CN113274969A - Composite material with formaldehyde adsorption function and preparation method thereof - Google Patents
Composite material with formaldehyde adsorption function and preparation method thereof Download PDFInfo
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- CN113274969A CN113274969A CN202110579765.5A CN202110579765A CN113274969A CN 113274969 A CN113274969 A CN 113274969A CN 202110579765 A CN202110579765 A CN 202110579765A CN 113274969 A CN113274969 A CN 113274969A
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 168
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical class [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims abstract description 79
- 239000004575 stone Substances 0.000 claims abstract description 68
- 239000000843 powder Substances 0.000 claims abstract description 67
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims abstract description 30
- 239000007864 aqueous solution Substances 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims description 32
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 25
- 238000001914 filtration Methods 0.000 claims description 24
- 238000009210 therapy by ultrasound Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid group Chemical group C(C(=O)O)(=O)O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 7
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical group [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 6
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 6
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 102000005348 Neuraminidase Human genes 0.000 claims description 5
- 108010006232 Neuraminidase Proteins 0.000 claims description 5
- DFPAKSUCGFBDDF-ZQBYOMGUSA-N [14c]-nicotinamide Chemical compound N[14C](=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-ZQBYOMGUSA-N 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 239000007853 buffer solution Substances 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 4
- 239000008363 phosphate buffer Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 13
- 239000000126 substance Substances 0.000 abstract description 3
- 230000002457 bidirectional effect Effects 0.000 abstract description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract description 2
- 238000010979 pH adjustment Methods 0.000 abstract description 2
- 230000009044 synergistic interaction Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 40
- 239000011148 porous material Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical compound NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 description 4
- 238000002715 modification method Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 3
- 239000012286 potassium permanganate Substances 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical class [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229960003966 nicotinamide Drugs 0.000 description 2
- 235000005152 nicotinamide Nutrition 0.000 description 2
- 239000011570 nicotinamide Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- 208000000059 Dyspnea Diseases 0.000 description 1
- 206010013975 Dyspnoeas Diseases 0.000 description 1
- 206010014561 Emphysema Diseases 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- 206010058467 Lung neoplasm malignant Diseases 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 206010028813 Nausea Diseases 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 208000006673 asthma Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 231100000003 human carcinogen Toxicity 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 201000005202 lung cancer Diseases 0.000 description 1
- 208000020816 lung neoplasm Diseases 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000008693 nausea Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000008055 phosphate buffer solution Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 125000006308 propyl amino group Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 206010039083 rhinitis Diseases 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- B01J20/04—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
- B01J20/048—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 phosphorus, e.g. phosphates, apatites, hydroxyapatites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/72—Organic compounds not provided for in groups B01D53/48 - B01D53/70, e.g. hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- 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
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- B01J35/61—
-
- B01J35/63—
-
- B01J35/64—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/704—Solvents not covered by groups B01D2257/702 - B01D2257/7027
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
Abstract
The invention discloses a composite material with a formaldehyde adsorption function and a preparation method thereof, wherein the composite material with the formaldehyde adsorption function is prepared from the following raw materials in parts by weight: 5-15 parts of modified hydroxyapatite, 5-20 parts of modified medical stone powder and 65-90 parts of sodium dodecyl sulfate aqueous solution. The composite material with the formaldehyde adsorption function is prepared from modified hydroxyapatite, modified medical stone powder and a sodium dodecyl sulfate aqueous solution, and does not contain other substances; the composite material can effectively adsorb and purify formaldehyde, the modified hydroxyapatite presents acidity, the modified medical stone powder has the performance of bidirectional pH adjustment, the pH of the modified hydroxyapatite can be improved, and after the modified hydroxyapatite and the modified hydroxyapatite are combined, the pH is improved, so that the modified hydroxyapatite and the modified hydroxyapatite have good adsorption activity and can realize synergistic interaction.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a composite material with a formaldehyde adsorption function.
Background
Modern people spend about 80% of their time indoors, where the indoor environment is closely related to people's health and work efficiency. Formaldehyde is a representative indoor volatile organic pollutant, and is a research hotspot in the field of indoor air quality control due to the universality of the formaldehyde in daily life and the influence on the physiological health of human bodies. Formaldehyde is listed as one of the known human carcinogens. It is highly irritating to the sensory and respiratory systems, and prolonged exposure can cause tearing, dyspnea, and other symptoms and diseases such as headache, nausea, rhinitis, emphysema, and lung cancer. Especially, the influence on children is larger, and asthma is very easy to cause.
CN112516787A discloses a preparation method of an indoor formaldehyde purification material, and specifically discloses a specific preparation method thereof: (1) firstly, mixing 1 part of modified hydroxyapatite, 5-8 parts of modified silicon carbide and 0.5-0.7 part of acrylic acid premix for reaction to obtain a mixed solution; (2) then adding 0.6-0.9 part of manganese sulfate monohydrate into the mixed solution, uniformly oscillating by ultrasonic waves, adding 10-12 parts of potassium permanganate solution with the mass concentration of 10-15% while stirring, reacting by stirring, centrifuging, and drying to obtain the indoor formaldehyde environment-friendly purification material; wherein, the modified hydroxyapatite is obtained by using hydroxyapatite as a raw material and performing modification treatment on 3- (N-rare propyl amino) propyl trimethoxy silane; the modified silicon carbide is prepared by taking silicon carbide as a raw material and modifying by 3-aminopropyl triethoxysilane and glutaric anhydride; the acrylic acid premix is obtained by mixing acrylic acid, a cross-linking agent and an initiator. The hydroxyapatite is modified by adopting a silane coupling agent, and the modification method is different from the method.
CN105080615A discloses an adsorption catalyst for fast removing formaldehyde and a preparation method thereof, which contains modified medical stone and a plurality of other substances, and specifically discloses a preparation method of modified medical stone powder: the medical stone powder and water are put into a high-pressure reaction kettle for hydrothermal reaction, dried, added into potassium permanganate aqueous solution for oscillation, filtered and dried to obtain the modified medical stone powder. The potassium permanganate aqueous solution is oscillated to oxidize and modify the medical stone powder, so that the oxygen-containing groups on the surface of the invention are obviously increased, the adsorption capacity to formaldehyde can be enhanced, and the preparation method of the invention is different from the preparation method of the invention.
At present, no document discloses that the modified hydroxyapatite and the modified medical stone powder are used together for purifying and adsorbing formaldehyde.
Disclosure of Invention
The invention provides a composite material with a formaldehyde adsorption function and a preparation method thereof.
The invention adopts the following technical scheme for solving the technical problems:
the composite material with the formaldehyde adsorption function is prepared from the following raw materials in parts by weight: 5-15 parts of modified hydroxyapatite, 5-20 parts of modified medical stone powder and 65-90 parts of sodium dodecyl sulfate aqueous solution.
As a preferable scheme, the formaldehyde adsorption function is prepared from the following raw materials in parts by weight: 10 parts of modified hydroxyapatite, 12 parts of modified medical stone powder and 78 parts of sodium dodecyl sulfate aqueous solution.
As a preferable scheme, the sodium dodecyl sulfate aqueous solution is prepared by mixing sodium dodecyl sulfate and deionized water according to a weight ratio of 1: 49-99 percent.
As a preferable scheme, the preparation method of the modified hydroxyapatite comprises the following steps:
s01, adding 6-10 parts by weight of hydroxyapatite into 20-30 parts by weight of hydrochloric acid solution, and uniformly dispersing to obtain a first mixed solution;
s02, adding 0.8-1.5 parts by weight of activating agent and 0.6-1.2 parts by weight of pore-forming agent into 8-15 parts by weight of deionized water, and carrying out ultrasonic treatment at 200-500W for 20-50 min to obtain a second mixed solution;
s03, heating the first mixed solution to 65-80 ℃, dripping the second mixed solution into the first mixed solution under the stirring action, carrying out ultrasonic treatment at 500-800W for 20-35 min, filtering, and drying to obtain pretreated hydroxyapatite;
s04, adding 6-10 parts by weight of pretreated hydroxyapatite, 0.8-1.2 parts by weight of ferrous oxide and 0.6-1.2 parts by weight of copper sulfate into 20-50 parts by weight of deionized water, carrying out ultrasonic treatment at 400-600W for 20-40 min, stirring at a rotating speed of 100-400 rpm for 8-12 h, filtering, and drying to obtain the modified hydroxyapatite.
The inventor of the invention found in a great deal of research that by modifying hydroxyapatite, specific surface area and pore volume are increased, surface hydroxyl is increased, pore diameter is deeper, activity is improved, adsorption is facilitated and subsequent introduction of Fe is facilitated, and Fe in Fe groups can be introduced into deep pores of hydroxyapatite, so that Fe in the Fe groups can be absorbed in Fe2+And Fe3+The catalytic oxidation of formaldehyde can be obviously improved, the activity is improved, and the catalytic oxidation performance, the adsorption activity and the mass transfer effect are ensured.
Meanwhile, the inventor of the invention finds that the catalytic oxidation performance of the catalyst is greatly reduced by replacing ferrous oxide with other metalates (such as platinum chloride and manganese chloride).
As a preferable scheme, the hydrochloric acid solution is 2-5 mol/L hydrochloric acid solution.
As a preferred embodiment, the activating agent is oxalic acid.
Preferably, the pore-forming agent is ammonium bicarbonate.
As a preferable scheme, the preparation method of the modified medical stone powder comprises the following steps:
s11, calcining the medical stone powder at 300-350 ℃ for 0.5-2 h to obtain calcined medical stone powder;
s12, dispersing 5-10 parts by weight of calcined medical stone powder into 20-30 parts by weight of phosphoric acid buffer solution, adding 0.1-0.4 part by weight of neuraminidase and 0.5-1 part by weight of nicotinamide, stirring at the rotating speed of 200-500 rpm at 50-80 ℃ for 3-8 hours, filtering, and drying to obtain the modified medical stone powder.
The inventor of the present invention has surprisingly found in a great deal of research that, by modifying the medical stone powder, on one hand, the specific surface area and the pore volume are increased, and the adsorption capacity is increased, and on the other hand, the adsorption activity of the medical stone powder is increased after modification, and the nicotinamide can significantly improve the adsorption capacity for formaldehyde due to the introduction of the nicotinamide containing functional group structures such as carbonyl, pyridine, amide and the like, nitrogen-containing functional groups and oxygen-containing functional groups.
Meanwhile, the inventor of the invention finds that the modified hydroxyapatite and the modified medical stone powder have obvious synergistic effect in a large amount of research.
Firstly, the modified hydroxyapatite presents acidity, the modified medical stone powder has the performance of bidirectional pH adjustment, the pH of the modified hydroxyapatite can be improved, and after the modified hydroxyapatite and the modified medical stone powder are combined, the pH is improved, so that the combination of the modified hydroxyapatite and the modified medical stone powder has good adsorption activity and can realize synergistic interaction.
Secondly, the formaldehyde is removed by the modified hydroxyapatite mainly through catalytic oxidation, and the formaldehyde is treated from two directions by the modified medical stone powder mainly through adsorption, physical adsorption and catalytic oxidation, so that the synergistic effect is exerted.
As a preferable scheme, the pH value of the phosphate buffer solution is 5-6.
The invention also provides a preparation method of the composite material with the formaldehyde adsorption function, which comprises the following steps:
s21, adding the modified hydroxyapatite into 30-60% of sodium dodecyl sulfate water solution by weight, and stirring at the rotating speed of 200-400 rpm for 3-6 hours;
s22, adding the modified medical stone powder into the residual sodium dodecyl sulfate aqueous solution, and carrying out ultrasonic treatment at 400-700W for 25-40 min;
and S23, uniformly mixing the product obtained in the step S21 with the product obtained in the step S22, filtering and drying to obtain the composite material with the formaldehyde adsorption function.
The invention has the beneficial effects that: (1) the composite material with the formaldehyde adsorption function is prepared from modified hydroxyapatite, modified medical stone powder and a sodium dodecyl sulfate aqueous solution, and does not contain other substances; (2) the composite material can effectively adsorb and purify formaldehyde, and the modified hydroxyapatite and the modified medical stone powder have a synergistic effect in the aspect of purifying and adsorbing formaldehyde.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the present invention, the parts are all parts by weight unless otherwise specified.
Example 1
The composite material with the formaldehyde adsorption function is prepared from the following raw materials in parts by weight: 10 parts of modified hydroxyapatite, 12 parts of modified medical stone powder and 78 parts of sodium dodecyl sulfate aqueous solution.
The sodium dodecyl sulfate aqueous solution is prepared from sodium dodecyl sulfate and deionized water according to the weight ratio of 1: 61.5.
The preparation method of the modified hydroxyapatite comprises the following steps:
s01, adding 9 parts by weight of hydroxyapatite into 21 parts by weight of 4mol/L hydrochloric acid solution, and uniformly dispersing to obtain a first mixed solution;
s02, adding 1.2 parts by weight of oxalic acid and 0.9 part by weight of ammonium bicarbonate into 12.9 parts by weight of deionized water, and carrying out 400W ultrasonic treatment for 30min to obtain a second mixed solution;
s03, heating the first mixed solution to 78 ℃, dripping the second mixed solution into the first mixed solution under the stirring action of the rotating speed of 200rpm, carrying out 700W ultrasonic treatment for 30min after dripping, filtering and drying to obtain pretreated hydroxyapatite;
s04, adding 8 parts by weight of pretreated hydroxyapatite, 1.1 parts by weight of ferrous oxide and 0.9 part by weight of copper sulfate into 30 parts by weight of deionized water, carrying out ultrasonic treatment for 30min at 500W, stirring at 300rpm for 10h, filtering and drying to obtain the modified hydroxyapatite.
The preparation method of the modified medical stone powder comprises the following steps:
s11, calcining the medical stone powder for 1 hour at 320 ℃ to obtain calcined medical stone powder;
s12, dispersing 9 parts by weight of calcined medical stone powder in 25 parts by weight of phosphoric acid buffer solution with pH value of 5.4, adding 0.2 part by weight of neuraminidase and 0.8 part by weight of nicotinamide, stirring at the rotating speed of 300rpm at 60 ℃ for 6 hours, filtering and drying to obtain the modified medical stone powder.
The preparation method of the composite material with the formaldehyde adsorption function comprises the following steps:
s21, adding the modified hydroxyapatite into a sodium dodecyl sulfate aqueous solution with the total weight of 50 percent, and stirring at the rotating speed of 300rpm for 4 hours;
s22, adding the modified medical stone powder into the residual sodium dodecyl sulfate aqueous solution, and carrying out ultrasonic treatment at 500W for 30 min;
and S23, uniformly mixing the product obtained in the step S21 with the product obtained in the step S22, filtering and drying to obtain the composite material with the formaldehyde adsorption function.
Example 2
The composite material with the formaldehyde adsorption function is prepared from the following raw materials in parts by weight: 5 parts of modified hydroxyapatite, 6 parts of modified medical stone powder and 65 parts of sodium dodecyl sulfate aqueous solution.
The sodium dodecyl sulfate aqueous solution is prepared from sodium dodecyl sulfate and deionized water according to the weight ratio of 1: 61.5.
The preparation method of the modified hydroxyapatite comprises the following steps:
s01, adding 10 parts by weight of hydroxyapatite into 20 parts by weight of 4mol/L hydrochloric acid solution, and uniformly dispersing to obtain a first mixed solution;
s02, adding 1 part by weight of oxalic acid and 1 part by weight of ammonium bicarbonate into 13 parts by weight of deionized water, and carrying out ultrasonic treatment at 300W for 35min to obtain a second mixed solution;
s03, heating the first mixed solution to 75 ℃, dripping the second mixed solution into the first mixed solution under the stirring action of the rotating speed of 200rpm, carrying out 600W ultrasonic treatment for 30min after dripping, filtering and drying to obtain pretreated hydroxyapatite;
s04, adding 9 parts by weight of pretreated hydroxyapatite, 1.2 parts by weight of ferrous oxide and 1 part by weight of copper sulfate into 28.8 parts by weight of deionized water, carrying out ultrasonic treatment for 30min at 500W, stirring at 300rpm for 10h, filtering and drying to obtain the modified hydroxyapatite.
The preparation method of the modified medical stone powder comprises the following steps:
s11, calcining the medical stone powder for 1 hour at 300 ℃ to obtain calcined medical stone powder;
s12, dispersing 8 parts by weight of calcined medical stone powder in 25 parts by weight of phosphoric acid buffer solution with pH value of 5.4, adding 0.3 part by weight of neuraminidase and 1 part by weight of nicotinamide, stirring at the rotating speed of 300rpm at 60 ℃ for 6 hours, filtering and drying to obtain the modified medical stone powder.
The preparation method of the composite material with the formaldehyde adsorption function comprises the following steps:
s21, adding the modified hydroxyapatite into a sodium dodecyl sulfate aqueous solution with the total weight of 50 percent, and stirring at the rotating speed of 300rpm for 4 hours;
s22, adding the modified medical stone powder into the residual sodium dodecyl sulfate aqueous solution, and carrying out ultrasonic treatment at 500W for 30 min;
and S23, uniformly mixing the product obtained in the step S21 with the product obtained in the step S22, filtering and drying to obtain the composite material with the formaldehyde adsorption function.
Example 3
The composite material with the formaldehyde adsorption function is prepared from the following raw materials in parts by weight: 11 parts of modified hydroxyapatite, 13 parts of modified medical stone powder and 90 parts of sodium dodecyl sulfate aqueous solution.
The sodium dodecyl sulfate aqueous solution is prepared from sodium dodecyl sulfate and deionized water according to the weight ratio of 1: 61.5.
The preparation method of the modified hydroxyapatite comprises the following steps:
s01, adding 8 parts by weight of hydroxyapatite into 22 parts by weight of 4mol/L hydrochloric acid solution, and uniformly dispersing to obtain a first mixed solution;
s02, adding 1 weight part of oxalic acid and 0.8 weight part of ammonium bicarbonate into 13.2 weight parts of deionized water, and carrying out 400W ultrasonic treatment for 30min to obtain a second mixed solution;
s03, heating the first mixed solution to 70 ℃, dripping the second mixed solution into the first mixed solution under the stirring action of the rotating speed of 250rpm, carrying out ultrasonic treatment for 35min at 500W after dripping, filtering and drying to obtain pretreated hydroxyapatite;
s04, adding 7 parts by weight of pretreated hydroxyapatite, 1 part by weight of ferrous oxide and 0.8 part by weight of copper sulfate into 31.2 parts by weight of deionized water, carrying out ultrasonic treatment for 30min at 500W, stirring at 300rpm for 10h, filtering and drying to obtain the modified hydroxyapatite.
The preparation method of the modified medical stone powder comprises the following steps:
s11, calcining the medical stone powder for 1 hour at 350 ℃ to obtain calcined medical stone powder;
s12, dispersing 10 parts by weight of calcined medical stone powder in 25 parts by weight of phosphoric acid buffer solution with pH value of 5.4, adding 0.1 part by weight of neuraminidase and 0.9 part by weight of nicotinamide, stirring at the rotating speed of 300rpm at 60 ℃ for 6 hours, filtering and drying to obtain the modified medical stone powder.
The preparation method of the composite material with the formaldehyde adsorption function comprises the following steps:
s21, adding the modified hydroxyapatite into a sodium dodecyl sulfate aqueous solution with the total weight of 50 percent, and stirring at the rotating speed of 300rpm for 4 hours;
s22, adding the modified medical stone powder into the residual sodium dodecyl sulfate aqueous solution, and carrying out ultrasonic treatment at 500W for 30 min;
and S23, uniformly mixing the product obtained in the step S21 with the product obtained in the step S22, filtering and drying to obtain the composite material with the formaldehyde adsorption function.
Comparative example 1
Comparative example 1 is different from example 1 in that comparative example 1 is a single modified hydroxyapatite, and the preparation method of the modified hydroxyapatite is the same as that of example 1, and the rest is the same.
Comparative example 2
Comparative example 2 is different from example 1 in that comparative example 1 is a single modified medical stone powder, and the preparation method of the modified medical stone powder is the same as that of example 1, and the rest is the same.
Comparative example 3
Comparative example 3 is different from example 1 in that comparative example 3 uses hydroxyapatite instead of modified hydroxyapatite, and the rest is the same.
Comparative example 4
Comparative example 4 is different from example 1 in that the preparation method of the modified hydroxyapatite is different, and in this comparative example, the hydroxyapatite is not pretreated, and the others are the same.
The preparation method of the modified hydroxyapatite comprises the following steps:
s01, adding 8 parts by weight of hydroxyapatite, 1.1 parts by weight of ferrous oxide and 0.9 part by weight of copper sulfate into 30 parts by weight of deionized water, carrying out ultrasonic treatment for 30min at 500W, stirring at 300rpm for 10h, filtering and drying to obtain the modified hydroxyapatite.
Comparative example 5
Comparative example 5 is different from example 1 in that the preparation method of the modified hydroxyapatite described in comparative example 5 is different, and in this comparative example, ferrous oxide and copper sulfate are replaced with the same amount of platinum chloride, and the others are the same.
The preparation method of the modified hydroxyapatite comprises the following steps:
s01, adding 9 parts by weight of hydroxyapatite into 21 parts by weight of 4mol/L hydrochloric acid solution, and uniformly dispersing to obtain a first mixed solution;
s02, adding 1.2 parts by weight of oxalic acid and 0.9 part by weight of ammonium bicarbonate into 12.9 parts by weight of deionized water, and carrying out 400W ultrasonic treatment for 30min to obtain a second mixed solution;
s03, heating the first mixed solution to 78 ℃, dripping the second mixed solution into the first mixed solution under the stirring action of the rotating speed of 200rpm, carrying out 700W ultrasonic treatment for 30min after dripping, filtering and drying to obtain pretreated hydroxyapatite;
s04, adding 8 parts by weight of pretreated hydroxyapatite and 2 parts by weight of platinum chloride into 30 parts by weight of deionized water, carrying out ultrasonic treatment for 30min at 500W, stirring at a rotating speed of 300rpm for 10h, filtering, and drying to obtain the modified hydroxyapatite.
Comparative example 6
Comparative example 6 is different from example 1 in that comparative example 6 uses medical stone powder instead of modified medical stone powder, and the others are the same.
Comparative example 7
Comparative example 7 is different from example 1 in that the medical stone powder described in comparative example 7 was acid-modified, and the rest was the same.
Comparative example 7 is different from example 1 in that the preparation method of the modified medical stone powder described in comparative example 7 is:
s11, calcining the medical stone powder for 1 hour at 350 ℃ to obtain calcined medical stone powder;
s12, dispersing 10 parts by weight of calcined medical stone powder in 40 parts by weight of concentrated sulfuric acid, stirring at the rotating speed of 300rpm at the temperature of 60 ℃ for 6 hours, filtering and drying to obtain the modified medical stone powder.
To further demonstrate the effect of the present invention, the following test methods were provided:
1. the detection method comprises the following steps: the composite materials of examples 1 to 3 and comparative examples 1 to 7 having an equivalent mass (10g) were placed at 1m3The same amount of formaldehyde is filled into the environmental test chamber, the formaldehyde filled in the test chamber is adsorbed, wherein the initial concentration of the pollutants is 100mg/L, a gas chromatograph is used for analyzing the concentration of the pollutants after 60 minutes, the purification rate is calculated, and the test result is shown in table 1.
TABLE 1 test results
| Formaldehyde purification rate/%) | |
| Example 1 | 97.6 |
| Example 2 | 92.0 |
| Example 3 | 92.9 |
| Comparative example 1 | 79.8 |
| Comparative example 2 | 78.7 |
| Comparative example 3 | 67.3 |
| Comparative example 4 | 76.9 |
| Comparative example 5 | 80.4 |
| Comparative example 6 | 68.2 |
| Comparative example 7 | 77.1 |
As can be seen from Table 1, the composite material of the present invention has a good formaldehyde adsorption function.
Compared with the examples 1 to 3, the modified hydroxyapatite and modified medical stone powder optimized by the formula and the modification method have good formaldehyde adsorption function.
Comparing example 1 with comparative example 1 and comparative example 2, it can be seen that the modified hydroxyapatite and modified medical stone powder of the present invention have synergistic effect in the aspect of adsorbing and purifying formaldehyde.
Comparing example 1 with comparative example 3, it can be seen that the present invention significantly improves the formaldehyde adsorption effect by modifying hydroxyapatite.
Compared with the comparative example 4, the embodiment 1 and the comparative example 4 show that the hydroxyapatite is pretreated, the specific surface area, the pore volume and the surface hydroxyl groups can be effectively improved, the pore diameter is deeper, the activity is improved, the adsorption is facilitated, the subsequent introduction of Fe is facilitated, and the formaldehyde adsorption effect is remarkably improved.
Comparing example 1 with comparative example 5, it can be seen that the formaldehyde adsorption is significantly reduced by replacing ferrous oxide with other metalates.
Comparing example 1 with comparative example 6, it can be seen that the present invention significantly improves the formaldehyde adsorption and purification effect by modifying the medical stone powder.
As is clear from comparison between example 1 and comparative example 7, the modification method of the present invention has a better formaldehyde adsorbing effect than other modification methods.
In light of the foregoing description of preferred embodiments according to the invention, it is clear that many changes and modifications can be made by the person skilled in the art without departing from the scope of the invention. The technical scope of the present invention is not limited to the contents of the specification, and must be determined according to the scope of the claims.
Claims (10)
1. The composite material with the formaldehyde adsorption function is characterized by being prepared from the following raw materials in parts by weight: 5-15 parts of modified hydroxyapatite, 5-20 parts of modified medical stone powder and 65-90 parts of sodium dodecyl sulfate aqueous solution.
2. The composite material with the formaldehyde adsorption function according to claim 1, which is characterized by being prepared from the following raw materials in parts by weight: 10 parts of modified hydroxyapatite, 12 parts of modified medical stone powder and 78 parts of sodium dodecyl sulfate aqueous solution.
3. The composite material with the formaldehyde adsorbing function as claimed in claim 1, wherein the aqueous solution of sodium dodecyl sulfate is prepared from sodium dodecyl sulfate and deionized water according to a weight ratio of 1: 49-99 percent.
4. The composite material with the formaldehyde adsorption function according to claim 1, wherein the preparation method of the modified hydroxyapatite comprises the following steps:
s01, adding 6-10 parts by weight of hydroxyapatite into 20-30 parts by weight of hydrochloric acid solution, and uniformly dispersing to obtain a first mixed solution;
s02, adding 0.8-1.5 parts by weight of activating agent and 0.6-1.2 parts by weight of pore-forming agent into 8-15 parts by weight of deionized water, and carrying out ultrasonic treatment at 200-500W for 20-50 min to obtain a second mixed solution;
s03, heating the first mixed solution to 65-80 ℃, dripping the second mixed solution into the first mixed solution under the stirring action, carrying out ultrasonic treatment at 500-800W for 20-35 min, filtering, and drying to obtain pretreated hydroxyapatite;
s04, adding 6-10 parts by weight of pretreated hydroxyapatite, 0.8-1.2 parts by weight of ferrous oxide and 0.6-1.2 parts by weight of copper sulfate into 20-50 parts by weight of deionized water, carrying out ultrasonic treatment at 400-600W for 20-40 min, stirring at a rotating speed of 100-400 rpm for 8-12 h, filtering, and drying to obtain the modified hydroxyapatite.
5. The composite material with the formaldehyde adsorption function according to claim 4, wherein the hydrochloric acid solution is 2-5 mol/L hydrochloric acid solution.
6. The composite material with formaldehyde adsorbing function as claimed in claim 4, wherein the activating agent is oxalic acid.
7. The composite material with formaldehyde adsorbing function as claimed in claim 4, wherein the pore-forming agent is ammonium bicarbonate.
8. The composite material with the formaldehyde adsorption function according to claim 1, wherein the preparation method of the modified medical stone powder comprises the following steps:
s11, calcining the medical stone powder at 300-350 ℃ for 0.5-2 h to obtain calcined medical stone powder;
s12, dispersing 5-10 parts by weight of calcined medical stone powder into 20-30 parts by weight of phosphoric acid buffer solution, adding 0.1-0.4 part by weight of neuraminidase and 0.5-1 part by weight of nicotinamide, stirring at the rotating speed of 200-500 rpm at 50-80 ℃ for 3-8 hours, filtering, and drying to obtain the modified medical stone powder.
9. The composite material with the formaldehyde adsorbing function as claimed in claim 8, wherein the pH of the phosphate buffer is 5-6.
10. The preparation method of the composite material with the formaldehyde adsorption function according to any one of claims 1 to 9, characterized by comprising the following steps:
s21, adding the modified hydroxyapatite into 30-60% of sodium dodecyl sulfate water solution by weight, and stirring at the rotating speed of 200-400 rpm for 3-6 hours;
s22, adding the modified medical stone powder into the residual sodium dodecyl sulfate aqueous solution, and carrying out ultrasonic treatment at 400-700W for 25-40 min;
and S23, uniformly mixing the product obtained in the step S21 with the product obtained in the step S22, filtering and drying to obtain the composite material with the formaldehyde adsorption function.
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