Detailed description of the invention
Main thought of the present invention is, by utilizing sepiolite powder to prepare adsorbent for raw material, for the treatment of oily waste water, cost is low, and treatment effect is good, and regeneration easily, can Reusability.
For making the object, technical solutions and advantages of the present invention clearly, below in conjunction with specific embodiment, the present invention is described in further detail.
A kind of adsorbent for the treatment of oily waste water according to the embodiment of the present invention provides: it comprises: sepiolite, pore-foaming agent, adhesive and solvent; Wherein, sepiolite, pore-foaming agent, quality proportioning between adhesive and solvent are 8 ~ 10:2 ~ 4:0.1 ~ 0.3:3 ~ 5.
In an embodiment of the present invention, the adsorbent for the treatment of oily waste water comprises 8-10g sepiolite, 2-4g pore-foaming agent, 0.1-0.3g adhesive and 3-5mL solvent.
Preferably, sepiolite is Powdered, and the average grain diameter of sepiolite is 74 ± 1 μm.Sepiolite has larger specific area, heat endurance and salt-resistance higher, the specific area of sepiolite can reach 900 ㎡/g, and larger specific area is conducive to oil-polluted water and is adsorbed to sepiolite surface, there is provided strong adsorptivity, it can absorb the water being greater than himself weight 200 ~ 250%; In preparation or reproducing adsorbent process, higher heat endurance makes this body structure of material to change, and its resistance to elevated temperatures reaches 1500 ~ 1700 DEG C; Oil-polluted water, in processing procedure, needs to add some chemical agents, have the characteristic of high salt, and adsorbent itself has higher salt-resistance after reacting, and can avoid reacting with the medicament in sewage, ensures the stability of adsorbent.The sepiolite choosing uniform particle sizes makes adsorbent, can ensure adsorbent in use, be convenient to even laying, and provide close adsorption capacity.
Preferably, the constituent of sepiolite comprises: SiO2, MgO, CaO, water and partial impurities, wherein: SiO2mass fraction to be the mass fraction of 58 ~ 65%, MgO the be mass fraction of 20 ~ 25%, CaO for being less than or equal to 2.71%, the mass fraction of water is less than or equal to 10%, and the mass fraction of impurity is less than or equal to 9.29%.
In an embodiment of the present invention, every 100g sepiolite comprises the SiO of 58 ~ 65g2, the solvent of the CaO of the MgO of 20 ~ 25g, 2.71g ,≤10mL and the impurity of≤9.29g.
Preferably, the pH value of sepiolite is between 8 ~ 8.5.When sepiolite powder is water-soluble, its pH value, between 7 ~ 9, has more superior adsorption effect after being prepared into adsorbent, pH value be accurately adjusted between 8 ~ 8.5 in order to ensure sepiolite.
Preferably, pore-foaming agent is epsom salt, and chemical formula is MgSO47H2o.MgSO47H2o is soluble in water, is dissolved in the crystallization water of self, loses the tetramolecular crystallization water when 70 ~ 80 DEG C 60 ~ 70 DEG C time.Lose all crystallizations water at 200 DEG C and become anhydride.Pore-foaming agent utilizes the solubility between liquid, hydrophilicrty different, and when meeting water, the space, original place of pore-foaming agent on sepiolite is replaced by water, then pore-foaming agent forms micropore on sepiolite.
Preferably, adhesive is sesbania powder.Sepiolite has elongated needle-like threadiness profile, and is gathered into pencil body, and when sepiolite is soluble in water, raphioid fiber will scatter, and therefore, needs adhesive to be bonded into network-like by the fiber of a large amount of weave in, to improve good adsorption capacity.Sesbania powder good water solubility, dissolution velocity is fast, is a kind of natural plant extracted from Sesbania seed processing.Can be scattered in cold water under normal temperature, water-soluble in thick, form the hydrosol solution that viscosity is very high, its viscosity generally than the sodium alginate under the same terms and starch high 5 ~ 10 times.Stable in pH value 6 ~ 11 scope.Sesbania powder can form the high viscosity elasticity jelly with tridimensional network, and its ratio of viscosities original gelatin is high 10 ~ 50 times, and has good anti-salt property.
Preferably, solvent is water.Sepiolite, pore-foaming agent, adhesive are all soluble in water, therefore select water, distilled water etc. as solvent.
Introduce the preparation method of the above-mentioned adsorbent for the treatment of oily waste water below.
According to a kind of adsorbent method for the preparation of process oily waste water that the embodiment of the present invention provides, comprise the steps:
The first step is dissolved in a heated condition in solvent by pore-foaming agent; Wherein, pore-foaming agent chooses MgSO usually47H2o, measures the MgSO of 2-4g47H2o, solvent chooses distilled water usually, measures 3-5mL distilled water; Water temperature is controlled at 50 DEG C.
Second step is added in the mixture of first step gained by adhesive, stirs and mix; Wherein, sesbania powder chosen usually by adhesive.Wherein, 0.1-0.3g sesbania powder is measured.
3rd step is added in the mixture of second step gained by sepiolite, stirs and mix; Wherein, measure 8-10g sepiolite powder, the average grain diameter of sepiolite is 74 ± 1 μm.
4th step is that the adsorbent mixtures of the 3rd step gained is squeezed into strip, and be dried to shaping after, cut into graininess.
5th step is by granular adsorbent heat-activated.
6th step is the granular adsorbent after taking out activation, namely obtains the adsorbent for the treatment of oily waste water after cooling.
In above-mentioned 4th step, the adsorbent after drying and moulding is cut into graininess, and the diameter of particle is 2 ~ 4mm, and length is 2 ~ 5mm.Granular adsorbent is conducive to oil and is adsorbed on its surface, is convenient to activation or regenerative operation.
In above-mentioned 5th step, the condition that adsorbent carries out activating comprises: activation temperature is 600 DEG C, and soak time is 2 ~ 4h.The object of activation is that structure by changing adsorbent itself is to improve the stability in space on the adsorptivity of adsorbent itself and adsorbent.
By controlling the ratio of each component accurately, and completing preparation process according to above-mentioned steps, adsorbent oily waste water to good removal ability can be obtained.
Introduce the method carrying out after the adsorbent got by above-mentioned preparation method uses regenerating below further.According to a kind of regeneration provided by the invention for the treatment of the adsorbent method of oily waste water, comprise the steps:
A used above-mentioned adsorbent is dried to weight by ().The object done like this is the moisture of adsorbent surface and the mass treatment of poor heat stability to fall, and is evaporated by the moisture in pore, makes a part of lower boiling organic matter also evaporate simultaneously.
B adsorbent thermal regeneration that () will dry in step (a) to weight.Adsorbent reactivation refers to that adsorbate removes by heating or additive method from adsorbent micropore when this body structure of adsorbent does not occur or seldom changes, thus the reusable processing procedure of the adsorbent enabling absorption saturated.
More than (c) repetition step (a) and (b) once.Repeatedly dry and regenerate, the regeneration effect of adsorbent can be improved, usually tertiary recycling operation repeatedly.
Preferably, in step (a), bake out temperature controls at 110 DEG C.The fusing point of grease is lower, and most of grease in liquid or solid state, may solidify above it after being adsorbed on adsorbent at normal temperatures, by drying adsorbent, grease is heated to be liquid state, collects the grease departing from adsorbent.
Preferably, the condition of regeneration comprises: regeneration temperature is 700 DEG C, and the recovery time is 4h.By raising adsorbent temperature, can make adsorbate desorption, adsorbent is regenerated.
Purposes according to a kind of adsorbent for the treatment of oily waste water provided by the invention: adsorbent is for the treatment of oily waste water.The preparation method of adsorbent and adsorbent is described above, no longer repeats at this.
In order to better understand and implement, describe the present invention in detail below in conjunction with embodiment.Below by specific embodiment, further illustrate adsorbent and remove the effect of pollutant and the removal pollutant effect after regenerating.
Embodiment 1:
First, precise 8g sepiolite powder respectively, selected sepiolite is Powdered, and average grain diameter is 74 ± 1 μm, and its constituent comprises: mass fraction is the SiO of 58%2, mass fraction is the MgO of 25%, and mass fraction is the CaO of 2.71%, and mass fraction is the impurity of the water of 10%, mass fraction 4.29%, and pH value is 8.5,2g pore-foaming agent, selects MgSO47H2o, as pore-foaming agent, 0.1g adhesive, selects sesbania powder as adhesive and 3mL solvent, selects distilled water as solvent; Secondly, by measured for scale pore-foaming agent MgSO47H2o adds in beaker, is heated to 50 DEG C of stirring and dissolving, treats MgSO with distilled water47H2after O all dissolves, measured for scale sesbania powder is slowly added in said mixture, is stirred to after mixing, add sepiolite powder, stir.The adsorbent mixtures obtained is put in self-control nodulizer, is first squeezed into strip, then cuts into the absorbent particles that diameter is about 2mm, length is about 2mm after drying.Then, activated in Muffle furnace by absorbent particles, activation temperature is 600 DEG C, and soak time is 2h.So far, adsorbent has been made.
Check the treatment effect of above-mentioned adsorbent below.
Adopt the absorbent particles treatment of simulated oily waste water after activation, simulation oil-containing water sample major parameter is as follows: COD concentration is 1021.00mgL-1, oil concentration is 682.72mgL-1, water sampling 40ml.
Consumption and the adsorption conditions of adsorbent comprise: the consumption of absorbent particles is 25g/L, measures 1g adsorbent as calculated, and adsorption temp is 40 DEG C, and adsorption time is 120min.
After monitoring process, the parameter of water sample is: the clearance of COD can reach 79.52%, and the clearance of oil can reach 78.08%.
As can be seen here, as follows through the adsorption effect of above-mentioned adsorbent to simulated oily wastewater, in water, remaining COD is about 209.10mgL-1, oil concentration is about 149.65mgL-1, above-mentioned adsorbent has good removal effect to COD in simulated oily wastewater and oil, can meet the requirement of preliminary treatment.
Embodiment 2:
First, difference precise: 9g sepiolite powder, selected sepiolite is Powdered, and average grain diameter is 74 ± 1 μm, and its constituent comprises: mass fraction is the SiO of 62%2, mass fraction is the MgO of 23%, and mass fraction is the CaO of 2%, and mass fraction is the impurity of the water of 6%, mass fraction 7%, and pH value is 8.2,3g pore-foaming agent, selects MgSO47H2o, as pore-foaming agent, 0.2g adhesive, selects sesbania powder as adhesive and 4mL solvent, selects distilled water as solvent; Secondly, by measured for scale pore-foaming agent MgSO47H2o adds in beaker, is heated to 50 DEG C of stirring and dissolving, treats MgSO with distilled water47H2after O all dissolves, measured for scale sesbania powder is slowly added in said mixture, is stirred to after mixing, add sepiolite powder, stir.The adsorbent mixtures obtained is put in self-control nodulizer, is first squeezed into strip, then cuts into the absorbent particles that diameter is about 3mm, length is about 4mm after drying.Then, activated in Muffle furnace by absorbent particles, activation temperature is 600 DEG C, and soak time is 3h.So far, adsorbent has been made.
Check the treatment effect of above-mentioned adsorbent below.
Adopt the absorbent particles treatment of simulated oily waste water after activation, simulation oil-containing water sample major parameter is as follows: COD concentration is 1021.00mgL-1, oil concentration is 682.72mgL-1, water sampling 40ml.
Consumption and the adsorption conditions of adsorbent comprise: the consumption of absorbent particles is 25g/L, measures 1g adsorbent as calculated, and adsorption temp is 40 DEG C, and adsorption time is 120min.
After monitoring process, the parameter of water sample is: the clearance of COD can reach 87.05%, and the clearance of oil can reach 82.42%.
As can be seen here, as follows through the adsorption effect of above-mentioned adsorbent to simulated oily wastewater, in water, remaining COD is about 132mgL-1, oil concentration is about 120mgL-1, above-mentioned adsorbent has good removal effect to COD in simulated oily wastewater and oil, can meet the requirement of preliminary treatment.
Embodiment 3:
First, precise 10g sepiolite powder respectively, selected sepiolite is Powdered, and average grain diameter is 74 ± 1 μm, and its constituent comprises: mass fraction is the SiO of 65%2, mass fraction is the MgO of 20%, and mass fraction is the CaO of 2.71%, and mass fraction is the impurity of the water of 3%, mass fraction 9.29%, and pH value is 8,4g pore-foaming agent, selects MgSO47H2o, as pore-foaming agent, 0.3g adhesive, selects sesbania powder as adhesive and 5mL solvent, selects distilled water as solvent; Secondly, by measured for scale pore-foaming agent MgSO47H2o adds in beaker, is heated to 50 DEG C of stirring and dissolving, treats MgSO with distilled water47H2after O all dissolves, measured for scale sesbania powder is slowly added in said mixture, is stirred to after mixing, add sepiolite powder, stir.The adsorbent mixtures obtained is put in self-control nodulizer, is first squeezed into strip, then cuts into the absorbent particles that diameter is about 4mm, length is about 5mm after drying.Then, activated in Muffle furnace by absorbent particles, activation temperature is 600 DEG C, and soak time is 4h.So far, adsorbent has been made.
Check the treatment effect of above-mentioned adsorbent below.
Adopt the absorbent particles treatment of simulated oily waste water after activation, simulation oil-containing water sample major parameter is as follows: COD concentration is 1021.00mgL-1, oil concentration is 682.72mgL-1, water sampling 40ml.
Consumption and the adsorption conditions of adsorbent comprise: the consumption of absorbent particles is 25g/L, measures 1g adsorbent as calculated, and adsorption temp is 40 DEG C, and adsorption time is 120min.
After monitoring process, the parameter of water sample is: the clearance of COD can reach 78.69%, and the clearance of oil can reach 79.33%.
As can be seen here, as follows through the adsorption effect of above-mentioned adsorbent to simulated oily wastewater, in water, remaining COD is about 217.58mgL-1, oil concentration is about 141.12mgL-1, above-mentioned adsorbent has good removal effect to COD in simulated oily wastewater and oil, can meet the requirement of preliminary treatment.
Next, above-mentioned used adsorbent is regenerated, in order to better understand and implement, describe the renovation process of the embodiment of the present invention in detail below in conjunction with embodiment.
Embodiment 4:
By used in embodiment 1, absorption after absorbent particles reclaim, so that subsequent regeneration process.First, by used in embodiment 1, absorption after absorbent particles dry to weight at 110 DEG C; Then, will dry the absorbent particles thermal regeneration to weight, regeneration temperature is 700 DEG C, and the recovery time is 4h.Finally, repeat to dry, the steps such as thermal regeneration, to above-mentioned steps successively in triplicate.
Absorbent particles after regeneration is dropped into test.Adopt the absorbent particles treatment of simulated oily waste water after regeneration, simulation oil-containing water sample major parameter is as follows: COD concentration is 1021.00mgL-1, oil concentration is 682.72mgL-1, get simulated oily wastewater 40ml.
Consumption and the adsorption conditions of adsorbent comprise: the consumption of absorbent particles is 25g/L, measures 1g adsorbent as calculated, and adsorption temp is 40 DEG C, and adsorption time is 120min.
After monitoring process, the parameter of water sample is: the clearance of COD can reach 75.38%, and the clearance of oil can reach 72.51%.
Embodiment 5:
By used in embodiment 2, absorption after absorbent particles reclaim, so that subsequent regeneration process.First, by used in embodiment 2, absorption after absorbent particles dry to weight at 110 DEG C; Then, will dry the absorbent particles thermal regeneration to weight, regeneration temperature is 700 DEG C, and the recovery time is 4h.Finally, repeat to dry, the steps such as thermal regeneration, to above-mentioned steps successively in triplicate.
Absorbent particles after regeneration is dropped into test.Adopt the absorbent particles treatment of simulated oily waste water after regeneration, simulation oil-containing water sample major parameter is as follows: COD concentration is 1021.00mgL-1, oil concentration is 682.72mgL-1, get simulated oily wastewater 40ml.
Consumption and the adsorption conditions of adsorbent comprise: the consumption of absorbent particles is 25g/L, measures 1g adsorbent as calculated, and adsorption temp is 40 DEG C, and adsorption time is 120min.
After monitoring process, the parameter of water sample is: the clearance of COD can reach 77.69%, and the clearance of oil can reach 74.56%.
Embodiment 6:
By used in embodiment 3, absorption after absorbent particles reclaim, so that subsequent regeneration process.First, by used in embodiment 3, absorption after absorbent particles dry to weight at 110 DEG C; Then, will dry the absorbent particles thermal regeneration to weight, regeneration temperature is 700 DEG C, and the recovery time is 4h.Finally, repeat to dry, the steps such as thermal regeneration, to above-mentioned steps successively in triplicate.
Absorbent particles after regeneration is dropped into test.Adopt the absorbent particles treatment of simulated oily waste water after regeneration, simulation oil-containing water sample major parameter is as follows: COD concentration is 1021.00mgL-1, oil concentration is 682.72mgL-1, get simulated oily wastewater 40ml.
Consumption and the adsorption conditions of adsorbent comprise: the consumption of absorbent particles is 25g/L, measures 1g adsorbent as calculated, and adsorption temp is 40 DEG C, and adsorption time is 120min.
After monitoring process, the parameter of water sample is: the clearance of COD can reach 72.11%, and the clearance of oil can reach 70.53%.
As can be seen here, under same experiment condition, compare, although the adsorbent treatment effect after regeneration slightly declines, but after regeneration, adsorbent has good removal effect to COD in simulated oily wastewater and oil, can meet the requirement of pretreatment or preliminary treatment.
Pass through above-described embodiment, adsorbent input simulated oily wastewater after the adsorbent do not come into operation, regeneration is carried out experiment known, the above-mentioned adsorbent of few consumption all has good removal effect to the COD of high concentration and high concentration oil, by the front end of this adsorbent as technological process, the requirement of pretreatment or preliminary treatment can be met.
Embodiment 7:
First, precise respectively: 9g sepiolite powder, 3g pore-foaming agent, selects MgSO47H2o, as pore-foaming agent, 0.1g adhesive, selects sesbania powder as adhesive and 4mL solvent, selects distilled water as solvent; Secondly, by measured for scale pore-foaming agent MgSO47H2o adds in beaker, is heated to 50 DEG C of stirring and dissolving, treats MgSO with distilled water47H2after O all dissolves, measured for scale sesbania powder is slowly added in said mixture, is stirred to after mixing, add sepiolite powder, stir.The adsorbent mixtures obtained is put in self-control nodulizer, is first squeezed into strip, then cuts into the absorbent particles that diameter is about 2mm, length is about 3mm after drying.Then, activated in Muffle furnace by absorbent particles, activation temperature is 600 DEG C, and soak time is 3h.So far, adsorbent has been made.
Check the treatment effect of above-mentioned adsorbent below.
Adopt the actual oily waste water of absorbent particles process machining factory after activation, simulation oil-containing water sample major parameter is as follows: COD concentration is 170.98mgL-1, oil concentration is 72.17mgL-1, water sampling 40ml.
Consumption and the adsorption conditions of adsorbent comprise: the consumption of absorbent particles is 125g/L, measures 5g adsorbent as calculated, and adsorption temp is 40 DEG C, and adsorption time is 120min.
After monitoring process, the parameter of water sample is: the clearance of COD can reach 92.33%, and the clearance of oil can reach 82.57%.
As can be seen here, as follows through the adsorption effect of above-mentioned adsorbent to actual oily waste water, in water, remaining COD is about 13mgL-1, oil concentration is about 13mgL-1.Above-mentioned adsorbent has good removal effect to COD in actual oily waste water and oil, substantially can meet the requirement of discharge.
By embodiment 7, the adsorbent do not come into operation being put into actual oily waste water, to carry out experiment known, and the oil of the isocyatic COD of above-mentioned adsorbent centering and intermediate concentration has good removal effect, arranges the requirement that first order reaction can reach discharge substantially.
In sum, the invention provides a kind of adsorbent for the treatment of oily waste water and preparation, renovation process and purposes, one, adsorbent adopts sepiolite to be substrate, and specific area is large, and Heat stability is good, has good adsorptivity; Pore-foaming agent and adhesive can improve adsorption capacity on the existing basis of sepiolite; Its two, adsorbent is made into graininess, and activates, from shape and activity, the absorption property of adsorbent can be improved further, improve the treatment effect to oily waste water; Its three, by thermal regeneration adsorbent, favorable regeneration effect, can Reusability, and after regeneration, adsorbent has good absorption property; They are four years old, preparation and renovation process operating procedure simple, a small amount of adsorbent just can reach process high concentration, intermediate concentration oily waste water effective, according to the actual parameter of oily waste water, as pretreatment or preliminary treatment goods advanced treating step, different removal objects can be realized.
The foregoing is only embodiments of the invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within right of the present invention.