CN104841437A - Method for preparing copper-zinc catalyst by using micro-channel reactor - Google Patents
Method for preparing copper-zinc catalyst by using micro-channel reactor Download PDFInfo
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- CN104841437A CN104841437A CN201510158737.0A CN201510158737A CN104841437A CN 104841437 A CN104841437 A CN 104841437A CN 201510158737 A CN201510158737 A CN 201510158737A CN 104841437 A CN104841437 A CN 104841437A
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Abstract
The invention provides a method for preparing a copper-zinc catalyst by using a micro-channel reactor. A preparation process of the catalyst is carried out in the micro-channel reactor, the micro-channel reactor comprises at least two inlets and corresponding mixing sections, and the equivalent diameter of each of the mixing sections is 0.01-5mm. The method solves the problem of easy agglomeration of nuclei in a coprecipitation preparation process, and allows catalyst crystal grains with large specific area and small particle size to be easily obtained. The size of the micro-reactor is small, so a diffusion distance among different materials can be well compressed, and Cu<+> and Zn<+> can be rapidly and uniformly mixed with a precipitating agent CO<3><2->, so Cu<2+> and Zn<2+> precipitation areas approach to each other as possible, the interaction between Cu and Zn is reinforced, and the mutual dispersion of copper and zinc components is enhanced.
Description
Technical field
The present invention relates to a kind of method utilizing micro passage reaction to prepare copper zinc catalyst, belong to catalysis material preparation field.Wherein, in Kaolinite Preparation of Catalyst process, micro passage reaction is used.
Background technology
Copper zinc catalyst can be used for the multiple reactions such as synthesising gas systeming carbinol, Water gas shift/WGS, methanol steam reforming.Research shows, the synergy between copper zinc and the specific area of Cu play important effect in the research and development of high activated catalyst, and the crystallite dimension of active ingredient copper is less, and the mutual degree of scatter of copper zinc is higher, and the activity of catalyst is also higher.Therefore in copper zinc catalyst preparation it is crucial that Homogeneous phase mixing between copper zinc and mutual dispersion good between metallic element.
Industrial copper zinc catalyst of preparing adopts coprecipitation at present.But traditional co-precipitation method is due to the restriction of device structure, be difficult to mix, local reaction condition heterogeneity, be unfavorable for the mutual dispersion of copper zinc component, and there is great back-mixing between the sediment do not generated in the same time and reaction raw materials liquid, reunite, make the granularity of particle and distribution be difficult to control.On the other hand, the structure (cuprozincite, aurichalcite etc. as Cu-Zn presoma) of presoma often determines the structure and activity of the catalyst finally obtained, but the formation of these presomas is very responsive to preparation condition, existing preparation method is difficult to accurate control.
Summary of the invention
In order to overcome the deficiencies in the prior art, the object of this invention is to provide a kind of method utilizing micro passage reaction to prepare copper zinc catalyst.For this reason, the present invention is by the following technical solutions:
A kind of method utilizing micro passage reaction to prepare copper zinc catalyst.It is characterized in that, the process preparing described catalyst is carried out in micro passage reaction, and described micro passage reaction at least has the mixing section of two entrances and correspondence, and the equivalent diameter of mixing section is at 0.01-5 mm.
Further, said method comprising the steps of:
1). containing Cu
2+, Zn
2+solution and containing the solution materials of carbonate, pump into two entrances of microreactor respectively, mix in micro passage reaction, after reaction, obtain precursor solution;
2). gained precursor solution after reaction is carried out suction filtration, washing, dry, then through roasting, after cooling processing, obtain copper zinc catalyst.
Further, the carbonate solution concentration described in step 1) is 0.1-1 mol/L, is preferably 0.2-0.5mol/L, most preferably is 0.3 mol/L.
Further, described in step 1) containing Cu
2+, Zn
2+solution in copper zinc mol ratio be 0.3-10:1, be preferably 0.5-5:1, most preferably be 1:1.
Further, the reaction temperature in the micro passage reaction described in step 1) is 20-100
oc, is preferably 40-80
oc, most preferably is 50
oc.
When adopting micro passage reaction to carry out Kaolinite Preparation of Catalyst, fluid is flow in the mode of laminar flow in pipe, and without back-mixing, and the time of staying is short, solves the problem that time prepared by coprecipitation, nucleus is easily reunited, the catalyst crystal grain that the specific area that is easy to get is large, particle diameter is less.Because the yardstick of microreactor is little, the diffusion length between different material can be compressed well, Cu
+and Zn
+with precipitating reagent CO
3 2-homogeneous phase mixing can be reached fast, make Cu
2+, Zn
2+precipitation zone is close as far as possible, strengthens the interaction between Cu, Zn, increases the mutual dispersion of copper zinc component.Meanwhile, by the control to flowing, the crystal structure of presoma can be regulated and controled well, effectively improve the activity catalyzing and synthesizing gas and prepare methyl alcohol, more be conducive to the low temperature liquid phase synthesis of methyl alcohol.
Accompanying drawing explanation
Fig. 1 is the TEM figure of copper zinc catalyst particle prepared by micro passage reaction.
Fig. 2 is the XRD figure of copper zinc catalyst granular precursor prepared by micro passage reaction.
Fig. 3 is the XRD figure of copper zinc catalyst particle prepared by micro passage reaction.
Fig. 4 is the TEM figure of copper zinc catalyst particle prepared by the precipitation method.
Detailed description of the invention
The present invention is further illustrated below in conjunction with drawings and Examples.
Embodiment 1.
Take 36.24 g nitrate trihydrate copper and 44.62 g zinc nitrate hexahydrates, be settled to 1 L by water-soluble solution, preparation molar concentration is the Cu-Zn solution of 0.3 mol/L; Separately take 63.59 g natrium carbonicum calcinatums, be settled to 2 L by water-soluble solution, preparation molar concentration is the Na of 0.3 mol/L
2cO
3solution.Be evacuated in micro passage reaction respectively with constant-flux pump and react, reaction temperature is 50
oc, regulate solution flow rate, control pH value of solution is 8-9.After having reacted, solution is carried out suction filtration, and spend deionized water 3 times.In 110
oCafter drying in baking oven, be milled into powdery, then in 350
oCroasting 4 h in Muffle furnace, obtained copper zinc catalyst.As shown in Figure 1, after granular precursor and roasting, the XRD spectra of particle is as shown in accompanying drawing 2,3 for the TEM figure of its gained catalyst granules.Scheme the basic soilless sticking phenomenon of its particle known by TEM, and size of microcrystal is less, deployment conditions is good.As can be seen from the XRD collection of illustrative plates of Fig. 2 granular precursor, the thing phase mainly aurichalcite (CuZn) of presoma
5(CO
3)
2(OH)
6with class malachite (CuZn)
2cO
3(OH)
2thing phase.As can be seen from the XRD collection of illustrative plates of Fig. 3 calcined catalyst particle, obtained catalyst has obvious CuO and ZnO crystal formation.
Catalyst activity examination is carried out in ethanol system, catalyzes and synthesizes gas methyl alcohol by copper zinc catalyst.Take catalyst obtained by 0.2 g in autoclave, measure 50 ml ethanol as solvent, be filled with 1 MPa CO and 2MPa H
2, in 170
oC4 h are reacted under condition.The reaction speed that unit catalyst produces methyl alcohol is 1305 mmolkg
-1h
-1, the reaction speed that unit catalyst produces Ethyl formate is 2464 mmolkg
-1h
-1.
Embodiment 2.
The preparation of copper zinc catalyst: according to the method Kaolinite Preparation of Catalyst that embodiment 1 is identical, difference is Cu-Zn solution and Na
2cO
3solution concentration is 0.1 mol/L, and copper zinc mol ratio is 1:5, and the reaction temperature in micro passage reaction is 20
oC.According to the catalyst obtained by the method examination that embodiment 1 is identical, the reaction speed that unit catalyst produces methyl alcohol is 637 mmolkg
-1h
-1, the reaction speed that unit catalyst produces Ethyl formate is 1558 mmolkg
-1h
-1.
Embodiment 3.
The preparation of copper zinc catalyst: according to the method Kaolinite Preparation of Catalyst that embodiment 1 is identical, difference is Cu-Zn solution and Na
2cO
3solution concentration is 1 mol/L, and copper zinc mol ratio is 10:1, and the reaction temperature in micro passage reaction is 100
oC.According to the catalyst obtained by the method examination that embodiment 1 is identical, the reaction speed that unit catalyst produces methyl alcohol is 896 mmolkg
-1h
-1, the reaction speed that unit catalyst produces Ethyl formate is 1727 mmolkg
-1h
-1.
Embodiment 4.
The preparation of copper zinc catalyst: according to the method Kaolinite Preparation of Catalyst that embodiment 1 is identical, difference is Cu-Zn solution concentration is 0.6 mol/L, and copper zinc mol ratio is 5:1, and the aqueous slkali of use is Na
2cO
3with the mixed solution of NaOH, take 127.19 g natrium carbonicum calcinatums and 48 g NaOH, be settled to 2L by water-soluble solution, preparation total mol concentration is the Na of 1.2 mol/L
2cO
3-NaOH solution (Na
2cO
3be 1:1 with NaOH mol ratio).Reaction temperature in micro passage reaction is 80
oC.According to the catalyst obtained by the method examination that embodiment 1 is identical, the reaction speed that unit catalyst produces methyl alcohol is 737 mmolkg
-1h
-1, the reaction speed that unit catalyst produces Ethyl formate is 1649 mmolkg
-1h
-1.
Comparative example.
Take 3.62 g nitrate trihydrate copper and 4.46 g zinc nitrate hexahydrates, be settled to 100 mL by water-soluble solution, preparation molar concentration is the Cu-Zn solution of 0.3 mol/L; Separately take 6.36 g natrium carbonicum calcinatums, be settled to 200 mL by water-soluble solution, preparation molar concentration is the Na of 0.3 mol/L
2cO
3solution.By Cu-Zn solution and Na
2cO
3solution is under agitation slowly added drop-wise in beaker simultaneously, and control pH value of solution is 8-9, and reaction temperature is 50
oC.After having reacted, solution is carried out suction filtration, and spend deionized water 3 times.In 110
oCafter drying in baking oven, be milled into powdery, then in 350
oCin Muffle furnace, roasting 4 h, namely obtains copper zinc catalyst by coprecipitation.As shown in Figure 4, as seen from the figure, the catalyst granules prepared by coprecipitation is relatively large, and has certain reunion for the TEM figure of this catalyst granules.According to the catalyst obtained by the method examination that embodiment 1 is identical, the reaction speed that unit catalyst produces methyl alcohol is 424 mmolkg
-1h
-1, the reaction speed that unit catalyst produces Ethyl formate is 1245 mmolkg
-1h
-1.
Claims (5)
1. the method utilizing micro passage reaction to prepare copper zinc catalyst, it is characterized in that, the process preparing described catalyst is carried out in micro passage reaction, and described micro passage reaction at least has the mixing section of two entrances and correspondence, and the equivalent diameter of mixing section is at 0.01-5 mm.
2. a kind of method utilizing micro passage reaction to prepare copper zinc catalyst as claimed in claim 1, it is characterized in that, it comprises the following steps:
1). containing Cu
2+, Zn
2+solution and containing the solution materials of carbonate, pump into two entrances of microreactor respectively, mix in micro passage reaction, after reaction, obtain precursor solution;
2). gained precursor solution after reaction is carried out suction filtration, washing, dry, then through roasting, after cooling processing, obtain copper zinc catalyst.
3. a kind of method utilizing micro passage reaction to prepare copper zinc catalyst according to claim 2, it is characterized in that, the carbonate solution concentration described in step 1) is 0.1-1 mol/L, is preferably 0.2-0.5mol/L, most preferably is 0.3 mol/L.
4. a kind of method utilizing micro passage reaction to prepare copper zinc catalyst according to claim 2, is characterized in that, described in step 1) containing Cu
2+, Zn
2+solution in copper zinc mol ratio be 0.3-10:1, be preferably 0.5-5:1, most preferably be 1:1.
5. a kind of method utilizing micro passage reaction to prepare copper zinc catalyst according to claim 2, is characterized in that the reaction temperature in the micro passage reaction described in step 1) is 20-100
oc, is preferably 40-80
oc, most preferably is 50
oc.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110237845A (en) * | 2018-03-07 | 2019-09-17 | 浙江大学 | A method of Cu-ZnO catalyst is prepared using microreactor |
| CN112138669A (en) * | 2020-09-30 | 2020-12-29 | 广东石油化工学院 | Method for continuously preparing copper-zinc-aluminum catalyst |
| CN112264043A (en) * | 2020-11-19 | 2021-01-26 | 清华大学 | Ni-Rh-based diesel reforming catalyst and preparation method and application thereof |
| CN112264005A (en) * | 2020-12-08 | 2021-01-26 | 南京工业大学 | Method for preparing zinc tungstate catalyst by using micro-channel precipitation method |
| CN112264029A (en) * | 2020-11-19 | 2021-01-26 | 清华大学 | Ni-based diesel reforming catalyst and preparation method and application thereof |
| CN112958097A (en) * | 2021-02-08 | 2021-06-15 | 清华大学 | Copper-based supported catalyst for synthesizing aniline by nitrobenzene hydrogenation and preparation method thereof |
| CN113145123A (en) * | 2021-04-26 | 2021-07-23 | 清华大学 | Low-temperature high-activity Ni-based catalyst and application thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110237845A (en) * | 2018-03-07 | 2019-09-17 | 浙江大学 | A method of Cu-ZnO catalyst is prepared using microreactor |
| CN110237845B (en) * | 2018-03-07 | 2020-09-01 | 浙江大学 | Method for preparing Cu-ZnO catalyst by using microreactor |
| CN112138669A (en) * | 2020-09-30 | 2020-12-29 | 广东石油化工学院 | Method for continuously preparing copper-zinc-aluminum catalyst |
| CN112264043A (en) * | 2020-11-19 | 2021-01-26 | 清华大学 | Ni-Rh-based diesel reforming catalyst and preparation method and application thereof |
| CN112264029A (en) * | 2020-11-19 | 2021-01-26 | 清华大学 | Ni-based diesel reforming catalyst and preparation method and application thereof |
| CN112264029B (en) * | 2020-11-19 | 2021-08-31 | 清华大学 | Ni-based diesel reforming catalyst and preparation method and application thereof |
| CN112264043B (en) * | 2020-11-19 | 2021-08-31 | 清华大学 | Ni-Rh-based diesel reforming catalyst and preparation method and application thereof |
| CN112264005A (en) * | 2020-12-08 | 2021-01-26 | 南京工业大学 | Method for preparing zinc tungstate catalyst by using micro-channel precipitation method |
| CN112958097A (en) * | 2021-02-08 | 2021-06-15 | 清华大学 | Copper-based supported catalyst for synthesizing aniline by nitrobenzene hydrogenation and preparation method thereof |
| CN113145123A (en) * | 2021-04-26 | 2021-07-23 | 清华大学 | Low-temperature high-activity Ni-based catalyst and application thereof |
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Application publication date: 20150819 |