CN103922433B - The method of Reactive Brilliant Blue KN-R dyestuff in waste water removed by a kind of nut-shell biomass charcoal sorbent material - Google Patents
The method of Reactive Brilliant Blue KN-R dyestuff in waste water removed by a kind of nut-shell biomass charcoal sorbent material Download PDFInfo
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Abstract
A method for Reactive Brilliant Blue KN-R dyestuff in waste water removed by nut-shell biomass charcoal sorbent material, belongs to technical field of waste water processing.The nut-shell biomass charcoal sorbent material obtained is joined initial pH is 2 ~ 11, in waste water containing 200 ~ 1000mg/L rhdamine B, add sodium-chlor makes its mass percent concentration be 2 ~ 30% simultaneously, to stir at 25 DEG C ~ 45 DEG C or after vibration absorption 12 ~ 24h, filtering separation, filtrate is adjusted to neutral rear discharge.The present invention is simple to operate, with low cost, and non-secondary pollution has industrialization prospect.
Description
Technical field
The invention belongs to technical field of waste water processing, specifically relate to a kind of method utilizing nut-shell biomass charcoal sorbent material to remove Reactive Brilliant Blue KN-R dyestuff in waste water.
Background technology
Dyestuff is widely used in the various industry such as printing and dyeing, leather, papermaking, makeup, paint, rubber, plastics, sterilant, wood preservative.In general, to know from experience to Natural Water containing the discharge of wastewater of 10 ~ 200mg/L dyestuff and cause murder by poisoning even to produce " three cause " effect (i.e. carcinogenic, mutagenesis, teratogenesis shape effect) to organism.Because of its characteristic such as complex structure and difficult degradation, dyestuff is difficult to decolouring, and this makes to remove dyestuff from waste water.According to chemical structure, dyestuff can be divided into azoic dyestuff, anthraquinone dye, triphenylmethane dye etc., and wherein azoic dyestuff is most widely used general, and anthraquinone dye takes second place.By application, conventional dyestuff can be divided into matching stain, basic dyestuff, reactive dyestuffs etc. again.
Compared with traditional dyeing water treatment technology (as ion exchange method, membrane separation process, chemical precipitation method and oxidation reduction process etc.), biosorption process has the irreplaceable advantage of other method in treatment of dyeing and printing, as high efficiency low cost, sorbing material wide material sources, non-secondary pollution etc.Gac is most widely used common adsorbents in dyeing waste water adsorption treatment, but because of expensive and be difficult to regeneration, limit it and further apply.Lot of domestic and foreign scholar successively have studied the adsorption bleaching effect of the cheap materials such as peat, wilkinite, flying dust, clay, tripoli, but these sorbent materials loading capacity is little generally, and need larger dosage.Therefore, the sorbent material developing more Cheap highly effective is necessary very much.Biomass charcoal sorbent material is a kind of typical biological adsorption agent, refers to a kind of biomass generated by cracking or incomplete combustion by the biomass being rich in carbon.Biomass charcoal has the features such as flourishing pore texture, high specific surface area and abundant surface functional group, and this makes biomass charcoal have wide practical use in biological adsorption field.
Agriculture and forestry organic waste material aboundresources, but mostly burned, landfill or abandon, as the agricultural wastes such as stalk burn in field, byproduct such as shell, the skin etc. of food-processing are taken as garbage loading embeading, wood chip, sawdust etc. that forestry products processing produces are simply discarded, not only pollute environment, also create the serious waste of resource.Therefore, how to dispose and utilize agriculture and forestry organic waste material to become one of focus paid close attention to countries in the world.
Walnut is a kind of traditional oil tree, all has establishing in large scale in the multiple area of China.According to statistics, China's walnut annual production 2008 is 830,000 t, and within 2009, be 980,000 t, within 2010, be 1,060,000 t, walnut output increases year by year fast.Current China walnut output occupies first place in the world.Account for 30% of walnut total mass according to the quality of nut-shell to calculate, then the output of nut-shell in 2010 is 31.8 ten thousand t.Walnut was sold as dry fruit in the past, directly abandoned after edible, and its shell is difficult to reclaim.At present, carried out deep processing in food-processing industry to walnut, although its processed side product nut-shell can system recoveries, majority is still burned or is abandoned, and causes the wasting of resources and environmental pollution.The main component of nut-shell is lignin, Mierocrystalline cellulose and hemicellulose, is a kind of fixed carbon and volatile content is higher and the carbonaceous material that ash content is less.If by discarded nut-shell for the preparation of biomass charcoal, its prospect is boundless.In this patent; provide the effective ways utilizing nut-shell to prepare Reactive Brilliant Blue KN-R (anthraquinone dyes) in biomass charcoal sorbent material removal dyeing waste water; not only can alleviate the carrying capacity of environment burned or abandon nut-shell in a large number and cause; can also turn waste into wealth; remove the Reactive Brilliant Blue KN-R dyestuff in waste water; the treatment of wastes with processes of wastes against one another, realizes effective utilization and the water environment protection of nut-shell resource.
Summary of the invention
The object of this invention is to provide a kind of method utilizing Reactive Brilliant Blue KN-R dyestuff in nut-shell biomass charcoal Adsorption waste water of high-efficiency environment friendly.
A kind of nut-shell biomass charcoal sorbent material, its preparation method comprises the following steps:
Nut-shell tap water is cleaned, drying, broken, be sized to 300 ~ 600 μm, liquor zinci chloridi with 30% ~ 70% fully soaks the nut-shell after fragmentation, again after 480 ~ 640W microwave heating, 10 ~ 20min, with the chlorohydric acid pickling gained nut-shell biomass charcoal of 10%, clean to pH in neutral with distilled water, drying, namely obtains nut-shell biomass charcoal sorbent material.
Described walnut is commercially available common walnut (plant JuglansRegia by name, nut-shell is hard and thick).
Nut-shell after preferred fragmentation and the impregnating ratio of liquor zinci chloridi and nut-shell (g): liquor zinci chloridi (g) is 1:6 ~ 1:10.
Above-mentioned nut-shell biomass charcoal sorbent material is for removing the Reactive Brilliant Blue KN-R dyestuff in waste water.
The nut-shell biomass charcoal sorbent material obtained is joined initial pH is 2 ~ 11, in waste water containing 200 ~ 1000mg/L rhdamine B, add sodium-chlor makes its mass percent concentration be 2 ~ 30% simultaneously, to stir at 25 DEG C ~ 45 DEG C or after vibration absorption 12 ~ 24h, filtering separation, filtrate is adjusted to neutral rear discharge.
The mass percent concentration of sodium-chlor is no more than 30%.
When above-mentioned nut-shell biomass charcoal sorbent material is for removing the Reactive Brilliant Blue KN-R in waste water, nut-shell biomass charcoal adsorbent amount is 1 ~ 5g/L, the preferred pH=2 of initial pH of waste water solution, the mass percent concentration of sodium-chlor preferably 2%, adsorption temp preferably 45 DEG C, the concentration of Reactive Brilliant Blue KN-R preferably 200 ~ 800mg/L in Reactive Brilliant Blue KN-R waste water.
Beneficial effect of the present invention is embodied in:
(1) nut-shell biomass charcoal sorbent material of the present invention has fabulous absorption property, and loading capacity is very large, Reactive Brilliant Blue KN-R maximum monolayer adsorption amount Q when 25 DEG C
0909.09mg/g.
(2) compared with the methods such as chemical precipitation, membrane sepn, redox, biological degradation, the method utilizing Reactive Brilliant Blue KN-R dyestuff in nut-shell biomass charcoal Adsorption waste water of the present invention, simple to operate, with low cost, non-secondary pollution, has industrialization prospect.
(3) the nut-shell biomass charcoal sorbent material prepared of the present invention, not only alleviates carrying capacity of environment, simultaneously for the utilization of nut-shell provides new way, achieves effective utilization and the water environment protection of resource.
Accompanying drawing explanation
Fig. 1 is the impact of pH on nut-shell biomass charcoal Adsorption Reactive Brilliant Blue KN-R effect.
Fig. 2 is the impact of sodium chloride concentration on nut-shell biomass charcoal Adsorption Reactive Brilliant Blue KN-R.
Fig. 3 is the impact of Reactive Brilliant Blue KN-R starting point concentration on nut-shell biomass charcoal Adsorption Reactive Brilliant Blue KN-R effect.
Fig. 4 is the Langmuir adsorption isothermal line of nut-shell biomass charcoal adsorption activity brilliant blue KN-R.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail, but the present invention is not restricted to embodiment.
The preparation of sorbent material
Get the shell of the commercially available common walnut of certain mass, clean with tap water, drying, broken, be sized to 300 ~ 600 μm, by the nut-shell after fragmentation and liquor zinci chloridi according to nut-shell quality (g): the ratio hybrid infusion that liquor zinci chloridi quality (g) is 1:6 is in Erlenmeyer flask, wherein the concentration of liquor zinci chloridi is 30%, again after 560W microwave heating 15min, with the chlorohydric acid pickling gained nut-shell biomass charcoal of 10%, clean to pH in neutral with distilled water, drying, namely obtains adsorbent A.
Get the shell of the commercially available common walnut of certain mass, clean with tap water, drying, broken, be sized to 300 ~ 600 μm, by the nut-shell after fragmentation and liquor zinci chloridi according to nut-shell quality (g): the ratio hybrid infusion that liquor zinci chloridi quality (g) is 1:7 is in Erlenmeyer flask, wherein the concentration of liquor zinci chloridi is 40%, again after 520W microwave heating 18min, with the chlorohydric acid pickling gained nut-shell biomass charcoal of 10%, clean to pH in neutral with distilled water, drying, namely obtains adsorbent B.
Get the shell of the commercially available common walnut of certain mass, clean with tap water, drying, broken, be sized to 300 ~ 600 μm, by the nut-shell after fragmentation and liquor zinci chloridi according to nut-shell quality (g): the ratio hybrid infusion that liquor zinci chloridi quality (g) is 1:8 is in Erlenmeyer flask, wherein the concentration of liquor zinci chloridi is 50%, again after 480W microwave heating 20min, with the chlorohydric acid pickling gained nut-shell biomass charcoal of 10%, clean to pH in neutral with distilled water, drying, namely obtains sorbent material C.
Get the shell of the commercially available common walnut of certain mass, clean with tap water, drying, broken, be sized to 300 ~ 600 μm, by the nut-shell after fragmentation and liquor zinci chloridi according to nut-shell quality (g): the ratio hybrid infusion that liquor zinci chloridi quality (g) is 1:9 is in Erlenmeyer flask, wherein the concentration of liquor zinci chloridi is 60%, again after 600W microwave heating 13min, with the chlorohydric acid pickling gained nut-shell biomass charcoal of 10%, clean to pH in neutral with distilled water, drying, namely obtains sorbent material D.
Get the shell of the commercially available common walnut of certain mass, clean with tap water, drying, broken, be sized to 300 ~ 600 μm, by the nut-shell after fragmentation and liquor zinci chloridi according to nut-shell quality (g): the ratio hybrid infusion that liquor zinci chloridi quality (g) is 1:10 is in Erlenmeyer flask, wherein the concentration of liquor zinci chloridi is 70%, again after 640W microwave heating 10min, with the chlorohydric acid pickling gained nut-shell biomass charcoal of 10%, clean to pH in neutral with distilled water, drying, namely obtains sorbent material E.
Embodiment 1
Get sorbent material C and sodium-chlor to add solution ph and be respectively 2,4,7,9,11, in the Reactive Brilliant Blue KN-R solution of 350mg/L, the wherein corresponding 2.0g sodium-chlor of every 0.10g sorbent material C, 50mL Reactive Brilliant Blue KN-R solution, at 35 DEG C stir or vibration 12h after, filtering separation, filtrate is adjusted to neutral rear discharge.
Different initial pH on the impact of Reactive Brilliant Blue KN-R removal effect as shown in Figure 1.Along with pH is increased to 11 by 2, the adsorptive value of sorbent material C to Reactive Brilliant Blue KN-R reduces to 111.93mg/g by 164.44mg/g, shows that the method for removal Reactive Brilliant Blue KN-R of the present invention has optimum handling effect to the waste water that pH=2 contains Reactive Brilliant Blue KN-R.
Embodiment 2
Getting sorbent material D adds in pH=2,600mg/L Reactive Brilliant Blue KN-R solution, wherein every 0.05g sorbent material D corresponding 50mL Reactive Brilliant Blue KN-R solution, add sodium-chlor makes its percent mass concentration be respectively 0%, 2%, 5%, 10%, 15%, 30% simultaneously, at 25 DEG C stir or vibration 15h after, filtering separation, filtrate is adjusted to neutral rear discharge.
Sodium chloride concentration on the impact of Reactive Brilliant Blue KN-R removal effect as shown in Figure 2.As seen from Figure 2, certain density sodium-chlor (≤30%) promotes Reactive Brilliant Blue KN-R.When sodium chloride concentration is between 2% ~ 10%, the adsorptive capacity of sorbent material D to Reactive Brilliant Blue KN-R reduces gradually.Adsorptive capacity increases along with the rising of sodium chloride concentration subsequently.Consider economy and removal efficiency, in the method for Adsorption Reactive Brilliant Blue KN-R of the present invention, add 1.0g sodium-chlor in every 50ml waste water, effect is best.
Embodiment 3
Get sorbent material E and sodium-chlor add pH=2, respectively containing 200,400,600,800, in the solution of 1000mg/L Reactive Brilliant Blue KN-R, the wherein corresponding 2.0g sodium-chlor of every 0.20g sorbent material E, 50mL Reactive Brilliant Blue KN-R solution, at 45 DEG C stir or vibration 20h after, filtering separation, filtrate is adjusted to neutral rear discharge.
Reactive Brilliant Blue KN-R starting point concentration on the impact of Reactive Brilliant Blue KN-R removal effect as shown in Figure 3.Under the driving of concentration gradient, along with Reactive Brilliant Blue KN-R starting point concentration is increased to 800mg/L by 200mg/L, adsorptive capacity rises to 370.86mg/g by 91.46mg/g, and clearance only drops to 90.56% by 93.22%.Reactive Brilliant Blue KN-R concentration is when 1000mg/L, and Reactive Brilliant Blue KN-R adsorptive value is 444.08mg/g, but removal efficiency is only 88.11%.This shows that the method for removal Reactive Brilliant Blue KN-R of the present invention has good treatment effect to the waste water containing 200 ~ 800mg/L Reactive Brilliant Blue KN-R.
Embodiment 4
Get adsorbent A and sodium-chlor joins pH=2 respectively, Reactive Brilliant Blue KN-R concentration is respectively 400,600,800, in 1000mg/L Reactive Brilliant Blue KN-R solution, the wherein corresponding 2.0g sodium-chlor of every 0.25g adsorbent A, 50mL Reactive Brilliant Blue KN-R solution, at 25 DEG C, 35 DEG C, 45 DEG C stir or vibration 24h after, filtering separation, filtrate is adjusted to neutral rear discharge.
Absorption result Langmuir adsorption isothermal line matching, as shown in Figure 4, fitting result is as shown in table 1 for the adsorption isothermal line under differing temps.As can be seen from Fig. 4 and table 1, Langmuir model is fine to the fitting effect of the isothermal adsorption testing data of Reactive Brilliant Blue KN-R to nut-shell biomass charcoal sorbent material, and therefore Langmuir model can describe the isothermal adsorption testing data of nut-shell biomass charcoal sorbent material to Reactive Brilliant Blue KN-R well.
When 25 DEG C, the maximum monolayer adsorption amount Q of the nut-shell biomass charcoal adsorbent Reactive Brilliant Blue KN-R calculated with Langmuir thermoisopleth
0be 909.09mg/g, different sorbent material is to the Q of Reactive Brilliant Blue KN-R
0more as shown in table 2.Result shows: nut-shell biomass charcoal sorbent material of the present invention is enough large to the loading capacity of Reactive Brilliant Blue KN-R, has the application prospect of industrialization.
Table 1Langmuir adsorption isothermal line parameter
The loading capacity of the different sorbent material of table 2 to Reactive Brilliant Blue KN-R compares
| Sorbent material | Maximum monolayer adsorption amount Q 0(mg/g) |
| Orange peel | 26.27 |
| Organically-modified attapulgite | 107.07 |
| Rice hull active carbon | 303.03 |
| Powdered Activated Carbon | 371.75 |
| Nut-shell biomass charcoal (the present invention) | 909.09 |
Above-described embodiment shows, the method utilizing nut-shell biomass charcoal sorbent material to remove Reactive Brilliant Blue KN-R dyestuff in waste water of the present invention, simple to operate, Cheap highly effective, has the application prospect of industrialization.
Claims (1)
1. a method for the Reactive Brilliant Blue KN-R dyestuff in waste water removed by nut-shell biomass charcoal sorbent material, it is characterized in that, comprises the following steps:
(1) shell of the commercially available common walnut of certain mass is got, clean with tap water, drying, fragmentation, be sized to 300 ~ 600 μm, by the nut-shell after fragmentation and liquor zinci chloridi according to nut-shell quality g: liquor zinci chloridi quality g is that the ratio hybrid infusion of 1:6 is in Erlenmeyer flask, wherein the concentration of liquor zinci chloridi is 30%, again after 560W microwave heating 15min, with the chlorohydric acid pickling gained nut-shell biomass charcoal of 10%, clean to pH in neutral with distilled water, drying, namely obtains adsorbent A;
(2) get adsorbent A and sodium-chlor joins pH=2 respectively, Reactive Brilliant Blue KN-R concentration is respectively 400,600,800, in 1000mg/L Reactive Brilliant Blue KN-R solution, the wherein corresponding 2.0g sodium-chlor of every 0.25g adsorbent A, 50mL Reactive Brilliant Blue KN-R solution, at 25 DEG C stir or vibration 24h after, filtering separation, filtrate is adjusted to neutral rear discharge.
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| CN110180500B (en) * | 2019-06-24 | 2022-05-24 | 吕梁学院 | Preparation method of walnut shell biomass carbon photocatalytic degradation-adsorbent and application of walnut shell biomass carbon photocatalytic degradation-adsorbent in removal of rhodamine B in dye wastewater |
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