CN107973442A - A kind of method of biological adsorption material and support type resin combination removing heavy metal - Google Patents
A kind of method of biological adsorption material and support type resin combination removing heavy metal Download PDFInfo
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- CN107973442A CN107973442A CN201711222204.XA CN201711222204A CN107973442A CN 107973442 A CN107973442 A CN 107973442A CN 201711222204 A CN201711222204 A CN 201711222204A CN 107973442 A CN107973442 A CN 107973442A
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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
- C02F9/00—Multistage 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
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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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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Abstract
A kind of method that the present invention provides biological adsorption material and support type resin combination removing heavy metal, the method absorbs heavy metal solution by biological adsorption material and nano particle support type resin composite materials, and the nano particle support type resin composite materials are concentrated with salpeter solution, return and load nano-zinc sulfide or the utilization of ferrous sulfide particle Posterior circle again, degraded is washed after biological adsorption material is leached residual heavy metal with nitric acid depth, realize deep purifying, the present invention solves biological adsorption and is difficult to the problem that engineering implements deep purifying, nano particle support type resin composite materials are significantly reduced frequently to desorb, regenerated number, the effective operation duration of absorption to resin material can play the role of good extension.
Description
Technical field
The invention belongs to nano material to adsorb heavy metal technical field, and in particular to a kind of biological adsorption material and support type
The method that resin combination removes heavy metal.
Background technology
The a class of pollutant such as heavy metal lead, cadmium, mercury, harm is obvious to all caused by environment.How efficiently, depth by its from
Removed in water body environment, for water resource recycle and the guarantee of people's life and health, all with very important meaning
Justice.The method of the heavy metals such as lead, cadmium, mercury in removing aqueous medium is very much, including the precipitation method, flocculence, absorption method, ion exchange
Method, membrane separation process etc., but it is low for concentration（It is ppm grades several）, the big purge cases of water, absorption is undoubtedly most competing
One of special technology of striving property.
Biological adsorption material is in aqueous medium in terms of the removing of heavy metal, with it is cheap, feature and the widely people such as efficiently
It is of interest, after the extensive research and development of nearly 30 years, although nowadays the biological adsorption material of real industrialization large-scale application is few
It is again few, but its reflected prominent cost advantage still makes us giving more sustained attention.One limitation biological adsorption material trend
The reason for industrial applications of generality, is, for the conventional separation techniques such as chemical precipitation, ion exchange, in its cost
Advantage be usually in secondary status because it is industrial no matter the application in terms of the depollution of environment, it wants the water purification of qualified discharge
Standard is more and more stringenter, almost so that biological adsorption, which rarely has, disposably economical to remove place up to standard.It is continuous to fill pillar
Change purification run, it is no doubt attractive, but this generally requires to be crosslinked and granulation is handled for vast biological adsorption material,
Thus sacrifice the advantage of its cost and adsorption capacity.Such Gao Bucheng, low awkward circumstances not, reflect really
Biological adsorption material is all the time where the birth defects of rare industrialization large-scale application.For that purpose it is necessary to further investigate,
Find a kind of application model or application scheme that can fully show the advantage of biological adsorption, and its advantage can be kept.By its with
The advantages that ion exchange resin is used in combination, and the cost for playing biological adsorption is low, capacity is big, absorption is fast, and ion friendship can be played
Change the advantages such as big, the continuous operation experience maturation of purification depth of resin pillar operation.But traditional ion exchange resin is general
Store-through is adsorption function is single, poor selectivity, small capacity the shortcomings of, it is therefore desirable to traditional ion exchange resin is explored new
The method for improving and improving its absorption property.
In recent years, nano material is people's favor as surrounding purifying material with its excellent, prominent purifying property
And extensive concern.But as people also draw the potential hazard of environment the deep understanding of nano ZnO, nano material
Deepest concern is played, so in reparation, environment purification, how effectively to play the positive effect of nano material, and it is latent to take precautions against it
Harm, be a very important thing really.Specifically, in water body purification, nano-oxide, sulfide, phosphoric acid
The excellent adsorption cleaning ability such as salt, is widely known.For example Imran Ali were in the Chemical Reviews of 2012
Delivered on 12 phase magazines《New Generation Adsorbents for Water Treatment》One text, is systematically introduced
The excellent properties of a variety of nano-metal-oxides, sulfide in terms of Water warfare；Chemical progress of the Li Liang et al. in 2017
On publish thesis《Nano metal sulfide adsorbent》, the nanometer sulfides such as ZnS, FeS, CuS, MoS2 are specially described to a huge sum of money
The adsorption effect of category, shows good application prospect；Ability of Pan third et al. is sent out on the J.Hazard. Mater. of 2012
Table paper《Heavy metal removal from water/wastewater by nanosized metal oxides: a
review》, review application performance of the Multimetal oxide nano material in terms of heavy metal adsorption.These work are undoubtedly all
Concern of the people for heavy metal pollution in nano material adsorption cleaning water is embodied, also embodies nano material in water body purification
The great potential of aspect.Nano material is so tiny, during for water body purification, how quickly and easily to divide it from water
Separate out, be unlikely to be trapped in water body and cause possible secondary environmental hazard, be a very real application obstacle.To solve
The problem, usually there is two kinds of resolving ideas, when by the basis material of nanomaterial loadings to magnanimity size, then can light mistake
Filter or sedimentation separation；It is another, it is that nano material is prepared into magnetic material so as to by magnetic separation.Prepared by magnetism can cause
Cost increase, and causes to interfere significantly with to absorption property, and for the experience accumulation on industrial practice it is still on the low side, therefore, and
It is not a solution that can generally consider.And loading rule has very big optional space, it can provide the base of load
Body material has biological adsorption material, activated carbon, charcoal, inorganic mineral porous material even sand etc., is multifarious, but
It is that the consistency of performance from support materials, stability, the practical operating experience of Industrial Engineering etc. carry out integrated survey, these materials
Expect to also have from practical application needs to cross over a distance from no small.Comparatively speaking, ion exchange resin then has very as support materials
Good industrial applications potentiality to be exploited, for aforementioned various support materials, its industrially ripe operation
Experience, ripe production technology and corollary equipment and Industry Control design etc. all have unrivaled advantage.This side
The research in face and commercial Application are many, embody the good application prospect of the mentality of designing.In contrast, metal oxide
Nanosizing material load polymer matrix composites research and development it is very much, and sulfide nano-material loaded resin based composites
Research and development are then less.And the huge superiority and potentiality that sulfide nano-material is shown in terms of heavy metal adsorption, actual value
It must further investigate and promote industrial applications to develop.For example patent 201310632485.1 is just with molecular sieve, zeolite, activated carbon etc.
As load matrix, nano-zinc sulfide, zinc selenide are loaded on these carriers, for removing the application of mercury pollution in water.But
It is from practical application, still there is certain distance, limitation sex chromosome mosaicism mainly also resides in the industrial operation fortune of these carrier materials
Row aspect experience is immature.Therefore, nanometer sulfide is loaded on resin, has not only imparted the more preferable absorption property of resin, but also
Carry attached and avoid nano particle and be scattering into the potential risk that secondary hazards are caused in water body so that nano material is able to fix.
The content of the invention
To solve the above-mentioned problems, the present invention provides a kind of biological adsorption material and support type resin combination removing heavy metal
Method, the method inhales heavy metal solution by biological adsorption material and nano particle support type resin composite materials
Receive, and the nano particle support type resin composite materials are concentrated with salpeter solution, load nano-zinc sulfide or vulcanization again
Ferrous particle Posterior circle utilizes, and washes degraded after biological adsorption material is leached residual heavy metal with nitric acid depth, realizes depth
Purification；
Further, the described method comprises the following steps：
1）Soluble lead salt, cadmium salt or mercury salt solution are taken, wherein containing micro heavy metal ion, concentration is in below 100mg/L；
2）Every cube of water addition 1 ~ 10kg biological adsorption material is added to step 1）Solution in, stirring reaction 1 ~ 24 it is small when after mistake
Filter；
3）By step 2）In filtered fluid collect after, with the flow velocity of 1 ~ 10 BV/h by crossover fixation bed, until wearing what is filtered out
Heavy metal concentration exceedes the standard of national regulation discharge in water, then stops using the crossover fixation bed, the crossover fixation bed
Layer is filled by the resin particle for having loaded nano-zinc sulfide or ferrous sulfide particle to be constructed；
4）1M salpeter solutions are passed in the crossover fixation bed using same flow velocity, amount of solution is 5BV ~ 10BV units, to
The recycling concentration of sulfide on resin, and the resin is loaded into nano-zinc sulfide or ferrous sulfide particle again；
Further, the step 4）It is middle load nanometer sulfide particle operating procedure be：
4-1）：By resin cation material, according to the solid-liquid ratio of 1g/5ml~1g/50ml, put into containing zinc or it is ferrous from
In the aqueous solution of son, the concentration control of metal ion is controlled between 1~7 in 0.01 ~ 1M, pH value, is kept stirring state, is kept
When time of contact 1~24 is small；
4-2）：Resin particle therein is isolated, puts into the Na of 0.1 ~ 1M2In S solution, described in the synchronous rapid 4-1 of solid-liquid ratio,
After when stirring immersion 10 is small, resin is separated and collected；
4-3）Dried after being washed to neutrality, you can the resin adsorbing material of zinc sulphide or ferrous sulfide particle has been loaded,
Metal sulfide granularity therein is between 10~100nm；
Further, the step 2）The middle biological adsorption material for having adsorbed heavy metal, can use 0.1M ~ 1M concentration nitric acid or
Lemon acid soak desorbs, and the biological adsorption material for recovering adsorption function can return to absorption process and is continuing with again, until losing
Adsorption effect, then leaches residual heavy metal therein by 3 grades of 1M nitric acid depth, common biomass castoff is used as after washing
Return and make composting material, make its natural degradation；
Further, the highly acid functional group includes sulfonic group；
Further, the faintly acid functional group is-COOH, phosphate or phenolic hydroxyl group；
Further, the resin cation material is commercial resins；
Beneficial effects of the present invention are as follows：
1）Solve biological adsorption and be difficult to the problem that engineering implements deep purifying；
2）Substantially reduce nano particle support type resin composite materials frequently desorb, regenerated number.
Brief description of the drawings
Fig. 1 is the integrated mode schematic diagram of biological adsorption of the present invention and heavy metal in ion exchange resin deep removal water.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, it is right
The present invention is explained in further detail.It should be appreciated that specific embodiment described herein is used only for explaining the present invention, and
It is not used in the restriction present invention.On the contrary, the present invention cover it is any be defined by the claims the present invention spirit and scope on do
Replacement, modification, equivalent method and scheme.Further, in order to make the public have a better understanding the present invention, below to this
It is detailed to describe some specific detail sections in the detailed description of invention.It is thin without these for a person skilled in the art
The description of section part can also understand the present invention completely.
The invention will be further described with specific embodiment below in conjunction with the accompanying drawings, but not as a limitation of the invention.
Below most preferred embodiment is enumerated for the present invention：
As shown in Figure 1, biosorption technology and nano particle support type resin composite materials are combined the invention discloses one kind
The new approaches used, dedicated for the deep purifying of micro heavy in water.Specific steps include：
1）Take soluble lead salt, cadmium salt, mercury salt solution, wherein each heavy metal ion containing micro-concentrations, 100mg/L with
Under be advisable, above solution can be prepared manually, also can use actual plant chimney stalk；
2）Add the biological adsorption material being modified to be added in above solution, additive amount adds 1 ~ 10kg with reference to every cube of water and inhales
Enclosure material is advisable, stirring reaction 1 ~ 24 it is small when after filter；Biological adsorption material herein recommends patent of invention
（The method that valuable metal ions prepare superfine powder in ZL201410283723.7 biological adsorption solution）Disclosed in modification side
Sorbing material prepared by method；The biological adsorption material of heavy metal has been adsorbed, nitric acid or the lemon acidleach of 0.1M ~ 1M concentration can be used
Bubble desorption, the biological adsorption material for recovering adsorption function can return to absorption process and is continuing with again, until adsorption effect is lost,
Then residual heavy metal therein is leached by 3 grades of 1M nitric acid depth, is returned after washing as common biomass castoff and make compost
Raw material, makes its natural degradation return to the Nature；
3）After above filtered fluid is collected, with the flow velocity of 1 ~ 10BV/h by having loaded nano-zinc sulfide or ferrous sulfide particle
Resin particle fills the crossover fixation bed constructed, until wearing heavy metal concentration in the water filtered out exceedes national regulation discharge
Standard, then stop using the resin column, then passes to 1M salpeter solutions using same flow velocity, amount of solution is 5BV ~ 10BV units
The recycling concentration of sulfide on the resin can be achieved, resin then returns to load nano-zinc sulfide or ferrous sulfide grain again
Son.Specifically the operating procedure of load nanometer sulfide particle is：By resin cation material, according to 1g/5ml~1g/50ml
Solid-liquid ratio, put into the aqueous solution containing zinc or ferrous ion, the control of the concentration of these metal ions in 0.01 ~ 1M,
PH value general control is kept stirring state between 1~7, when being kept for time of contact 1~24 small；Tree therein is then demultiplex out
Fat particle, puts into the Na of 0.1 ~ 1M2In S solution, solid-liquid ratio is same as above described in face, stirring immersion 10 it is small when after, separate and collect
Resin, after being washed to neutrality, drying, you can the resin adsorbing material of zinc sulphide or ferrous sulfide particle has been loaded, its
In metal sulfide granularity between 10~100nm, therefore be the resin based composite adsorption material of load nano particle.
Resin matrix herein is polystyrene or acrylic acid series, contains highly acid functional group such as sulfonic group on resin matrix, or weak
Acid functional group such as-COOH, phosphate or phenolic hydroxyl group, carrier prioritizing selection D001, D113, Amberlite IR-120,
The commercial resins brand such as Amberlite IR-200, Amberlite IRA-130.
The present invention solves biological adsorption and is difficult to the problem that engineering implements deep purifying, adds nano particle support type
Resin composite materials frequently desorb, regenerated number.
Embodiment 1
The mine wastewater in certain ore dressing plant is taken, first tentatively filters out solid particulate matter therein, sampling, which measures, wherein contains Pb2+
256mg/L, and other impurities such as calcium, magnesium, sulfate radical etc., take 10 liters of the waste water, its pH is adjusted to 5.0, then stirs feelings
Added under condition 80 mesh granularities saponification be modified prepare 50 grams of Cortex Bulbus Allii sorbing material, then stir 2 it is small when after, remained in water
Pb2+Concentration is 21mg/L, filters to isolate absorbent particles, with 200 milliliters of 0.5M nitric acid immersion 0.5 it is small when, you can obtain dense
Contracting obtains nitric acid leading crystal containing the dope that lead concentration is 12g/L, evaporative crystallization；And sorbing material after desorbing, after washing
Absorption is returned again, after the absorption-desorptions repeatedly of about 60 times, the efficiency of its adsorpting lead ion is reduced to 80% or so, this
When can undergo 0.5M nitric acid dousings processing half an hour, after being repeated 3 times, washing is clean, as composting material, makes its natural degradation.
And the absorption mine wastewater after filtering, filled with the flow velocity of 5BV/h by having loaded the resin particle of nano zinc sulfide particles
The crossover fixation bed constructed, until wearing Pb in the water filtered out2+Concentration is then stopped using the resin column, is then adopted more than 1mg/L
1M salpeter solutions are passed to same flow velocity, amount of solution is that the recycling concentration of vulcanized lead on the resin, tree can be achieved for 5BV units
Fat then returns to load nano zinc sulfide particles again.The operating procedure of nanometer sulfide particle is specifically loaded in the present embodiment
For：By D001 resin cation materials, according to the solid-liquid ratio of 1g/10ml, put into the aqueous solution containing 0.1M zinc ions,
PH value 4.8, is kept stirring state, when being kept for time of contact 4 small；Resin particle therein is then demultiplex out, after washing 1 time, throws
Enter the Na to 0.5M2In S solution, solid-liquid ratio is same as above described in face, stirring immersion 10 it is small when after, separate and collect resin, be washed to
After neutrality, drying, you can loaded the resin adsorbing material of zns particle, metal zinc sulphide granularity therein exists
10nm or so.
Embodiment 2
The mine wastewater in certain ore dressing plant is taken, first tentatively filters out solid particulate matter therein, sampling, which measures, wherein contains Pb2+
256mg/L, and other impurities such as calcium, magnesium, sulfate radical etc., take 10 liters of the waste water, its pH is adjusted to 5.0, then stirs feelings
Added under condition 80 mesh granularities saponification be modified prepare 30 grams of citrus pulp sorbing material, then stir 2 it is small when after, remained in water
Pb2+Concentration is 33mg/L, filters to isolate absorbent particles, with 200 milliliters of 0.5M nitric acid immersion 0.5 it is small when, you can obtain dense
Contracting obtains nitric acid leading crystal containing the dope that lead concentration is 11g/L, evaporative crystallization；And sorbing material after desorbing, after washing
Absorption is returned again, after the absorption-desorptions repeatedly of about 20 times, the efficiency of its adsorpting lead ion is reduced to 80% or so, this
When can undergo 0.5M nitric acid dousings processing half an hour, after being repeated 3 times, washing is clean, as composting material, makes its natural degradation.
And the absorption mine wastewater after filtering, filled with the flow velocity of 5BV/h by having loaded the resin particle of nano zinc sulfide particles
The crossover fixation bed constructed, until wearing Pb in the water filtered out2+Concentration is then stopped using the resin column, is then adopted more than 1mg/L
1M salpeter solutions are passed to same flow velocity, amount of solution is that the recycling concentration of vulcanized lead on the resin, tree can be achieved for 5BV units
Fat then returns to load nano zinc sulfide particles again.The operating procedure of nanometer sulfide particle is specifically loaded in the present embodiment
For：By Amberlite IR-120 resin cation materials, according to the solid-liquid ratio of 1g/10ml, put into containing 0.1M zinc from
In the aqueous solution of son, pH value 4.8, is kept stirring state, when being kept for time of contact 4 small；Resin particle therein is then demultiplex out,
After washing 1 time, the Na of 0.5M is put into2In S solution, solid-liquid ratio is same as above described in face, stirring immersion 10 it is small when after, separate and collect
Resin, after being washed to neutrality, drying, you can loaded the resin adsorbing material of zns particle, metal sulphur therein
Change zinc granule degree in 10nm or so.
Embodiment 3
The mine wastewater in certain ore dressing plant is taken, first tentatively filters out solid particulate matter therein, sampling, which measures, wherein contains Pb2+
256mg/L, and other impurities such as calcium, magnesium, sulfate radical etc., take 10 liters of the waste water, its pH is adjusted to 5.0, then stirs feelings
Added under condition 80 mesh granularities saponification be modified prepare 30 grams of citrus pulp sorbing material, then stir 2 it is small when after, remained in water
Pb2+Concentration is 33mg/L, filters to isolate absorbent particles, with 200 milliliters of 0.5M nitric acid immersion 0.5 it is small when, you can obtain dense
Contracting obtains nitric acid leading crystal containing the dope that lead concentration is 11g/L, evaporative crystallization；And sorbing material after desorbing, after washing
Absorption is returned again, after the absorption-desorptions repeatedly of about 20 times, the efficiency of its adsorpting lead ion is reduced to 80% or so, this
When can undergo 0.5M nitric acid dousings processing half an hour, after being repeated 3 times, washing is clean, as composting material, makes its natural degradation.
And the absorption mine wastewater after filtering, filled out with the flow velocity of 5BV/h by having loaded the resin particle of nanometer ferrous sulfide particle
The crossover fixation bed constructed is filled, until wearing Pb in the water filtered out2+Concentration then stops using the resin column, then more than 1mg/L
1M salpeter solutions are passed to using same flow velocity, amount of solution is that the recycling concentration of vulcanized lead on the resin can be achieved for 5BV units,
Resin then returns to load a nanometer ferrous sulfide particle again.The specifically operation of load nanometer sulfide particle in the present embodiment
Step is：By D001 resin cation materials, according to the solid-liquid ratio of 1g/10ml, the water containing 0.1M ferrous ions is put into
In solution, pH value 5.8, keeps nitrogen bubbling stirring, when being kept for time of contact 4 small；Resin therein is then demultiplex out
Grain, after washing 1 time, puts into the Na of 0.5M2In S solution, solid-liquid ratio is same as above described in face, keeps nitrogen bubbling stirring,
10 it is small when after, separate and collect resin, after being washed to neutrality, vacuum drying, you can loaded the resin of ferrous sulfide particle
Adsorbing material, metal ferrous sulfide granularity therein is in 15nm or so.
Embodiment 4
The mine wastewater in certain ore dressing plant is taken, first tentatively filters out solid particulate matter therein, sampling, which measures, wherein contains Cd2+
73mg/L, and other impurities such as calcium, magnesium, sulfate radical etc., take 10 liters of the waste water, its pH are adjusted to 5.0, then stirring state
It is lower add 80 mesh granularities saponification be modified prepare 100 grams of Cortex Bulbus Allii sorbing material, then stir 2 it is small when after, Cd is remained in water2+
Concentration is 6mg/L, filters to isolate absorbent particles, with 200 milliliters of 0.5M nitric acid immersion 0.5 it is small when, you can concentrated
Containing the dope that cadmium concentration is 3.4g/L, evaporative crystallization obtains cadmium nitrate crystal；And sorbing material after desorbing, returned again after washing
Resorption is attached, and after the absorption-desorptions repeatedly of about 60 times, the efficiency of its Adsorption of Cadmium is reduced to 80% or so, at this time may be used
0.5M nitric acid dousings processing half an hour is undergone, after being repeated 3 times, washing is clean, as composting material, makes its natural degradation.And mistake
Absorption mine wastewater after filter, structure is filled with the flow velocity of 5BV/h by having loaded the resin particle of nanometer ferrous sulfide particle
The crossover fixation bed built, until wearing Cd in the water filtered out2+Concentration is then stopped using the resin column, is then adopted more than 0.1mg/L
1M salpeter solutions are passed to same flow velocity, amount of solution is that the recycling concentration of cadmium sulfide on the resin, tree can be achieved for 5BV units
Fat then returns to load a nanometer ferrous sulfide particle again.Specifically the operation of load nanometer sulfide particle walks in the present embodiment
Suddenly it is：By Amberlite IR-200 resin cation materials, according to the solid-liquid ratio of 1g/10ml, put into sub- containing 0.1M
In the aqueous solution of iron ion, pH value 5.8, keeps nitrogen bubbling stirring, when being kept for time of contact 4 small；It is then demultiplex out
In resin particle, after washing 1 time, put into the Na of 0.5M2In S solution, solid-liquid ratio is same as above described in face, keeps nitrogen bubbling
Stirring, 10 it is small when after, separate and collect resin, after being washed to neutrality, vacuum drying, you can loaded ferrous sulfide
The resin adsorbing material of particle, metal ferrous sulfide granularity therein is in 11nm or so.
Embodiment 5
The mine wastewater in certain ore dressing plant is taken, first tentatively filters out solid particulate matter therein, sampling, which measures, wherein contains Hg2+
121mg/L, and other impurities such as calcium, magnesium, sulfate radical etc., take 10 liters of the waste water, its pH is adjusted to 5.0, then stirs feelings
Added under condition 80 mesh granularities saponification be modified prepare 100 grams of Cortex Bulbus Allii sorbing material, then stir 2 it is small when after, remained in water
Hg2+Concentration is 26mg/L, filters to isolate absorbent particles, with 200 milliliters of 0.5M nitric acid immersion 0.5 it is small when, you can obtain dense
The mercurous concentration of contracting is the dope of 4.6g/L, has sent qualification processing unit specially to recycle；And sorbing material after desorbing, pass through
Absorption is returned to after washing again, after the absorption-desorptions repeatedly of about 30 times, it adsorbs the efficiency of mercury ion and is reduced to 80%
Left and right, can undergo 0.5M nitric acid dousings processing half an hour at this time, and after being repeated 3 times, washing is clean, as composting material, make it certainly
So degraded.And the absorption mine wastewater after filtering, with the flow velocity of 5BV/h by having loaded the resin of nanometer ferrous sulfide particle
Grain fills the crossover fixation bed constructed, until wearing Hg in the water filtered out2+Concentration then stops using the tree more than 0.01mg/L
Fat column, then passes to 1M salpeter solutions using same flow velocity, and amount of solution is that mercuric sulphide on the resin can be achieved for 5BV units
Recycling concentration, resin then return to load a nanometer ferrous sulfide particle again.Nanometer sulfide is specifically loaded in the present embodiment
The operating procedure of particle is：By Amberlite IRA-130 resin cation materials, according to the solid-liquid ratio of 1g/10ml, put into
Into the aqueous solution containing 0.1M ferrous ions, pH value 5.8, keeps nitrogen bubbling stirring, when being kept for time of contact 4 small；
Resin particle therein is then demultiplex out, after washing 1 time, puts into the Na of 0.5M2In S solution, solid-liquid ratio is same as above described in face,
Keep nitrogen bubbling stirring, 10 it is small when after, separate and collect resin, after being washed to neutrality, vacuum drying, you can born
The resin adsorbing material of ferrous sulfide particle is carried, metal ferrous sulfide granularity therein is in 9nm or so.
One kind of embodiment described above, simply more preferably embodiment of the invention, those skilled in the art
The usual variations and alternatives that member carries out in the range of technical solution of the present invention should all include within the scope of the present invention.
Claims (8)
1. a kind of method of biological adsorption material and support type resin combination removing heavy metal, it is characterised in that the method is led to
Cross biological adsorption material and nano particle support type resin composite materials absorb heavy metal solution, and by the nanometer
Particle loading type resin composite materials are concentrated with salpeter solution, load nano-zinc sulfide or ferrous sulfide particle Posterior circle profit again
With, by biological adsorption material with nitric acid depth leach residual heavy metal after wash degrade, realize deep purifying.
2. according to the method described in claim 1, it is characterized in that, it the described method comprises the following steps：
1）Soluble lead salt, cadmium salt or mercury salt solution are taken, wherein containing micro heavy metal ion, concentration is in below 100mg/L；
2）Every cube of water addition 1 ~ 10kg biological adsorption material is added to step 1）Solution in, stirring reaction 1 ~ 24 it is small when after mistake
Filter；
3）By step 2）In filtered fluid collect after, with the flow velocity of 1 ~ 10 BV/h by crossover fixation bed, until wearing what is filtered out
Heavy metal concentration exceedes the standard of national regulation discharge in water, then stops using the crossover fixation bed, the crossover fixation bed
Layer is filled by the resin particle for having loaded nano-zinc sulfide or ferrous sulfide particle to be constructed；
4）1M salpeter solutions are passed in the crossover fixation bed using same flow velocity, amount of solution is 5BV ~ 10BV units, to
The recycling concentration of sulfide on resin, and the resin is loaded into nano-zinc sulfide or ferrous sulfide particle again.
3. the according to the method described in claim 2, it is characterized in that, step 4）The operation of middle load nanometer sulfide particle
Step is：
4-1）：By resin cation material, according to the solid-liquid ratio of 1g/5ml~1g/50ml, put into containing zinc or it is ferrous from
In the aqueous solution of son, the concentration control of metal ion is controlled between 1~7 in 0.01 ~ 1M, pH value, is kept stirring state, is kept
When time of contact 1~24 is small；
4-2）：Resin particle therein is isolated, puts into the Na of 0.1 ~ 1M2In S solution, described in the synchronous rapid 4-1 of solid-liquid ratio,
After when stirring immersion 10 is small, resin is separated and collected；
4-3）Dried after being washed to neutrality, you can the resin adsorbing material of zinc sulphide or ferrous sulfide particle has been loaded,
Metal sulfide granularity therein is between 10~100nm.
4. the according to the method described in claim 3, it is characterized in that, 4-1）The skeleton of middle resin cation material is benzene second
Alkene system or acrylic acid series, contain highly acid functional group or faintly acid functional group on the skeleton of the resin material.
5. the according to the method described in claim 2, it is characterized in that, step 2）The middle biological adsorption material for having adsorbed heavy metal
Material, the nitric acid or lemon acid soak that can use 0.1M ~ 1M concentration desorb, and the biological adsorption material for recovering adsorption function can return to again
It is continuing with to absorption process, until losing adsorption effect, then leaches a residual huge sum of money therein by 3 grades of 1M nitric acid depth
Belong to, returned after washing as common biomass castoff and make composting material, make its natural degradation.
6. according to the method described in claim 4, it is characterized in that, the highly acid functional group includes sulfonic group.
7. according to the method described in claim 4, it is characterized in that, the faintly acid functional group is-COOH, phosphate or phenol hydroxyl
Base.
8. according to the method described in claim 4, it is characterized in that, the resin cation material is commercial resins.
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| CN114029040A (en) * | 2021-11-15 | 2022-02-11 | 南开大学 | Iron disulfide resin composite material and preparation method and application thereof |
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| CN103623771A (en) * | 2013-12-02 | 2014-03-12 | 上海交通大学 | Waste solution mercury removal adsorbent, preparation method and application method thereof |
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| CN101186357A (en) * | 2007-12-18 | 2008-05-28 | 南京大学 | Method for deep purifying heavy metal micro-polluted water by resin-base nano hydrated ferric oxide |
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| CN103212383A (en) * | 2013-04-03 | 2013-07-24 | 燕山大学 | Method for removing trace heavy metal in water by zirconium-loaded nanometer hybrid material |
| CN103623771A (en) * | 2013-12-02 | 2014-03-12 | 上海交通大学 | Waste solution mercury removal adsorbent, preparation method and application method thereof |
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