CN103920493B - A kind of preparation method of the hollow copper oxide catalyst for the synthesis of methylchlorosilane - Google Patents
A kind of preparation method of the hollow copper oxide catalyst for the synthesis of methylchlorosilane Download PDFInfo
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Abstract
The invention provides a kind of preparation method of the hollow copper oxide catalyst for the synthesis of methylchlorosilane, belong to organic silicon monomer field of catalyst preparation.Cupric oxide powder is first dissolved in the mixed solution of ammoniacal liquor and ammonium salt by the preparation method of the hollow copper oxide catalyst for the synthesis of methylchlorosilane of the present invention, then mixed with organic solvent by this solution and carry out solvent thermal reaction, product obtains hollow cupric oxide after separation, washing, drying and roasting.Method preparation technology provided by the present invention is succinct efficient, response parameter is controlled, be easy to scale synthesis, and prepared hollow cupric oxide has higher reactivity and selective as catalyst for the synthesis of methyl chlorosilane monomer.By the present invention, achieve the business solid copper powders of the low catalytic activity of random pattern to change into there is highly active hollow copper oxide catalyst, there is important scientific meaning and using value.
Description
Technical field
The present invention relates to organic silicon monomer catalyst preparation technical field, particularly relate to a kind of preparation method of the hollow copper oxide catalyst for the synthesis of methylchlorosilane.
Background technology
As a class p-type semiconductor transition metal oxide, cupric oxide is widely used in the key areas such as catalyst, lithium ion battery material, super capacitor material.Especially in organic silicon monomer synthesis field, cupric oxide can improve the selective of dimethyldichlorosilane in methylchlorosilane product as a kind of efficient copper catalyst.As everyone knows, the pattern of material, size and structure are the key factors affecting its physical and chemical performance.Therefore, the copper oxide material with different-shape and structure causes the great interest of people.At present, the copper oxide material of the different morphologies such as nano wire, nanometer rods, nanotube, nanocube, flower-like microsphere, hollow ball has been synthesized.Wherein, cupric oxide hollow ball is with the low-density of its uniqueness, high-ratio surface architectural feature, it is expected in organic silicon monomer building-up process, hollow cupric oxide increases the contact area with reactant silica flour with its higher specific surface, cause the course of reaction hollow core cupric oxide silica flour that deepens continuously inner, accelerate the conversion rate of silica flour, increase the productive rate of product dimethyl dichlorosilane.Meanwhile, the lower density of hollow copper oxide catalyst self, greatly saves consumption, reduces the production cost of methyl chlorosilane monomer.
At present, the synthesis of hollow cupric oxide mainly by mantoquita as reaction raw materials, adopt hydro-thermal or solvent thermal reaction to obtain.The general organic formwork agent adding costliness in course of reaction assists synthesis, or accuracy controlling response parameter is carried out, and product morphology not easily repeats, and reappearance is lower, not easily scale synthesis.Therefore, design a kind of simple effectively, reappearance method that is high, that be easy to scale synthesis prepares the technical barrier that hollow copper oxide material remains this field.
Summary of the invention
For the deficiencies in the prior art, the object of the present invention is to provide that a kind of technique is simple efficient, product morphology favorable reproducibility, be easy to scale synthesis and the preparation method of hollow copper oxide catalyst for methyl chlorosilane monomer synthesis.
Technological core of the present invention is to take cupric oxide powder as reaction raw materials, forms cupric ammine complex solution with ammoniacal liquor and carbon ammonium, then makes cupric ammine complex change into hollow-core construction copper presoma by solvent heat process, obtains hollow copper oxide material finally by roasting.Meaning of the present invention is SA business-like random solid copper powders to be transformed by technical method of the present invention to form highly active hollow copper oxide catalyst.
The present invention adopts following technical scheme:
The concrete steps of the preparation method of the hollow copper oxide catalyst for the synthesis of methylchlorosilane of the present invention are as follows:
(1) first cupric oxide is dissolved in the mixed solution of ammoniacal liquor and ammonium salt;
(2) in the mixed solution of step (1), N is added, dinethylformamide, mixed solution and N, the volume ratio of dinethylformamide is 0.01 ~ 1.0, make copper ion concentration in solution be 0.05mol/l ~ 1.0mol/l, after mixing, put into stainless steel still, then carry out adding thermal response, reaction temperature is 100 DEG C ~ 220 DEG C, and the reaction time is 5h ~ 24h;
(3), after reaction terminates, carry out being separated, washing, products therefrom roasting 2h ~ 10h at 250 DEG C ~ 600 DEG C is obtained hollow cupric oxide.
In step (1), described ammonium salt is the one in ammonium carbonate, carbonic hydroammonium.
In step (2), preferably make copper ion concentration in solution be 0.05mol/l ~ 0.5mol/l, more preferably make copper ion concentration in solution be 0.1mol/l ~ 0.5mol/l.
In step (2), the volume ratio of preferred mixed solution and DMF is 0.01 ~ 0.5, and more preferably the volume ratio of mixed solution and DMF is 0.01 ~ 0.3.
In step (2), preferable reaction temperature is 120 DEG C ~ 200 DEG C, and the reaction time is 8h ~ 20h, and more preferably reaction temperature is 130 DEG C ~ 180 DEG C, and the reaction time is 10h ~ 15h.
In step (3), preferred sintering temperature is 250 DEG C ~ 500 DEG C, and more preferably sintering temperature is 300 DEG C ~ 500 DEG C.
Its advantage of method of the hollow copper oxide catalyst of synthesis provided by the present invention is:
1) preparation method provided by the invention take cupric oxide powder as raw material, and form cupric ammine complex, then constructed the copper presoma of hollow-core construction by solvent thermal reaction, process is simply controlled, and with cupric oxide for also not have relevant report.
2) the present invention regulates and controls the pattern of cobaltosic oxide by controlling the composition of solvent and solvent heat temperature and time, control condition and means easy to implement, and product pattern favorable reproducibility.
3) preparation technology of the present invention is simply efficient, without the need to any complex device, is a kind of simple and effective, environmental friendliness, is easy to the preparation method of the hollow copper oxide catalyst of high activity of scale synthesis.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of the hollow cupric oxide that embodiment 1 obtains.
Fig. 2 is the SEM figure of the hollow cupric oxide that embodiment 1 obtains.
Fig. 3 is the TEM figure of the hollow cupric oxide that embodiment 1 obtains.
Fig. 4 is the electron diffraction diagram of the hollow cupric oxide that embodiment 1 obtains.
Fig. 5 is the nitrogen adsorption/desorption isotherm figure of the hollow cupric oxide that embodiment 1 obtains.
Detailed description of the invention
The following examples describe in further detail of the present invention.
Embodiment 1:
Take 0.40g cupric oxide and be dissolved in 5ml containing in the ammoniacal liquor of ammonium carbonate (33.3wt%), then 45mlN is added, dinethylformamide (DMF, mixed solution and DMF volume ratio 0.1, copper ion concentration is 0.1mol/l), mix and mixed solution is transferred to 100ml stainless steel water heating kettle, be heated to 130 DEG C of insulation 15h, by product separation, washing after reaction terminates, dry, then obtain black powder product at 500 DEG C of roasting 2h.
The D/max-rB type Multi-functional X ray diffractometer produced in Japanese Shimadzu Corporation by the black powder product of above-mentioned preparation carries out XRD test.Fig. 1 is the XRD spectra of the black powder product that embodiment 1 obtains, and the diffraction maximum in spectrogram is typical cupric oxide characteristic diffraction peak, and according to standard powder diffraction card (JCPDSNo.48-1548), its crystal structure is monoclinic system.XRD spectra confirms that gained black product is cupric oxide.By the S4800 model field emission scanning electron microscope observation surface topography that the cupric oxide of above-mentioned preparation is produced in HIT.Fig. 2 is the SEM figure of the cupric oxide that embodiment 1 obtains, and cupric oxide is typical hollow shape pattern as seen from the figure, and its size is about 8.5 μm.
By the JEM-2100 lanthanum hexaboride transmission electron microscopy observation particle information that the cupric oxide of above-mentioned preparation is produced in company of NEC.Fig. 3 is the TEM figure of the cupric oxide that embodiment 1 obtains, and cupric oxide is hollow shape pattern as seen from the figure, and it is of a size of 8.1 μm.Electronic diffraction photo (Fig. 4) shows clearly point diffraction, shows that hollow cupric oxide is made up of single crystal nanoparticles, has very high crystallinity.The surface analysis instrument test specific surface of the Omnisorp100CX model that the hollow cupric oxide of above-mentioned preparation is produced in Coulter Corporation of the U.S..Fig. 5 is the nitrogen adsorption/desorption isotherm figure of the hollow cupric oxide that embodiment 1 obtains.At the IV type thermoisopleth at relative partial pressure about 0.8 ~ 1.0 place, hysteresis loop shows that hollow cupric oxide has meso-hole structure, BET specific surface is 48.6m
2/ g.
Embodiment 2:
Take 2.0g cupric oxide and be dissolved in 11.5ml containing in the ammoniacal liquor of ammonium carbonate (33.3wt%), then 38.5mlN is added, dinethylformamide (DMF, mixed solution and DMF volume ratio 0.3, copper ion concentration is 0.5mol/l), mix and mixed solution is transferred to 100ml stainless steel water heating kettle, be heated to 120 DEG C of insulation 20h, by product separation, washing after reaction terminates, dry, then obtain black powder product at 300 DEG C of roasting 4h.
XRD spectra assay products is monoclinic system cupric oxide.SEM photo display product is hollow shape pattern, and its size is about 7.2 μm.TEM photo confirms that product has hollow-core construction further, and it is of a size of 7.1 μm.Electronic diffraction photo confirms that product is made up of single crystal nanoparticles.The hollow cupric oxide of surface analysis instrument test display Pu has meso-hole structure, and BET specific surface is for being 56.2m
2/ g.
Embodiment 3:
Take 0.2g cupric oxide and be dissolved in 16.7ml containing in the ammoniacal liquor of ammonium carbonate (33.3wt%), then 33.3mlN is added, dinethylformamide (DMF, mixed solution and DMF volume ratio 0.5, copper ion concentration is 0.05mol/l), mix and mixed solution is transferred to 100ml stainless steel water heating kettle, be heated to 180 DEG C of insulation 10h, by product separation, washing after reaction terminates, dry, then obtain black powder product at 250 DEG C of roasting 10h.
XRD spectra assay products is monoclinic system cupric oxide.SEM photo display product is hollow shape pattern, and its size is about 6.5 μm.TEM photo confirms that product has hollow-core construction further, and it is of a size of 6.3 μm.Electronic diffraction photo confirms that product is made up of single crystal nanoparticles.The hollow cupric oxide of surface analysis instrument test display Pu has meso-hole structure, and BET specific surface is for being 57.9m
2/ g.
Embodiment 4:
Take 1.2g cupric oxide and be dissolved in 8.3ml containing in the ammoniacal liquor of ammonium carbonate (33.3wt%), then 41.7mlN is added, dinethylformamide (DMF, mixed solution and DMF volume ratio 0.2, copper ion concentration is 0.3mol/l), mix and mixed solution is transferred to 100ml stainless steel water heating kettle, be heated to 200 DEG C of insulation 8h, by product separation, washing after reaction terminates, dry, then obtain black powder product at 400 DEG C of roasting 5h.
XRD spectra assay products is monoclinic system cupric oxide.SEM photo display product is hollow shape pattern, and its size is about 7.9 μm.TEM photo confirms that product has hollow-core construction further, and it is of a size of 7.6 μm.Electronic diffraction photo confirms that product is made up of single crystal nanoparticles.The hollow cupric oxide of surface analysis instrument test display Pu has meso-hole structure, and BET specific surface is for being 50.1m
2/ g.
Embodiment 5:
Take 1.6g cupric oxide and be dissolved in 14.3ml containing in the ammoniacal liquor of ammonium carbonate (33.3wt%), then 35.7mlN is added, dinethylformamide (DMF, mixed solution and DMF volume ratio 0.4, copper ion concentration is 0.4mol/l), mix and mixed solution is transferred to 100ml stainless steel water heating kettle, be heated to 160 DEG C of insulation 8h, by product separation, washing after reaction terminates, dry, then obtain black powder product at 350 DEG C of roasting 7h.
XRD spectra assay products is monoclinic system cupric oxide.SEM photo display product is hollow shape pattern, and its size is about 7.5 μm.TEM photo confirms that product has hollow-core construction further, and it is of a size of 7.3 μm.Electronic diffraction photo confirms that product is made up of single crystal nanoparticles.The hollow cupric oxide of surface analysis instrument test display Pu has meso-hole structure, and BET specific surface is for being 53.2m
2/ g.
Catalytically active assessment
Be in the glass fixed bed of 20mm at diameter, add by silica flour 15g, the homogeneous mixture that the copper oxide catalyst 1.5g prepared in zinc powder 0.15g and above-described embodiment is formed, be heated to 330 DEG C, pass into the chloromethanes after preheating and react, chloromethanes speed is 30mL/min, reaction 24h, obtain mix products, calculate through gas chromatographic analysis, the catalytic activity results such as the selective of dimethyldichlorosilane and silica flour conversion ratio can be obtained.
Table 1 copper oxide catalyst catalytically active assessment result
Note: (1) M1: Trichloromethyl silane, M2: dimethyldichlorosilane, M3: tri-methyl-chlorosilane
As shown in Table 1, the hollow copper oxide catalyst prepared by method of the present invention is all better than business solid copper powders to the selective of dimethyldichlorosilane and the important technical indicator of silica flour conversion ratio these two.
Applicant declares, although illustrate and describe embodiments of the invention, for the ordinary skill in the art, be appreciated that and can carry out multiple change, amendment, replacement and modification to these embodiments without departing from the principles and spirit of the present invention, scope of the present invention is by claims and equivalents thereof.
Claims (9)
1. for the synthesis of a preparation method for the hollow copper oxide catalyst of methylchlorosilane, it is characterized in that: the concrete steps of described method are as follows:
(1) be first dissolved in by cupric oxide in the mixed solution of ammoniacal liquor and ammonium salt, described ammonium salt is the one in ammonium carbonate, carbonic hydroammonium;
(2) in the mixed solution of step (1), N is added, dinethylformamide, mixed solution and N, the volume ratio of dinethylformamide is 0.01 ~ 1.0, make copper ion concentration in solution be 0.05mol/l ~ 1.0mol/l, after mixing, put into stainless steel still, then carry out adding thermal response, reaction temperature is 100 DEG C ~ 220 DEG C, and the reaction time is 5h ~ 24h;
(3), after reaction terminates, carry out being separated, washing, products therefrom roasting 2h ~ 10h at 250 DEG C ~ 600 DEG C is obtained hollow cupric oxide.
2. preparation method as claimed in claim 1, is characterized in that: in step (2), makes copper ion concentration in solution be 0.05mol/l ~ 0.5mol/l.
3. preparation method as claimed in claim 1, is characterized in that: in step (2), makes copper ion concentration in solution be 0.1mol/l ~ 0.5mol/l.
4. preparation method as claimed in claim 1, it is characterized in that: in step (2), the volume ratio of mixed solution and DMF is 0.01 ~ 0.5.
5. preparation method as claimed in claim 1, it is characterized in that: in step (2), the volume ratio of mixed solution and DMF is 0.01 ~ 0.3.
6. preparation method as claimed in claim 1, it is characterized in that: in step (2), reaction temperature is 120 DEG C ~ 200 DEG C, and the reaction time is 8h ~ 20h.
7. preparation method as claimed in claim 1, it is characterized in that: in step (2), reaction temperature is 130 DEG C ~ 180 DEG C, and the reaction time is 10h ~ 15h.
8. preparation method as claimed in claim 1, it is characterized in that: in step (3), sintering temperature is 250 DEG C ~ 500 DEG C.
9. preparation method as claimed in claim 1, it is characterized in that: in step (3), sintering temperature is 300 DEG C ~ 500 DEG C.
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| CN102502770A (en) * | 2011-10-21 | 2012-06-20 | 中国科学院过程工程研究所 | Flower-like copper oxide catalyst and preparation method and application thereof |
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| 过渡族金属氧化物纳米材料的水热法制备及表征;邬剑波;《中国优秀硕士学位论文全文数据库工程科技I辑》;20070815(第02期);正文第1-26页 * |
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