CN102179250A - Magnetic nano solid alkaline catalyst and method for synthesizing pseudoionone in presence of magnetic nano solid alkaline catalyst - Google Patents

Magnetic nano solid alkaline catalyst and method for synthesizing pseudoionone in presence of magnetic nano solid alkaline catalyst Download PDF

Info

Publication number
CN102179250A
CN102179250A CN2011100668743A CN201110066874A CN102179250A CN 102179250 A CN102179250 A CN 102179250A CN 2011100668743 A CN2011100668743 A CN 2011100668743A CN 201110066874 A CN201110066874 A CN 201110066874A CN 102179250 A CN102179250 A CN 102179250A
Authority
CN
China
Prior art keywords
magnetic nano
nano solid
solid base
base catalyst
preparation
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.)
Pending
Application number
CN2011100668743A
Other languages
Chinese (zh)
Inventor
张法智
宋芳艳
赵晓非
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.)
Beijing University of Chemical Technology
Original Assignee
Beijing University of Chemical Technology
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 Beijing University of Chemical Technology filed Critical Beijing University of Chemical Technology
Priority to CN2011100668743A priority Critical patent/CN102179250A/en
Publication of CN102179250A publication Critical patent/CN102179250A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Landscapes

  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a magnetic nano solid alkaline catalyst and a method for synthesizing pseudoionone in presence of the magnetic nano solid alkaline catalyst, and belongs to the field of magnetic solid alkaline catalysts. In the invention, the magnetic nano solid alkaline catalyst which is a MgO and MgFe2O4 composite is prepared by using a laminar dihydroxy composite metal hydroxide precursor and by high-temperature baking. The catalyst has the characteristics that: particle size is of nano grade; activity and selectivity in catalytic reactions are high; and recycling of the catalyst can be realized by applying an external magnetic field.

Description

The method of a kind of magnetic Nano solid base catalyst and catalytic synthesis of pseudo-ionone thereof
Technical field
The invention belongs to the magnetic solid base catalytic field, be specifically related to by a kind of magnetic Nano solid base catalyst of hydrotalcite precursor roasting preparation and the method for catalytic synthesis of pseudo-ionone thereof.
Background technology
Hydrotalcite-based compound comprises hydrotalcite and houghite, and its main body generally is made of the hydroxide of two kinds of metals, therefore is called laminated dihydroxy composite metal hydroxide (Layered Double Hydroxide is abbreviated as LDH) again.The intercalation compound of LDH is called intercalated houghite.Hydrotalcite, houghite and intercalated houghite are referred to as hydrotalcite intercalation material (LDHs).Hydrotalcite-based compound is because of having extremely people's attention of special layer structure and character, and is widely used in catalytic field.LDHs and for all having the alkali center in the resulting product of roasting of roasting presoma, thereby can be used for base catalysis.LDHs mainly is used to two big class reactions as base catalyst: alkylene oxide polymerization and aldol reaction.Many literature research the aldehyde ketone polycondensation reaction on the LDHs, find that the LDHs of a lot of thermal activations all reveals catalytic activity preferably to such reaction table.
In the catalyticing research field, nano material has huge specific area, have good surperficial adsorptive concentration effect, absorption directionality effect and quantum size effect, be expected to make the nanocatalyst of high-specific surface area, efficient, high selectivity, and realize the MOLECULE DESIGN of catalyst.Therefore, nano-catalytic and application study are just becoming the research focus of catalytic chemistry.Nanocatalyst also exists some problems simultaneously aspect Application and Development, do not grasp as yet such as its stable performance control technology, too tiny particle powder has very high surface can, in reaction system, be easy to reunite, performance is very unstable, and traditional filtration, centrifugal method waste time and energy, and can not reach fully and reclaim, thereby brought obstacle for their application, and reduced its effective utilization.
In view of the catalytic performance of the excellence of nanocatalyst be difficult to reclaim the application limitation of use, people are in the method for making great efforts to explore more efficiently recovery separating catalyst.Because the special nature of magnetic material, Magnetic Isolation becomes the research topic that receives much attention in recent years.Magnetic Isolation, it is the recycling that realizes nanocatalyst by the effect of externally-applied magnetic field easily, the process that is considered to a kind of green, it has avoided the problem such as loss, oxidation of the catalyst that traditional separate mode brings, and makes catalyst keep higher activity simultaneously.
Summary of the invention
The method that the purpose of this invention is to provide a kind of magnetic Nano solid base catalyst and catalytic synthesis of pseudo-ionone thereof.The present invention uses single catalyst precarsor MgFe-LDHs to make final catalyst through roasting: MgO and MgFe 2O 4Compound, this catalyst can catalysis acetone and the aldol condensation synthesis of pseudo-ionone of citral, and can realize the recovery of catalyst by Magnetic Isolation.
Concrete preparation process of the present invention is as follows:
A, preparation MgFe-LDHs precursor: take by weighing Mg (NO 3) 26H 2O and Fe (NO 3) 39H 2O is dissolved in and is made into mixing salt solution, wherein Mg in the deionized water 2+Concentration is 0.12-6mol/L, Mg 2+With Fe 3+Mol ratio is 2-4; And then take by weighing NaOH and Na 2CO 3Be dissolved in and be made into mixed ammonium/alkali solutions in the deionized water, wherein n (Na 2CO 3)/[n (Fe 3+)]=2.0-2.5, n (NaOH)/[n (Mg 2+)+n (Fe 3+)]=1.8-2.5, NaOH concentration is 1.0-6.0mol/L, n (NaOH), n (Mg 2+), n (Fe 3+), n (Na 2CO 3) be respectively NaOH, Mg 2+, Fe 3+, Na 2CO 3Molal quantity; Above-mentioned mixing salt solution and mixed ammonium/alkali solutions are added full back-mixing liquid film reactor simultaneously, slit width between conditioned reaction device rotor and the stator is 0.01-0.03mm, operating voltage is 80-120V, rotor speed is 3500-6000rpm, reaction time 1-5min will stir crystallization in the mixed serum adding crystallizing kettle that obtain, and keeping the temperature of mixed serum in the still is 80-120 ℃, backflow crystallization 6-12h obtains magnesium molten iron talcum precursor slurry; Magnesium molten iron talcum precursor slurry to pH=7-8, behind 80-200 ℃ of dry 12-48h, promptly gets the MgFe-LDHs precursor through centrifuge washing;
B, preparation magnetic Nano solid base catalyst: the MgFe-LDHs precursor of above-mentioned gained is put into crucible, 700-900 ℃ of roasting 2-4h in Muffle furnace, concrete scheme is: the Muffle furnace initial temperature is 15-30 ℃, then with the heating rate temperature programming of 1-10 ℃/min to 700-900 ℃, and then keep 1-4h, naturally cool to room temperature afterwards; After roasting finishes, the magnetic Nano solid base catalyst that makes is taken out, put into drier and preserve.
The magnetic Nano solid base catalyst of step B preparation is MgO and MgFe 2O 4Compound has magnetic, and granule size is a nanoscale.
Be used for the aldol reaction synthesis of pseudo-ionone of acetone and citral with the magnetic Nano solid base catalyst of the present invention preparation, its chemical equation is C 3H 6O+C 10H 16O → C 13H 20O+H 2O, reaction condition is as follows: reaction pressure is a normal pressure, reaction temperature 40-150 ℃, reaction time 2-8h, the mol ratio of acetone and citral is 1-10, adds the magnetic Nano solid base catalyst of above-mentioned steps B preparation, and addition is the 5-20% of acetone and citral quality sum.
The magnetic Nano solid base catalyst of the present invention's preparation has the nanometer particle size, can catalysis acetone and the aldol condensation synthesis of pseudo-ionone of citral, higher activity and selectivity are arranged in catalytic reaction, can realize the recycling of catalyst by externally-applied magnetic field, it is a kind of process of green that Magnetic Isolation reclaims, avoided the problem such as loss, oxidation of the catalyst that traditional separate mode brings, made catalyst keep higher activity simultaneously.
Description of drawings
Fig. 1 is the XRD spectra of the prepared magnetic Nano solid base catalyst of embodiment 1.
Fig. 2 is the SEM image of the prepared magnetic Nano solid base catalyst of embodiment 1.
The specific embodiment
The invention will be further described below in conjunction with embodiment:
Embodiment 1
A: take by weighing 115.38g Mg (NO 3) 26H 2O and 60.60g Fe (NO 3) 39H 2O is dissolved in and is made into the 500mL mixing salt solution in the deionized water; And then take by weighing 108.00g NaOH and 31.78g Na 2CO 3Be dissolved in and be made into the 500mL mixed ammonium/alkali solutions in the deionized water; Above-mentioned two kinds of mixed solutions are added full back-mixing liquid film reactor simultaneously, slit width between conditioned reaction device rotor and the stator is 0.02mm, operating voltage is 100V, commentaries on classics is 4000rpm from rotating speed, back-mixing time 2min, to stir crystallization in the mixed serum adding crystallizing kettle that obtain, keeping the temperature of mixed serum in the still is 80 ℃ of backflow crystallization 6h, obtains magnesium molten iron talcum precursor slurry; Magnesium molten iron talcum precursor slurry to pH=7.5, behind the dry 24h, promptly gets the MgFe-LDHs precursor through centrifuge washing in 80 ℃ of electric heating constant temperature air dry ovens;
B: the MgFe-LDHs precursor of above-mentioned gained is put into crucible, 900 ℃ of roasting 4h in Muffle furnace, concrete scheme is: the Muffle furnace initial temperature is 25 ℃, then with the heating rate temperature programming to 900 of 1 ℃/min ℃, and then 900 ℃ of maintenance 4h, naturally cool to room temperature afterwards; After roasting finishes, the magnetic Nano solid base catalyst that makes is taken out, put into drier and preserve.
The magnetic Nano solid base catalyst of step B preparation is MgO and MgFe 2O 4Compound has magnetic, and granule size is a nanoscale.
Generate pseudoionone with this magnetic Nano solid base catalyst catalysis acetone and citral reaction: in the 25mL there-necked flask, add acetone 2.35mL, citral 2.33mL, mix the back and add the magnetic Nano solid base catalyst that 0.39g step B makes, reaction pressure is a normal pressure, 70 ℃ of reaction temperatures, reaction time 6h, the conversion ratio of citral is 81.20%, and the selectivity of pseudoionone is 65.00%.
Embodiment 2
A: take by weighing 71.79g Mg (NO 3) 26H 2O and 56.56g Fe (NO 3) 39H 2O is dissolved in and is made into the 350mL mixing salt solution in the deionized water; And then take by weighing 78.40g NaOH and 29.68g Na 2CO 3Be dissolved in and be made into the 350mL mixed ammonium/alkali solutions in the deionized water; Above-mentioned two kinds of mixed solutions are added full back-mixing liquid film reactor simultaneously, slit width between conditioned reaction device rotor and the stator is 0.01mm, operating voltage is 100V, rotor speed is 4000rpm, back mixing time 2min, to stir crystallization in the mixed serum adding crystallizing kettle that obtain, keeping the temperature of mixed serum in the still is 80～90 ℃ of backflow crystallization 6h, obtains magnesium molten iron talcum precursor slurry; Magnesium molten iron talcum precursor slurry to pH=7.5, behind the dry 12h, promptly gets the MgFe-LDHs precursor through centrifuge washing in 80 ℃ of electric heating constant temperature air dry ovens;
B: the MgFe-LDHs precursor of above-mentioned gained is put into crucible, 800 ℃ of roasting 4h in Muffle furnace, concrete scheme is: the Muffle furnace initial temperature is 30 ℃, then with the heating rate temperature programming to 800 of 5 ℃/min ℃, and then 800 ℃ of maintenance 4h, naturally cool to room temperature afterwards; After roasting finishes, the magnetic Nano solid base catalyst that makes is taken out, put into drier and preserve.
The magnetic Nano solid base catalyst of step B preparation is MgO and MgFe 2O 4Compound has magnetic, and granule size is a nanoscale.
Generate pseudoionone with this magnetic Nano solid base catalyst catalysis acetone and citral reaction: in the 25mL there-necked flask, add acetone 2.2mL, citral 5mL, mix the back and add the magnetic Nano solid base catalyst that 0.31g step B makes, reaction pressure is a normal pressure, 50 ℃ of reaction temperatures, reaction time 5h, the conversion ratio of citral is 81.48%, and the selectivity of pseudoionone is 55.23%.
Embodiment 3
A: take by weighing 172.3g Mg (NO 3) 26H 2O and 67.87g Fe (NO 3) 39H 2O is dissolved in and is made into the 700mL mixing salt solution in the deionized water; And then take by weighing 147.84g NaOH and 35.61g Na 2CO 3Be dissolved in and be made into the 700mL mixed ammonium/alkali solutions in the deionized water; Above-mentioned two kinds of mixed solutions are added full back-mixing liquid film reactor simultaneously, slit width between conditioned reaction device rotor and the stator is 0.02mm, operating voltage is 100V, rotor speed is 4000rpm, back mixing time 2min, to stir crystallization in the mixed serum adding crystallizing kettle that obtain, keeping the temperature of mixed serum in the still is 80～90 ℃ of backflow crystallization 6h, obtains magnesium molten iron talcum precursor slurry; Magnesium molten iron talcum precursor slurry to pH=8.0, behind the dry 24h, promptly gets the MgFe-LDHs precursor through centrifuge washing in 80 ℃ of electric heating constant temperature air dry ovens;
B: the MgFe-LDHs precursor of above-mentioned gained is put into crucible, 700 ℃ of roasting 2h in Muffle furnace, concrete scheme is: the Muffle furnace initial temperature is 25 ℃, then with the heating rate temperature programming to 700 of 10 ℃/min ℃, and then 700 ℃ of maintenance 2h, naturally cool to room temperature afterwards; After roasting finishes, the magnetic Nano solid base catalyst that makes is taken out, put into drier and preserve.
The magnetic Nano solid base catalyst of step B preparation is MgO and MgFe 2O 4Compound has magnetic, and granule size is a nanoscale.
Generate pseudoionone with this magnetic Nano solid base catalyst catalysis acetone and citral reaction: in the 50mL there-necked flask, add acetone 11mL, citral 5mL, mix the back and add the magnetic Nano solid base catalyst that 0.66g step B makes, reaction pressure is a normal pressure, 100 ℃ of reaction temperatures, reaction time 5h, the conversion ratio of citral is 85.65%, and the selectivity of pseudoionone is 70.00%.

Claims (4)

1. the preparation method of a magnetic Nano solid base catalyst is characterized in that, its concrete preparation process is as follows:
A, preparation MgFe-LDHs precursor: take by weighing Mg (NO 3) 26H 2O and Fe (NO 3) 39H 2O is dissolved in and is made into mixing salt solution, wherein Mg in the deionized water 2+Concentration is 0.12-6mol/L, Mg 2+With Fe 3+Mol ratio is 2-4; And then take by weighing NaOH and Na 2CO 3Be dissolved in and be made into mixed ammonium/alkali solutions in the deionized water, wherein n (Na 2CO 3)/[n (Fe 3+)]=2.0-2.5, n (NaOH)/[n (Mg 2+)+n (Fe 3+)]=1.8-2.5, NaOH concentration is 1.0-6.0mol/L, n (NaOH), n (Mg 2+), n (Fe 3+), n (Na 2CO 3) be respectively NaOH, Mg 2+, Fe 3+, Na 2CO 3Molal quantity; Above-mentioned mixing salt solution and mixed ammonium/alkali solutions are added full back-mixing liquid film reactor simultaneously, slit width between conditioned reaction device rotor and the stator is 0.01-0.03mm, operating voltage is 80-120V, rotor speed is 3500-6000rpm, reaction time 1-5min will stir crystallization in the mixed serum adding crystallizing kettle that obtain, and keeping the temperature of mixed serum in the still is 80-120 ℃, backflow crystallization 6-12h obtains magnesium molten iron talcum precursor slurry; Magnesium molten iron talcum precursor slurry to pH=7-8, behind 80-200 ℃ of dry 12-48h, promptly gets the MgFe-LDHs precursor through centrifuge washing;
B, preparation magnetic Nano solid base catalyst: the MgFe-LDHs precursor of above-mentioned gained is put into crucible, 700-900 ℃ of roasting 2-4h in Muffle furnace, concrete scheme is: the Muffle furnace initial temperature is 15-30 ℃, then with the heating rate temperature programming of 1-10 ℃/min to 700-900 ℃, and then keep 1-4h, naturally cool to room temperature afterwards; After roasting finishes, the magnetic Nano solid base catalyst that makes is taken out, put into drier and preserve.
2. according to the preparation method of the described a kind of magnetic Nano solid base catalyst of claim 1, it is characterized in that the magnetic Nano solid base catalyst of step B preparation is MgO and MgFe 2O 4Compound has magnetic, and granule size is a nanoscale.
3. the magnetic Nano solid base catalyst of method preparation according to claim 1 and 2 is characterized in that it is applied to the aldol reaction synthesis of pseudo-ionone of acetone and citral.
4. magnetic Nano solid base catalyst according to claim 3 is characterized in that, the chemical equation of the aldol reaction synthesis of pseudo-ionone of described acetone and citral is C 3H 6O+C 10H 16O → C 13H 20O+H 2O, reaction condition is: reaction pressure is a normal pressure, reaction temperature 40-150 ℃, reaction time 2-8h, the mol ratio of acetone and citral is 1-10, the addition of magnetic Nano solid base catalyst is the 5-20% of acetone and citral quality sum.
CN2011100668743A 2011-03-18 2011-03-18 Magnetic nano solid alkaline catalyst and method for synthesizing pseudoionone in presence of magnetic nano solid alkaline catalyst Pending CN102179250A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2011100668743A CN102179250A (en) 2011-03-18 2011-03-18 Magnetic nano solid alkaline catalyst and method for synthesizing pseudoionone in presence of magnetic nano solid alkaline catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2011100668743A CN102179250A (en) 2011-03-18 2011-03-18 Magnetic nano solid alkaline catalyst and method for synthesizing pseudoionone in presence of magnetic nano solid alkaline catalyst

Publications (1)

Publication Number Publication Date
CN102179250A true CN102179250A (en) 2011-09-14

Family

ID=44565650

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2011100668743A Pending CN102179250A (en) 2011-03-18 2011-03-18 Magnetic nano solid alkaline catalyst and method for synthesizing pseudoionone in presence of magnetic nano solid alkaline catalyst

Country Status (1)

Country Link
CN (1) CN102179250A (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1470323A (en) * 2002-07-23 2004-01-28 �Ϻ���ͨ��ѧ Magnetic nano solid base catalyst and its preparnig method
CN101816950A (en) * 2010-04-30 2010-09-01 北京化工大学 Hydrotalcite-like structuring catalyst and method for catalytic synthesis of pseudo-ionone

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1470323A (en) * 2002-07-23 2004-01-28 �Ϻ���ͨ��ѧ Magnetic nano solid base catalyst and its preparnig method
CN101816950A (en) * 2010-04-30 2010-09-01 北京化工大学 Hydrotalcite-like structuring catalyst and method for catalytic synthesis of pseudo-ionone

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
《Chemical Engineering Science》 20080523 Yanchang Wang et al Preparation of macrospherical magnesia-rich magnesium aluminate spinel catalysts for methanolysis of soybean oil 1-4 第63卷, *
《中国优秀硕士学位论文全文数据库》 20051231 齐荣 磁性纳米固体碱催化剂的结构设计与性能研究 3-4 , *

Similar Documents

Publication Publication Date Title
Tahir Hierarchical 3D VO2/ZnV2O4 microspheres as an excellent visible light photocatalyst for CO2 reduction to solar fuels
Dahl et al. Composite titanium dioxide nanomaterials
Yi et al. CeO2/Bi2MoO6 heterostructured microspheres with synergistic effect for accelerating photogenerated charge separation
CN105170186B (en) A kind of preparation method of core shell structure BiOX@MIL (Fe) photochemical catalyst
CN101229510B (en) Synthesis and applications of silicate containing Bi
CN102626634B (en) Bismuth ferrite-graphene compounding magnetism visible light catalyst, as well as preparation method and application of same
CN103143376B (en) High-activity hydrotalcite loaded gold nanocluster catalyst and preparation method thereof
CN101822981B (en) Supported gold catalyst and preparation method thereof
CN103071492B (en) Preparation method of efficient formaldehyde catalytic conversion catalyst
CN100382890C (en) Aluminium-based pseudo-hydrotalcite structuralization catalyst, and its prepn. method
CN105600828B (en) A kind of porous nano CuFe2O4Preparation method
WO2018138618A1 (en) Preparation method and application of supported noble metal tricobalt tetraoxide nanocatalyst
WO2012083511A1 (en) Preparation method and use of manganese dioxide nano-rod
CN109847766A (en) A kind of coplanar ZnIn2S4/WO3Z architecture catalyst material
CN103586035B (en) A kind of self-propagating reaction prepares copper zinc or the method for copper Zinc-aluminium catalyst
CN104148098B (en) A kind of silver phosphate modified magnetic separation Hollow Compound photocatalyst and preparation method thereof
CN101797492B (en) Method for preparing laminated dihydroxy composite metal hydroxide porous microspheres
Li et al. An efficient CeGeO4 catalyst for degradation of organic dyes without light irradiation at room temperature
CN106423161A (en) Preparation method of hydrogenation catalyst and catalyst
CN102350353A (en) Preparation method of Fe3O4/C/TiO2 composite photocatalyst
Xiang et al. ZIF-67-derived hierarchical hollow Co3O4@ CoMn2O4 nanocages for efficient catalytic oxidation of formaldehyde at low temperature
CN102145924B (en) Method for preparing alkaline cobalt carbonate under hyper-gravity hydrothermal condition
CN108380197A (en) A kind of methane CO based on microwave activation2Preparing synthetic gas by reforming nucleocapsid catalyst and preparation method thereof
CN109926048A (en) A kind of one pack system double activated position Cu2O-CuO nanometers of mixed phase structure copper oxide catalysts, preparation method and application
CN106082298A (en) A kind of preparation method of cerium bismuth composite oxide nano-bar material

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C12 Rejection of a patent application after its publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20110914