CN104710014A - Method for adsorbing heavy metal ion chromium in water by using modified Ascophyllum Nodosum - Google Patents
Method for adsorbing heavy metal ion chromium in water by using modified Ascophyllum Nodosum Download PDFInfo
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Abstract
The invention discloses a method for adsorbing heavy metal ion chromium in water by using modified Ascophyllum Nodosum, which comprises the following steps: (1) modification treatment of Ascophyllum Nodosum: adding 70-100mL of modifier into every gram of Ascophyllum Nodosum, stirring at room temperature for 18-22 hours, filtering, drying the filter residue, pulverizing and screening; and (2) adding 3-8g of the modified Ascophyllum Nodosum into every liter of water to be treated, regulating the pH value to 1-1.5, and carrying out adsorption treatment at 30-40 DEG C for 5-8 hours. In the step (1), the modifier is composed of 0.005-0.05 mol/L iron chloride, a mixed solution of anhydrous ethanol and acetic acid in a volume ratio of 5:1, 0.1 mol/L citric acid, and 0.1 mol/L sulfanilic acid or acetone. The method disclosed by the invention can selectively adsorb low-concentration Cr<6+> in water, has the advantages of high removal rate, high efficiency and environment friendliness, and can not cause secondary pollution.
Description
Technical field
The present invention relates to a kind of method utilizing modification bladder wrack absorbing heavy metal ions in water chromium.
Background technology
Cr (VI) is the heavy metal that a kind of toxicity is very strong, is one of 129 priority pollutants that U.S. EPA is generally acknowledged, the pollutent of same Ye Shi China emphasis regulation.Along with the fast development of China's industry, the use of heavy metal is more and more extensive, and incident heavy metal pollution problem is also on the rise.All discharge a large amount of containing chromium (VI) waste water in Industrial processes such as plating process hides, dyestuff, film etc.Chromium (VI) is main with Cr in water body
2o
7 2-and CrO
4 2-form exists, and oxidisability is very strong, has strong toxicity, is carcinogenic substance, and is easily absorbed by the body and accumulates in vivo.Therefore chromium (VI) is an important indicator of water pollution control.
By the development and application time, two large classes are divided into the purifying treatment method of chromate waste water: traditional contains chromium (VI) method of wastewater treatment and brand-new treatment process.Although traditional treatment process has certain effect as chemical precipitation method, ion-exchange-resin process, absorption method etc., all exist costly and easily cause the problem of secondary pollution; The photochemical reduction, microorganism adsorption method etc. of recent studies on exploitation are effective, and energy consumption is low, and raw material sources is wide, effectively make use of environmental resources, reaches environmental protection object.In recent years, microorganism is utilized to achieve multinomial achievement from the research of adsorption in dilute solution chromium (VI), from application, utilize microorganism adsorption method superior traditional administering method in investment, operation, operational administrative and metal recovery, Water circulation etc.The advantages such as biological process is little with its investment, working cost is low, non-secondary pollution, obtain significant progress very soon.Current biological process is mainly divided into inactive microorganism absorption method and living microorganism method.With inactive microorganism Adsorption chromium, not only take full advantage of cheap raw material, and have preferably except chromium effect.
The treatment process of microorganism adsorption method is compared with traditional physical and chemical process, and maximum differential is that microorganism can constantly breed in operational process, and the amount removing metal ion increases with biomass and increases.And the exchange capacity of ion exchange method ion exchange resin is limited, reaches capacity after absorption, just can not remove metal ion again; In chemical precipitation method, the stoichiometry of Substrate is also certain, without the possibility of propagation.Therefore, development and utilization biological adsorption agent process heavy metal wastewater thereby makes the technology of wastewater treatment stride forward major step towards direction that is nontoxic, harmless, non-secondary pollution.
Biosorption process utilizes the chemical structure of some organism itself and ingredient properties to adsorb metal ion soluble in water, then remove the method for metal ion by solid-liquid two-phase laminated flow.All there is separating metal ability from solution organism or the derivative prepared of organism all can be described as biological adsorption agent, mainly contain thalline, algae, cell extract etc.To absorption, what mainly work is alga cells to algae bio sorbent material.The chemical composition and structure of alga cells wall decides metal ion and its interaction property.The cell walls of algae is that the reticulated structure formed by cellulosic micro-fibril is formed as a rule, containing abundant polysaccharide, as pectin (superpolymer of the poly half bore uronic acid containing a small amount of hexose, rhamnosyl), wood sugar, seminose, alginic acid or usnic acid.Polysaccharide is electronegative, can be combined by electrostatic attraction with many metal ions.Due to the special construction of alga cells, heavy metal ion has very large affinity.The major advantage that heavy metal ions in water removed by algae bio sorbent material is: (1) at low concentrations, metal can optionally be removed; (2) energy-conservation, processing efficiency is high; (3) pH value during operation and temperature condition wide ranges; (4) Separation and Recovery heavy metal is easy to; (5) the easy regeneration of sorbent material; (6) invest little, working cost is low, non-secondary pollution.
The complicated mechanism of algae Adsorption of Heavy Metals, and also there is difference (live body algae in the adsorption mechanism of live body algae and dead volume algae, first by heavy metal adsorption on cell walls, absorption is fast, and do not rely on energy metabolism, this stage is similar to the absorption of dead algae heavy metal, is then then transported in cell by heavy metal by active transport), so far many problems are not fully aware of, and the adsorption mechanism comparing accreditation mainly contains complexing, ion-exchange etc.Algae is complicated physics, chemistry and a bioprocess in the absorption of heavy metal.Macroscopically say, the principal element affecting algae adsorptive capacity has pH value, temperature, coexisting ion content, adsorption time, pre-treatment etc., also comprises biological adsorption agent and by the physicochemical property of ion itself of adsorbing and operating environment.
Heavy metal is as a kind of very harmful poisonous pollutent, concentration in water of being everlasting is lower, but exceeded prescribed value, use traditional method reduced price very high or impossible in this case, the technology that biosorption process removes heavy metal in water receives great concern in recent years, not only due to the validity of its Adsorption of Heavy Metals, but also be its potential using value.That lives can heavy metal ion in planar water with dead microorganism, as biological adsorption agent biogenic can from lower concentration containing heavy metal ion the aqueous solution Adsorption of Heavy Metals, microorganism with practical value easily obtains, such as: the yeast in fermenting process is the good biogenic of biological adsorption agent, in a large number from the biogenic that the algae in ocean is also cheap.
Heavy metal poisonous in using microbe adsorption aqueous solution has many investigators and attempts, and achieves good effect.Greene uses the gold of algae removal water, and Tsezos, Mara-non use the uranium in fungi planar water, Ferguson and Breuer etc. utilize the Fe in sphagnum moss removal water, the metal ions such as Al, Pb, Cu, Cd, Zn.Barkley utilizes algae to be adsorbed with Cd in organic waste water, the metal ions such as Cu.Mark Spinti etc. are fixed on sphagnum moss in the polymerization sulfuryl matter of porous in the acid mine water being successfully applied to and removing containing metal ions such as Zn, Cd, Mg; the coccode physical strength that sphagnum moss makes is fixed large with polymerization sulfone; stable chemical performance, regenerating easily, does not expand and does not shrink.
There is the patent using dead microorganism to make heavy metal in biological adsorption agent removal water at present abroad, such as: AMT-BIOCLAIM technique is exactly utilize dead genus bacillus to make spherical biological adsorption agent absorbing heavy metal ions in water.Have in the U.S. biological adsorption agent that the research of Liang Ge scientific research institution provides commercial use, one is that another take algae as object with discarded microorganism for object.
In the process of microbiological treatment heavy metal wastewater thereby, there is significant difference to same metal biosorption amount and removal efficiency in different types of microorganism, and treatment condition required during different algal species process heavy metal ions in wastewater are also different.Bladder wrack is the marine algae of class wide material sources, does not also have the report utilizing bladder wrack process heavy metal in waste water chromium at present, therefore, provides a kind of method based on bladder wrack process heavy metal in waste water chromium to have broad application prospects.
Summary of the invention
For above-mentioned prior art, the object of this invention is to provide a kind of method utilizing modification bladder wrack absorbing heavy metal ions in water chromium, the method can the optionally Cr of lower concentration in planar water
6+, clearance is high, high-efficiency environment friendly, can not cause secondary pollution.
For achieving the above object, the present invention adopts following technical proposals:
Utilize a method for modification bladder wrack absorbing heavy metal ions in water chromium, step is as follows:
(1) modification of bladder wrack: add properties-correcting agent in bladder wrack, the ratio of bladder wrack and properties-correcting agent add-on is 1g:70-100mL, stirs 18-22 hour under normal temperature, filters, filter residue and drying, pulverizes, sieves;
(2) join in pending water by the bladder wrack after step (1) modification, heavy metal ion chromium carries out adsorbing (Cr
6+), the add-on of bladder wrack is (3-8) g/L (namely adding the bladder wrack after 3-8g modification in every premium on currency), and adjustment pH is 1-1.5, and temperature is 30-40 DEG C, adsorption treatment 5-8h.
In step (1), described properties-correcting agent is selected from the iron(ic) chloride of 0.005-0.05mol/L, the solution of dehydrated alcohol and acetic acid 5:1 mixing by volume, the citric acid of 0.1mol/L, any one in the Sulphanilic Acid of 0.1mol/L or acetone;
Preferably, described properties-correcting agent is the iron(ic) chloride of 0.005-0.05mol/L; Preferred further, be the iron(ic) chloride of 0.01mol/L.
In step (2), the add-on of bladder wrack is preferably 5g/L.
In step (2), pH is preferably 1, and temperature is 30 DEG C.
In step (2), the pseudo-second order kinetic model that the bladder wrack heavy metal ion chromium after modification carries out adsorbing is: y=0.0921X+0.1343; Wherein y represent time/adsorptive capacity, X represents the time.
Parameter Conditions selected in treatment process of the present invention is not conventional selection, wherein, modification can improve the adsorption effect of bubble liquid algae, for properties-correcting agent iron(ic) chloride, when adopting iron(ic) chloride modification, iron ion can react with the cellulosic oh group on bladder wrack surface, generates (R-COH)
2m (OH)
2, thus increase clearance.The concentration of properties-correcting agent is also very crucial for the effect of modification, under finite concentration scope, the concentration increasing properties-correcting agent can improve the effect of modification, but the concentration of properties-correcting agent is also unsuitable too high, the molysite of high density can make the Mierocrystalline cellulose generation hydrolytic side reactions in bladder wrack cell, the functional group making bladder wrack surface that ion-exchange occur reduces, and causes reducing the clearance of chromium (VI).
The add-on of bladder wrack is also evaluate the important evaluation index of absorption property and adsorption effect, when practical application, also need the cost considering to run, therefore, in the present invention, the add-on of bladder wrack considers to have seen adsorption effect and running cost and the optimum value that draws.
Beneficial effect of the present invention:
The method of absorbing heavy metal ions in water chromium of the present invention can the optionally Cr of lower concentration in planar water
6+, clearance is high, high-efficiency environment friendly, can not cause secondary pollution.
Accompanying drawing explanation
Fig. 1 is chromium typical curve;
Fig. 2 is the change of clearance after different modifier modification, 1. unmodified bladder wrack, 2.HTMDA, 3.NaOH+ glycerol, 4. acetone, 5. Sulphanilic Acid, 6. citric acid, 7. acetic acid+ethanol, 8. iron(ic) chloride;
Fig. 3 is properties-correcting agent FeCl
3concentration on the impact of adsorption effect;
Fig. 4 is the impact of add-on on adsorption effect of bladder wrack;
Fig. 5 is the impact of pH value on adsorption effect;
Fig. 6 is the impact of temperature on adsorption effect;
Fig. 7 is the impact of adsorption time on adsorption effect;
Fig. 8 is bladder wrack absorption Cr
6+pseudo-first-order kinetics model of biosorption;
Fig. 9 is bladder wrack absorption Cr
6+accurate secondary absorption kinetic model.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated, should be noted that following explanation is only to explain the present invention, not limiting its content.
Experiment material, reagent and instrument used in the embodiment of the present invention are as follows:
Experiment material: bladder wrack;
Common agents: acetone, potassium bichromate, diphenylcarbazide, the vitriol oil, concentrated hydrochloric acid, sodium hydroxide; Be commercially available prod;
Modifying agent: ferric sesquichloride, cetyl trimethylammonium bromide, glycerol, dehydrated alcohol, Glacial acetic acid, Sulphanilic Acid, citric acid; Be commercially available prod;
Chromium standard solution: 5mg/L;
Laboratory apparatus: in table 1.
The list of table 1 laboratory apparatus
| Instrument title | INSTRUMENT MODEL | Manufacturer |
| Electronic analytical balance | FC-204 type | Shanghai Hengping Science Instrument Co., Ltd. |
| Constant-temperature shaking incubator | HZQ-F160 type | East, Harbin connection electronics |
| Atomic absorption spectrophotometer | Hitachi Z-2000 | FDAC equipment company |
| Ultraviolet-visible pectrophotometer | 7200 types | Shanghai City the 3rd analytical instrument factory |
| Acidometer | PB-10 | Shanghai Hengping Science Instrument Co., Ltd. |
| Crusher for Chinese herbal medicine | FW135 type | Tianjin Stettlen Instrument Ltd. |
| Electric heating constant-temperature blowing drying box | DHG-9076A | The grand experimental installation company limited of upper Nereid |
| Whizzer | TDL-60B | Anting Scientific Instrument Factory, Shanghai |
| Fourier infrared spectrograph | Day island | Shimadzu equipment company of Japan |
Embodiment 1: modification bladder wrack absorbing heavy metal ions in water chromium related process parameters is investigated
1. the modification condition of bladder wrack is investigated
The pre-treatment of 1.1 bladder wracks: smashed by bladder wrack crusher for Chinese herbal medicine, by 45 object sieve, dries 24 hours under 60 degrees Celsius, preserves in drying place;
The selection of 1.2 properties-correcting agent:
Prepare different types of properties-correcting agent respectively, investigate its modified effect to bladder wrack, concrete process for preparation is as follows:
0.1mol/L Sulphanilic Acid: get analytically pure Sulphanilic Acid 1.73g and be dissolved in small beaker, with the volumetric flask constant volume of 100ml, and shifts in 150ml Erlenmeyer flask, stand-by.
0.01mol/L iron(ic) chloride: get six water ferric sesquichloride 0.27g and be dissolved in small beaker, with the volumetric flask constant volume of 100ml, and shift in 150ml Erlenmeyer flask, stand-by.
0.1mol/L citric acid: get citric acid 2.1g and be dissolved in small beaker, with the volumetric flask constant volume of 100ml, and shifts in 150ml Erlenmeyer flask, stand-by.
0.1mol/L cetyl trimethylammonium bromide: get cetyl trimethylammonium bromide 3.64g and be dissolved in small beaker, with the volumetric flask constant volume of 100ml, and shifts in 150ml Erlenmeyer flask, stand-by.
Volume ratio is 5:1 dehydrated alcohol and acetic acid: get dehydrated alcohol 83ml, and acetic acid 17ml is mixed in 150ml Erlenmeyer flask, stand-by.
Volume ratio is 1:1 sodium hydroxide and glycerol: prepare two solution of 18% respectively, each 50ml is mixed in 150ml Erlenmeyer flask stand-by.
The modification of 1.3 bladder wracks:
The 0.1mol/l Sulphanilic Acid prepared, 0.1mol/l iron(ic) chloride, 0.1mol/l citric acid, 0.1mol/l cetyl trimethylammonium bromide, 5:1 dehydrated alcohol and acetic acid, add the bladder wrack of 1.5g drying in 1:1 sodium hydroxide and each 100ml of glycerol respectively, stir 20 hours at normal temperatures.The bladder wrack of modification is filtered, and dries 10 hours in the baking oven of 60 DEG C, grind with mortar, sieve.
The drafting of 1.4 chromium typical curves:
1.4.1 the preparation of chromium standard reserving solution: take the 110 degrees Celsius of dryings potassium bichromate of 2 hours (top grade is pure) 0.2829g, after water dissolution, moves in the volumetric flask of 1L, is diluted with water to graticule, shakes up.This solution 1ml is containing 0.1mg sexavalent chrome.
1.4.2 the preparation of chromium standard solution: draw 25.00ml chromium standard reserving solution and be placed in 500ml volumetric flask, be diluted with water to graticule, shake up.This solution 1ml is containing 5.00ug sexavalent chrome, both 5mg/L.Used prepared this solution the same day.
1.4.3 the drafting of chromium typical curve:
Get 9 50ml colorimetric cylinders, add 0,0.20,0.50,1.00,2.00,4.00,6.00,8.00 and 10.00ml chromium standard solution successively, be diluted to graticule, survey absorbancy with diphenyl carbazide spectrophotometry, draw out Cr
6+typical curve as shown in Figure 1.
1.5 modification bladder wrack absorption Cr
6+effectiveness comparison
1.5.1 adsorption treatment: get 0.5g respectively by the modified bladder wrack (adding rear concentration is 5g/L) of the method for " 1.3 ", add in the hexavalent chromium solution of 100ml 50mg/L, pH value is 1,30 DEG C, 150r/min vibration absorption 3h.Through 5000r/min centrifuging and taking supernatant liquor, dilute 50 times, measure and calculate concentration, clearance, adsorptive capacity after adsorbing.The results are shown in Figure 2.
As shown in Figure 2, in various properties-correcting agent, FeCl
3modified effect best, improve 17.78%, and cetyl trimethylammonium bromide is modified, and clearance can reduce by 19.24%.It is that the cellulosic oh group on iron ion and bladder wrack surface reacts and generates (R-COH) that modified clearance improves possible reason
2m (OH) 2, the clearance increased.
The present invention adopts the concentration of ultraviolet-visible spectrophotometry determination of hexavalent chromium ion.Bladder wrack is calculated as follows chromic clearance W's and adsorptive capacity Q:
W＝(Ci-Ct)/Ci×100％
Q＝(Ci-Ct)/Cb
Ci in formula: hexavalent chromium initial concentration (mg/L)
Ct: hexavalent chromium ultimate density (mg/L)
Cb: the concentration (g/L) of bladder wrack.
1.5.2 the concentration of properties-correcting agent is on the impact of modified effect
According to the experimental result of 1.5.1, to there being the iron(ic) chloride reagent of best modified effect to establish concentration gradient, measuring modified effect, the results are shown in Figure 3.
As can be seen from Figure 3, FeCl
3concentration from 0.005mol/L to 0.01mol/L time, the clearance of Cr6+ can increase by 8%, and during from 0.01mol/L to 0.05mol/L, clearance reduces about 4%, from the angle of proportioning raw materials, when FeCl3 concentration is large, modified effect should be better than concentration low time, and result is just in time contrary, reason may be the Mierocrystalline cellulose generation hydrolytic side reactions that the molysite of high density can make in bladder wrack cell, the functional group making bladder wrack surface that ion-exchange occur reduces, and causes reducing the clearance of chromium (VI).
2. the add-on of bladder wrack, pH value, temperature and adsorption time are on the impact of adsorption effect
Chromate waste water is simulated wastewater, and chromic measuring method is with reference to diphenyl carbazide spectrophotometry.Adopt unitary variant method, the Cr of process waste water
6+concentration is 50mg/L.
(1) adsorbent amount is on the impact of absorption.Chromium (VI) ion starting point concentration is 50mg/L, adsorbent amount is respectively 1,3,5,8,11g/L, pH value is 1,30 DEG C, 150r/min vibration absorption 3h.Through 5000r/min centrifuging and taking supernatant liquor, dilute 50 times, measure and calculate concentration, clearance, adsorptive capacity after adsorbing.The results are shown in Figure 4.
In practical situations both, consider running cost, therefore the amount of sorbent material evaluates the important parameter of absorption property.The amount of sorbent material is less than 8g/L as shown in Figure 4, along with the increase of adsorbent amount, clearance constantly raises, the adsorptive capacity of unit mass bladder wrack reduces gradually, for no other reason than that adsorbent amount increases, sorbent material total surface area increases, and the quantity of total adsorption site increases, increase the touch opportunity of adsorbent surface and heavy metal ion, thus improve Cr
6+clearance.Within the scope of 8g/L-11g/L, along with the increase of adsorbent amount, Cr
6+clearance slowly increase, this mainly because the consumption height of sorbent material time, the Cr in solution
6+relative concentration is lower, and define the competitive adsorption of heavy metal ion between adsorber particles, adsorption site is in unsaturated state, considers adsorption effect and cost, and the amount choosing optimum absorbent is 5g/L, and clearance is now 69%.
(2) pH value is on the impact of absorption.Chromium (VI) ion starting point concentration is 50mg/L, adsorbent amount 5.0g/L, and pH value is respectively 1,1.5,2,3,4,30 DEG C, 150r/min vibration absorption 3h.Through 5000r/min centrifuging and taking supernatant liquor, dilute 50 times, measure and calculate concentration, clearance, adsorptive capacity after adsorbing.The results are shown in Figure 5.
PH value is the important factor affecting bladder wrack adsorption effect.The existence of heavy metal ion and the chemical property of adsorbent surface adsorption site in major effect solution.As shown in Figure 5, pH is lower, and the clearance of Cr6+ is higher.This is because Cr6+ exists with anionic forms such as HCrO4-in the solution, pH is lower, and the functional group of sorbent material cell surface is protonated, positively charged, by electrostatic adsorption, HCrO4-is adsorbed on cell surface, therefore Cr
6+clearance higher.Along with pH raises, in solution, H+ concentration reduces, and protonatedly weakens, and the H+ be adsorbed on functional group can disintegrate down, thus be unfavorable for the absorption of HCrO4-, and the clearance of Cr6+ reduces, and therefore selects optimal adsorption pH value to be 1.
(3) temperature is on the impact of absorption.Chromium (VI) ion starting point concentration is 50mg/L, and adsorbent amount is 5.0g/L, and pH value is 1, temperature is set as 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 150r/min vibration absorption 3h.Through 5000r/min centrifuging and taking supernatant liquor, dilute 50 times, measure and calculate concentration, clearance, adsorptive capacity after adsorbing.The results are shown in Figure 6.
As shown in Figure 6, the absorption property impact of temperature on bladder wrack is larger, between 20 DEG C-40 DEG C, along with temperature raises, the adsorptive capacity of Cr6+ clearance and bladder wrack significantly improves, between 40 DEG C-60 DEG C, along with temperature raises, clearance and adsorptive capacity slowly increase, and the clearance 50 DEG C time reaches more than 99%.Reason may mostly be porous material due to biological adsorption material, and diffusion is the rate constants of porous material, and is endothermic process, so the rising of temperature can make adsorptive spread faster in adsorbent pores.Heat up the intrinsic chemical bond rupture that also may make near some avtive spots, thus increase adsorption site.Consider that temperature is too high and can increase cost, therefore select temperature to be 30 DEG C.
(4) adsorption time is on the impact of absorption.Chromium (VI) ion starting point concentration is 50mg/L, adsorbent amount 5.0g/L, and pH value is 1,30 DEG C, 150r/min vibrate respectively absorption 1,3,5,7,9h.Through 5000r/min centrifuging and taking supernatant liquor, dilute 50 times, measure and calculate concentration, clearance, adsorptive capacity after adsorbing.The results are shown in Figure 7.
As shown in Figure 7, within 11 hours, the adsorption curve of Cr6+ is a convex curve, and bladder wrack presents a process first quick and back slow substantially to the absorption of Cr6+, in beginning within an hour, adsorption rate is than very fast, between 1h-7h, adsorption rate substantially constant, after 7h, clearance slowly increases, and absorption almost reaches balance.Biological adsorption is divided into two stages, the first stage be adsorbed as passive adsorption, speed, do not need energy, mainly by biological adsorption that Van der Waals force, electrostatic force and the capillary force between the functional group of cell wall and heavy metal ion is carried out.Subordinate phase, clearance increases slowly, until reach adsorption equilibrium, reason may be that the group of adsorbent surface, with heavy metal, the network of complexity and the process of reaction occurs, and the time reaching balance is longer.
3. kinetics of adsorption research
From kinetics of adsorption, pseudo-first-order kinetics model of biosorption and accurate secondary absorption kinetic model are the two kinds of kinetics model of biosorptions generally applied.
Pseudo-first-order kinetics of adsorption formula: ln (q
e-q)=lnq
e-k
1t;
Accurate secondary absorption dynamics formula:
In above formula, q
e, q is respectively the adsorptive capacity of adsorption equilibrium and t, (mg/g);
T is adsorption time, (h);
K
1be as the criterion primary adsorption rate constant, (h
-1);
K
2the secondary absorption that is as the criterion rate constant, (gmg
-1h
-1).
Above-mentioned two kinds of models are adopted to simulate bladder wrack adsorption process of the present invention, bladder wrack absorption Cr of the present invention
6+pseudo-first-order kinetics model of biosorption see Fig. 8, bladder wrack absorption Cr
6+accurate secondary absorption kinetic model see Fig. 9.
The relation conefficient of Adsorption Model is in table 2.
The relation conefficient of table 2 kinetics model of biosorption
As can be seen from Fig. 8, Fig. 9 and table 2, the Sorption rate equation of bladder wrack sorbent material of the present invention more meets accurate secondary absorption kinetic model.
4. conclusion
Result of study shows, bladder wrack is to the Cr in solution
6+have good adsorption effect, clearance can reach more than 70%, the impact of the factor such as amount, pH, temperature, adsorption time of adsorption process sorbent suspension, and wherein the amount of sorbent material, pH, temperature are to being adsorbed with considerable influence.
Bladder wrack absorption Cr
6+process can simulate with primary adsorption rate process and secondary absorption rate process, but the simulate effect of secondary absorption rate process is better.
The impact of the adsorption effect after more different modifier modification bladder wrack, result shows through FeCl
3the bladder wrack of modification is to Cr
6+adsorption effect best, clearance is 86.18%, improves 17.78%.
Embodiment 2: the application utilizing metal ion chromium in modification bladder wrack process waste water
First, carry out modification to bladder wrack, concrete grammar is: in bladder wrack, add properties-correcting agent (0.01mol/L, FeCl
3), the ratio of bladder wrack and properties-correcting agent add-on is 1g:70mL, stirs 20 hours under normal temperature, and dries 10 hours in the baking oven of 60 DEG C, grinds with mortar, crosses 80 mesh sieves.
Then join in pending waste water by the bladder wrack after modification, the add-on of bladder wrack is 5g/L (namely adding the bladder wrack after 5g modification in every premium on currency), and regulate pH to be 1, temperature is 30 DEG C, adsorption treatment 7h.
Before and after difference check processing, the concentration of heavy metal in waste water chromium ion, the results are shown in Table 3.
Table 3 modification bladder wrack water treatment effect
| Before process | After process | Adsorption rate | |
| Cr 6+Concentration | 50mg/L | 6.91mg/L | 86.18％， |
Claims (6)
1. utilize a method for modification bladder wrack absorbing heavy metal ions in water chromium, it is characterized in that, step is as follows:
(1) modification of bladder wrack: add properties-correcting agent in bladder wrack, the ratio of bladder wrack and properties-correcting agent add-on is 1g:70-100mL, stirs 18-22 hour under normal temperature, filters, filter residue and drying, pulverizes, sieves;
(2) bladder wrack after step (1) modification is joined in pending water, heavy metal ion chromium adsorbs, and the add-on of bladder wrack is (3-8) g/L, and adjustment pH is 1-1.5, temperature is 30-40 DEG C, adsorption treatment 5-8h;
In step (1), described properties-correcting agent is selected from the iron(ic) chloride of 0.005-0.05mol/L, the solution of dehydrated alcohol and acetic acid 5:1 mixing by volume, the citric acid of 0.1mol/L, any one in the Sulphanilic Acid of 0.1mol/L or acetone.
2. utilize the method for modification bladder wrack absorbing heavy metal ions in water chromium as claimed in claim 1, it is characterized in that, described properties-correcting agent is the iron(ic) chloride of 0.005-0.05mol/L.
3. utilize the method for modification bladder wrack absorbing heavy metal ions in water chromium as claimed in claim 2, it is characterized in that, described properties-correcting agent is the iron(ic) chloride of 0.01mol/L.
4. utilize the method for modification bladder wrack absorbing heavy metal ions in water chromium as claimed in claim 1, it is characterized in that, in step (2), the add-on of bladder wrack is 5g/L.
5. utilize the method for modification bladder wrack absorbing heavy metal ions in water chromium as claimed in claim 1, it is characterized in that, in step (2), pH is 1, and temperature is 30 DEG C.
6. utilize the method for modification bladder wrack absorbing heavy metal ions in water chromium as claimed in claim 1, it is characterized in that, in step (2), the pseudo-second order kinetic model that the bladder wrack heavy metal ion chromium after modification carries out adsorbing is: y=0.0921X+0.1343; Wherein y represent time/adsorptive capacity, X represents the time.
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| CN105668681A (en) * | 2016-01-25 | 2016-06-15 | 长沙理工大学 | Method for adsorbing and removing arsenic and hexavalent chromium in water by using modified shaddock peel |
| CN111170439A (en) * | 2018-11-09 | 2020-05-19 | 天津工业大学 | Citric acid/iron ethylene diamine tetraacetate modified cotton fabric for removing chromium ions in water and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1657430A (en) * | 2005-01-28 | 2005-08-24 | 湖南大学 | Method for adsorbing chromium-contained in industrial waste water using mushroom culture medium waste material |
| KR20110077125A (en) * | 2009-12-30 | 2011-07-07 | 주식회사 포스코 | Method for manufacturing adsorbent of heavy metal and method for removing heavy metal |
| KR101049575B1 (en) * | 2008-12-11 | 2011-07-15 | (주)에코바이오 | Purification and Method for Purifying Arsenic-Contaminated Wastewater Using Natural Adsorbents Made from Seaweeds |
| CN102500334A (en) * | 2011-11-07 | 2012-06-20 | 广东轻工职业技术学院 | Ammonium thiocyanate modified seaweed biotype absorbent and preparation method and application thereof |
| CN102887559A (en) * | 2011-07-21 | 2013-01-23 | 中国科学院生态环境研究中心 | Electrochemical reduction assistance-based biosorption integrated reactor and treatment method of hexavalent chromium-containing wastewater |
| CN103130297A (en) * | 2013-03-21 | 2013-06-05 | 中国环境科学研究院 | Method for treating mercury-containing wastewater by using modified blue-green algae |
| CN103170313A (en) * | 2013-03-29 | 2013-06-26 | 赣县世瑞新材料有限公司 | Heavy metal modified bioadsorbent and preparation method thereof as well as application of heavy metal modified bioadsorbent in tungsten-containing waste water treatment |
-
2015
- 2015-03-23 CN CN201510127697.3A patent/CN104710014B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1657430A (en) * | 2005-01-28 | 2005-08-24 | 湖南大学 | Method for adsorbing chromium-contained in industrial waste water using mushroom culture medium waste material |
| KR101049575B1 (en) * | 2008-12-11 | 2011-07-15 | (주)에코바이오 | Purification and Method for Purifying Arsenic-Contaminated Wastewater Using Natural Adsorbents Made from Seaweeds |
| KR20110077125A (en) * | 2009-12-30 | 2011-07-07 | 주식회사 포스코 | Method for manufacturing adsorbent of heavy metal and method for removing heavy metal |
| CN102887559A (en) * | 2011-07-21 | 2013-01-23 | 中国科学院生态环境研究中心 | Electrochemical reduction assistance-based biosorption integrated reactor and treatment method of hexavalent chromium-containing wastewater |
| CN102500334A (en) * | 2011-11-07 | 2012-06-20 | 广东轻工职业技术学院 | Ammonium thiocyanate modified seaweed biotype absorbent and preparation method and application thereof |
| CN103130297A (en) * | 2013-03-21 | 2013-06-05 | 中国环境科学研究院 | Method for treating mercury-containing wastewater by using modified blue-green algae |
| CN103170313A (en) * | 2013-03-29 | 2013-06-26 | 赣县世瑞新材料有限公司 | Heavy metal modified bioadsorbent and preparation method thereof as well as application of heavy metal modified bioadsorbent in tungsten-containing waste water treatment |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105668681A (en) * | 2016-01-25 | 2016-06-15 | 长沙理工大学 | Method for adsorbing and removing arsenic and hexavalent chromium in water by using modified shaddock peel |
| CN105668681B (en) * | 2016-01-25 | 2018-03-23 | 长沙理工大学 | A kind of method of Cr VI and arsenic in modified pomelo peel Adsorption water |
| CN111170439A (en) * | 2018-11-09 | 2020-05-19 | 天津工业大学 | Citric acid/iron ethylene diamine tetraacetate modified cotton fabric for removing chromium ions in water and preparation method thereof |
| CN111170439B (en) * | 2018-11-09 | 2022-07-12 | 天津工业大学 | Preparation method of citric acid/iron ethylenediamine tetraacetate modified cotton fabric for removing chromium ions in water |
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