CN103962163A - Transition metal-doped hydroxyapatite preparation method and application of transition metal-doped hydroxyapatite for catalytic oxidation of formaldehyde - Google Patents
Transition metal-doped hydroxyapatite preparation method and application of transition metal-doped hydroxyapatite for catalytic oxidation of formaldehyde Download PDFInfo
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- CN103962163A CN103962163A CN201410163446.6A CN201410163446A CN103962163A CN 103962163 A CN103962163 A CN 103962163A CN 201410163446 A CN201410163446 A CN 201410163446A CN 103962163 A CN103962163 A CN 103962163A
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- doped hydroxyapatite
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Abstract
The invention belongs to the technical field of pollution control and relates to a transition metal-doped hydroxyapatite preparation method and application of transition metal-doped hydroxyapatite for catalytic oxidation of formaldehyde. The preparation method comprises the following steps: using a CaNO3 and M(NO3)x solution and a (NH4)2HPO4 solution as precursors of the transition metal-doped hydroxyapatite; mixing and ensuring the molar ratio value of Ca+M and P is equal to 1.67, adjusting the pH to be 9-11, and reacting for 4-12 h at the temperature of 20-70 DEG C; crystallizing for 8-12 h in a reaction kettle at the temperature of 100-200 DEG C, centrifuging and washing; drying for 12-24 h at the temperature of 80-100 DEG C; calcinating for 2-3 h at the temperature of 500-800 DEG C, so that the transition metal-doped hydroxyapatite is obtained, wherein M is Co, Mn or Cu, and x is equal to 2 or 3. By adopting the preparation method provided by the invention, the preparation of hydroxyapatite and transition metal doping are completed at one step, the steps are simple, the period is short, new-phase substances are formed in the synthetic process, and new characteristics and application are brought.
Description
Technical field
The invention belongs to pollute and control and technical field, relate to the preparation method of transient metal doped hydroxyapatite and for PARA FORMALDEHYDE PRILLS(91,95) catalytic oxidation.
Background technology
Formaldehyde has higher toxicity and is defined as carcinogenic and teratogen by the World Health Organization.Short term contact formaldehyde can stimulate eyes, nasal cavity and respiratory tract and cause allergic reaction, and this stimulation toxicity main manifestations is nerve and Respiratory symptoms.Long Term Contact low dosage formaldehyde can increase nasopharyngeal carcinoma, leukaemia and dead possibility.Even the formaldehyde of low dosage, Long Term Contact also can produce infringement to human body.Formaldehyde wide material sources, building decoration and finishing material and indoor slowly release formaldehyde of multiple daily necessities.Therefore, formaldehyde has caused people's extensive concern because of its toxicity having and ubiquitous route of exposure.
The treatment technology of formaldehyde comprises bioanalysis, absorption method, plasma technique, method of chemical treatment and catalytic oxidation technology at present.Wherein catalytic oxidation has simple and effective, safety is easy to operate and do not produce the advantages such as secondary pollution, has good research and application prospect.The research of PARA FORMALDEHYDE PRILLS(91,95) catalyst for catalytic oxidation in recent years mainly concentrates on the oxide of noble metal catalyst and transition metal.Noble metal oxidant has generally shown good catalytic activity, but the higher cost of noble metal has caused it to be difficult to obtain practical application widely.For transition metal oxide, as carried noble metal not, its activity is unsatisfactory, and conversion temperature even may reach more than 200 DEG C.In addition, some transition metal oxide has toxicity, causes the unsafe factor in practical application.
Based on the defect of current institute Study of Catalyst system, be necessary to develop safe, economical, and PARA FORMALDEHYDE PRILLS(91,95) catalytic oxidation has certain activity and has the new material of active room for promotion.Hydroxyapatite is the natural inorganic composition of bone and tooth, and it has a wide range of applications at biomedical sector for a long time as a kind of bioactive materials.There is the stable and wide material sources of safety non-toxic, phase, the feature such as cheap and easy to get, met the requirement of environmental safety and good economy performance.In addition, it has shown certain activity as the catalyst of formaldehyde through catalytic oxidation, is a kind of base metal material for formaldehyde through catalytic oxidation with good development prospect.
Summary of the invention
The object of the present invention is to provide the preparation method of transient metal doped hydroxyapatite and probe into its PARA FORMALDEHYDE PRILLS(91,95) catalytic oxidation performance.Prepared catalyst safety economy of the present invention, and transient metal doped hydroxyapatite is applied to formaldehyde through catalytic oxidation as a kind of non-precious metal catalyst and has shown considerable catalytic activity.
The invention provides the preparation method of transient metal doped hydroxyapatite, the major part of this preparation method using hydroxyapatite as catalyst, transition metal Co, the Mn or the Cu that mix.
The preparation method of transient metal doped hydroxyapatite provided by the invention is a step precipitation-hydro-thermal method, comprises following technology path:
(1) by CaNO
3+ M (NO
3)
xsolution and (NH
4)
2hPO
4solution, as the precursor of the transient metal doped hydroxyapatite of preparation, and ensures Ca+M and P mol ratio=1.67;
Wherein, M=Co, Mn or Cu; X=2 or 3.
(2) by above-mentioned CaNO
3+ M (NO
3)
xsolution and (NH
4)
2hPO
4solution mixes, and regulates pH to 9～11, under 20～70 DEG C of conditions, reacts 4～12h;
(3) gained mixture in step (2) is placed in to reactor, 100～200 DEG C of crystallization 8～12h;
(4) that product step (3) crystallization being obtained carries out is centrifugal, washing, dry 12～24h at 80～100 DEG C;
(5) step (4) is calcined to 2～3h through the powder of super-dry at 500～800 DEG C, obtain transient metal doped hydroxyapatite.
Formaldehyde through catalytic oxidation reaction is carried out in straight pipe type fixed bed continuous-flow differential reactor, this straight pipe type fixed bed continuous-flow differential reactor is straight crystal reaction tube, the loadings of transient metal doped hydroxyapatite is 100～400mg, and reaction gas consists of the air that contains 200～700ppm formaldehyde.Pass into chromatogram from straight pipe type fixed bed continuous-flow differential reactor gas out and survey its composition measurement formaldehyde conversion ratio.
Transient metal doped hydroxyapatite preparation method reaction condition gentleness provided by the present invention, simple and easy to operate and raw material is cheap and easy to get, has higher feasibility.One step precipitation-hydrothermal preparing process step is simple, manufacturing cycle is short, has completed the doping of transition metal, and in resulting materials, have the formation of cenotype when hydroxyapatite structure forms, can bring new characteristic to material.Said method can mix the component of difference and different amounts as required, and reaction condition is as the easy-regulating such as pH, temperature and time.The change of different condition can obtain the transient metal doped hydroxyapatite that structure and performance there are differences, and has the associating of potential multiple application, as removal and the anti-biotic material etc. of formaldehyde.
Brief description of the drawings
Fig. 1 is the transient metal doped hydroxyapatite of the difference prepared of a step precipitation-hydro-thermal method and the activity figure of unadulterated hydroxyapatite (HAP).
Fig. 2 is the hydroxyapatite of a step precipitation-hydro-thermal method Cu doping and the X-ray diffractogram of hydroxyapatite.
Detailed description of the invention
Describe specific embodiments of the invention in detail below in conjunction with technical scheme and brief description of the drawings.
Embodiment 1
The preparation of Cu doped hydroxyapatite: by 4.248g Ca (NO
3)
4h
2o and 0.483gCu (NO
3)
36H
2o adds in 100mL deionized water, and stirring is fully dissolved it and obtained 0.2M Ca (NO
3)
2+ Cu (NO
3)
3solution; Take 1.584g (NH
4)
2hPO
4be dissolved in and in 40mL deionized water, obtain 0.3M (NH
4)
2hPO
4solution; By Ca (NO
3) solution is placed in 40 DEG C of water-baths, under agitation splashes into (NH
4)
2hPO
4solution.After solution mixes completely, splash into ammoniacal liquor pH is adjusted to 10, reaction 8h.The mixture obtaining is moved into 100 DEG C of crystallization 12h in reactor.After crystallization by the product obtaining repeatedly centrifugal, washing, dry 24h at 100 DEG C.The powder obtaining is 700 DEG C of calcining 2h in Muffle furnace, obtain Cu doped hydroxyapatite.
Embodiment 2
According to the preparation method of embodiment 1, for 100mL0.2MCa (NO
3)
2+ Cu (NO
3)
3, can use 100mL0.2MCa (NO
3)
2+ Mn (NO
3)
2solution or 100mL0.2MCa (NO
3)
2+ Co (NO
3)
2solution replaces, and it is identical that all the other steps keep, and obtains Mn doped hydroxyapatite and Co doped hydroxyapatite.
Embodiment 3
According to preparation method's preparation of embodiment 1, for 100mL0.2MCa (NO
3)
2+ Cu (NO
3)
3, can use 100mL0.2M Ca (NO
3)
2replace, it is identical that all the other steps keep, and obtains unadulterated hydroxyapatite.
Embodiment 4
According to the preparation method of embodiment 1, pH is adjusted to 9,11, it is identical that all the other steps keep, and obtains the Cu doped hydroxyapatite of differential responses pH condition.
Embodiment 5
According to the preparation method of embodiment 1, change bath temperature into 20 DEG C, 70 DEG C, it is identical that all the other steps keep, and obtains the Cu doped hydroxyapatite of differential responses temperature.
Embodiment 6
According to the preparation method of embodiment 1, change calcining heat into 500 DEG C, 600 DEG C or the 800 DEG C Cu doped hydroxyapatites that obtain different calcining heats.
Claims (2)
1. the preparation method of transient metal doped hydroxyapatite, is characterized in that, concrete steps are as follows:
(1) by CaNO
3+ M (NO
3)
xsolution and (NH
4)
2hPO
4solution, as the precursor of the transient metal doped hydroxyapatite of preparation, and ensures Ca+M and P mol ratio=1.67; Wherein M=Co, Mn or Cu; X=2 or 3;
(2) by above-mentioned CaNO
3+ M (NO
3)
xsolution and (NH
4)
2hPO
4solution mixes, and regulates pH to 9～11, under 20～70 DEG C of conditions, reacts 4～12h;
(3) gained mixture in step (2) is placed in to reactor, 100～200 DEG C of crystallization 8～12h;
(4) that product step (3) crystallization being obtained carries out is centrifugal, washing, dry 12～24h at 80～100 DEG C;
(5) step (4) is calcined to 2～3h through the powder of super-dry at 500～800 DEG C, obtain transient metal doped hydroxyapatite.
2. the transient metal doped hydroxyapatite that prepared by claim 1 is for PARA FORMALDEHYDE PRILLS(91,95) catalytic oxidation, it is characterized in that, formaldehyde through catalytic oxidation reaction is carried out in straight pipe type fixed bed continuous-flow differential reactor, and this straight pipe type fixed bed continuous-flow differential reactor is crystal reaction tube; The loadings of transient metal doped hydroxyapatite is 100～400mg, and reaction gas consists of the air that contains 200～700ppm formaldehyde.
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|---|---|---|---|
| CN201410163446.6A CN103962163A (en) | 2014-04-22 | 2014-04-22 | Transition metal-doped hydroxyapatite preparation method and application of transition metal-doped hydroxyapatite for catalytic oxidation of formaldehyde |
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|---|---|---|---|
| CN201410163446.6A CN103962163A (en) | 2014-04-22 | 2014-04-22 | Transition metal-doped hydroxyapatite preparation method and application of transition metal-doped hydroxyapatite for catalytic oxidation of formaldehyde |
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ID=51232449
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|---|---|---|---|
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109908928A (en) * | 2017-12-13 | 2019-06-21 | 中国石油化工股份有限公司 | A kind of noble metal ozone catalytic oxidation catalyst and preparation method thereof |
| CN110252357A (en) * | 2019-07-03 | 2019-09-20 | 福州大学 | A kind of hydroxy apatite-base catalyst for methane catalytic combustion |
| CN110272271A (en) * | 2018-03-13 | 2019-09-24 | 中国科学院上海硅酸盐研究所 | A kind of trace manganese doped hydroxyapatite bioceramic powder material and its preparation method and application |
| CN110975898A (en) * | 2019-11-08 | 2020-04-10 | 江汉大学 | Platinum catalyst loaded on hydroxyapatite composite cobaltosic oxide and preparation method thereof |
| CN111569916A (en) * | 2020-05-11 | 2020-08-25 | 四川大学 | Modified hydroxyapatite denitration catalyst and preparation method thereof |
| CN113941349A (en) * | 2021-10-25 | 2022-01-18 | 湖南大学 | Bone carbon supported catalyst and preparation method and application thereof |
| CN113941350A (en) * | 2021-10-25 | 2022-01-18 | 湖南大学 | Bone carbon supported catalyst and preparation method and application thereof |
| CN114029077A (en) * | 2021-11-30 | 2022-02-11 | 中国石油大学(华东) | Catalyst for preparing hydroxy acid by catalytic oxidation of polyol and method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5073357A (en) * | 1989-08-01 | 1991-12-17 | Toagosei Chemical Industry, Co., Ltd. | Process for producing hydroxylapatites |
| CN101623514A (en) * | 2009-08-07 | 2010-01-13 | 陕西科技大学 | Preparation method for nano hydroxylapatite doped with metal ions |
-
2014
- 2014-04-22 CN CN201410163446.6A patent/CN103962163A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5073357A (en) * | 1989-08-01 | 1991-12-17 | Toagosei Chemical Industry, Co., Ltd. | Process for producing hydroxylapatites |
| CN101623514A (en) * | 2009-08-07 | 2010-01-13 | 陕西科技大学 | Preparation method for nano hydroxylapatite doped with metal ions |
Non-Patent Citations (2)
| Title |
|---|
| JING XU ET AL.: "Hydroxyapatite Foam as a Catalyst for Formaldehyde Combustion at Room Temperature", 《J.AM.CHEM.SOC.》 * |
| 吴从亮等: "水热合成铝掺杂羟基磷灰石分析", 《实验科学与技术》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109908928A (en) * | 2017-12-13 | 2019-06-21 | 中国石油化工股份有限公司 | A kind of noble metal ozone catalytic oxidation catalyst and preparation method thereof |
| CN110272271B (en) * | 2018-03-13 | 2022-04-08 | 中国科学院上海硅酸盐研究所 | Trace manganese-doped hydroxyapatite biological ceramic powder material and preparation method and application thereof |
| CN110272271A (en) * | 2018-03-13 | 2019-09-24 | 中国科学院上海硅酸盐研究所 | A kind of trace manganese doped hydroxyapatite bioceramic powder material and its preparation method and application |
| CN110252357A (en) * | 2019-07-03 | 2019-09-20 | 福州大学 | A kind of hydroxy apatite-base catalyst for methane catalytic combustion |
| CN110975898A (en) * | 2019-11-08 | 2020-04-10 | 江汉大学 | Platinum catalyst loaded on hydroxyapatite composite cobaltosic oxide and preparation method thereof |
| CN111569916B (en) * | 2020-05-11 | 2021-08-24 | 四川大学 | Modified hydroxyapatite denitration catalyst and preparation method thereof |
| CN111569916A (en) * | 2020-05-11 | 2020-08-25 | 四川大学 | Modified hydroxyapatite denitration catalyst and preparation method thereof |
| CN113941349A (en) * | 2021-10-25 | 2022-01-18 | 湖南大学 | Bone carbon supported catalyst and preparation method and application thereof |
| CN113941350A (en) * | 2021-10-25 | 2022-01-18 | 湖南大学 | Bone carbon supported catalyst and preparation method and application thereof |
| CN113941350B (en) * | 2021-10-25 | 2023-04-28 | 湖南大学 | Bone carbon supported catalyst and preparation method and application thereof |
| CN113941349B (en) * | 2021-10-25 | 2023-05-30 | 湖南大学 | Bone carbon supported catalyst and preparation method and application thereof |
| CN114029077A (en) * | 2021-11-30 | 2022-02-11 | 中国石油大学(华东) | Catalyst for preparing hydroxy acid by catalytic oxidation of polyol and method thereof |
| CN114029077B (en) * | 2021-11-30 | 2024-01-19 | 中国石油大学(华东) | Catalyst for preparing hydroxy acid by catalytic oxidation of polyol and method thereof |
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Application publication date: 20140806 |