of mineral floatabilities of sulphur.The ore dressing plants Tang Dan use house type magnetic-type magnetic water
Device handles flotation water, small-sized with the processed water flotation cupric oxide ore of magnetic processor compared with the hard water of unmagnetized processing
The concentrate copper recovery of experiment improves 2%~3%.Have an impact to flotation to verify magnetization, the researchs such as Wang Qiufeng magnetization is yellow
Medicine is to PbS, ZnS, FeS2The influence of flotation.The result shows that magnetization xanthate significantly enhances the flotation of mineral.For PbS and
For ZnS, when xanthate dosage is 1.5 × 10-5When mol/L, magnetization and unmagnetized have a long way to go, and the PbS rate of recovery improves 15%,
And the rate of recovery of ZnS improves 23%, for FeS2, when xanthate dosage is 6.24 × 10-5When mol/L, magnetization xanthate with it is non-magnetic
Change xanthate to compare, the rate of recovery improves 20%.These experimental datas effectively demonstrate magnetization medicament and are conducive to PbS, ZnS and FeS2
Floating.Ke Washefu discovery magnetic pretreatment floating copper ores use water in magnetic induction intensity≤3.6T, and the rate of recovery of copper carries
It is high by 1%~6%.Magnetization ore pulp can equally increase the rate of recovery of copper, but magnetize medicament just not certain rule.Have very
More people have studied influence of the magnetization floatation to iron mineral, and belotecan assorted (BeloshEN) is using natural pure bloodstone, magnetic iron ore and vacation
As the ore pulp of bloodstone is in various field strength, test result shows：Magnetic field processing ore pulp improves the floatability of iron oxide ore.
Strange gold (ChikimYum) has studied the preceding magnetic field pre-processing titanium iron ore of flotation and magnetic iron ore mixture, as a result also indicates that the pre- place of magnetization
Reason significantly improves flotation effect.Magnetic treatment technique acts on scheelite ore dressing, also achieves certain effect.By measuring mine
The electrokinetic potential on object surface, medicament have studied influence of the magnetic field to Scheelite Flotation rate in the adsorbance of mineral surfaces.Research knot
Fruit shows that magnetic field promotes absorption of the collecting agent in mineral surfaces, improves flotation rate, moreover it is possible to simplify flowage structure.The author
When studying the mine of multi-metal oxygen containing gold and silver, conventional flotation is carried out and has added the contrast test of magnetic field flotation, test result is found
In the case where gold and silver concentrate grade is held essentially constant, the golden rate of recovery improves 5%, and the silver-colored rate of recovery improves 2%.
The researchs such as magnetization floatation nonmetallic ore bear man of virtue and ability power find that magnetization treatment coal slime ore pulp can improve the floatability of coal, add
The difference of big wetability between coal and gangue, pyrite, is conducive to the effect for strengthening coal slime flotation desulfurization and deashing.And
According to test result, show that coal slurry can also improve its strainability after magnetic treatment.Main cause, which is magnetic treatment, can reduce object
Expect surface potential, change the granularmetric composition in slurry system, the surface area for keeping solid particle total is reduced, and grain size increases, and improves object
The strainability of material reflects onto dehydration equipment, can improve its dehydration efficiency, there is certain prospects for commercial application.Bian Ping Xin etc.
Following 3 conclusions are proposed by studying influence of the magnetization treatment to flotation pulp property.1. magnetization treatment can cause ore flotation
Starch the variation of oxygen content, pH value, surface Zeta potential and the heat of wetting；The property (magnetism) of water and mineral grain can be to flotation pulp
Magnetization effect has an impact.2. magnetization treatment flotation pulp improves the floatability of coal, increase coal and gangue, pyrite it
Between wetability difference.3. magnetization treatment can promote light diesel fuel in the fixed degree on coal surface, weaken light diesel fuel to gangue and
The collecting of pyrite acts on, and improves the selectivity of light diesel fuel, is conducive to the effect for strengthening coal slime flotation desulfurization and deashing.Using
Na2CO3、Na2SiO3, some conventional doses such as oleic acid and alum, magnetic treatment Oxidized copper ores have been carried out to fluorite.Result of study table
It is bright, fluorite and quartzy FLOTATION SEPARATION structure can be simplified using magnetic treatment technique, strengthen the inhibition to quartz, improve quartzy flotation
With drop silicon effect.Zhu Jujian etc. has studied flotation medium water after magnetization treatment, the variation of quartzy Floatation Rate and PH values
Relationship and its mechanism of action, experimental study show that magnetization treatment can be such that quartzy Floatation Rate reduces, make Ca2+To quartz
Activation capacity reduces, it is believed that the reason of generating above-mentioned variation is the mean kinetic energy that magnetization treatment increases hydrone, weakens water
Dispersion force, induction force between molecule and dipole-dipole force reduce quartz to H+The steric effect of absorption, makes Ca2+In quartz surfaces
Competitive Adsorption it is more difficult, to make Ca2+The activation capacity of quartz is minimized.
The result of study of above-mentioned magnetic treatment metallic ore and nonmetallic ore all demonstrates magnetization treatment ore pulp, medicament, water system etc.
Really may advantageously facilitate mineral sorts separation.But in flotation of ore pulp magnetization treatment act on it is effective with it is invalid, two kinds relatively
Vertical idea happens occasionally.Such as the pungent magnetized water of carat research shows that magnetic treatment can make water in structure, density and wetability
It changes.Bar sodium husband is drawn to think that magnetized water changes the content of suspended matter, magnetic conductivity, the electromotive force of mineral and some mineral
Flotation rate.And the impurity that Calvi sharp (CalverleyRA) then proposes in the effect and ore pulp of magnetic treatment flotation of ore pulp has
It closes, and it is impossible that a kind of impurity all exists in any ore, the extensive magnetic treatment condition used in the former Soviet Union makes karr
Wei Li thinks to test difference and different field strength, flow velocity are unrelated.He thinks that magnetization treatment water is not that be one kind of mineral floating have
The approach of effect.Bohumil Kubát about C1-esteraseremmer-N by experiment obtain the result is that magnetized water or solution do not change density, viscosity and
Resistance.Bar sodium husband is drawn to be also considered as the content that magnetization does not change the result and gas in water of water from essence, also without change water
Specific heat, therefore the physico-chemical property of water does not change.It is believed that conclusion should be unique on certain level
, and largely experiment and data prove that magnetization can promote the flotation of mineral really.But if magnetization really enhances mine
How the floatability of object is strengthened on earth, what kind of the rule, the theoretical foundation of reinforcing of its reinforcing is againThis just needs
It is studied in our scientific research personnel are further.
Application of the magnetic treatment technique in Chemical Leaching is as magnetization floatation, if magnetic treatment technique is referred to chemistry
In extract technology, just claim magnetic treatment Chemical Leaching technique.Currently, being concentrated mainly on gold, silver to the research of magnetic treatment Chemical Leaching
In terms of the leaching mine of equal precious metal ores, also there are the research of document report in other aspects, such as magnetic treatment leaching bismuth, leaching arsenic certainly.
The research that domestic and international some magnetic treatments in recent years are applied to extract technology has been summarized below.
Under conditions of rare earth mother solution is added in ammonium bicarbonate soln, fixed magnetization time 40min, experiment proves different magnetic
It is different to the influence degree of rare earth to change intensity, is 600kA/m in the intensity of magnetization, and carry out the magnetic of magnetic treatment to entire precipitation system
Effect is best when change mode, under Optimum magnetic intensity magnetic treatment can make rare-earth precipitation object purity improve 3%~4%.The work
Person thinks that the process that magnetic treatment influences rare earth crystallization mainly has both sides reason, first, crystallization kinetics of the magnetic treatment to solution
It has an impact, under the conditions of suitable magnetic treatment, carbonated rare earth can be obviously promoted, crystalline substance is changed by unformed flocculent deposit
Type precipitates.Second is that magnetic treatment has an impact the parameter of aqueous solution, to promote carbonated rare earth to be easy to form nucleus.Have according to foreign countries
Research is closed under high-energy magnetic impulse action, since the bond strength between lattice in mineral constituent weakens, is formed in ore very much
Microfissure is conducive to cyanide solution and penetrates into the particulate dip dyeing goldc grains of the mineral that cure, quartz and other mineral package.By
Golden leaching rate improves in the exposure and dissolving of this difficult form gold, leaching process.It is pre- using magnetic field impulse before cyaniding
Processing can improve the cyaniding process of gold ore.For the various raw mineral materials studied, with the material composition and gold of ore
Occurrence status it is different, golden leaching rate improves 0.6%~9.0%.Magnetic field impulse pretreatment is not only efficient, but also low energy consumption
(0.5kW·h/t).The main technique of many golden ore dressing plant processing gold ores of Russian and CIS country and concentrate is cyaniding
Method, while Russia is also that research magnetic treatment technique is national earlier.Russian center non-ferrous metal and noble metal geological prospecting
The result of study that Science Institute and Center Of Technical Excellence are completed shows that magnetic field impulse pretreatment has the raising of gold ore cyaniding rate
Play the role of.Such as：Mineral deposit quartz-feldspar gold containing ore (contains Au:20.5g/t) when cyaniding, after magnetic field impulse processing, golden leaching
Extracting rate improves 0.5%~2.0%；Gold extracting shop currently exploits quartz-feldspar gold ore, gold grade 12.1g/t, in ore
Containing a small amount of carbonate mineral and gold-containing sulfurating mineral, ore dressing plant is exactly to handle this ore using cyaniding.Magnetic field impulse is located in advance
Influence of the logos to ore cyaniding the result shows that, golden leaching rate improves 3.0%~4.0% after magnetic field impulse pretreatment.In ore dressing
Factory's Gold Concentrate under Normal Pressure (contains Au:44~47g/t) the pretreated test result of cyaniding process application magnetic field impulse show magnetic field impulse pre-process
Afterwards, golden leaching rate improves 1.0%~1.5%.In difficult concentrate selection cyaniding, the leaching of gold can be improved in the pretreated application of magnetic field impulse
Extracting rate 9.0%.
Show that magnetic treatment technique is applied to extract technology from above-mentioned obtained data information, concentrate recycling can be improved
Rate increases economic benefit.In summary the example of magnetic treatment illustrates that magnetic treatment technique has in mineral processing and widely answers
With feature is mainly：1. it is fast, efficient to handle ore pulp, water and medicament speed, the effect of medicament and target minreal can be accelerated
Speed, quickening sort speed；2. magnetic treatment technique can enhance the otherness of mineral surfaces property, increase mineral sorts effect
The otherness answered is conducive to the grade and the rate of recovery that improve target minreal.
Invention content
One of the objects of the present invention is to provide a kind of water treatment agents of heavy metal contaminants.
The heavy metal contaminants inorganic agent group containing catalyst compounds that another object of the present invention is to provide a kind of
Close object.
Another object of the present invention is to provide the catalyst compounds of catalytic adsorption rate.
Further object of the present invention is to provide the purposes of above-mentioned catalyst compounds.
The present invention is achieved through the following technical solutions：
A kind of modified glauconite, the modified glauconite are prepared by heating, crushing, dedusting and magnetic separation.
Preferably, the mode of heating is microwave heating method, infrared heating method or contact heating, the heating temperature
It is 180-700 DEG C, preferably 300-400 DEG C；
The grinding mode is mechanical crushing, ultrasonic grind, resonant frequency crushes, temperature contrast crushes or cavitation effect
It crushes；
The magnetic separation mode is using ore magnetic separator.
Wherein, the step of preparing modified glauconite further includes 5 microns of glauconites below of screening, preferably screen 1 micron with
Under glauconite.
The preparation method of the modification glauconite, includes the following steps：
The modified glauconite is prepared by heating, crushing, dedusting, magnetic separation and screening；
The mode of heating is microwave heating method, infrared heating method or contact heating, and the heating temperature is 180-
700 DEG C, preferably 300-400 DEG C；
The grinding mode is mechanical crushing, ultrasonic grind, resonant frequency crushes, temperature contrast crushes or cavitation effect
It crushes；
The magnetic separation mode is using ore magnetic separator；
5 millimeters of glauconites below are screened, 1 millimeter of glauconite below is preferably screened.
A kind of water treatment agent of heavy metal contaminants contains the modification glauconite, quartz, muscovite, feldspar, boiling
Stone, chlorite and catalyst compounds.
Preferably, modified glauconite is 15-25 parts by weight, quartz is 50-70 parts by weight, muscovite 5-10 parts by weight, length
Stone 5-10 parts by weight, zeolite 2-6 parts by weight, chlorite 0.5-1 parts by weight, catalyst compounds 0.1-0.2 parts by weight；
Wherein, the catalyst compounds are as follows：
A is selected from following structures：
R is independently selected from H, halogen, hydroxyl, C1-C6 alkyl, C2-C6 alkenyls, C2-C6 alkynyls, C3-C8 naphthenic base, C1-
C6 alkoxies, C3-C8 methyl cycloalkyls, the C1-C6 alkyl of halogen substitution, the C1-C6 alkyl of hydroxyl substitution, alkoxy substitution
C1-C6 alkyl, the C1-C6 alkyl of amino substitution, C6-10Substitution or unsubstituting aromatic yl contain 1-4 originals miscellaneous in N, O and S
The 5-10 members substitution of son or unsubstituting heterocycle, the C1-C6 alkyl of alkyl amine group substitution, nitro, cyano ,-OR1,-N (R1)2,-
SR1,-C (O) OR1,-C (O) N (R1)2,-C (O) R1,
-S(O)R1,-S (O)2R1,-S (O)2N(R1)2,-N (R) C (O) R1；
R1Independently selected from H, C1-C6 alkyl, C2-C6 alkenyls, C2-C6 alkynyls, C3-C8 naphthenic base, C3-C8 naphthenic base first
Base, the C1-C6 alkyl of halogen substitution, the substitution C1-C6 alkyl of hydroxyl, the C1-C6 alkyl of alkoxy substitution, amino substitution
C1-C6 alkyl, the C1-C6 alkyl of alkyl amine group substitution, C6-10Substitution or unsubstituting aromatic yl, containing 1-4 selected from N, O and
Heteroatomic 5-10 members substitution or unsubstituting heterocycle in S.
Preferably, R be selected from H, chlorine, bromine, hydroxyl, C1-C6 alkyl, C2-C6 alkenyls, C2-C6 alkynyls, C3-C8 naphthenic base,
C1-C6 alkoxies, C3-C8 methyl cycloalkyls, the C1-C6 alkyl of halogen substitution, the C1-C6 alkyl of hydroxyl substitution, alkoxy take
The C1-C6 alkyl in generation；Preferably, R is selected from chlorine, C1-C6 alkyl, C1-C6 alkoxies；It is highly preferred that being selected from following compounds：
Preferably, the grain size of each component is 0.1-5 microns, more preferable 1 micron or less.
Modified glauconite has some particular features, embodiment of these attributes actually to glauconite mineral self-organizing process
Have with development decisive.They are listed below：
There is colloidal dispersion so as to cause high-hydrophilic with polymolecularity, can be formed when infiltrating glauconite and determine it
The molten gel phase of cohesion adhesion has the plasticity as natural adhesive material；
With all buffering sexual factors specific to this rocks, these buffering sexual factors ensure or control glauconite is steady
Surely it is present in its specific pH value section, and the pH value section of medium depends on the material composition and crystal structure of mineral；
Physical and chemical activity with glauconite height shows as the absorbability synthesis of high adsorption capacity and existence component complexity
Body.
It is horizontal with the distinctive nature pH of glauconite, the reason is that glauconite contains readily soluble and salt, humus and corruption of indissoluble
Phytic acid also contains organic compound on the basis of them for having an impact rock medium reaction；
In the case where humidity is constant, restore the ability (thixotropy) of cataclastic structure with spontaneous isothermal, this is self-organizing
The reason of practical embodiment of process, this is the most representative attribute of glauconite, causes this characteristic is then dispersion and molten
Gel phase mutually converts；
According to intrinsic initial configuration (genetic code), glauconite has power of regeneration.
Process the best-of-breed technology of natural magnesium ferrosilicate：Double layer dry electromagnetic separation method, the method use non-standard ore
Processing method and chemical thermal activation step, to improve the adsorptivity and chromophore characteristic of glauconite.(nitrogen low adsorption method) is had proven to,
When carrying out chemical activation to glauconite, Kong Rong, specific surface area and porosity will improve 20%.According to the technology system worked out
At industrial products, such as pigment, adsorbent, mineral fertilizer with higher performance.It has been demonstrated that, new fertilizer raw material is in economy
Worthwhile 1.5-1.7 times more more economical than existing raw material in parameter；Their production process significantly reduces the shadow to ambient enviroment
It rings.
The application of glauconite through overactivation/improvement：The regeneration of sewage is not directly to be realized by chemical reagent,
But the alumo silicate matrix of the hydrolysis by specially preparing, the i.e. molten gel systems of the mineral matrices of polydispersity, specific table
Existing form is activated adoption cream, with dilution of sewage activated adoption cream, obtains activated adoption suspension.Gained suspension is introduced into simultaneously
It is dispersed in equipped in the whole container that need to purify liquid.At the same time, the chemistry to pollutant generated through solution is inhaled
Attached effect, and form the sediment harmless to ecology.Clarification is carried out to processed activated adoption suspension and needs 20-30 points
Clock.Sediment has lower hydrophily, sticky and higher drainage.Next it (is acted on strongly, so in round the clock in preceding 2-3
Weaken gradually afterwards) self-organizing process-sediment consolidation occurs in sediment.
About from pollutant the physical chemistry essence of the new method of purified water be presented below.By activated adoption suspension
When being mixed with the liquid that need to be purified, chemisorption occurs and absorbs the pollutant in molten gel phase and polydispersity mineral matrices, it is more
Dispersed mineral matrices are made of corase particles, fine particle and colloidal dispersions particle.According to the suppression of known Le Chatelier's principle
System resists principle, and mineral matrices can do one's utmost to restore the original chemical equilibrium state of oneself, and this point will lead in this case
The process of " reduction " mineral formation manually caused is crossed to realize.Water-proof aluminium silicate-base in " early diagenesis " state
The steady state of initially Jie of body promotes all types of chemism pollutants that process mentioned above is added.So according to upper
Text mention during mineral intergrowth genetic code, with decentralized medium active constituent interact during, decentralized medium meeting
It is subjected to corresponding phase transformation.The listed characteristic about mineral matrices chemisorption water pollutant (being heavy metal first) process is said
It is bright to be obtained by cementing material blending theory in a dispersion medium.Therefore, with the new struggle side of ambient contaminants
Case is substantially mineral associations property.
One important feature of the mineral matrices chemisorption techniques studied is the advantages of it has both known method (chemistry
Reagent method-yield is high, and adsorbent method-depuration quality is high), to eliminate its intrinsic disadvantage.At the same time mineral matrices
It learns adsorption technology to can be applied not only to specifically for the factory equipped with fixed cumbersome apparatus, the water for applying also for polluted-water is net
Change.And the activated adoption suspension that application is specially prepared enough becomes cloudy the water for needing purification in pond.What clarification need to purify
The water of (becoming cloudy) will continue 1-2 hours, and (the suspension liquid energy made of natural clay is kept for dozens of hour at this time, or even very
It is multiple round the clock, such as the suspension made of montmorillonitic clay).The condition for the High-speed clarification muddy water being indicated above is that activity is inhaled
High dispersive particle in attached suspension, which is in, to be born in molten gel phase cohesion and the state of flocculation.
The reuse of wastewater new method is known as very high economy, because activated adoption cream dosage is relatively low (it is recommended that ratio
Example-solid：Liquid phase 1:400-1:1000 or higher, depend primarily on the degree of water pollution), and inexpensive (its valence
Lattice unlike building mortar height, several times less than needed for the methods of chemical-agent technique, adsorbent method or electrocoagulation chemical agent or
The expense of electric power).In addition to this with known purification method unlike, obtained by mineral matrices chemisorption techniques
Sediment is environmentally friendly, need not use special landfill measure.
Embodiment
Below by embodiment, the invention will be further described.It should be understood that the method for the embodiment of the present invention
It is only used for illustrating the present invention, rather than limiting the invention, to preparation side of the invention under the concept thereof of the present invention
The simple modifications of method belong to the scope of protection of present invention.All raw materials and solvent used in embodiment are commercially available production
Product.
The preparation embodiment of catalyst compounds：
Embodiment 1：
1,2,4,5- benzene tetramine, four hydrochloride (20mmol), 100mL glacial acetic acid and sodium acetate are added in the reaction vessel
The Bisdemethoxycurcumin (41mmol) being dissolved in 50 milliliters of glacial acetic acid is slowly added dropwise in (40mmol), stirring, and reflux is anti-
It answers, TLC monitoring reactions.It after reaction is completed, is cooled to room temperature, with saturation NaHCO3Solution adjusts pH about 8, is extracted with dichloromethane
It takes three times, merges organic layer, MgSO4Dry, absolute ethyl alcohol recrystallization obtains the following formula: compound of yellow powdery solid, receives
Rate 76%.
1H NMR(400MHz,DMSO)δ9.68(s,OH,4H),7.64(d,H,4H),7.45(s,CH,8H),6.95(d,
H,4H),6.75(s,CH,2H),6.59(d,H,8H),2.97(s,CH2,4H).
Embodiment 2：
Sequentially added in dry reaction vessel compound (5mmol), chlorobenzoyl chloride (21mmol) described in embodiment 1 and
Toluene solution (100mL).Stirring, back flow reaction, TLC monitoring reactions are to terminating.It is cooled to room temperature, reaction system is poured into ice water
It in system, filters, solid ethyl alcohol recrystallization is dried to obtain following compounds of sheet white solid, yield 62%.
1H NMR(400MHz,DMSO)δ8.16(t,CH,8H),7.72(t,CH,4H),7.69(m,CH,8H),7.64(d,
H,4H),7.62(m,CH,8H),7.36(m,CH,8H),6.95(d,H,4H),6.75(s,CH,2H),2.97(s,CH2,4H).
Embodiment 3：
With the reaction step and condition similar to embodiment 2, chlorobenzoyl chloride is replaced with into corresponding chloroacetic chloride raw material, is prepared
Following compounds, yield 66%.
1H NMR(400MHz,DMSO)δ7.64(d,H,4H),7.62(t,CH,8H),7.28(d,CH,8H),6.95(d,
H,4H),6.75(s,CH,2H),2.31(s,4CH3,12H),2.97(s,CH2,4H).
The preparation embodiment of modified glauconite
50 kilograms of glauconite roughing sand is crushed, dedusting at about 350 DEG C by microwave heating on kibbler roll.Then
Under different magnetic field induction, sample is claimed to carry out magnetic sorting to sample by leakage on roll-type magnetic separator.Meanwhile in higher
Under induction, next step sorting is carried out to the non magnetic product of low induction.
Material, which is placed into kibbler roll, carries out break process to sift out the sample material that grade is less than 0.5 millimeter.Grain
Grade more than 0.5 millimeter of material after broken and classification processing at frangible or be easier broken mineral aggregate,
Wherein contain a small amount of glauconite and granite stones.After processing, 2 staged magnetic separations are carried out on technique sample material.
In the vibrating screen Ultimate Screener of Kroosh technologies Ltd companies of Israel research and developmentTMIn it is right
Coarse fraction material is sieved (1500 х 500 of model ULS).The material of -20+10 millimeters of grades can pass through 0.5 milli completely
The net of rice, and the material of+20 millimeters of grades cannot pass through.So the material of this grade is crushed in crusher, so
It is sieved afterwards according to 0.5 millimeter particle grade.
The preparation embodiment of inorganic agent
Inorganic agent embodiment 1：
By 21 grams of glauconite, 59 grams of quartz, 7 grams of muscovite, 8 grams of feldspar, 4 grams of zeolite, 1 gram of chlorite and embodiment 1
0.1 gram of catalyst compounds, be processed into the particle of about 1 micron of grain size according to method well known in the prior art, preparation processing
Agent.
Compare inorganic agent embodiment 1：
By 21 grams of glauconite, 59 grams of quartz, 7 grams of muscovite, 8 grams of feldspar, 4 grams of zeolite, 1 gram of chlorite, according to existing skill
Known method is processed into the particle of about 1 micron of grain size in art, prepares inorganic agent.
Inorganic agent embodiment 2：
It will modified 21 grams of glauconite, 59 grams of quartz, 7 grams of muscovite, 8 grams of feldspar, 4 grams of zeolite, 1 gram of chlorite and implementation
0.1 gram of the catalyst compounds of example 1, are processed into the particle of about 1 micron of grain size according to method well known in the prior art, at preparation
Manage agent.
Wastewater treatment test：
1, waste water water sample：
Total row's saliva 1：From certain Lead And Zinc Smelter all rows mouth be collected to water treatment plant before front end waste water, i.e. water process
The waste water of factory's inlet channel.
Total row's saliva 2：Same inlet channel, waste water in different time periods are come from total row's saliva 1.
Lead waste water：The simulated wastewater of use for laboratory plumbi nitras configuration.
1 waste water water pollutant content of table and corresponding discharge standard (mg/L)
Note：As, Sb, Cd, Pb are used《Tin, antimony, mercury emission of industrial pollutants standard》(GB30770-2014)
Tl is used《Hunan Province's industrial wastewater thallium pollution object discharge standard》(DB43968-2014).
2, process and method are tested
2.1 total row's saliva 1 processing experiments
10L is always arranged to saliva 1 to pour into porcelain enamel barrel, staticly settles an evening.The supernatant that 500ml always arranges saliva 1 is respectively taken to set
In A beakers, water sample is obtained.It is about 7 to measure water sample pH with pH test paper.It weighs 6g sodium hydroxides to dissolve in 300ml water, be configured to
The sodium hydroxide solution of 0.5mol/L.Sodium hydroxide solution is taken with pipette, adjusts A beaker water sample pH to 7.5 or more.Use 100g
It compares inorganic agent embodiment 1, inorganic agent embodiment 1 and inorganic agent embodiment 2 and forms three self-control Filter columns, pillar height about 5cm.Point
Water sample in A beakers is not poured into repeatedly to three on a small quantity to filter, the filtrate after the completion of filtering is denoted as No. 1 sample, No. 2 samples respectively
With No. 3 samples.Analysis detection is carried out to arsenic, antimony, lead, cadmium, the thallium in No. 1 sample, No. 2 samples, No. 3 samples.
2.2 total row's saliva 2 processing experiments
By the water sample of total row's saliva 1, the water sample of total discharge outlet 2 is changed into.According to 2.1 similar experiment processes, at 100g
It manages agent embodiment 1 and inorganic agent embodiment 2 forms two self-control Filter columns, pillar height about 5cm.Filtrate difference after the completion of being filtered
It is denoted as No. 4 samples and No. 5 samples.
2.3 lead containing wastewater treatments are tested
It weighs 0.0173g plumbi nitras to be put into beaker H, dissolve in 1L water, be configured to the lead nitrate solution of 10.65mg/g.
It weighs 100g inorganic agents embodiment 2 to pour into self-control Filter column, pillar height is about 5cm.Lead nitrate solution was repeatedly poured on a small quantity
In filter column, the filtrate after the completion of filtering is denoted as No. 6 samples.
2 ion-exchanger wastewater treatment experimental result (mg/L) of table
Claims (8)
1. a kind of modified glauconite, it is characterised in that：The modified glauconite is prepared by heating, crushing, dedusting and magnetic separation
It arrives.
2. modified glauconite according to claim 1, it is characterised in that：
The mode of heating is microwave heating method, infrared heating method or contact heating, and the heating temperature is 180-700
DEG C, preferably 300-400 DEG C；
The grinding mode is mechanical crushing, ultrasonic grind, resonant frequency crushes, temperature contrast crushes or cavitation effect powder
It is broken；
The magnetic separation mode is using ore magnetic separator.
3. modified glauconite according to claim 2, it is characterised in that：The step of preparing modified glauconite further includes screening
5 microns of glauconites below preferably screen 1 micron of glauconite below.
4. the preparation method of any modification glauconites of claim 1-3, it is characterised in that include the following steps：
The modified glauconite is prepared by heating, crushing, dedusting, magnetic separation and screening；
The mode of heating is microwave heating method, infrared heating method or contact heating, and the heating temperature is 180-700
DEG C, preferably 300-400 DEG C；
The grinding mode is mechanical crushing, ultrasonic grind, resonant frequency crushes, temperature contrast crushes or cavitation effect powder
It is broken；
The magnetic separation mode is using ore magnetic separator；
5 millimeters of glauconites below are screened, 1 millimeter of glauconite below is preferably screened.
5. a kind of water treatment agent of heavy metal contaminants, it is characterised in that sea green containing any modifications of claim 1-3
Stone, quartz, muscovite, feldspar, zeolite, chlorite and catalyst compounds.
6. the water treatment agent of heavy metal contaminants according to claim 5, it is characterised in that modified glauconite is 15-25 weights
Measure part, quartz is 50-70 parts by weight, muscovite 5-10 parts by weight, feldspar 5-10 parts by weight, zeolite 2-6 parts by weight, chlorite
0.5-1 parts by weight, catalyst compounds 0.1-0.2 parts by weight；
Wherein, the catalyst compounds are as follows：
A is selected from following structures：
R is independently selected from H, halogen, hydroxyl, C1-C6 alkyl, C2-C6 alkenyls, C2-C6 alkynyls, C3-C8 naphthenic base, C1-C6 alkane
Oxygroup, C3-C8 methyl cycloalkyls, the C1-C6 alkyl of halogen substitution, the C1-C6 alkyl of hydroxyl substitution, the C1- of alkoxy substitution
C6 alkyl, the C1-C6 alkyl of amino substitution, C6-10It is substitution or unsubstituting aromatic yl, heteroatomic in N, O and S containing 1-4
5-10 members replace or unsubstituting heterocycle, the C1-C6 alkyl of alkyl amine group substitution, nitro, cyano ,-OR1,-N (R1)2,-SR1,-C
(O)O R1,-C (O) N (R1)2,-C (O) R1,-S (O) R1,-S (O)2R1,-S (O)2N(R1)2,-N (R) C (O) R1；
R1Independently selected from H, C1-C6 alkyl, C2-C6 alkenyls, C2-C6 alkynyls, C3-C8 naphthenic base, C3-C8 methyl cycloalkyls, halogen
The C1-C6 alkyl of element substitution, the substitution C1-C6 alkyl of hydroxyl, the C1-C6 alkyl of alkoxy substitution, the C1-C6 alkane of amino substitution
Base, the C1-C6 alkyl of alkyl amine group substitution, C6-10It is substitution or unsubstituting aromatic yl, heteroatomic in N, O and S containing 1-4
5-10 members replace or unsubstituting heterocycle.
7. the water treatment agent of heavy metal contaminants according to claim 6, it is characterised in that：R be selected from H, chlorine, bromine, hydroxyl,
C1-C6 alkyl, C2-C6 alkenyls, C2-C6 alkynyls, C3-C8 naphthenic base, C1-C6 alkoxies, C3-C8 methyl cycloalkyls, halogen take
The C1-C6 alkyl in generation, the C1-C6 alkyl of hydroxyl substitution, the C1-C6 alkyl of alkoxy substitution；Preferably, R is selected from chlorine, C1-C6
Alkyl, C1-C6 alkoxies；It is highly preferred that being selected from following compounds：
8. the water treatment agent of heavy metal contaminants according to claim 5, it is characterised in that：The grain size of each component is 0.1-
5 microns, preferably 1 micron or less.
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