CN114192113A - Preparation method of renewable modified kaolin for adsorbing petrochemical wastewater - Google Patents
Preparation method of renewable modified kaolin for adsorbing petrochemical wastewater Download PDFInfo
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- CN114192113A CN114192113A CN202111551687.4A CN202111551687A CN114192113A CN 114192113 A CN114192113 A CN 114192113A CN 202111551687 A CN202111551687 A CN 202111551687A CN 114192113 A CN114192113 A CN 114192113A
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical class O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 239000002351 wastewater Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000010902 straw Substances 0.000 claims abstract description 105
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 51
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 48
- 238000001035 drying Methods 0.000 claims abstract description 48
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 46
- 238000010438 heat treatment Methods 0.000 claims abstract description 33
- 238000007873 sieving Methods 0.000 claims abstract description 30
- 238000000227 grinding Methods 0.000 claims abstract description 23
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000007787 solid Substances 0.000 claims abstract description 18
- 238000001816 cooling Methods 0.000 claims abstract description 17
- 238000000967 suction filtration Methods 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 230000003213 activating effect Effects 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000012634 fragment Substances 0.000 claims description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 15
- 239000012153 distilled water Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- 238000004380 ashing Methods 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 239000003607 modifier Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 238000004065 wastewater treatment Methods 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 13
- 238000001179 sorption measurement Methods 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 10
- 239000011148 porous material Substances 0.000 abstract description 3
- 238000002715 modification method Methods 0.000 abstract description 2
- 238000011282 treatment Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000012266 salt solution Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011229 interlayer Substances 0.000 description 4
- 239000012286 potassium permanganate Substances 0.000 description 4
- 238000002336 sorption--desorption measurement Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 231100001261 hazardous Toxicity 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 231100000570 acute poisoning Toxicity 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 231100000739 chronic poisoning Toxicity 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/046—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing halogens, e.g. halides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- Geochemistry & Mineralogy (AREA)
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Abstract
The invention provides a preparation method of renewable modified kaolin for adsorbing petrochemical wastewater, which comprises the steps of preparing active straw biochar, fully stirring and heating the straw biochar, magnesium chloride and kaolin in a water bath oscillator, standing, cooling, carrying out suction filtration, collecting solids, drying the solids, heating, activating, grinding and sieving to prepare modified kaolin, reacting the modified kaolin with the petrochemical wastewater, carrying out centrifugal filtration, drying, grinding and sieving to prepare the renewable modified kaolin. The modification method provided by the invention can optimize the pore structure, the specific surface area and the chemical activity of the raw kaolin, improve the adsorption capacity of the kaolin, has the advantages of simple preparation method, low cost and no pollution, can be recycled, and can be used for treating wastewater in the field of petrochemical industry.
Description
Technical Field
The invention belongs to the technical field of water environment, and particularly relates to a preparation method of renewable modified kaolin for adsorbing petrochemical wastewater.
Background
Petrochemical wastewater has the characteristics of large water quantity, high concentration, high organic pollutant content, complex components, toxicity, harm, difficulty in biodegradation and the like, and is a great problem in industrial sewage treatment. Petrochemical wastewater is very hazardous, it causes many environmental problems and is hazardous to human health. Common treatment methods include both adsorption and degradation, and finding highly effective adsorbents and degrading materials has been the goal of relevant researchers. Because the organic pollutants in the wastewater are various and the components of the wastewater are complex, various intermediate products are still in the wastewater in a large amount after chemical and biological degradation, and acute or chronic poisoning of aquatic organisms and human bodies can be caused through drinking water and food chains.
The kaolin exists in a crystal form of silicon and aluminum atoms which have good stability and are not easy to damage, and after the kaolin is calcined at a certain temperature, the internal silicon and aluminum atoms form an oxide with chemical activity, and the oxide is easy to be invaded by acid and alkali ions so as to be modified. The straw is used as agricultural waste, is an important biomass resource, is rich in reserve on the earth, and has a good adsorption property due to the pore structure and the large specific surface area. Aiming at the problems, the research on the treatment of petrochemical wastewater is rarely reported by improving the chemical activity of the surface of kaolin, removing impurities on the surface of minerals of kaolin and improving the adsorption capacity and cation exchange capacity of kaolin in a manner of doping straw biochar.
Disclosure of Invention
The invention aims to provide a preparation method of recyclable modified kaolin for adsorbing petrochemical wastewater.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of renewable modified kaolin for adsorbing petrochemical wastewater comprises the following steps:
(1) mechanically crushing the straw raw material, sieving the crushed straw raw material by a sieve of 60-80 meshes, collecting straw fragments, and drying the straw fragments in a drying oven at the temperature of 55-60 ℃ for 8-10 hours;
(2) cooling the straw fragments to room temperature, adding 18-22% acetic acid solution, stirring and uniformly mixing at 38-42 ℃ to form activated straw particles, centrifuging, filtering, and drying in a drying oven at 75-85 ℃ for 3.5-4.5 hours;
(3) placing the straw particles treated in the step (2) into a tubular furnace, heating to 145-155 ℃ by a program under the protection of nitrogen, activating for 2-2.5 hours, then heating the tubular furnace to 400 ℃, ashing the straw particles for 3-3.2 hours, and finally grinding and sieving with a 100-mesh sieve to prepare the straw biochar;
(4) uniformly mixing a modifier and raw kaolin according to a mass ratio, adding the straw biochar, heating on a water bath oscillator at 55-65 ℃ for 2-2.5 hours, standing, cooling to be close to room temperature, performing suction filtration, adding a small amount of distilled water in the suction filtration process, cleaning, and collecting solids on filter paper;
(5) drying the collected solid in an oven at 75-85 ℃ for 3-3.5 hours, then heating to 100-105 ℃ for activation for 2-2.2 hours, and finally grinding and sieving with a 200-mesh sieve to obtain modified kaolin;
(6) after the modified kaolin is reacted with petrochemical wastewater, oscillating for 45-60 min in an oscillator, centrifugally filtering, collecting the modified kaolin on filter paper, drying in an oven at 100-105 ℃ for 3-3.5 h, grinding and sieving with a 200-mesh sieve to obtain the recycled modified kaolin.
In the step (4), the doping amount of the modifier in the raw kaolin is 16-18%, and the mass ratio of the raw kaolin to the straw biochar is 4.8-5.2: 1.
Furthermore, the doping amount of the modifier in the raw kaolin is 16.67%, and the mass ratio of the raw kaolin to the straw biochar is 5: 1.
The modifier is magnesium chloride.
The invention provides a novel kaolin modification method for adsorbing petrochemical wastewater, which is characterized in that modified kaolin is doped with straw biochar to improve the pore structure, specific surface area and chemical activity of the kaolin, so that the adsorption performance of the kaolin serving as an adsorbent on pollutants in the petrochemical wastewater is improved, the modified kaolin is recycled in a desorption regeneration mode, and the treatment cost of the petrochemical wastewater is reduced.
Compared with the prior art, the invention has the following characteristics and advantages:
(1) according to the invention, the straw biochar is doped with kaolin and is subjected to synergistic heating treatment, the interlayer spacing of the kaolin is increased under the auxiliary effects of the straw biochar, a modifier, magnesium chloride and the like, so that the straw biochar is attached to the interlayer structure of the kaolin to form a new interlayer aggregation structure, the specific surface area of the kaolin is increased, the surface active point position of the kaolin is increased, and the adsorption effect of the kaolin is improved.
(2) The renewable modified kaolin prepared by the invention can be used in combination with a conventional petrochemical wastewater treatment method, so that the treatment efficiency of the petrochemical wastewater is improved, and the residues of effluent organic matters and intermediate products thereof are effectively reduced.
(3) The modified kaolin provided by the invention has the advantages of simple preparation method and low synthesis cost, and still has higher adsorption capacity after multiple desorption treatments, thereby reducing the wastewater treatment cost.
Drawings
FIG. 1 is an SEM photograph of example 1 of the present invention.
Detailed Description
Example 1
Preparation of magnesium chloride and straw biochar modified kaolin
(1) Mechanically crushing the straw raw material, sieving the crushed straw raw material by a 60-mesh sieve, collecting straw fragments, and drying the straw fragments in a drying oven at the temperature of 60 ℃ for 8 hours;
(2) cooling the straw fragments to room temperature, adding 20% acetic acid solution, stirring and mixing uniformly at 40 ℃ to form activated straw particles, centrifuging, filtering, and drying in a drying oven at 80 ℃ for 4 hours;
(3) placing the straw particles treated in the step (2) into a tubular furnace, heating to 150 ℃ by a program under the protection of nitrogen, activating for 2 hours, then heating the tubular furnace to 400 ℃, ashing the straw particles for 3 hours, and finally grinding and sieving with a 100-mesh sieve to prepare the straw biochar;
(4) dissolving magnesium chloride serving as a salt solution in 100ml of distilled water, adding 10g of kaolin and 2g of straw biochar, wherein the doping amount of magnesium chloride in the kaolin is 16.67%, heating for 2 hours on a 60 ℃ oscillator (the rotating speed is 190r/min) to fully mix the kaolin, the magnesium chloride and the straw biochar, standing, cooling to be close to room temperature, carrying out suction filtration, adding a small amount of distilled water in the suction filtration process, cleaning, and collecting solids on filter paper;
(5) transferring the collected solid into a culture dish, drying in an oven at 80 ℃ for 3 hours, then heating to 105 ℃ to activate for 2 hours, and finally grinding and sieving with a 200-mesh sieve to obtain the modified kaolin.
The obtained modified kaolin is subjected to removal effect test by adopting the following experimental method: the COD of the wastewater in the petrochemical industry park with a certain volume is detected, and the change of the COD in the wastewater after the treatment of the unmodified kaolin and the modified kaolin in the embodiment is compared.
Comparative example 1
Preparation of ferric chloride and straw biochar modified kaolin
(1) Mechanically crushing the straw raw material, sieving the crushed straw raw material by a 60-mesh sieve, collecting straw fragments, and drying the straw fragments in a drying oven at the temperature of 60 ℃ for 8 hours;
(2) cooling the straw fragments to room temperature, adding 20% acetic acid solution, stirring and mixing uniformly at 40 ℃ to form activated straw particles, centrifuging, filtering, and drying in a drying oven at 80 ℃ for 4 hours;
(3) placing the straw particles treated in the step (2) into a tubular furnace, heating to 150 ℃ by a program under the protection of nitrogen, activating for 2 hours, then heating the tubular furnace to 400 ℃, ashing the straw particles for 3 hours, and finally grinding and sieving with a 100-mesh sieve to prepare the straw biochar;
(4) dissolving ferric chloride serving as a salt solution in 100ml of distilled water, adding 10g of kaolin and 2g of straw biochar, wherein the doping amount of the ferric chloride in the kaolin is 16.67%, heating for 2 hours on a 60 ℃ oscillator (the rotating speed is 190r/min) to fully mix the kaolin, the ferric chloride and the straw biochar, standing and cooling to be close to room temperature, carrying out suction filtration, adding a small amount of distilled water in the suction filtration process for cleaning, and collecting solids on filter paper;
(5) transferring the collected solid into a culture dish, drying in an oven at 80 ℃ for 3 hours, then heating to 105 ℃ to activate for 2 hours, and finally grinding and sieving with a 200-mesh sieve to obtain the modified kaolin.
The obtained modified kaolin is subjected to removal effect test by adopting the following experimental method: the COD of the wastewater in the petrochemical industry park with a certain volume is detected, and the change of the COD in the wastewater after the treatment of the unmodified kaolin and the modified kaolin in the embodiment is compared.
Comparative example 2
Preparation of potassium permanganate and straw biochar modified kaolin
(1) Mechanically crushing the straw raw material, sieving the crushed straw raw material by a 60-mesh sieve, collecting straw fragments, and drying the straw fragments in a drying oven at the temperature of 60 ℃ for 8 hours;
(2) cooling the straw fragments to room temperature, adding 20% acetic acid solution, stirring and mixing uniformly at 40 ℃ to form activated straw particles, centrifuging, filtering, and drying in a drying oven at 80 ℃ for 4 hours;
(3) placing the straw particles treated in the step (2) into a tubular furnace, heating to 150 ℃ by a program under the protection of nitrogen, activating for 2 hours, then heating the tubular furnace to 400 ℃, ashing the straw particles for 3 hours, and finally grinding and sieving with a 100-mesh sieve to prepare the straw biochar;
(4) dissolving potassium permanganate serving as a salt solution in 100ml of distilled water, adding 10g of kaolin and 2g of straw biochar, wherein the doping amount of potassium permanganate in the kaolin is 16.67%, heating for 2 hours on an oscillator (the rotating speed is 190r/min) at 60 ℃ to fully mix the kaolin, ferric chloride and the straw biochar, standing, cooling to be close to room temperature, carrying out suction filtration, adding a small amount of distilled water in the suction filtration process, cleaning, and collecting solids on filter paper;
(5) transferring the collected solid into a culture dish, drying in an oven at 80 ℃ for 3 hours, then heating to 105 ℃ to activate for 2 hours, and finally grinding and sieving with a 200-mesh sieve to obtain the modified kaolin.
The obtained modified kaolin is subjected to removal effect test by adopting the following experimental method: the COD of the wastewater in the petrochemical industry park with a certain volume is detected, and the change of the COD in the wastewater after the treatment of the unmodified kaolin and the modified kaolin in the embodiment is compared.
Example 2
Preparation of magnesium chloride and straw biochar modified kaolin (through 1 adsorption-desorption)
(1) Mechanically crushing the straw raw material, sieving the crushed straw raw material by a 60-mesh sieve, collecting straw fragments, and drying the straw fragments in a drying oven at the temperature of 60 ℃ for 8 hours;
(2) cooling the straw fragments to room temperature, adding 20% acetic acid solution, stirring and mixing uniformly at 40 ℃ to form activated straw particles, centrifuging, filtering, and drying in a drying oven at 80 ℃ for 4 hours;
(3) placing the straw particles treated in the step (2) into a tubular furnace, heating to 150 ℃ by a program under the protection of nitrogen, activating for 2 hours, then heating the tubular furnace to 400 ℃, ashing the straw particles for 3 hours, and finally grinding and sieving with a 100-mesh sieve to prepare the straw biochar;
(4) dissolving magnesium chloride serving as a salt solution in 100ml of distilled water, adding 10g of kaolin and 2g of straw biochar, wherein the doping amount of magnesium chloride in the kaolin is 16.67%, heating for 2 hours on a 60 ℃ oscillator (the rotating speed is 190r/min) to fully mix the kaolin, the magnesium chloride and the straw biochar, standing, cooling to be close to room temperature, carrying out suction filtration, adding a small amount of distilled water in the suction filtration process, cleaning, and collecting solids on filter paper;
(5) transferring the collected solid into a culture dish, drying in an oven at 80 ℃ for 3 hours, then heating to 105 ℃ to activate for 2 hours, and finally grinding and sieving with a 200-mesh sieve to prepare modified kaolin;
(6) reacting the modified kaolin with petrochemical wastewater once, oscillating for 45min in an oscillator, centrifugally filtering, collecting the modified kaolin on filter paper, drying for 3h in an oven at 105 ℃, grinding and sieving with a 200-mesh sieve to obtain the recycled modified kaolin.
And (3) taking actual wastewater in a petrochemical industrial park with a certain volume to detect COD (chemical oxygen demand), and detecting the change of COD in the wastewater after the modified kaolin is treated.
Example 3
Preparation of magnesium chloride and straw biochar modified kaolin (through 2 times of adsorption-desorption)
(1) Mechanically crushing the straw raw material, sieving the crushed straw raw material by a 60-mesh sieve, collecting straw fragments, and drying the straw fragments in a drying oven at the temperature of 60 ℃ for 8 hours;
(2) cooling the straw fragments to room temperature, adding 20% acetic acid solution, stirring and mixing uniformly at 40 ℃ to form activated straw particles, centrifuging, filtering, and drying in a drying oven at 80 ℃ for 4 hours;
(3) placing the straw particles treated in the step (2) into a tubular furnace, heating to 150 ℃ by a program under the protection of nitrogen, activating for 2 hours, then heating the tubular furnace to 400 ℃, ashing the straw particles for 3 hours, and finally grinding and sieving with a 100-mesh sieve to prepare the straw biochar;
(4) dissolving magnesium chloride serving as a salt solution in 100ml of distilled water, adding 10g of kaolin and 2g of straw biochar, wherein the doping amount of magnesium chloride in the kaolin is 16.67%, heating for 2 hours on a 60 ℃ oscillator (the rotating speed is 190r/min) to fully mix the kaolin, the magnesium chloride and the straw biochar, standing, cooling to be close to room temperature, carrying out suction filtration, adding a small amount of distilled water in the suction filtration process, cleaning, and collecting solids on filter paper;
(5) transferring the collected solid into a culture dish, drying in an oven at 80 ℃ for 3 hours, then heating to 105 ℃ to activate for 2 hours, and finally grinding and sieving with a 200-mesh sieve to prepare modified kaolin;
(6) reacting the modified kaolin with petrochemical wastewater twice, oscillating for 45min in an oscillator, centrifugally filtering, collecting the modified kaolin on filter paper, drying in an oven at 105 ℃ for 3h, grinding and sieving with a 200-mesh sieve to obtain the recycled modified kaolin.
And (3) taking actual wastewater in a petrochemical industrial park with a certain volume to detect COD (chemical oxygen demand), and detecting the change of COD in the wastewater after the modified kaolin is treated.
Example 4
Preparation of magnesium chloride and straw biochar modified kaolin (through 3 times of adsorption-desorption)
(1) Mechanically crushing the straw raw material, sieving the crushed straw raw material by a 60-mesh sieve, collecting straw fragments, and drying the straw fragments in a drying oven at the temperature of 60 ℃ for 8 hours;
(2) cooling the straw fragments to room temperature, adding 20% acetic acid solution, stirring and mixing uniformly at 40 ℃ to form activated straw particles, centrifuging, filtering, and drying in a drying oven at 80 ℃ for 4 hours;
(3) placing the straw particles treated in the step (2) into a tubular furnace, heating to 150 ℃ by a program under the protection of nitrogen, activating for 2 hours, then heating the tubular furnace to 400 ℃, ashing the straw particles for 3 hours, and finally grinding and sieving with a 100-mesh sieve to prepare the straw biochar;
(4) dissolving magnesium chloride serving as a salt solution in 100ml of distilled water, adding 10g of kaolin and 2g of straw biochar, wherein the doping amount of magnesium chloride in the kaolin is 16.67%, heating for 2 hours on a 60 ℃ oscillator (the rotating speed is 190r/min) to fully mix the kaolin, the magnesium chloride and the straw biochar, standing, cooling to be close to room temperature, carrying out suction filtration, adding a small amount of distilled water in the suction filtration process, cleaning, and collecting solids on filter paper;
(5) transferring the collected solid into a culture dish, drying in an oven at 80 ℃ for 3 hours, then heating to 105 ℃ to activate for 2 hours, and finally grinding and sieving with a 200-mesh sieve to prepare modified kaolin;
(6) reacting the modified kaolin with petrochemical wastewater for three times, oscillating for 45min in an oscillator, centrifugally filtering, collecting the modified kaolin on filter paper, drying for 3h in an oven at 105 ℃, grinding and sieving with a 200-mesh sieve to obtain the recycled modified kaolin.
And (3) taking actual wastewater in a petrochemical industrial park with a certain volume to detect COD (chemical oxygen demand), and detecting the change of COD in the wastewater after the modified kaolin is treated.
The results of the COD measurements of the petrochemical wastewater obtained in comparative example 1, comparative example 2 and examples 1-4 are shown in Table 1.
TABLE 1
As can be seen from Table 1, under normal temperature adsorption, the adsorption capacity of the modified doped straw biochar-kaolin is obviously higher than that of unmodified kaolin, the removal rate of COD in petrochemical wastewater after modification is improved by 11.6%, and the doped magnesium chloride is beneficial to improving the interlayer spacing of kaolin original soil, improving chemical activity and effectively improving the trapping effect of active groups in the kaolin on organic matters. The results of comparative examples 1 and 2 show that the adsorption capacity of the modified straw-doped biochar-kaolin modified by ferric chloride and potassium permanganate is improved to a certain extent, but the modified adsorption effect is lower than that of kaolin modified by magnesium chloride. The results of examples 2-4 show that the magnesium chloride modified straw-doped biochar-kaolin is relatively stable in chemical properties, and the removal effect of petrochemical wastewater after 3 times of adsorption-desorption recycling can still reach 59.98%.
The above-described examples are only one of the preferred embodiments of the present invention, and those skilled in the art will be able to make various changes and substitutions within the scope of the embodiments of the present invention.
Claims (8)
1. A preparation method of renewable modified kaolin for adsorbing petrochemical wastewater is characterized by comprising the following steps:
(1) mechanically crushing and sieving straw raw materials, collecting straw fragments, and drying the straw fragments;
(2) cooling the dried straw fragments to room temperature, adding 18-22% acetic acid solution, stirring and uniformly mixing at 38-42 ℃ to form activated straw particles, centrifuging, filtering and drying;
(3) placing the straw particles treated in the step (2) into a tubular furnace, raising the temperature to 145-155 ℃ by a program under the protection of nitrogen, activating for 2-2.5 hours, then raising the temperature of the tubular furnace to 400 ℃, ashing the straw particles for 3-3.2 hours, and finally grinding through a sieve 1 to prepare straw biochar;
(4) uniformly mixing a modifier and raw kaolin according to a mass ratio, adding the straw biochar, heating on a water bath oscillator at 55-65 ℃ for 2-2.5 hours, standing, cooling to be close to room temperature, performing suction filtration, adding a small amount of distilled water in the suction filtration process, cleaning, and collecting solids on filter paper;
(5) and (3) drying the collected solid in an oven at 75-85 ℃ for 3-3.5 hours, then heating to 100-105 ℃ for activation for 2-2.2 hours, and finally grinding and sieving with a 200-mesh sieve to obtain the modified kaolin.
2. The preparation method of the renewable modified kaolin for adsorbing petrochemical wastewater according to claim 1, characterized by further comprising the step (6) of reacting the modified kaolin with the petrochemical wastewater, oscillating for 45-60 min in an oscillator, performing centrifugal filtration, collecting the modified kaolin on the filter paper, drying for 3-3.5 h in an oven at 100-105 ℃, and grinding and sieving to obtain the renewable modified kaolin.
3. The preparation method of the renewable modified kaolin for adsorbing petrochemical wastewater according to claim 1, wherein in the step (1), the straw fragments are dried in a drying oven at 55-60 ℃ for 8-10 hours.
4. The method for preparing the renewable modified kaolin for adsorbing petrochemical wastewater according to claim 1, wherein in the step (1), the drying is performed in a drying oven at 75-85 ℃ for 3.5-4.5 hours.
5. The preparation method of the renewable modified kaolin for adsorbing petrochemical wastewater according to claim 1, wherein in the step (4), the doping amount of the modifier in the raw kaolin is 16-18%, and the mass ratio of the raw kaolin to the straw biochar is 4.8-5.2: 1.
6. The method for preparing the renewable modified kaolin for adsorbing petrochemical wastewater according to claim 5, wherein the doping amount of the modifier in the raw kaolin is 16.67%, and the mass ratio of the raw kaolin to the straw biochar is 5: 1.
7. The method for preparing the renewable modified kaolin for adsorbing petrochemical wastewater according to claim 1, wherein in the step (4), the modifying agent is magnesium chloride.
8. The modified kaolin obtained by the preparation method according to any one of claims 1 to 7 is applied to petrochemical wastewater treatment.
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