CN110876919B - Preparation method of high-salinity wastewater nitrate radical adsorbent - Google Patents
Preparation method of high-salinity wastewater nitrate radical adsorbent Download PDFInfo
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Abstract
The invention belongs to the field of sewage treatment, and particularly relates to a preparation method of a nitrate radical adsorbent for high-salinity wastewater. The preparation method of the high-salt wastewater nitrate radical adsorbent comprises the steps of respectively preparing hydrotalcite with adjustable and controllable interlayer structures and polypyrrole-modified montmorillonite, changing the surface electrical property of the material by utilizing the adjustable and variable characteristics of the type and quantity of positive ions of a hydrotalcite polar plate, forming steric hindrance by utilizing the modification of the polypyrrole-modified montmorillonite, and finally carrying out composite bonding intercalation on the hydrotalcite and the montmorillonite to form a layered structure composite material with certain steric hindrance, wherein the layered structure composite material is applied to adsorbing nitrate radicals in high-salt wastewater (particularly high-salt wastewater with high sulfate radical content), has good adsorption selectivity and adsorption capacity, and has the removal rate of the nitrate radicals in the wastewater of more than or equal to 57%.
Description
Technical Field
The invention belongs to the field of sewage treatment, and particularly relates to a preparation method of a nitrate radical adsorbent for high-salinity wastewater.
Background
Nitrate will pass through after accumulating in human bodyNitrite is generated by the action of nitrate reductase, and is converted into nitrosamine and nitrosophthalide which are carcinogenic, teratogenic and mutagenic under the action of various nitrogenous organic compounds such as amine, urea, cyanamide and the like, so that various tumors such as intestinal tumors, nervous system tumors, brain tumors, skin tumors, bone tumors and the like are induced to generate in a human body. Nitrate is also easy to cause goiter, inhibits the thyroid from taking in inorganic iodine, and even in a water body with high iodine content, if the content of nitrate in water is high, endemic goiter is easy to cause. Nitrite also reacts with hemoglobin in the blood to form methemoglobin, which affects the oxygen transport in the blood and makes the cell tissue anoxic, even leading to respiratory cycle failure in severe cases. Compared with adults, infants are sensitive to the potential toxicity of nitrate, and when the content of the nitrate in drinking water reaches 90-140mg/L, the infants are easy to suffer from methemoglobinemia, the skin of the infants turns into blue gray, which is commonly called as 'blue infant disease', and serious people can cause suffocation. Since nitrate pollution can be harmful to human health, various countries around the world set standards for nitrate content in drinking water, where the world health organization stipulates Nitrate (NO) 3 -N) not more than 10mg/L, Nitrite (NO) 2 -N) not more than 0.91mg/L, the U.S. EPA specified maximum limit being (NO) 3 -N)10mg/L,(NO 2 -N)1mg/L, and the content of nitrate nitrogen in water is less than or equal to 10mg/L according to the water quality standard of domestic drinking water (GBS749-2006) in China.
The pollution of nitrate has received extensive attention, and the research on the nitrate control technology is increasing at home and abroad. At present, the control technology of nitrate mainly comprises a biological method, a physical chemical method and a chemical reduction method. The biological method is a method for gradually converting nitrogen-containing substances in sewage into nitrogen under the action of microorganisms. The physical and chemical methods mainly include a membrane separation method, an ion exchange method and an adsorption method. However, these methods generally have high running cost and complicated regeneration process. The chemical reduction method is a very effective method for degrading nitrate, but how to reduce harmful substances, namely ammonia nitrogen and nitrite in a reduction product and improve the selectivity of nitrogen of the reduction product is a research hotspot at present. Although the catalytic hydrogenation reduction method can effectively improve the selectivity of nitrogen in the reduction product, the method uses hydrogen as a reducing agent, has certain potential safety hazard, and has low solubility of hydrogen in water and low utilization rate.
Patent CN 107694541A discloses a preparation and application of a nitrate treating agent, which takes cotton as a template, adopts a coprecipitation method to synthesize zinc-titanium-iron ternary hydrotalcite-like compound with biological morphology, and obtains the nitrate treating agent by roasting in a muffle furnace. The invention also provides application of the nitrate treating agent prepared by the method in nitrate wastewater treatment. The nitrate treating agent prepared by the method has good adsorption effect on nitrate, is convenient to separate, has simple and easy regeneration method, and has wide application prospect in the field of nitrate wastewater treatment. But the treatment agent has better effect when being applied to the treatment of the conventional nitrate-containing wastewater, and does not relate to the absorption of nitrate in high-salinity wastewater. The salt content in the high-salt wastewater severely limits the adsorption effect of the adsorbent, so that the adsorbent needs to have certain adsorption selectivity in the process of adsorbing nitrate by the high-salt wastewater.
In the literature, "research on adsorption and degradation of nitrate ions by modified montmorillonite", authors provide that modified montmorillonite is obtained by exchanging interlayer cations of montmorillonite with polydiallyldimethylammonium chloride, and the structural ferric ions of montmorillonite are chemically reduced to the structural ferrous ions. The capacity of unmodified montmorillonite in different oxidation states for adsorbing and degrading nitrate ions is measured; the level of nitrate ion adsorption by the oxidized modified montmorillonite under different charging conditions; the ability of the reduced modified montmorillonite to degrade nitrate ions. The experimental results show that: the oxidized unmodified montmorillonite can hardly adsorb and reduce and degrade nitrate ions; the reduced state unmodified montmorillonite can absorb nitrate ions of about 0.0054mmol/g, and generates a very small amount of low-valence nitro products; the oxidation state modified montmorillonite can adsorb nitrate ions of 0.23mmol/g, and the adsorption capacity of the oxidation state modified montmorillonite is increased along with the increase of the concentration of interlayer polymerization cations. The modified clay mineral is proved to be capable of strongly adsorbing nitrate ions, and a potential research direction is provided for the treatment of nitrate ion pollution. The article also does not relate to the treatment of waste water in which sulfate ions are present in the waste water in competition for adsorption with nitrate ions.
Currently, nitrate radical adsorbents are mostly applied to treating conventional wastewater containing nitrate radical ions, and the salt content in the wastewater is low. However, when the adsorbent is applied to the treatment of high-salinity wastewater, other anions in the wastewater rapidly occupy the adsorption sites on the surface of the adsorbent due to the competitive adsorption effect, so that the adsorption effect of nitrate is reduced.
Disclosure of Invention
The invention aims to provide a preparation method of a nitrate radical adsorbent for high-salinity wastewater, the prepared adsorbent is applied to adsorbing high-salinity wastewater, particularly high-salinity wastewater with higher sulfate radical content, the adsorption selectivity and the adsorption capacity of nitrate radicals have better effects, and the removal rate of nitrate radicals in the wastewater is more than or equal to 57%.
The preparation method of the nitrate adsorbent for high-salinity wastewater comprises the following steps:
stage one, hydrotalcite preparation:
(1) preparation of Mg (NO) 3 ) 2 ·6H 2 O and Fe (NO) 3 ) 3 ·9H 2 Mixed salt solution A of O, NaOH and Na 2 CO 3 The mixed solution B of (1);
(2) adding deionized water into a reactor, dropwise adding the mixed salt solution A and the mixed solution B into the reactor, stirring vigorously, and controlling the pH value of the mixed stirring liquid in the reactor to be 9-10;
(3) after the dropwise addition is finished, the slurry is subjected to heat preservation and stirring at 60 ℃, aged for 12 hours, the formed hydrotalcite is filtered and washed, and a filter cake is transferred to a crucible and dried for later use;
and stage two, modifying the montmorillonite polypyrrole:
(4) pulverizing montmorillonite raw soil to less than 50 meshes, adding into deionized water, stirring with a stirrer for 30-60 min, standing, removing montmorillonite slurry on the upper layer, and removing sand and stone on the lower layer; adjusting the pH value of the montmorillonite slurry to acidity, then heating and flocculating for 10-15 minutes, standing at room temperature, drying after centrifugal separation, and grinding to obtain montmorillonite fine soil;
(5) adding refined montmorillonite soil into deionized water, stirring for 60-90min, and adding FeCl of the same quality as the refined montmorillonite soil at 25-35 deg.C 3 Then adding pyrrole, reacting for 3-4h at 30 ℃, respectively centrifugally washing for 3-4 times by using water and acetone to obtain modified montmorillonite, and drying for later use;
and a third stage: high shear bonding;
(6) and (3) adding the hydrotalcite prepared in the step (3) and the modified montmorillonite prepared in the step (5) into deionized water, shearing for 60-90min by using a high-shear disperser, centrifugally washing for 3 times by using the deionized water, drying in an air-blast drying box at 110 ℃, roasting a dried sample at 250-300 ℃ for 4h, and preparing the nitrate radical adsorbent.
Wherein:
in the step (1), in the mixed salt solution A, Mg 2+ The mass concentration of the substance is 0.6-0.8mol/L, Fe 3+ The mass concentration of the substance is 0.15-0.2 mol/L; in the mixed solution B, Na 2 CO 3 The mass concentration of the substance is 0.3-0.4mol/L, and the mass concentration of the NaOH substance is 1.5-2 mol/L.
In the step (2), the dropping speed is 600-800ml/h, and the volume ratio of the deionized water to the mixed salt solution A to the mixed solution B is 2: 1: 1-2.5: 1: 1.
in the step (3), the drying temperature is 105 ℃, and the drying time is 12 hours.
In the step (4), the mass ratio of the montmorillonite raw soil to the deionized water is 0.05-0.2: 1.
in the step (4), the granularity of the montmorillonite fine soil is less than 200 meshes.
In the step (5), the mass ratio of the montmorillonite refined soil to the deionized water is 0.05-0.2: 1.
in the step (5), the mass ratio of the pyrrole to the montmorillonite fine soil is 0.06-0.25: 1.
in the step (6), the mass ratio of the hydrotalcite to the modified montmorillonite is 1: 2-4: 1.
preferably, the preparation method of the nitrate adsorbent for high-salt wastewater provided by the invention specifically comprises the following steps:
stage one, hydrotalcite preparation:
(1) preparation Mg(NO 3 ) 2 ·6H 2 O and Fe (NO) 3 ) 3 ·9H 2 Mixed salt solution A of O, solution Mg 2+ The mass concentration of the substance is 0.6-0.8mol/L, Fe 3+ The mass concentration of the substance is 0.15-0.2 mol/L; preparing NaOH and Na 2 CO 3 Mixed solution B of (1), Na in solution 2 CO 3 The mass concentration of the substance is 0.3-0.4mol/L, and the mass concentration of the NaOH substance is 1.5-2 mol/L. Mixing the mixed salt solution A and the mixed salt solution B according to a volume ratio of 1: a ratio of 1 for standby.
(2) Adding a certain volume of deionized water into a reactor, dropwise adding the mixed salt solution A and the mixed solution B into the reactor, stirring vigorously, and controlling the pH value of the mixed stirring liquid in the reactor to be 9-10. Wherein the dropping speed is 600-800ml/h, and the volume ratio of the deionized water to the solution A and the solution B is 2: 1: 1-2.5: 1: 1.
(3) after titration, the slurry is stirred at the temperature of 60 ℃ and aged for 12 h. Filtering the formed hydrotalcite after aging, washing and filtering repeatedly for three times, transferring a filter cake into a crucible, drying for 12 hours in a drying oven at 105 ℃, and placing the product into a dryer for later use.
And stage two, modifying the montmorillonite polypyrrole:
(4) pulverizing raw montmorillonite soil to less than 50 meshes, weighing a certain mass of pulverized montmorillonite, and adding the montmorillonite into a certain volume of deionized water, wherein the mass ratio of the montmorillonite to the deionized water is 0.05-0.2: 1, stirring for 30-60 minutes by a stirrer, standing, removing montmorillonite slurry on the upper layer, and removing sand and stones on the lower layer. Adjusting the pH value of the montmorillonite slurry on the upper layer to be acidic, then heating and flocculating for 10-15 minutes on an electric furnace, standing for a certain time at room temperature, centrifugally separating to remove partial water and salt, drying, and grinding to obtain the montmorillonite fine soil with a certain particle size.
(5) Adding purified montmorillonite refined soil into deionized water according to the mass ratio of 0.05-0.2, mechanically stirring for 60-90min, and adding FeCl with the same mass as montmorillonite at the controlled temperature of 25-35 deg.C 3 Then adding pyrrole with the mass ratio of 0.06-0.25 to the montmorillonite, reacting for 3-4h at 30 ℃, and respectively centrifugally washing with water and acetoneAfter 3-4 times, obtaining the modified montmorillonite, and drying for later use.
And a third stage: high shear bonding
(6) Mixing the hydrotalcite prepared in the step (3) and the modified montmorillonite prepared in the step (5) according to the mass ratio of 1: 1-4: 1, shearing the mixture for 60-90min by a high-shear disperser, centrifugally washing the mixture for 3 times by deionized water, drying the mixture in an air drying oven at 110 ℃, and roasting the dried sample for 4 hours at 300 ℃ to prepare the nitrate radical adsorbent.
The method takes the desulfurization and denitrification wastewater of the oil refinery as the target water quality, the wastewater is high-salinity wastewater, the content of nitrate ions in the wastewater is 300-plus-300 ppm, the content of sulfate ions in the wastewater is 3000ppm, the conventional nitrate radical adsorbent is adopted, the adsorption effect is poor, and the removal rate of nitrate radicals in the wastewater is more than or equal to 57 percent when the adsorbent provided by the patent is adopted to treat the wastewater.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention respectively prepares hydrotalcite with adjustable and controllable interlayer structure and polypyrrole modified montmorillonite, utilizes the adjustable and variable characteristics of the type and the quantity of cations of a hydrotalcite polar plate to change the surface electrical property of the material, utilizes the modification of the montmorillonite and the polypyrrole to form steric hindrance, and finally carries out composite bonding intercalation on the hydrotalcite and the montmorillonite to form a layered structure composite material with certain steric hindrance.
2. The adsorbent prepared by the invention is applied to the process of adsorbing nitrate radical in high-salt wastewater, can be regenerated and reused through an adsorbent regeneration tower at 220 ℃ after the adsorption of the adsorbent is saturated, and can be applied to the process of adsorbing nitrate radical in high-salt wastewater after the regeneration is finished, so that the removal rate of the nitrate radical is still stable to be more than or equal to 57%.
Detailed Description
The present invention is further described below with reference to examples.
The starting materials used in the examples are all commercially available except where otherwise indicated.
Example 1
The preparation method of the high-salinity wastewater nitrate radical adsorbent comprises the following steps:
(1) 2L of Mg (NO) is prepared 3 ) 2 ·6H 2 O and Fe (NO) 3 ) 3 ·9H 2 Mixed salt solution A of O, in solution, Mg 2+ The mass concentration of the substance is 0.6mol/L, Fe 3+ The mass concentration of the substance is 0.15 mol/L; preparation of 2L NaOH and Na 2 CO 3 Mixed solution B, Na of 2 CO 3 The mass concentration of the substance is 0.3mol/L, and the mass concentration of the NaOH substance is 1.5 mol/L. After 4L of deionized water is added into the reactor, the mixed salt solution A and the mixed solution B are dropwise added into the reactor at the dropping speed of 800ml/h while being vigorously stirred, and the pH value of the mixed and stirred solution in the reactor is controlled to be 9. After titration, the slurry is stirred at the temperature of 60 ℃ and aged for 12 hours. Filtering the formed hydrotalcite after aging, washing and filtering repeatedly for three times, transferring a filter cake into a crucible, drying for 12 hours in a drying oven at 105 ℃, and placing the product into a dryer for later use.
(2) Weighing 1kg of raw montmorillonite, crushing to less than 50 meshes, weighing 0.5kg of crushed montmorillonite, adding 10L of deionized water, stirring for 30 minutes by using a stirrer, standing, removing montmorillonite slurry on the upper layer, and removing sand and stones on the lower layer. Adjusting the pH value of the montmorillonite slurry on the upper layer to acidity, then heating and flocculating for 10 minutes on an electric furnace, standing for a certain time at room temperature, centrifugally separating to remove partial water and salt, drying and grinding. Adding 100g of finely ground montmorillonite fine soil into 2L of deionized water, mechanically and vigorously stirring for 60min, controlling the temperature to be below 25 ℃, and adding FeCl 3 100g, then adding 12.5ml of pyrrole, reacting for 3h at 30 ℃, respectively centrifugally washing for 3 times by using water and acetone to obtain the modified montmorillonite, and drying for later use.
(3) Accurately weighing 5g of hydrotalcite for later use in the step (1) and 10g of modified montmorillonite for later use in the step (2), adding the hydrotalcite and the modified montmorillonite into 1L of deionized water, shearing the mixture for 60min by using a high-shear disperser, centrifugally washing the mixture for 3 times by using the deionized water, drying the mixture in a forced air drying oven at 110 ℃, and roasting the dried sample for 4 hours at 250 ℃ to prepare the nitrate radical adsorbent.
Taking desulfurization and denitrification wastewater of an oil refinery, wherein the concentration of nitrate in the wastewater is 300mg/L, the concentration of sulfate radical is 2880mg/L, the dosage of a nitrate radical adsorbent is 1g/L, the reaction time is 60min, after sedimentation is performed for 30min, supernatant is taken for detection, the concentration of nitrate radical in effluent is 126mg/L, the removal rate of nitrate radical is 58%, the concentration of sulfate radical in effluent is 2825mg/L, and the adsorption quantity of sulfate radical is 55mg/L, which shows that the adsorbent has a better selective adsorption effect on nitrate radical in the desulfurization and denitrification wastewater.
After the absorbent is adsorbed and saturated, the absorbent is placed in a muffle furnace for regeneration at 220 ℃, the absorbent is repeatedly used in the nitrate radical adsorption process of high-salinity wastewater after regeneration, and the nitrate radical removal rate can be stably maintained above 57%.
Example 2
The preparation method of the high-salinity wastewater nitrate radical adsorbent comprises the following steps:
(1) formulation 2LMg (NO) 3 ) 2 ·6H 2 O and Fe (NO) 3 ) 3 ·9H 2 Mixed salt solution A of O, in solution, Mg 2+ The mass concentration of the substance is 0.8mol/L, Fe 3+ The mass concentration of the substance is 0.2 mol/L; configuration 2LNaOH and Na 2 CO 3 Mixed solution B, Na of 2 CO 3 The mass concentration of the substance is 0.4mol/L, and the mass concentration of the NaOH substance is 2.0 mol/L. After 5L of deionized water is added into the reactor, the mixed salt solution A and the mixed solution B are dropwise added into the reactor at a dropping speed of 600ml/h while being stirred vigorously, and the pH value of the mixed and stirred solution in the reactor is controlled to be 10. After titration, the slurry is stirred at the temperature of 60 ℃ and aged for 12 hours. Filtering the formed hydrotalcite after aging, washing and filtering repeatedly for three times, transferring a filter cake into a crucible, drying for 12 hours in a drying oven at 105 ℃, and placing the product into a dryer for later use.
(2) Weighing raw montmorillonite soil 2kg, pulverizing to less than 50 mesh, weighing the pulverized raw montmorillonite, adding into a plastic bucket, adding 10L deionized water, stirring with a stirrer for 60min, standing, removing the upper layer montmorillonite slurry, and removing the lower layer sandstone. Adjusting pH of the montmorillonite slurry to acidity, heating and flocculating for 15 min in an electric furnace, standing at room temperature for a certain time, centrifuging to remove partial water and salt, oven drying, and mixingAnd (4) grinding. Adding 200g of finely ground montmorillonite fine soil into 1L of deionized water, mechanically and violently stirring for 90min, controlling the temperature to be below 35 ℃, and adding FeCl 3 200g, then adding 25ml of pyrrole, reacting for 4h at 30 ℃, respectively centrifugally washing for 4 times by using water and acetone to obtain the modified montmorillonite, and drying for later use.
(3) Accurately weighing 20g of hydrotalcite for later use in the step (1) and 5g of modified montmorillonite for later use in the step (2), adding the hydrotalcite and the modified montmorillonite into 2L of deionized water, shearing the mixture for 90min by using a high-shear disperser, centrifugally washing the mixture for 3 times by using the deionized water, drying the mixture in a forced air drying oven at 110 ℃, and roasting the dried sample for 4 hours at 300 ℃ to prepare the nitrate radical adsorbent.
Taking desulfurization and denitrification wastewater of an oil refinery, wherein the nitrate concentration of the wastewater is 270mg/L, the sulfate concentration is 2830mg/L, the adding amount of a nitrate adsorbent is 1g/L, the reaction time is 60min, after sedimentation is performed for 30min, supernatant is taken for detection, the nitrate concentration of effluent is 115mg/L, the removal rate of nitrate is 57.4%, the sulfate concentration of effluent is 2792mg/L, and the sulfate adsorption amount is 38mg/L, which shows that the adsorbent has a better selective adsorption effect on nitrate in the desulfurization and denitrification wastewater.
After the adsorption of the adsorbent is saturated, the adsorbent is placed in a muffle furnace for regeneration at 220 ℃, and the regenerated adsorbent is repeatedly used in the nitrate adsorption process of high-salt wastewater, so that the nitrate removal rate can be stably maintained at over 57 percent.
Comparative example 1
The magnesium-aluminum hydrotalcite commodity sold in the market is applied to desulfurization and denitrification wastewater of a certain oil refinery, the nitrate concentration of the wastewater is 270mg/L, the adding amount of the nitrate adsorbent is 1g/L, the reaction time is 60min, after sedimentation is carried out for 30min, supernatant is taken for detection, the nitrate concentration of effluent is 267mg/L, the nitrate removal rate is 1.1%, and the removal effect is poor.
Comparative example 2
When the magnesium-iron hydrotalcite prepared in the step (1) in the embodiment 1 is applied to desulfurization and denitrification wastewater of a certain oil refinery, the nitrate concentration of the wastewater is 270mg/L, the sulfate concentration is 2830mg/L, the adding amount of the hydrotalcite is 1g/L, the reaction time is 60min, after the hydrotalcite is settled for 30min, a supernatant is taken for detection, the nitrate concentration of effluent is 219mg/L, the removal rate of nitrate is 18.9%, the sulfate concentration of effluent is 2770mg/L, the sulfate adsorption capacity is 60mg/L, and the removal effect is poor.
Comparative example 3
The pyrrole-modified montmorillonite prepared in the step (2) in the example 1 is independently applied to desulfurization and denitrification wastewater of an oil refinery, the nitrate concentration of the wastewater is 270mg/L, the sulfate radical concentration is 2830mg/L, the adding amount of hydrotalcite is 1g/L, the reaction time is 60min, after the precipitation is carried out for 30min, a supernatant is taken for detection, the effluent nitrate concentration is 185mg/L, the nitrate radical removal rate is 31.5%, the effluent sulfate radical concentration is 2810mg/L, and the sulfate radical adsorption amount is 20 mg/L.
Comparative example 4
10g of magnesium-iron hydrotalcite prepared in the step (1) of the example 1 and 2g of pyrrole-modified montmorillonite prepared in the step (2) of the example 1 are added into 2L of deionized water, and after being sheared for 90min by a high shear disperser, the mixture is centrifugally washed for 3 times by the deionized water, and then the mixture is dried in a forced air drying oven at 110 ℃, and a sample is roasted for 4h at 300 ℃ after being dried, so that the nitrate radical adsorbent is prepared.
The adsorbent is used for desulfurization and denitrification wastewater of a certain oil refinery, the concentration of nitrate in the wastewater is 300mg/L, the concentration of sulfate radical in the wastewater is 2880mg/L, the dosage of the nitrate radical adsorbent is 1g/L, the reaction time is 60min, after sedimentation is carried out for 30min, supernatant is taken for detection, the concentration of nitrate radical in effluent is 176mg/L, the removal rate of nitrate radical is 41.3%, the concentration of sulfate radical in effluent is 2799mg/L, and the adsorption quantity of sulfate radical is 81 mg/L.
Comparative example 5
5g of magnesium-iron hydrotalcite prepared in the step (1) of the example 1 and 10g of pyrrole-modified montmorillonite prepared in the step (2) of the example 1 are added into 2L of deionized water, and after being sheared for 90min by a high shear disperser, the mixture is centrifugally washed for 3 times by the deionized water, and then the mixture is dried in a forced air drying oven at 110 ℃, and a sample is roasted for 4h at 300 ℃ after being dried, so that the nitrate radical adsorbent is prepared.
The adsorbent is used for desulfurization and denitrification wastewater of a certain oil refinery, the concentration of nitrate in the wastewater is 300mg/L, the concentration of sulfate radical in the wastewater is 2880mg/L, the dosage of the nitrate radical adsorbent is 1g/L, the reaction time is 60min, after 30min of sedimentation, supernatant liquid is taken for detection, the concentration of nitrate radical in effluent is 169mg/L, the removal rate of nitrate radical is 43.6%, the concentration of sulfate radical in effluent is 2811mg/L, and the adsorption quantity of sulfate radical is 69 mg/L.
Comparative example 6
The carbon nano tube and the powdered activated carbon are respectively applied to desulfurization and denitrification wastewater of a certain oil refinery, the nitrate concentration of the wastewater is 270mg/L, the adding amount of the carbon nano tube and the powdered activated carbon is 1g/L, the reaction time is 60min, after 30min of sedimentation, a supernatant is taken for detection, the nitrate concentration of effluent water adsorbed by the carbon nano tube is 175mg/L, the removal rate of the nitrate is 35.2%, the nitrate concentration of effluent water adsorbed by the powdered activated carbon is 182mg/L, and the nitrate concentration is 32.6%.
Comparative example 7
The method comprises the steps of modifying commercially available zeolite with hydrochloric acid, and then applying the modified zeolite to desulfurization and denitrification wastewater of a certain oil refinery, wherein the nitrate concentration of the wastewater is 270mg/L, the adding amount of the modified zeolite is 1g/L, the reaction time is 60min, after settling for 30min, the supernatant is taken for detection, the nitrate concentration of effluent is 218mg/L, and the nitrate removal rate is 19.3%.
Comparative example 8
The method comprises the steps of preparing zinc-titanium-iron ternary hydrotalcite, applying the zinc-titanium-iron ternary hydrotalcite to desulfurization and denitrification wastewater of an oil refinery, wherein the nitrate concentration of the wastewater is 270mg/L, the sulfate concentration is 2830mg/L, the adding amount of the zinc-titanium-iron ternary hydrotalcite is 1g/L, the reaction time is 60min, after settling for 30min, taking supernate for detection, the nitrate concentration of effluent is 142mg/L, the removal rate of nitrate is 47.4%, the sulfate concentration is 2620mg/L, and the sulfate adsorption capacity is 210 mg/L.
Comparative example 9
The adsorbent prepared in example 1 is applied to low-salt wastewater, the nitrate concentration in the wastewater is 190mg/L, sulfate ions cannot be basically detected, the dosage of the nitrate adsorbent is 0.5g/L, the reaction time is 60min, after sedimentation is carried out for 30min, supernatant is taken for detection, the nitrate concentration of effluent is 10mg/L, and the nitrate removal rate is 94.7%.
Comparative example 10
When the adsorbent prepared in example 1 is applied to certain low-salt wastewater, the nitrate concentration in the wastewater is 190mg/L, sulfate ions cannot be basically detected, the dosage of the nitrate adsorbent is 1g/L, the reaction time is 60min, after sedimentation is carried out for 30min, supernatant is taken for detection, the nitrate concentration of effluent is 7mg/L, and the nitrate removal rate is 96.3%.
Claims (8)
1. A preparation method of a high-salinity wastewater nitrate adsorbent is characterized by comprising the following steps: the method comprises the following steps:
stage one, hydrotalcite preparation:
(1) preparation of Mg (NO) 3 ) 2 ·6H 2 O and Fe (NO) 3 ) 3 ·9H 2 Mixed salt solution A of O, NaOH and Na 2 CO 3 The mixed solution B of (1);
(2) adding deionized water into a reactor, dropwise adding the mixed salt solution A and the mixed solution B into the reactor, stirring simultaneously, and controlling the pH value of the mixed stirring liquid in the reactor to be 9-10;
(3) after the dropwise addition is finished, the slurry is subjected to heat preservation and stirring at 60 ℃, aged for 12 hours, the formed hydrotalcite is filtered and washed, and a filter cake is transferred to a crucible and dried for later use;
and stage two, modifying the montmorillonite polypyrrole:
(4) pulverizing montmorillonite raw soil to less than 50 meshes, adding into deionized water, stirring for 30-60 min, standing, removing montmorillonite slurry on the upper layer, and removing sand and stone on the lower layer; adjusting the pH value of the montmorillonite slurry to acidity, then heating and flocculating for 10-15 minutes, standing at room temperature, centrifugally separating, drying, and grinding to obtain montmorillonite fine soil;
(5) adding refined montmorillonite soil into deionized water, stirring for 60-90min, and adding FeCl with the same mass as the refined montmorillonite soil at 25-35 deg.C 3 Then adding pyrrole, reacting for 3-4h at 30 ℃, respectively centrifugally washing for 3-4 times by using water and acetone to obtain modified montmorillonite, and drying for later use;
and a third stage: high shear bonding;
(6) adding the hydrotalcite prepared in the step (3) and the modified montmorillonite prepared in the step (5) into deionized water, shearing for 60-90min by using a high-shear disperser, centrifugally washing for 3 times by using the deionized water, drying in a forced air drying box at 110 ℃, roasting a dried sample for 4h at 250-300 ℃ to prepare a nitrate radical adsorbent;
in the step (6), the mass ratio of the hydrotalcite to the modified montmorillonite is 1: 2-4: 1;
the content of nitrate ions in the high-salt wastewater is 100-300ppm, and the content of sulfate ions in the high-salt wastewater is 2000-3000 ppm.
2. The method for preparing the nitrate adsorbent for high-salt wastewater according to claim 1, wherein: in the step (1), in the mixed salt solution A, Mg 2+ The mass concentration of the substance is 0.6-0.8mol/L, Fe 3+ The mass concentration of the substance is 0.15-0.2 mol/L; in the mixed solution B, Na 2 CO 3 The mass concentration of the substance is 0.3-0.4mol/L, and the mass concentration of the NaOH substance is 1.5-2 mol/L.
3. The method for preparing the nitrate adsorbent for high-salt wastewater according to claim 1, wherein: in the step (2), the dropping speed is 600-800mL/h, and the volume ratio of the deionized water to the mixed salt solution A to the mixed solution B is 2: 1: 1-2.5: 1: 1.
4. the method for preparing the nitrate adsorbent for high-salt wastewater according to claim 1, wherein: in the step (3), the drying temperature is 105 ℃, and the drying time is 12 hours.
5. The method for preparing the nitrate adsorbent for high-salt wastewater according to claim 1, wherein: in the step (4), the mass ratio of the montmorillonite raw soil to the deionized water is 0.05-0.2: 1.
6. the method for preparing the nitrate adsorbent for high-salt wastewater according to claim 1, wherein: in the step (4), the granularity of the montmorillonite fine soil is less than 200 meshes.
7. The method for preparing the nitrate adsorbent for high-salt wastewater according to claim 1, wherein: in the step (5), the mass ratio of the montmorillonite refined soil to the deionized water is 0.05-0.2: 1.
8. the method for preparing the nitrate adsorbent for high-salt wastewater according to claim 1, wherein: in the step (5), the mass ratio of the pyrrole to the montmorillonite fine soil is 0.06-0.25: 1.
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