CN109174201B - Preparation method of three-dimensional mesh-type adsorption catalyst based on spent bleaching clay - Google Patents
Preparation method of three-dimensional mesh-type adsorption catalyst based on spent bleaching clay Download PDFInfo
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- CN109174201B CN109174201B CN201811186400.0A CN201811186400A CN109174201B CN 109174201 B CN109174201 B CN 109174201B CN 201811186400 A CN201811186400 A CN 201811186400A CN 109174201 B CN109174201 B CN 109174201B
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- 238000001179 sorption measurement Methods 0.000 title claims abstract description 74
- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 239000004927 clay Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000004061 bleaching Methods 0.000 title claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 99
- 239000000843 powder Substances 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 41
- 239000002131 composite material Substances 0.000 claims abstract description 25
- 230000008569 process Effects 0.000 claims abstract description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 72
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 239000002689 soil Substances 0.000 claims description 34
- 239000008367 deionised water Substances 0.000 claims description 32
- 229910021641 deionized water Inorganic materials 0.000 claims description 32
- 239000011259 mixed solution Substances 0.000 claims description 29
- 229920001661 Chitosan Polymers 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 229920002678 cellulose Polymers 0.000 claims description 16
- 239000001913 cellulose Substances 0.000 claims description 16
- 238000009210 therapy by ultrasound Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 15
- 229910001385 heavy metal Inorganic materials 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 12
- 239000003242 anti bacterial agent Substances 0.000 claims description 10
- 229940088710 antibiotic agent Drugs 0.000 claims description 10
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 10
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 10
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 claims description 10
- 239000004809 Teflon Substances 0.000 claims description 8
- 229920006362 Teflon® Polymers 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 238000007873 sieving Methods 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- 239000010935 stainless steel Substances 0.000 claims description 8
- 229910004619 Na2MoO4 Inorganic materials 0.000 claims description 4
- 239000011684 sodium molybdate Substances 0.000 claims description 4
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000011572 manganese Substances 0.000 abstract description 88
- 239000002699 waste material Substances 0.000 abstract description 34
- KIPLYOUQVMMOHB-MXWBXKMOSA-L [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O Chemical compound [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O KIPLYOUQVMMOHB-MXWBXKMOSA-L 0.000 abstract description 9
- 229940063650 terramycin Drugs 0.000 abstract description 9
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 abstract description 8
- 229960001545 hydrotalcite Drugs 0.000 abstract description 8
- 229910001701 hydrotalcite Inorganic materials 0.000 abstract description 8
- PCEXQRKSUSSDFT-UHFFFAOYSA-N [Mn].[Mo] Chemical compound [Mn].[Mo] PCEXQRKSUSSDFT-UHFFFAOYSA-N 0.000 abstract description 6
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 239000011852 carbon nanoparticle Substances 0.000 abstract description 4
- 238000005470 impregnation Methods 0.000 abstract description 4
- 239000013335 mesoporous material Substances 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 18
- 230000000694 effects Effects 0.000 description 16
- 238000006555 catalytic reaction Methods 0.000 description 14
- 239000004100 Oxytetracycline Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- IWVCMVBTMGNXQD-PXOLEDIWSA-N oxytetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3[C@H](O)[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-PXOLEDIWSA-N 0.000 description 7
- 229960000625 oxytetracycline Drugs 0.000 description 7
- 235000019366 oxytetracycline Nutrition 0.000 description 7
- IWVCMVBTMGNXQD-UHFFFAOYSA-N terramycin dehydrate Natural products C1=CC=C2C(O)(C)C3C(O)C4C(N(C)C)C(O)=C(C(N)=O)C(=O)C4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-UHFFFAOYSA-N 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910015667 MoO4 Inorganic materials 0.000 description 6
- 239000003344 environmental pollutant Substances 0.000 description 6
- 231100000719 pollutant Toxicity 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 239000002957 persistent organic pollutant Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 208000031295 Animal disease Diseases 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 description 1
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 239000010871 livestock manure Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229940068041 phytic acid Drugs 0.000 description 1
- 235000002949 phytic acid Nutrition 0.000 description 1
- 239000000467 phytic acid Substances 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical group 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229940072172 tetracycline antibiotic Drugs 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/32—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of manganese, technetium or rhenium
-
- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
-
- 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
- B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
-
- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3214—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the method for obtaining this coating or impregnating
-
- B01J35/61—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
Abstract
The invention relates to a preparation method of a three-dimensional mesh adsorption catalyst based on spent bleaching clay, which comprises the preparation process of (Mn, Mo-LDH) (manganese molybdenum hydrotalcite) powder; the composite process of SBE and (Mn, Mo-LDH) (waste clay and manganese molybdenum hydrotalcite) powder; a preparation process of a three-dimensional net-shaped SBE/C- (Mn, Mo-LDH) adsorption catalyst (a three-dimensional net-shaped adsorption catalyst compounded by waste clay with carbon nano-particles attached to the surface and manganese-molybdenum hydrotalcite). The adsorption catalyst is a mesoporous material prepared by an impregnation mode, has high specific surface area, is compounded with (Mn, Mo-LDH), has improved adsorption and degradation capacity, and Cd2+And the removal rate of terramycin is respectively increased by 68 percent and 74 percent. Meanwhile, the recycling of the waste argil is realized, and the method is simple, easy to implement, green and environment-friendly.
Description
Technical Field
The invention relates to a method for modifying waste argil, belonging to the technical field of material preparation. In particular to a modified waste clay which has three-dimensional high adsorption and high degradation capacity and is compounded with (Mn, Mo-LDH) (hydrotalcite with Mn and Mo as cations in a layer, the same below) by carbonizing oil on the surface of the waste clay; in particular to a preparation method of a three-dimensional reticular adsorption catalyst based on spent bleaching clay.
Background
In the process of oil product refining, 2% -3% of activated clay is usually used for carrying out supplementary refining on the oil product, and the clay losing adsorption activity after the oil product is refined is waste clay (SBE patent laying earth). The main components of the waste clay are the raw activated clay and about 30% of oil content. For a long time, the treatment of the waste clay is a difficult problem facing all countries in the world, and a plurality of enterprises directly bury the waste clay, or burn the waste clay or send the waste clay to an environmental protection department for treatment. Therefore, the waste argil is not fully and reasonably utilized, the environment is seriously polluted, the underground water quality is endangered, the environment for plant growth is destroyed, and meanwhile, the high unsaturated oil in the waste argil is easy to generate oxidation reaction due to contact with oxygen in the air, a large amount of heat is released, spontaneous combustion is generated, and fire is caused. In order to utilize waste clay as a resource, there are many treatment methods such as a high-pressure press method, a centrifugal separation method, a water boiling method, a surfactant method, and the like. However, the processes for treating the waste clay by the methods have certain limitations, and the waste clay cannot be well utilized comprehensively.
The geochemistry survey report on cultivated land in china (2015) published in 2015 shows that: in cultivated land in China, the proportion of heavy metal polluted or overproof point positions accounts for 8.2 percent, and the coverage area is nearly 1.14 hundred million acres. The accumulation degree of Cd is the highest, and the average value is 0.25mg/kg, which is 2.6 times of the background value of soil. Antibiotics play an important role in preventing and treating animal diseases, improving production efficiency and the like, and are often used as feed additives. Because the metabolism rate of antibiotics in vivo is low, the antibiotics are often detected from livestock and poultry manure and waste water, wherein the terramycin is a tetracycline antibiotic with high detection rate. The search for an adsorption catalyst which is cheap, easy to obtain, environment-friendly and strong in selectivity and can simultaneously remove heavy metals and antibiotics is urgent.
CN106753417A discloses a saline-alkali soil improver based on waste argil and desulfurized gypsum and a saline-alkali soil improving method. The modifier consists of the following components in percentage by weight: 65-75% of waste carclazyte, 0.5-2% of compound microbial agent, 3-6% of phytic acid, 10-15% of desulfurized gypsum and 3-21.5% of fatty alcohol-polyoxyethylene ether; according to the patent, fatty alcohol-polyoxyethylene ether is a nonionic surfactant, and researches show that the nonionic surfactant can inhibit soil from desorbing polychlorinated biphenyl, can compete with heavy metals in soil for adsorption, and can reduce the mobility and bioavailability of cadmium in soil when the mass fraction of the nonionic surfactant is too high. The effect of the modifier on removing heavy metals is not ideal. CN102284276A discloses a method for preparing a composite adsorbent from waste clay, which comprises the steps of fully mixing the waste clay with a pore-forming agent and a binder, kneading, granulating, carbonizing and carrying out hydrothermal activation to obtain the composite granular adsorbent. The waste argil directly participates in production without squeezing and deoiling, can cause eutrophication of soil, breed a large amount of bacteria, and change the physicochemical property of the soil. The patent is limited to the purification of air and water quality, and cannot be applied to the purification of soil due to the addition of water glass. In addition, the patent does not report the removal effect of heavy metals and antibiotics.
Hydrotalcite-like compounds (LDH), also known as layered metal hydroxides or anionic clays, are compounds with a layered bishydroxy octahedral structure with exchangeable anions between layers and adjustable cations in the layers. The carbonized nano carbon spent bleaching clay is compounded with LDH, so that high adsorption capacity is realized. The high adsorption capacity of the adsorbent can be attributed to the synergistic effect of the carbon species and the LDH. The waste clay with the surface containing the carbon nano-particles is compounded with the LDH, so that the adsorption capacity is improved by 43.9 percent compared with that of activated clay, and the adsorption catalyst has great catalytic oxidation capacity on organic pollutants because cations in the LDH are adjustable and can realize stronger catalytic capacity. The existing (Mg, Al-LDH), (Fe, Ni-LDH) can not generate OH with oxidation capability, and (Mn, Mo-LDH) can generate a large amount of OH due to the existence of Mn and Mo, so that stronger catalytic oxidation capability can be realized. At present, water, atmosphere and soil are seriously polluted, and a high-performance adsorption catalyst is urgently needed to improve the environmental problem. The adsorption catalyst of the present invention is expected to improve environmental problems.
Disclosure of Invention
The invention inherits the concept of green and pollution-free and provides a method for removing organic pollutants and heavy metals in water, atmosphere and soil. The inventor utilizes the carbonized oil to separate the waste argil and then the surface of the waste argil contains a large amount of components similar to carbon nano particlesThe adsorption effect of the activated carbon is achieved, and the heavy metal Cd in the soil is removed. We propose Mn, Mo as cation in hydrotalcite, Mn2+And Mo3+The catalyst has high catalytic effect, OH generated in the catalytic process has strong oxidizing property, and the oxytetracycline can be decomposed into water and carbon dioxide and other small molecules harmless to soil. The three-dimensional structure, carbonization of oil in the waste argil and compounding of (Mn, Mo-LDH) greatly improve the adsorption performance of the adsorption catalyst and the super-strong catalytic capability of Mn and Mo, and further degrade organic pollutants into water and carbon dioxide, so that secondary pollution is avoided. The adsorption catalyst integrates adsorption and catalysis, can realize waste utilization, can also realize higher adsorption and catalysis capacity, can be repeatedly utilized for many times, and is an adsorption and catalysis material with great prospect.
As a substance commonly existing in nature, cellulose has the advantages of abundant resources, good biocompatibility, renewability and the like, and is widely applied to production and life. The natural cellulose is formed by interleaving micro and nano fibers, has a unique hierarchical porous network structure, has a large number of hydroxyl groups and ether bonds on the surface, can be combined with various object substances through hydrogen bonds and covalent bonds, and can be used as a template or a scaffold for constructing three-dimensional materials. The larger specific surface area of the cellulose three-dimensional network structure increases the chance of contacting pollutants, and the porous structure promotes pollutant molecules to diffuse into the 3D structure, so that the adsorption catalyst is soaked in the cellulose, on one hand, the high specific surface area and the high adsorption catalytic capacity are further realized, and on the other hand, the soil is not damaged. Can be used for the treatment of water, atmosphere and soil, and is an adsorption catalyst with great prospect.
The purpose of the invention is realized by the following scheme:
a preparation method of a three-dimensional mesh adsorption catalyst based on spent bleaching clay comprises the following steps:
(1) a preparation process of (Mn, Mo-LDH) (manganese molybdenum hydrotalcite) powder;
(2) the composite process of SBE and (Mn, Mo-LDH) (waste clay and manganese molybdenum hydrotalcite) powder;
(3) a preparation process of a three-dimensional net-shaped SBE/C- (Mn, Mo-LDH) adsorption catalyst (a three-dimensional net-shaped adsorption catalyst compounded by waste clay with carbon nano-particles attached to the surface and manganese-molybdenum hydrotalcite).
The specific process of the step (1) is as follows: mixing MnSO4·4H2O、Na2MoO4·2H2O and CO (NH)2)2Dissolving the mixed solution in deionized water to prepare a mixed solution (30-60 mL), adding the mixed solution into a stainless steel autoclave with a Teflon lining, and calcining at 100-200 ℃ to obtain (Mn, Mo-LDH) powder.
Preferably MnSO4·4H2O:Na2MoO4·2H2O:CO(NH2)2The molar ratio is 1:1: 5-1: 6: 10.
The calcination time is preferably 0.5-3 h.
The specific process of the step (2) is as follows: dissolving chitosan, acetic acid, SBE and (Mn, Mo-LDH) in deionized water to prepare a mixed solution (30-60 mL), and performing ultrasonic treatment at 50-70 kHz for 20-50 min; and then transferring the mixed solution into a muffle furnace, calcining at the temperature of 150-250 ℃, cooling to 23-25 ℃, washing with deionized water to remove redundant acetic acid, washing with ethanol to remove redundant chitosan and SBE, drying in a vacuum oven, grinding, and sieving with a 200-300-mesh sieve to obtain the composite powder (SBE/C- (Mn, Mo-LDH)) of SBE and (Mn, Mo-LDH).
Preferably, the mass ratio of chitosan to acetic acid to SBE (Mn, Mo-LDH) is 4:2:1: 3-8: 5:1: 5.
Preferably, the calcination time is 4-6 h; and drying in the vacuum oven at 50-100 ℃ for 3-5 hours.
The specific process of the step (3) is as follows: dispersing the composite powder (SBE/C- (Mn, Mo-LDH)) in the step (2) into deionized water, and carrying out ultrasonic treatment for 1-5H (SBE/C- (Mn, Mo-LDH): H) at 50-70 kHz2The mass ratio of O is 1: 5-1: 10), then soaking cellulose in a mass ratio of SBE/C- (Mn, Mo-LDH) to cellulose of 3: 5-3: 7 for 24-72 hours, and drying in a vacuum oven at 60-150 ℃ for 5-10 hours to obtain the three-dimensional net-shaped SBE/C- (Mn, Mo-LDH) adsorption catalyst.
The three-dimensional reticular adsorption catalysis based on the waste argil prepared by the invention is applied to the treatment of heavy metals and antibiotics in soil.
The soil contains various heavy metal ions and some organic pollutants, the adsorption catalyst is uniformly mixed with the polluted soil according to the mass ratio of 1: 6-1: 10, and the adsorption catalyst is used for adsorbing heavy metal ions (Cd) in the soil under the condition of the mass ratio2+) The removal effect is obvious (the removal rate is 84.72 percent), the degradation effect on the antibiotics (the oxytetracycline) is excellent (the removal rate is 73.66 percent), and the method can be applied to the degradation of the heavy metals and the antibiotics in the soil.
The invention has the following advantages:
(1) the adsorption catalyst is a mesoporous material prepared by an impregnation mode, has high specific surface area, is compounded with (Mn, Mo-LDH), has improved adsorption and degradation capacity, and has Cd2+And the removal rate of terramycin is respectively increased by 68 percent and 74 percent. Meanwhile, the recycling of the waste argil is realized, and the method is simple, easy to implement, green and environment-friendly.
(2) After organic matters contained in the waste argil are carbonized, the organic matters are loaded on the surface of the waste argil in the form of carbon nano particles, and the carbon nano tubes are equivalent to carbon nano tubes, so that the mechanical property of the waste argil is enhanced, and the carbon nano tubes have high adsorption performance.
(3) The large specific surface area (increased by 56% compared with that before the cellulose is soaked) of the three-dimensional reticular cellulose increases the chance of contacting pollutants, and the porous structure promotes pollutant molecules to diffuse into a 3D structure, is easy to degrade, has no secondary pollution and is safe to soil.
(4) The adsorption catalyst integrates adsorption catalysis (removal rate Cd)2+84.72 percent of oxytetracycline and 73.66 percent of oxytetracycline), and the synergistic effect ensures that the adsorption catalysis effect is better than that of single adsorption (the removal rate of Cd)2+21.32% and terramycin 13.25%) or catalysis (removal rate Cd)2+11.93 percent and terramycin 20.21 percent), has better effect, can be repeatedly utilized for many times, has no secondary pollution, is green and environment-friendly, and is an adsorption catalysis material with great prospect.
(5) The ultrasonic impregnation makes the impregnation of the adsorption catalyst more uniform, and can better exert the adsorption catalysis effect.
Detailed Description
Example 1
(1) The preparation of (Mn, Mo-LDH) powder comprises the following specific steps: respectively taking 2.23g of MnSO4·4H2O、2.42gNa2MoO4·2H2O、3gCO(NH2)2Dissolving in deionized water to obtain mixed solution (MnSO)4·4H2The O concentration is 0.33 mol.L-1) The solution prepared above was put into a stainless steel autoclave lined with Teflon and calcined at 100 ℃ for 0.5h to obtain (Mn, Mo-LDH) powder.
(2) The SBE and (Mn, Mo-LDH) powder are compounded, and the specific process is as follows: respectively dissolving 4g of chitosan, 2g of acetic acid, 1g of SBE and 3g of (Mn, Mo-LDH) in deionized water to prepare a mixed solution (the concentration of the acetic acid is 1.11 mol. L)-1) And performing ultrasonic treatment at 50kHz for 20min, transferring the mixed solution into a muffle furnace, calcining at the temperature of 150 ℃ for 4h, cooling to 23 ℃, washing with deionized water for 3 times to remove excessive acetic acid, washing with ethanol for 3 times to remove excessive chitosan and SBE, drying in a vacuum oven at 50 ℃ for 3h, grinding, and sieving with a 200-mesh sieve to obtain the composite powder (SBE/C- (Mn, Mo-LDH)) of SBE and (Mn, Mo-LDH).
(3) The preparation method of the three-dimensional net-shaped SBE/C- (Mn, Mo-LDH) adsorption catalyst comprises the following specific steps: taking the composite powder (SBE/C- (Mn, Mo-LDH)) in the step (2), dispersing the composite powder into deionized water, and carrying out ultrasonic treatment at 50kHz for 1H (SBE/C- (Mn, Mo-LDH) and H2The mass of O is 1g and 5g respectively), then 1.67g of cellulose is taken to be soaked in the solution for 24h, and the solution is dried in a vacuum oven at 60 ℃ for 5h to obtain the three-dimensional net-shaped SBE/C- (Mn, Mo-LDH) adsorption catalyst.
Example 2
(1) The preparation of (Mn, Mo-LDH) powder comprises the following specific steps: respectively taking 2.23g of MnSO4·4H2O、4.84gNa2MoO4·2H2O、4.2gCO(NH2)2Dissolving in deionized water to obtain mixed solution (MnSO)4·4H2The O concentration is 0.2 mol.L-1) The solution prepared above was taken and put into a stainless steel autoclave lined with Teflon and calcined at 150 ℃ for 1 hour to obtain (Mn, Mo-LDH) powder.
(2) The SBE and (Mn, Mo-LDH) powder are compounded, and the specific process is as follows: 5g of chitosan, 3g of acetic acid, 1g of SBE and 4g of (Mn, Mo-LDH) are respectively dissolved in deionized water to prepare a mixed solution (the concentration of the acetic acid is 1.00 mol. L)-1) And performing ultrasonic treatment at 55kHz for 30min, transferring the mixed solution into a muffle furnace, calcining at the temperature of 200 ℃ for 5h, cooling to 24 ℃, washing with deionized water for 4 times to remove excessive acetic acid, washing with ethanol for 4 times to remove excessive chitosan and SBE, drying in a vacuum oven at 60 ℃ for 4h, grinding, and sieving with a 250-mesh sieve to obtain the composite powder (SBE/C- (Mn, Mo-LDH)) of SBE and (Mn, Mo-LDH).
(3) The preparation method of the three-dimensional net-shaped SBE/C- (Mn, Mo-LDH) adsorption catalyst comprises the following specific steps: taking the composite powder (SBE/C- (Mn, Mo-LDH)) in the step (2), dispersing the composite powder into deionized water, and carrying out ultrasonic treatment at 55kHz for 2H (SBE/C- (Mn, Mo-LDH) and H2The mass of O is 1g and 10g respectively), then 2g of cellulose is soaked in the solution for 36h, and the solution is dried in a vacuum oven at 80 ℃ for 6h to obtain the three-dimensional net-shaped SBE/C- (Mn, Mo-LDH) adsorption catalyst.
Example 3
(1) The preparation of (Mn, Mo-LDH) powder comprises the following specific steps: respectively taking 2.23g of MnSO4·4H2O、7.26gNa2MoO4·2H2O、4.8gCO(NH2)2Dissolving in deionized water to obtain mixed solution (MnSO)4·4H2The O concentration is 0.17 mol.L-1) The solution prepared above was taken and put into a stainless steel autoclave lined with Teflon and calcined at 200 ℃ for 1.5 hours to obtain (Mn, Mo-LDH) powder.
(2) The SBE and (Mn, Mo-LDH) powder are compounded, and the specific process is as follows: respectively dissolving 6g of chitosan, 4g of acetic acid, 1g of SBE and 5g of (Mn, Mo-LDH) in deionized water to prepare a mixed solution (the concentration of the acetic acid is 1.11 mol. L)-1) Performing ultrasonic treatment at 60kHz for 40min, transferring the mixed solution into a muffle furnace, calcining at 250 ℃ for 6h, cooling to 25 ℃, washing with deionized water for 5 times, removing excessive acetic acid, washing with ethanol for 5 times, removing excessive chitosan and SBE, drying in a vacuum oven at 70 ℃ for 5h, grinding, and sieving with a 300-mesh sieve to obtain SBE and (Mn, Mo), wherein the mixed solution is subjected to calcination at 250 ℃ for 5h-LDH) (SBE/C- (Mn, Mo-LDH)).
(3) The preparation method of the three-dimensional net-shaped SBE/C- (Mn, Mo-LDH) adsorption catalyst comprises the following specific steps: taking the composite powder (SBE/C- (Mn, Mo-LDH)) in the step (2), dispersing the composite powder into deionized water, and carrying out ultrasonic treatment at 60kHz for 3H (SBE/C- (Mn, Mo-LDH) and H2The mass of O is 1g and 8g respectively), then 2.3g of cellulose is taken to be soaked in the solution for 48 hours, and the solution is dried in a vacuum oven at 100 ℃ for 7 hours to obtain the three-dimensional net-shaped SBE/C- (Mn, Mo-LDH) adsorption catalyst.
Example 4
(1) The preparation of (Mn, Mo-LDH) powder comprises the following specific steps: respectively taking 2.23g of MnSO4·4H2O、9.68gNa2MoO4·2H2O、5.4gCO(NH2)2Dissolving in deionized water to obtain mixed solution (MnSO)4·4H2The O concentration is 0.25 mol.L-1) The solution prepared above was taken and put into a stainless steel autoclave lined with Teflon and calcined at 130 ℃ for 2 hours to obtain (Mn, Mo-LDH) powder.
(2) The SBE and (Mn, Mo-LDH) powder are compounded, and the specific process is as follows: respectively dissolving 7g of chitosan, 5g of acetic acid, 1g of SBE and 5g of (Mn, Mo-LDH) in deionized water to prepare a mixed solution (the concentration of the acetic acid is 1.67 mol. L)-1) And performing ultrasonic treatment at 65kHz for 50min, transferring the mixed solution into a muffle furnace, calcining at the temperature of 180 ℃ for 6h, cooling to 25 ℃, washing with deionized water for 5 times to remove excessive acetic acid, washing with ethanol for 5 times to remove excessive chitosan and SBE, drying in a vacuum oven at 80 ℃ for 5h, grinding, and sieving with a 300-mesh sieve to obtain the composite powder (SBE/C- (Mn, Mo-LDH)) of SBE and (Mn, Mo-LDH).
(3) The preparation method of the three-dimensional net-shaped SBE/C- (Mn, Mo-LDH) adsorption catalyst comprises the following specific steps: taking the composite powder (SBE/C- (Mn, Mo-LDH)) in the step (2), dispersing the composite powder into deionized water, and carrying out ultrasonic treatment at 65kHz for 4H (SBE/C- (Mn, Mo-LDH) and H2The mass of O is 1g and 10g respectively), then 2g of cellulose is soaked in the solution for 60h, and the solution is dried in a vacuum oven at 120 ℃ for 8h to obtain the three-dimensional net-shaped SBE/C- (Mn, Mo-LDH) adsorption catalyst.
Example 5
(1) The preparation of (Mn, Mo-LDH) powder comprises the following specific steps: respectively taking 2.23g of MnSO4·4H2O、12.1gNa2MoO4·2H2O、6gCO(NH2)2Dissolving in deionized water to obtain mixed solution (MnSO)4·4H2The O concentration is 0.20 mol.L-1) The solution prepared above was taken and put into a stainless steel autoclave lined with Teflon and calcined at 160 ℃ for 2.5 hours to obtain (Mn, Mo-LDH) powder.
(2) The SBE and (Mn, Mo-LDH) powder are compounded, and the specific process is as follows: respectively dissolving 8g of chitosan, 5g of acetic acid, 1g of SBE and 5g of (Mn, Mo-LDH) in deionized water to prepare a mixed solution (the concentration of the acetic acid is 1.67 mol. L)-1) And performing ultrasonic treatment at 70kHz for 35min, transferring the mixed solution into a muffle furnace, calcining at 230 ℃ for 6h, cooling to 25 ℃, washing with deionized water for 5 times to remove excessive acetic acid, washing with ethanol for 5 times to remove excessive chitosan and SBE, drying in a 90 ℃ vacuum oven for 5h, grinding, and sieving with a 300-mesh sieve to obtain the composite powder (SBE/C- (Mn, Mo-LDH)) of SBE and (Mn, Mo-LDH).
(3) The preparation method of the three-dimensional net-shaped SBE/C- (Mn, Mo-LDH) adsorption catalyst comprises the following specific steps: taking the composite powder (SBE/C- (Mn, Mo-LDH)) in the step (2), dispersing the composite powder into deionized water, and carrying out ultrasonic treatment at 70kHz for 5H (SBE/C- (Mn, Mo-LDH) and H2The mass of O is 1g and 10g respectively), then 2g of cellulose is soaked in the solution for 72h, and the solution is dried in a vacuum oven at 150 ℃ for 9h to obtain the three-dimensional net-shaped SBE/C- (Mn, Mo-LDH) adsorption catalyst.
Example 6
(1) The preparation of (Mn, Mo-LDH) powder comprises the following specific steps: respectively taking 2.23g of MnSO4·4H2O、14.52gNa2MoO4·2H2O、6gCO(NH2)2Dissolving in deionized water to obtain mixed solution (MnSO)4·4H2The O concentration is 0.20 mol.L-1) The solution prepared above was added to a stainless steel autoclave lined with Teflon and calcined at 180 ℃ for 3 hours to obtain (Mn, Mo-LDH) powder.
(2) The SBE and (Mn, Mo-LDH) powder are compounded, and the specific process is as follows: respectively taking 4g of shellsDissolving glycan, 5g acetic acid, 1g SBE and 5g (Mn, Mo-LDH) in deionized water to prepare a mixed solution (the concentration of acetic acid is 1.67 mol. L)-1) And performing ultrasonic treatment at 60kHz for 45min, transferring the mixed solution into a muffle furnace, calcining at the temperature of 200 ℃ for 6h, cooling to 25 ℃, washing with deionized water for 5 times to remove excessive acetic acid, washing with ethanol for 5 times to remove excessive chitosan and SBE, drying in a vacuum oven at 100 ℃ for 5h, grinding, and sieving with a 300-mesh sieve to obtain the composite powder (SBE/C- (Mn, Mo-LDH)) of SBE and (Mn, Mo-LDH).
(3) The preparation method of the three-dimensional net-shaped SBE/C- (Mn, Mo-LDH) adsorption catalyst comprises the following specific steps: taking the composite powder (SBE/C- (Mn, Mo-LDH)) in the step (2), dispersing the composite powder into deionized water, and carrying out ultrasonic treatment at 60kHz for 5H (SBE/C- (Mn, Mo-LDH) and H2The mass of O is 1g and 10g respectively), then 2g of cellulose is soaked in the solution for 24h, and the solution is dried in a vacuum oven at 150 ℃ for 10h to obtain the three-dimensional net-shaped SBE/C- (Mn, Mo-LDH) adsorption catalyst.
Example 7
Three-dimensional net-shaped SBE/C- (Mn, Mo-LDH) adsorption catalyst pair for removing heavy metal (Cd) in soil2+) The experiment for detecting the effect of the antibiotic (oxytetracycline) comprises the following specific processes:
the three-dimensional net-shaped SBE/C- (Mn, Mo-LDH) adsorption catalysts prepared in examples 1-6 are respectively and uniformly stirred with polluted soil.
The adsorption catalysis experimental conditions of each example are as follows:
detecting Cd in Tianjin certain farmland2+And terramycin pollution state, namely respectively taking Cd contents of 6g/kg, 8g/kg and 10g/kg according to the soil pollution state2+Concentrations of 40mg/kg, 80mg/kg and 120mg/kg of oxytetracycline-containing soil were recorded as A, B, C, D, E, F for examples 1-6. G. H is respectively Cd without adding the adsorption catalyst2+And terramycin contaminated soil. 10g of the three-dimensional reticular adsorption catalyst prepared in the examples 1-6 is added into the polluted soil respectively, stirred for 30min at room temperature, and then the Cd in the soil is measured respectively2+And the removal rate of oxytetracycline.
The results of the experiments are shown in the following table. From the adsorption catalysis experimental results, the adsorption catalyst prepared by the method has good adsorption catalysis effect, has good removal effect on various heavy metals and organic pollutants, and can be used for soil improvement and water and atmosphere purification.
SBE/C- (Mn, Mo-LDH) for Cd in soil2+Removal rate of
As shown in the table, the pollutant concentration has certain influence on the adsorption catalysis effect, but the adsorption catalyst has the concentration of 6g/kg, 8g/kg and 10g/kg containing Cd2+Removing Cd from the soil2+The effect is good, the removal rate can reach more than 70 percent, and the method can be used in actual production.
Removal rate of SBE/C- (Mn, Mo-LDH) to terramycin in soil
As shown in the table, the pollutant concentration has certain influence on the adsorption catalysis effect, but the adsorption catalyst has good effect of removing the terramycin from the soil with the concentrations of 40mg/kg, 80mg/kg and 120mg/kg, and can be used in actual production.
The method of the present invention has been described in detail with reference to the above embodiments, but the present invention is not limited to the above embodiments, and the experimental conditions and the method can be flexibly changed without departing from the scope of the present invention, which falls within the protection scope of the present invention. Therefore, the patent and protection scope of the present invention should be subject to the appended claims.
Claims (9)
1. A preparation method of a three-dimensional mesh adsorption catalyst based on spent bleaching clay is characterized by comprising the following steps:
(1) a preparation process of Mn, Mo-LDH powder;
(2) a compounding process of SBE and Mn, Mo-LDH powder;
(3) a preparation process of a three-dimensional net-shaped SBE/C- (Mn, Mo-LDH) adsorption catalyst;
the specific process of the step (2) is as follows: dissolving chitosan, acetic acid, SBE, Mn and Mo-LDH in deionized water to prepare a mixed solution, and performing ultrasonic treatment at 50-70 kHz for 20-50 min; and then transferring the mixed solution into a muffle furnace, calcining at the temperature of 150-250 ℃, cooling to 23-25 ℃, washing with deionized water to remove redundant acetic acid, washing with ethanol to remove redundant chitosan and SBE, drying in a vacuum oven, grinding, and sieving with a 200-300-mesh sieve to obtain SBE/C- (Mn, Mo-LDH) composite powder of SBE and Mn, Mo-LDH.
2. The method as claimed in claim 1, wherein the step (1) comprises the following steps: mixing MnSO4·4H2O、Na2MoO4·2H2O and CO (NH)2)2Dissolving the mixed solution in deionized water to prepare a mixed solution, adding the mixed solution into a stainless steel autoclave with a Teflon lining, and calcining at 100-200 ℃ to obtain Mn, Mo-LDH powder.
3. The process as claimed in claim 2, characterized by MnSO4·4H2O:Na2MoO4·2H2O:CO(NH2)2The molar ratio is 1:1: 5-1: 6: 10.
4. The method according to claim 2, wherein the calcination time is 0.5 to 3 hours at 100 to 200 ℃.
5. The method of claim 1, wherein the molar ratio of chitosan to acetic acid to SBE to Mn to Mo-LDH is 4:2:1:3 to 8:5:1: 5.
6. The method of claim 5, wherein the calcination time is 4 to 6 hours at 150 to 250 ℃; and drying in the vacuum oven at 50-100 ℃ for 3-5 h.
7. The method as claimed in claim 1, wherein the step (3) comprises the following steps: dispersing the composite powder SBE/C- (Mn, Mo-LDH) in the step (2) into deionized water, and carrying out ultrasonic treatment for 1-5H at 50-70 kHz, wherein SBE/C- (Mn, Mo-LDH): H2And (3) soaking the cellulose in a mass ratio of SBE/C- (Mn, Mo-LDH) to cellulose of 3: 5-3: 7 for 24-72 h, and drying in a vacuum oven at 60-150 ℃ for 5-10 h to obtain the three-dimensional mesh-type SBE/C- (Mn, Mo-LDH) adsorption catalyst, wherein the mass ratio of O is 1: 5-1: 10.
8. The use of the three-dimensional reticular adsorption catalyst prepared by the method of claim 1 in the treatment of soil heavy metals and antibiotics.
9. The three-dimensional reticular adsorption catalyst prepared by the method of claim 1, which is applied to the treatment of soil heavy metals and antibiotics.
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