CN113274969B - Composite material with formaldehyde adsorption function and preparation method thereof - Google Patents

Composite material with formaldehyde adsorption function and preparation method thereof Download PDF

Info

Publication number
CN113274969B
CN113274969B CN202110579765.5A CN202110579765A CN113274969B CN 113274969 B CN113274969 B CN 113274969B CN 202110579765 A CN202110579765 A CN 202110579765A CN 113274969 B CN113274969 B CN 113274969B
Authority
CN
China
Prior art keywords
parts
weight
stone powder
medical stone
modified
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110579765.5A
Other languages
Chinese (zh)
Other versions
CN113274969A (en
Inventor
请求不公布姓名
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Qingdao Longping Thermal Insulation Building Materials Co ltd
Original Assignee
Qingdao Longping Thermal Insulation Building Materials Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Qingdao Longping Thermal Insulation Building Materials Co ltd filed Critical Qingdao Longping Thermal Insulation Building Materials Co ltd
Priority to CN202110579765.5A priority Critical patent/CN113274969B/en
Publication of CN113274969A publication Critical patent/CN113274969A/en
Application granted granted Critical
Publication of CN113274969B publication Critical patent/CN113274969B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • 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
    • 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
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Analytical Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Disinfection, Sterilisation Or Deodorisation Of Air (AREA)

Abstract

The invention discloses a composite material with formaldehyde adsorption function and a preparation method thereof, wherein the composite material with formaldehyde adsorption function is prepared from the following raw materials in parts by weight: 5 to 15 parts of modified hydroxyapatite, 5 to 20 parts of modified medical stone powder and 65 to 90 parts of sodium dodecyl sulfate aqueous solution. The composite material with formaldehyde adsorption function is prepared from modified hydroxyapatite, modified medical stone powder and sodium dodecyl sulfate aqueous solution, and does not contain other substances; the composite material can effectively adsorb and purify formaldehyde, the modified hydroxyapatite is acidic, the modified medical stone powder has the property of bidirectionally regulating the pH value, the pH value of the modified hydroxyapatite can be improved, and after the modified medical stone powder and the modified medical stone powder are combined, the pH value is improved, so that the modified medical stone powder and the modified medical stone powder have good adsorption activity, and can be synergistically used.

Description

Composite material with formaldehyde adsorption function and preparation method thereof
Technical Field
The invention relates to the technical field of composite materials, in particular to a composite material with formaldehyde adsorption function.
Background
Modern people spend about 80% of their time indoors, where the indoor environment is closely related to the health and work efficiency of people. Formaldehyde is used as the most representative indoor volatile organic pollutant, and is a research hot spot 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. Has strong irritation to sensory and respiratory systems, and can cause lacrimation, dyspnea, and other symptoms and diseases such as headache, nausea, rhinitis, emphysema, and lung cancer. Especially, the effect on children is larger, and asthma is extremely 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, carrying out ultrasonic oscillation uniformly, adding 10-12 parts of 10-15% potassium permanganate solution with mass concentration while stirring, stirring for reaction, centrifuging, and drying to obtain the indoor formaldehyde environment-friendly purifying material; wherein, the modified hydroxyapatite is obtained by taking hydroxyapatite as a raw material and modifying the hydroxyapatite by 3- (N-allylamino) propyl trimethoxy silane; the modified silicon carbide is obtained by using silicon carbide as a raw material and carrying out modification treatment on 3-aminopropyl triethoxysilane and glutaric anhydride; the acrylic acid premix is obtained by mixing acrylic acid with a cross-linking agent and an initiator. The modification method for the hydroxyapatite adopts a silane coupling agent, and the modification method is different from the modification method.
CN105080615a discloses an adsorption catalyst for rapidly removing formaldehyde and a preparation method thereof, which contains modified medical stone and contains a plurality of other substances, and specifically discloses a preparation method of the modified medical stone powder: and (3) filling the medical stone powder and water into a high-pressure reaction kettle for hydrothermal reaction, drying, adding the medical stone powder and the water into a potassium permanganate aqueous solution for oscillation, filtering and drying to obtain the modified medical stone powder. The medical stone powder is subjected to oxidative modification by adopting potassium permanganate aqueous solution oscillation, so that oxygen-containing groups on the surface of the medical stone powder are obviously increased, the adsorption capacity to formaldehyde can be enhanced, and the preparation method is different from the preparation method.
At present, no document discloses that modified hydroxyapatite and modified medical stone powder are combined for purifying and adsorbing formaldehyde.
Disclosure of Invention
The invention provides a composite material with formaldehyde adsorption function and a preparation method thereof, and the composite material can effectively adsorb formaldehyde.
The invention solves the technical problems by adopting the following technical scheme:
a composite material with formaldehyde adsorption function is prepared from the following raw materials in parts by weight: 5 to 15 parts of modified hydroxyapatite, 5 to 20 parts of modified medical stone powder and 65 to 90 parts of sodium dodecyl sulfate aqueous solution.
As a preferable scheme, the formaldehyde adsorption material 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 sulfonate aqueous solution is prepared from sodium dodecyl sulfonate and deionized water according to a weight ratio of 1:49 to 99.
As a preferred 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 an activating agent and 0.6-1.2 parts by weight of a pore-forming agent into 8-15 parts by weight of deionized water, and performing 200-500W ultrasonic treatment 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, performing 500-800W ultrasonic treatment 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, performing ultrasonic treatment for 20-40 min at 400-600W, stirring for 8-12 h at a rotating speed of 100-400 rpm, filtering and drying to obtain modified hydroxyapatite.
The inventors of the present invention found in a great deal of research that by modifying hydroxyapatite, the specific surface area, pore volume and surface hydroxyl groups are increased, the pore diameter is deeper, the activity is improved, adsorption is facilitated and subsequent Fe introduction is facilitated, by introducing Fe groups into itIn profound pores, fe in Fe groups can be as follows 2+ And Fe (Fe) 3+ The conversion is circulated, 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 discovers that the catalytic oxidation performance of the ferrous oxide is greatly reduced by adopting other metallics to replace the ferrous oxide (such as platinum chloride and manganese chloride).
As a preferable mode, the hydrochloric acid solution is a hydrochloric acid solution of 2-5 mol/L.
As a preferred embodiment, the activator is oxalic acid.
As a preferable scheme, 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 hours 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 aminoplast and 0.5-1 part by weight of nicotinamide, stirring at a speed of 200-500 rpm for 3-8 hours at 50-80 ℃, filtering, and drying to obtain modified medical stone powder.
The inventor of the invention surprisingly found in a great deal of researches that by modifying medical stone powder, on one hand, the specific surface area and the pore volume of the medical stone powder are improved, and on the other hand, after modification, the adsorption activity of the medical stone powder is improved, and the nicotinamide can obviously improve the adsorption capacity of formaldehyde due to the introduction of nitrogen-containing functional groups and oxygen-containing functional groups because of the functional group structures of carbonyl groups, pyridines, amides and the like.
Meanwhile, the inventor of the invention discovers that the modified hydroxyapatite and the modified medical stone powder have obvious synergistic effect in a large amount of researches.
Firstly, the modified hydroxyapatite is acidic, and the modified medical stone powder has the property of bidirectionally regulating the pH, so that the pH of the modified hydroxyapatite can be improved, and after the modified medical stone powder and the modified medical stone powder are combined, the pH is improved, so that the modified medical stone powder and the modified medical stone powder have good adsorption activity, and can be synergistically used.
Secondly, formaldehyde is removed by the modified hydroxyapatite mainly through catalytic oxidation, and formaldehyde is treated from two directions by the modified medical stone powder mainly through adsorption, physical adsorption and catalytic oxidation, so that a synergistic effect is exerted.
As a preferable mode, the pH of the phosphate buffer is 5-6.
The invention also provides a preparation method of the composite material with formaldehyde adsorption function, which comprises the following steps:
s21, adding the modified hydroxyapatite into a sodium dodecyl sulfate aqueous solution accounting for 30-60% of the total weight, and stirring for 3-6 h at a rotating speed of 200-400 rpm;
s22, adding the modified medical stone powder into the residual sodium dodecyl sulfate aqueous solution, and performing ultrasonic treatment for 25-40 min at 400-700W;
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 formaldehyde adsorption function.
The invention has the beneficial effects that: (1) The composite material with formaldehyde adsorption function is prepared from modified hydroxyapatite, modified medical stone powder and 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 purifying and adsorbing formaldehyde.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the present invention, the parts are parts by weight unless specifically stated otherwise.
Example 1
A composite material with 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 a 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 performing 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 a rotating speed of 200rpm, performing ultrasonic treatment for 30min at 700W 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, performing 500W ultrasonic treatment for 30min, stirring at 300rpm for 10h, filtering and drying to obtain modified hydroxyapatite.
The preparation method of the modified medical stone powder comprises the following steps:
s11, calcining medical stone powder at 320 ℃ for 1h 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 of 5.4, adding 0.2 part by weight of aminoplast and 0.8 part by weight of nicotinamide, stirring at 60 ℃ for 6 hours at a speed of 300rpm, filtering, and drying to obtain modified medical stone powder.
The preparation method of the composite material with 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%, and stirring for 4 hours at a speed of 300 rpm;
s22, adding modified medical stone powder into the residual sodium dodecyl sulfate aqueous solution, and performing 500W ultrasonic treatment for 30min;
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 formaldehyde adsorption function.
Example 2
A composite material with 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 a 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 performing 300W ultrasonic treatment 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 200rpm, performing 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, performing 500W ultrasonic treatment for 30min, stirring at 300rpm for 10h, filtering and drying to obtain modified hydroxyapatite.
The preparation method of the modified medical stone powder comprises the following steps:
s11, calcining medical stone powder at 300 ℃ for 1h 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 of 5.4, adding 0.3 part by weight of aminopeptidase and 1 part by weight of nicotinamide, stirring at the speed of 300rpm for 6 hours at the temperature of 60 ℃, filtering, and drying to obtain the modified medical stone powder.
The preparation method of the composite material with 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%, and stirring for 4 hours at a speed of 300 rpm;
s22, adding modified medical stone powder into the residual sodium dodecyl sulfate aqueous solution, and performing 500W ultrasonic treatment for 30min;
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 formaldehyde adsorption function.
Example 3
A composite material with 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 a 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 part by weight of oxalic acid and 0.8 part by weight of ammonium bicarbonate into 13.2 parts by weight of deionized water, and performing 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 a rotating speed of 250rpm, performing 500W ultrasonic treatment for 35min 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, performing 500W ultrasonic treatment for 30min, stirring at 300rpm for 10h, filtering and drying to obtain modified hydroxyapatite.
The preparation method of the modified medical stone powder comprises the following steps:
s11, calcining medical stone powder at 350 ℃ for 1h 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 of 5.4, adding 0.1 part by weight of aminopeptidase and 0.9 part by weight of nicotinamide, stirring at 60 ℃ for 6 hours at a speed of 300rpm, filtering, and drying to obtain modified medical stone powder.
The preparation method of the composite material with 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%, and stirring for 4 hours at a speed of 300 rpm;
s22, adding modified medical stone powder into the residual sodium dodecyl sulfate aqueous solution, and performing 500W ultrasonic treatment for 30min;
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 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 example 1, except that the other methods are 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, except that the preparation method is the same.
Comparative example 3
Comparative example 3 differs from example 1 in that comparative example 3 uses hydroxyapatite instead of modified hydroxyapatite, all other things being equal.
Comparative example 4
Comparative example 4 differs from example 1 in that the preparation method of the modified hydroxyapatite is different, and in this comparative example, the hydroxyapatite is not subjected to pretreatment and is the same as the other.
The preparation method of the modified hydroxyapatite comprises the following steps:
s01, 8 parts by weight of hydroxyapatite, 1.1 parts by weight of ferrous oxide and 0.9 part by weight of copper sulfate are added into 30 parts by weight of deionized water, 500W is subjected to ultrasonic treatment for 30min, and the mixture is stirred at 300rpm for 10h, filtered and dried to obtain 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, the same amount of platinum chloride is used instead of ferrous oxide and copper sulfate, and the other is 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 performing 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 a rotating speed of 200rpm, performing ultrasonic treatment for 30min at 700W 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, performing 500W ultrasonic treatment for 30min, stirring at 300rpm for 10h, filtering, and drying to obtain the modified hydroxyapatite.
Comparative example 6
Comparative example 6 differs from example 1 in that comparative example 6 uses medical stone powder instead of modified medical stone powder, all of which 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 all other things were 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 as follows:
s11, calcining medical stone powder at 350 ℃ for 1h to obtain calcined medical stone powder;
s12, dispersing 10 parts by weight of calcined medical stone powder in 40 concentrated sulfuric acid, stirring at 60 ℃ for 6 hours at a speed of 300rpm, filtering, and drying to obtain 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 composites of examples 1 to 3 and comparative examples 1 to 7, having equal mass (10 g), were placed at 1m 3 And (3) filling equal amount of formaldehyde into the environment test cabin, and adsorbing the formaldehyde filled into the test cabin, wherein the initial concentration of the pollutant is 100mg/L, analyzing the concentration of the pollutant by using a gas chromatograph after 60 minutes, and calculating the purification rate, wherein 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.
Comparative examples 1 to 3 show that the modified hydroxyapatite and the modified medical stone powder optimized by the formula and the modification method have good formaldehyde adsorption function.
The comparison example 1, the comparison example 1 and the comparison example 2 show that the modified hydroxyapatite and the modified medical stone powder have synergistic effect in the aspect of absorbing and purifying formaldehyde.
Comparative example 1 and comparative example 3 show that the adsorption effect on formaldehyde is remarkably improved by modifying the hydroxyapatite.
As can be seen from comparative examples 1 and 4, the pretreatment of hydroxyapatite can effectively increase specific surface area, pore volume and surface hydroxyl groups, the pore diameter is deeper, the activity is improved, adsorption is facilitated, subsequent introduction of Fe is facilitated, and thus the formaldehyde adsorption effect is remarkably improved.
Comparative examples 1 and 5 show that the adsorption of formaldehyde is significantly reduced by replacing the ferrous oxide with other metallics.
As can be seen from comparative examples 1 and 6, the adsorption and purification effects of the medical stone powder on formaldehyde are remarkably improved by modifying the medical stone powder.
As can be seen from comparative examples 1 and 7, the modification method of the present invention has a better formaldehyde adsorption effect than other modification methods.
With the above-described preferred embodiments according to the present invention as an illustration, the above-described descriptions can be used by persons skilled in the relevant art to make various changes and modifications without departing from the scope of the technical idea of the present invention. The technical scope of the present invention is not limited to the description, but must be determined according to the scope of the claims.

Claims (5)

1. The composite material with the formaldehyde adsorption function is characterized by being prepared from the following raw materials in parts by weight: 5 to 15 parts of modified hydroxyapatite, 5 to 20 parts of modified medical stone powder and 65 to 90 parts of sodium dodecyl sulfate aqueous solution;
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 an activating agent and 0.6-1.2 parts by weight of a pore-forming agent into 8-15 parts by weight of deionized water, and performing 200-500W ultrasonic treatment 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, performing 500-800W ultrasonic treatment 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, performing ultrasonic treatment for 20-40 min at 400-600W, stirring for 8-12 h at a rotating speed of 100-400 rpm, filtering and drying to obtain modified hydroxyapatite;
the activator is oxalic acid;
the pore-forming agent is ammonium bicarbonate;
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 hours 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 aminoplast and 0.5-1 part by weight of nicotinamide, stirring at a speed of 200-500 rpm for 3-8 hours at 50-80 ℃, filtering, and drying to obtain modified medical stone powder.
2. The composite material with the formaldehyde adsorption function according to claim 1, wherein 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.
3. The composite material with formaldehyde adsorption function according to claim 1, wherein the sodium dodecyl sulfonate aqueous solution comprises sodium dodecyl sulfonate and deionized water according to a weight ratio of 1:49 to 99.
4. The composite material with formaldehyde adsorption function according to claim 1, wherein the hydrochloric acid solution is 2-5 mol/L hydrochloric acid solution.
5. The composite material with formaldehyde adsorption function according to claim 1, wherein the pH value of the phosphate buffer solution is 5-6.
CN202110579765.5A 2021-05-26 2021-05-26 Composite material with formaldehyde adsorption function and preparation method thereof Active CN113274969B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110579765.5A CN113274969B (en) 2021-05-26 2021-05-26 Composite material with formaldehyde adsorption function and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110579765.5A CN113274969B (en) 2021-05-26 2021-05-26 Composite material with formaldehyde adsorption function and preparation method thereof

Publications (2)

Publication Number Publication Date
CN113274969A CN113274969A (en) 2021-08-20
CN113274969B true CN113274969B (en) 2024-02-06

Family

ID=77282108

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110579765.5A Active CN113274969B (en) 2021-05-26 2021-05-26 Composite material with formaldehyde adsorption function and preparation method thereof

Country Status (1)

Country Link
CN (1) CN113274969B (en)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102872796A (en) * 2012-10-30 2013-01-16 烟台迪康环境科技有限公司 Preparation method of medical stone purifying agent for adsorbing and decomposing formaldehyde
CN103772154A (en) * 2014-01-21 2014-05-07 湘潭大学 Method for catalyzed synthesis of bisphenol F by using modified hydroxyapatite
CN105080615A (en) * 2015-07-29 2015-11-25 安徽科浦环保科技有限公司 Adsorption catalyst capable of removing formaldehyde quickly and preparing method thereof
CN106731506A (en) * 2017-01-13 2017-05-31 杭州蓝山环保科技有限公司 A kind of efficient, long-acting formaldehyde eliminating agent and preparation method thereof
WO2018121509A1 (en) * 2016-12-30 2018-07-05 苏州律点信息科技有限公司 Formaldehyde adsorbing building coating
CN110339810A (en) * 2018-04-02 2019-10-18 广西大学 A kind of formaldehyde absorbing active carbon and preparation method thereof
CN111100652A (en) * 2019-12-31 2020-05-05 卢再亮 Heavy metal contaminated soil remediation agent and preparation method and application method thereof
CN112516787A (en) * 2020-10-20 2021-03-19 俞春亚 Indoor formaldehyde purification material and preparation method thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102872796A (en) * 2012-10-30 2013-01-16 烟台迪康环境科技有限公司 Preparation method of medical stone purifying agent for adsorbing and decomposing formaldehyde
CN103772154A (en) * 2014-01-21 2014-05-07 湘潭大学 Method for catalyzed synthesis of bisphenol F by using modified hydroxyapatite
CN105080615A (en) * 2015-07-29 2015-11-25 安徽科浦环保科技有限公司 Adsorption catalyst capable of removing formaldehyde quickly and preparing method thereof
WO2018121509A1 (en) * 2016-12-30 2018-07-05 苏州律点信息科技有限公司 Formaldehyde adsorbing building coating
CN106731506A (en) * 2017-01-13 2017-05-31 杭州蓝山环保科技有限公司 A kind of efficient, long-acting formaldehyde eliminating agent and preparation method thereof
CN110339810A (en) * 2018-04-02 2019-10-18 广西大学 A kind of formaldehyde absorbing active carbon and preparation method thereof
CN111100652A (en) * 2019-12-31 2020-05-05 卢再亮 Heavy metal contaminated soil remediation agent and preparation method and application method thereof
CN112516787A (en) * 2020-10-20 2021-03-19 俞春亚 Indoor formaldehyde purification material and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Experimental study on the adsorption of dissolved heavy metals by nano-hydroxyapatite;Yang Zheng et al.;《Water Science & Technology》;第82卷(第9期);第1825-1832页 *
Formaldehyde catalytic oxidation over hydroxyapatite modified with various organic molecules;Yahui Sun et al.;《催化学报》;第35卷(第12期);第1927-1936页 *

Also Published As

Publication number Publication date
CN113274969A (en) 2021-08-20

Similar Documents

Publication Publication Date Title
CN112107997B (en) High-molecular air purifying material and preparation method thereof
CN107737578B (en) Preparation method of anion antibacterial adsorption material composition
CN104437401A (en) Activated carbon material having electrostatic adsorption and anion releasing effect and preparation method thereof
CN105170177B (en) The manufacturing method of exhaust gas purification catalyst
CN102335588B (en) Method for preparing molecular sieve with air-purification function
CN113025093B (en) Inorganic coating with air purification function and preparation method thereof
CN112111211B (en) Environment-friendly coating
CN104437403A (en) Cactus-containing antibacterial and anti-radiation activated carbon filtering material and preparation method thereof
CN108854432A (en) A kind of active carbon removing formaldehyde/bacteria cellulose compounded mix and preparation method
CN106747047A (en) A kind of preparation method of environment-friendly diatom ooze interior wall coating
CN105964290B (en) Catalysis oxidation removes formaldehyde catalyst and preparation method thereof
CN113274969B (en) Composite material with formaldehyde adsorption function and preparation method thereof
CN110538553A (en) Preparation method of tourmaline-based negative ion air purification functional composite filter material
CN114835477B (en) Multifunctional water purification ceramic material
CN109317146A (en) A kind of magnetic oxygenated graphene composite catalyst of titanium dioxide-and preparation method thereof
CN109926033B (en) Modified small pore molecular sieve adsorbent and its preparation method and use
CN108993533B (en) Preparation method of toluene low-temperature combustion catalyst and toluene low-temperature combustion catalyst
CN110590227A (en) Diatom ooze capable of efficiently and durably removing formaldehyde and preparation method thereof
CN110170306B (en) Process for preparing adsorbent for efficiently removing low-concentration formaldehyde in air at normal temperature by two-step modification method, product and application thereof
CN116119767A (en) Modified mineral-based water purifying agent for deep treatment of coking wastewater
CN110124727B (en) Coal ash-based denitration catalyst, preparation method thereof and denitration method
CN112755953B (en) Adsorbent for removing nitrogen oxides in fluid, preparation method and application
CN109603781A (en) A kind of adsorbent and its preparation method and application
CN107899430A (en) A kind of processing method of nitrogen-containing wastewater
KR20090116846A (en) Functional materials manufacture methods for remove of sick house syndrome

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right
TA01 Transfer of patent application right

Effective date of registration: 20240110

Address after: 266000 in zaohu Community Industrial Park, Chengyang street, Chengyang District, Qingdao City, Shandong Province

Applicant after: Qingdao Longping Thermal Insulation Building Materials Co.,Ltd.

Address before: 530004 100 East University Road, XiXiangTang District, Nanning, the Guangxi Zhuang Autonomous Region

Applicant before: GUANGXI University

GR01 Patent grant
GR01 Patent grant