CN105642263A - A preparing method of a modified layered bi-metal oxide - Google Patents
A preparing method of a modified layered bi-metal oxide Download PDFInfo
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- CN105642263A CN105642263A CN201410652956.XA CN201410652956A CN105642263A CN 105642263 A CN105642263 A CN 105642263A CN 201410652956 A CN201410652956 A CN 201410652956A CN 105642263 A CN105642263 A CN 105642263A
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Abstract
A preparing method of a modified layered bi-metal oxide is provided. The method includes 1) preparing a layered bi-metal hydroxide, 2) reacting the layered bi-metal hydroxide with an alkali in an organic alcohol to prepare an alkali-modified layered bi-metal hydroxide and 3) calcinating the layered bi-metal hydroxide at 800 DEG C or below to prepare the modified layered bi-metal oxide. The modified layered bi-metal oxide prepared by the method is used as a catalyst for a reaction between butyl acetate and ethylene oxide, and is high in catalysis activity, and an obtained product is high in yield and high in purity.
Description
Technical field
The present invention relates to the preparation method of a kind of layered bi-metal oxide compound, be specially a kind of can the reaction of catalysis N-BUTYL ACETATE and oxyethane, to prepare the preparation method of the layered bi-metal oxide compound of the modification of 2-Butoxyethyl acetate.
Background technology
2-Butoxyethyl acetate is colourless transparent liquid, is slightly soluble in water, can with most of immiscible organic solvent. It is a kind of high boiling point, glycol ether esters solvent containing multiple functional radical, what can be used as emulsion paint helps coalescing agent, owing to polytype paint and metallic paint are had excellent solubility property by it, make it obtain in multicolor finish and emulsion coatings and apply widely. Diethylene Glycol monobutyl ether acetate has very high boiling point, is mainly used in the high boiling solvent of the roasting porcelain of high temperature and printing-ink, and what be also used as emulsion paint helps coalescing agent; Owing to this solvent evaporation rate is very slow, in water, solubleness is low, so can be used as the solvent of screen printing ink, and the solvent of polystyrene paint printing glaze; Also can be used as entrainer being separated for alcohol and ketone.
The prior synthesizing method of 2-Butoxyethyl acetate carries out esterification synthesis by butyl glycol ether and acetic acid under sulphuric acid catalysis, but this method side reaction is many, and product purity is not high, and equipment corrosion is serious, and containing a large amount of acid waste water in aftertreatment, it is easy to cause environmental pollution.
In the field such as catalytic esterification, alkoxylation, there is extremely important effect as a kind of heterogeneous catalyst using complex metal oxides more than binary or binary. Existing complex metal oxides preparation method mostly is and first adopts the precipitator method, rehydration method etc. to prepare complex metal hydroxide, then roasting under the high temperature of gained complex hydroxide more than 500 DEG C is obtained. But, carry out the reaction of N-BUTYL ACETATE and oxyethane by catalyzer of existing complex metal oxides, there is many shortcomings such as catalytic activity is low, low conversion rate, selectivity are low.
Summary of the invention
For solving the problems of the technologies described above, the present invention provides the preparation method of the layered bi-metal oxide compound of a kind of modification, comprising:
1) layered double hydroxide is prepared;
2) layered double-metal hydroxide and alkali are reacted in organic alcohol, the layered double hydroxide of obtained alkali modification;
3) by layered double hydroxide roasting below 800 DEG C of described alkali modification, the layered bi-metal oxide compound of obtained described modification.
According to an embodiment of the present invention, the layered bi-metal oxide compound of wherein said modification comprises at least one the IIth A family metal oxide and at least one group IIIA metal oxide.
According to another embodiment of the present invention, wherein said IIth A family metal oxide is the oxide compound of magnesium and/or calcium, and described group IIIA metal oxide is the oxide compound of aluminium and/or gallium.
According to another embodiment of the present invention, the content of wherein said IIth A family metal oxide is 10��70wt%, and the content of described group IIIA metal oxide is 30��90wt%, taking the gross weight of the layered bi-metal oxide compound of described modification as benchmark.
According to another embodiment of the present invention, wherein said organic alcohol is selected from C1��C6Saturated monohydroxy alcohol or polyvalent alcohol, it is preferable to C1��C6Saturated monohydroxy alcohol or dibasic alcohol.
According to another embodiment of the present invention, wherein said alkali is organic bases or mineral alkali, and its consumption is 0.01��0.1 times of layered double-metal hydroxide by weight.
According to another embodiment of the present invention, wherein said organic bases be selected from sodium methylate, potassium ethylate, n-Butyl Lithium, Monomethylamine, diethylamine, triethylamine, urea, pyridine one or more; Described mineral alkali be selected from sodium hydroxide, potassium hydroxide, salt of wormwood, sodium carbonate, sodium bicarbonate one or more.
According to another embodiment of the present invention, wherein said step 2) comprising: the layered double hydroxide that layered double-metal hydroxide and alkali are reacted in organic alcohol solvent at 100��150 DEG C 1��5 hour obtained described alkali modification; The layered double hydroxide of described alkali modification is filtered and is washed till neutrality, and at 60��80 DEG C dry 12��24 hours.
According to another embodiment of the present invention, wherein said step 3) maturing temperature be 300��800 DEG C, roasting time is 3��6 hours.
The layered bi-metal oxide compound of the modification that the method for the present invention obtains, for the catalyzer of N-BUTYL ACETATE and reacting ethylene oxide, not only catalytic activity height, and products obtained therefrom receipts rate height, purity height.
Accompanying drawing explanation
Fig. 1 is the gas chromatogram of the embodiment of the present invention 1 products therefrom;
Fig. 2 is the gas chromatogram of the embodiment of the present invention 2 products therefrom;
Fig. 3 is the gas chromatogram of the embodiment of the present invention 3 products therefrom;
Fig. 4 is the gas chromatogram of the embodiment of the present invention 4 products therefrom;
Fig. 5 is the gas chromatogram of the embodiment of the present invention 5 products therefrom;
Fig. 6 A, 6B, 6C are the TEM figure of the embodiment of the present invention 2, comparative example 1 and comparative example 2 gained catalyzer.
Fig. 7 is the XRD figure spectrum of the embodiment of the present invention 2 and comparative example 1, comparative example 2 gained catalyzer;
Fig. 8 is the infrared spectra spectrogram of the embodiment of the present invention 2 and comparative example 1, comparative example 2 gained catalyzer.
Fig. 9 is the CO of the embodiment of the present invention 2 and comparative example 1, comparative example 2 gained catalyzer2-TPD spectrogram.
Embodiment
The exemplary embodiments embodying feature of present invention and advantage will describe in the following description in detail. Iting should be understood that the present invention can have various changes in different embodiments, it does not all depart from the scope of the present invention, and explanation wherein and to be shown in be use when explain in essence, and is not used to restriction the present invention.
The present invention take N-BUTYL ACETATE as the direct synthesizing butyl cellosolve acetic ester of single stage method ethoxylation addition reaction of raw material, and correlated response equation is shown below.
Above-mentioned reaction is the atom economic reaction of raw material complete utilization, does not generate the by product such as water or alcohol, and product is easily separated, shortens flow process; Equipment is not almost caused corrosion by production process. And raw material sources are extensively cheap, reactions steps is few, and technological operation is simple, environmental friendliness. Therefore the preparation method of the 2-Butoxyethyl acetate of the present invention has the clear and definite market requirement, significant economic benefit and social value.
The present invention taking the layered bi-metal oxide compound of modification as catalyzer synthesizing butyl cellosolve acetic ester, products obtained therefrom receipts rate height, purity height.
The preparation method of the layered bi-metal oxide compound of the modification of the present invention, comprising:
1) layered double hydroxide (LDH) is prepared;
2) gained layered double hydroxide and alkali are reacted in organic alcohol, the layered double hydroxide of obtained alkali modification;
3) by layered double hydroxide roasting below 800 DEG C of gained alkali modification, the layered bi-metal oxide compound of obtained modification.
The layered bi-metal oxide compound of the modification of the present invention comprises at least one the IIth A race metal ion and the mixed oxide of at least one group IIIA metal ion composition, and the IIth A race metal can be magnesium and/or calcium, and group IIIA metal can be aluminium and/or gallium. Wherein, the content of the IIth A family metal oxide is 10��70wt%, and the content of group IIIA metal oxide is 30��90wt%, taking the gross weight of the layered bi-metal oxide compound of modification as benchmark.
The present invention is to step 1) preparation method of laminate double-metal hydroxide do not limit, and it can adopt any means of prior art to obtain, such as, coprecipitation method can be adopted to prepare LDH, and by its at 60��80 DEG C dry 12��24 hours.
Step 2) alkali can be organic bases or mineral alkali, its consumption is 0.01��0.1 times of LDH by weight. Preferably, organic bases be selected from sodium methylate, potassium ethylate, n-Butyl Lithium, Monomethylamine, diethylamine, triethylamine, urea, pyridine one or more; Mineral alkali be selected from sodium hydroxide, potassium hydroxide, salt of wormwood, sodium carbonate, sodium bicarbonate one or more.
In the present invention, step 2) can comprise further: the layered double hydroxide that LDH and alkali are reacted in organic alcohol solvent at 100��150 DEG C 1��5 hour obtained alkali modification.
In the present invention, organic alcohol is preferably C1��C6Saturated monohydroxy alcohol or polyvalent alcohol, its consumption is 10��100 times of LDH by weight; This organic alcohol more preferably C1��C6Saturated monohydroxy alcohol or dibasic alcohol, such as methyl alcohol, ethanol, Virahol, ethylene glycol etc.
In the present invention, step 2) also can comprise: the layered double hydroxide of gained alkali modification is filtered and is washed till neutrality, and at 60��80 DEG C dry 12��24 hours.
In the present invention, step 3) maturing temperature can be 300��800 DEG C.
In the preparation method of the 2-Butoxyethyl acetate of the present invention, catalyst levels is the 1��3% of raw material N-BUTYL ACETATE and oxyethane total mass, the temperature of reaction of N-BUTYL ACETATE and oxyethane is 100��180 DEG C, the charge ratio (mol/mol) that reaction pressure is 0.1��0.5MPa, N-BUTYL ACETATE and oxyethane is 1:2��10:1.
Below, in conjunction with specific embodiments the preparation method of the 2-Butoxyethyl acetate of the present invention is described further.
Wherein, the hydrotalcite catalyzed agent of synthesis carries out XRD test on RigakuD/Max2400 type X-ray diffractometer.Using Cu, Ka gamma ray source, graphite monochromator, pipe pressure 40KV, pipe stream 30mA, scanning leg speed is 0.02 degree, and scanning angle is from 5��80 ��. FT-IR spectrum is 4cm by BrukerEQUINOX55 resolving power-1Infrared spectrometer record, be specially the catalyzer after by compressing tablet and be placed in infrared sample pool, after de-attached 1 hour, obtain the infrared spectrum of sample at 120 DEG C. Adopt the JEOLJEM-2010 type transmission electron microscope of Japan to obtain the TEM photo of hydrotalcite sample, first adopt ultrasonic oscillation before test by sample dispersion in ethanol, then get one online in the copper being loaded with carbon film, observe in Electronic Speculum after drying. Adopt CO2Temperature programmed desorption(TPD) method characterizes the total alkali content of catalyzer on U.S. Quantachrome company CHEMBET-3000 type chemisorption analyser, adopts normal pressure thermal desorption method purification sample, CO absorption at 120 DEG C2, take off attached with the temperature rise rate of 10 DEG C/min in the high pure nitrogen stream of 40mL/min, detection stream is 140mA. Gas chromatogram fixative is analyzed EO affixture composition and is carried out on SHIMADZUGC-14C gas chromatograph (Shimadzu company of Japan): SE-30 capillary column (30m �� 0.32mm �� 0.5um), post temperature 310 DEG C, gasification temperature 310 DEG C, hydrogen flame detector (FID), detected temperatures 320 DEG C, carrier gas N2��
Embodiment 1
1, the preparation of catalyzer
Take 192gMg (NO3)2��6H2O crystal and 113gAl (NO3)3��9H2O crystal is dissolved in 1L deionized water, is made into Al (NO3)3With Mg (NO3)2Mixing solutions. The Na of 0.90mol/L2CO3Solution 300mL joins in above-mentioned mixing solutions. Drip in mixing solutions by the NaOH solution of 2.25mol/L again, regulate pH value to 10 �� 0.5 of solution. At room temperature continue to be uniformly mixed solution about 5��6 hours, then take out filter, washing to neutral, dry in 80 DEG C of baking ovens and spend the night, obtained LDH.
Get the sample LDH10g after oven dry, join in the aqueous isopropanol of potassium hydroxide that 400mL concentration is 0.002g/mL, reflux at 110��120 DEG C about 2 hours, and then take out filter, washing to neutral, dry in 80 DEG C of baking ovens and spend the night. Last in retort furnace at 300 DEG C roasting 6 hours, namely obtain the layered bi-metal oxide catalyst of modification.
2, the preparation of 2-Butoxyethyl acetate
Above-mentioned to the butylacetate of 50.6g and 0.89g metal oxide catalyst is at room temperature added in the autoclave of dried and clean, after inspection resistance to air loss and nitrogen are replaced, it is warming up to 80��90 DEG C. Then continuing to lead in reactor by 38.6g oxyethane, be warming up to 170��180 DEG C, control reactor pressure is no more than 0.4MPa. Lead to and stir into during oxyethane, and the increase along with reinforced quality, improve agitation revolution (agitation revolution is increased to 240r/min gradually from 160r/min) gradually. After end to be fed, turning off feed valve, start aging, digestion time is 30min (minute), stops heating, is cooled to 80��90 DEG C, by emptying for pressure in still, opens still discharging, elimination catalyzer, namely obtain 2-Butoxyethyl acetate. Its gas chromatogram is shown in Fig. 1, product content analysis in table 1.
Table 1
| Peak number | Retention time | Area | Peak height | Concentration | Unit | Component name |
| 1 | 1.734 | 230606.7 | 172333.1 | 15.25877 | % | Raw material |
| 2 | 2.193 | 418.2 | 298.2 | 0.02767 | ||
| 3 | 2.445 | 586.3 | 363.8 | 0.03879 | ||
| 4 | 2.52 | 1193.3 | 770.3 | 0.07896 | % | Diox |
| 5 | 2.586 | 1091261.1 | 643378.1 | 72.20652 | % | 1EO |
| 6 | 2.727 | 3616 | 2044.8 | 0.23926 | % | EG |
| 7 | 2.907 | 2626.9 | 1343.6 | 0.17382 | ||
| 8 | 5.232 | 2516.5 | 806.7 | 0.16651 | ||
| 9 | 5.89 | 139884.8 | 38758.4 | 9.25589 | % | 2EO |
| 10 | 5.995 | 6335 | 2107.9 | 0.41917 | % | DE |
| 11 | 6.665 | 407.2 | 87.1 | 0.02694 | ||
| 12 | 9.426 | 2667.3 | 1085.5 | 0.17649 | ||
| 13 | 9.84 | 1612.6 | 668.1 | 0.10671 | ||
| 14 | 9.934 | 22073.6 | 10177.9 | 1.46057 | % | 3EO |
| 15 | 12.468 | 4300.8 | 1199.1 | 0.28457 | % | 4EO |
| 16 | 15.813 | 1199.2 | 238.1 | 0.07935 | % | 5EO |
Wherein, Diox represents dioxane, and 1EO represents target product 2-Butoxyethyl acetate CH3COOCH2CH2OC4H9, 2EO represents CH3COO(CH2CH2O)2C4H9, 3EO represents CH3COO(CH2CH2O)3C4H9, 4EO represents CH3COO(CH2CH2O)4C4H9, 5EO represents CH3COO(CH2CH2O)5C4H9, EG represents ethylene glycol, and DE represents glycol ether.
Embodiment 2
1, the preparation of catalyzer
Take 192gMg (NO3)2��6H2O crystal and 56gAl (NO3)3��9H2O crystal is dissolved in 1L deionized water, is made into Al (NO3)3With Mg (NO3)2Mixing solutions. The Na of 0.90mol/L2CO3Solution 300mL joins in above-mentioned mixing solutions. Drip in mixing solutions by the NaOH solution of 2.25mol/L again, regulate pH value to 10 �� 0.5 of solution. At room temperature continue to be uniformly mixed solution about 5��6 hours, then take out filter, washing to neutral, dry in 80 DEG C of baking ovens and spend the night, obtained LDH.
Get the sample 10g after oven dry, join in the aqueous isopropanol of triethylamine that 400mL concentration is 0.0025g/mL, reflux at 130��140 DEG C about 2 hours, and then take out filter, washing to neutral, dry in 80 DEG C of baking ovens and spend the night. Last in retort furnace at 500 DEG C roasting 5 hours, namely obtain the layered bi-metal oxide catalyst of modification.
2, the preparation of 2-Butoxyethyl acetate
Above-mentioned to the butylacetate of 51.1g and 0.90g O composite metallic oxide catalyst is at room temperature added in the autoclave of dried and clean, after inspection resistance to air loss and nitrogen are replaced, reaction is warming up to 80��90 DEG C. Then continuing to lead in reactor by 38.7g oxyethane, be warming up to 150��160 DEG C, control reactor pressure is no more than 0.4MPa. Lead to and stir into during oxyethane, and the increase along with reinforced quality, improve agitation revolution (agitation revolution is increased to 280r/min gradually from 160r/min) gradually. After end to be fed, turning off feed valve, start aging, digestion time is 30min, stops heating, is cooled to 80��90 DEG C, by emptying for pressure in still, opens still discharging, elimination catalyzer, namely obtain 2-Butoxyethyl acetate. Its gas chromatogram is shown in Fig. 2, product content analysis in table 2.
Table 2
| Peak number | Retention time | Area | Peak height | Concentration | Unit | Component name |
| 1 | 2.837 | 102583.5 | 64442.7 | 5.22735 | % | Raw material |
| 2 | 5.004 | 2700.9 | 912.7 | 0.13763 | ||
| 3 | 6.242 | 6719.5 | 2732.6 | 0.34241 | % | Diox |
| 4 | 6.707 | 1615272.6 | 251196.2 | 82.30945 | % | 1EO |
| 5 | 7.194 | 11249.1 | 5232.3 | 0.57322 | % | EG |
| 6 | 7.49 | 2171.7 | 941.6 | 0.11066 | ||
| 7 | 11.339 | 4812.1 | 1910.8 | 0.24521 | ||
| 8 | 11.917 | 162981.1 | 53476.3 | 8.30503 | % | 2EO |
| 9 | 12.026 | 9524.6 | 3807 | 0.48535 | % | DE |
| 10 | 14.703 | 15073.4 | 6499.4 | 0.7681 | ||
| 11 | 15.201 | 2189.2 | 934.8 | 0.11155 | ||
| 12 | 15.266 | 20392.9 | 8346.6 | 1.03916 | % | 3EO |
| 13 | 17.477 | 2224.5 | 771.9 | 0.11336 | ||
| 14 | 18.338 | 4543.8 | 955.6 | 0.23154 | % | 4EO |
Embodiment 3
1. the preparation of catalyzer
Take 128gCa (NO3)2��4H2O crystal and 37gAl (NO3)3��9H2O crystal is dissolved in 1L deionized water, is made into Al (NO3)3With Mg (NO3)2Mixing solutions. The Na of 1.00mol/L2CO3Solution 300mL joins in above-mentioned mixing solutions. Drip in mixing solutions by the NaOH solution of 2.25mol/L again, regulate pH value to 10 �� 0.5 of solution. At room temperature continue to be uniformly mixed solution about 5��6 hours, then take out filter, washing to neutral, dry in 80 DEG C of baking ovens and spend the night, obtained LDH.
Get the sample 10g after oven dry, join in the aqueous isopropanol of urea that 400mL concentration is 0.0025g/mL, reflux at 130��140 DEG C about 2 hours, and then take out filter, washing to neutral, dry in 80 DEG C of baking ovens and spend the night. Last in retort furnace at 500 DEG C roasting 5 hours, namely obtain the layered bi-metal oxide catalyst of modification.
2. the preparation of 2-Butoxyethyl acetate
Above-mentioned to the butylacetate of 51.1g and 0.90g O composite metallic oxide catalyst is at room temperature added in the autoclave of dried and clean, after inspection resistance to air loss and nitrogen are replaced, reaction is warming up to 80��90 DEG C. Then continuing to lead in reactor by 38.7g oxyethane, be warming up to 150��160 DEG C, control reactor pressure is no more than 0.4MPa. Lead to and stir into during oxyethane, and the increase along with reinforced quality, improve agitation revolution (agitation revolution is increased to 280r/min gradually from 160r/min) gradually. After end to be fed, turning off feed valve, start aging, digestion time is 30min, stops heating, is cooled to 80��90 DEG C, by emptying for pressure in still, opens still discharging, elimination catalyzer, namely obtain 2-Butoxyethyl acetate.Its gas chromatogram is shown in Fig. 3, product content analysis in table 3.
Table 3
Embodiment 4
1. the preparation of catalyzer
Take 154gCa (NO3)2��4H2O crystal and 45gAl (NO3)3��9H2O crystal is dissolved in 1L deionized water, is made into Al (NO3)3With Mg (NO3)2Mixing solutions. The Na of 1.00mol/L2CO3Solution 300mL joins in above-mentioned mixing solutions. Drip in mixing solutions by the NaOH solution of 2.25mol/L again, regulate pH value to 10 �� 0.5 of solution. At room temperature continue to be uniformly mixed solution about 5��6 hours, then take out filter, washing to neutral, dry in 80 DEG C of baking ovens and spend the night, obtained LDH.
Get the sample 10g after oven dry, join in the methanol solution of sodium methylate that 400mL concentration is 0.0025g/mL, reflux at 130��140 DEG C about 2 hours, and then take out filter, washing to neutral, dry in 80 DEG C of baking ovens and spend the night. Last in retort furnace at 500 DEG C roasting 5 hours, namely obtain the layered bi-metal oxide catalyst of modification.
2. the preparation of 2-Butoxyethyl acetate
Above-mentioned to the butylacetate of 51.1g and 0.90g O composite metallic oxide catalyst is at room temperature added in the autoclave of dried and clean, after inspection resistance to air loss and nitrogen are replaced, reaction is warming up to 80��90 DEG C. Then continuing to lead in reactor by 38.7g oxyethane, be warming up to 150��160 DEG C, control reactor pressure is no more than 0.4MPa. Lead to and stir into during oxyethane, and the increase along with reinforced quality, improve agitation revolution (agitation revolution is increased to 280r/min gradually from 160r/min) gradually. After end to be fed, turning off feed valve, start aging, digestion time is 30min, stops heating, is cooled to 80��90 DEG C, by emptying for pressure in still, opens still discharging, elimination catalyzer, namely obtain 2-Butoxyethyl acetate. Its gas chromatogram is shown in Fig. 4, product content analysis in table 4.
Table 4
| Peak number | Retention time | Area | Peak height | Concentration | Unit | Component name |
| 1 | 1.734 | 230606.7 | 172333.1 | 14.25687 | % | Raw material |
| 2 | 2.193 | 418.2 | 298.2 | 0.02656 | ||
| 3 | 2.445 | 586.3 | 363.8 | 0.03457 | ||
| 4 | 2.52 | 1193.3 | 770.3 | 0.09746 | % | Diox |
| 5 | 2.586 | 1091261.1 | 643378.1 | 82.20652 | % | 1EO |
| 6 | 2.727 | 3616 | 2044.8 | 0.23834 | % | EG |
| 7 | 2.907 | 2626.9 | 1343.6 | 0.17832 | ||
| 8 | 5.232 | 2516.5 | 806.7 | 0.16561 | ||
| 9 | 5.89 | 139884.8 | 38758.4 | 9.15895 | % | 2EO |
| 10 | 5.995 | 6335 | 2107.9 | 0.42017 | % | DE |
| 11 | 6.665 | 407.2 | 87.1 | 0.06294 | ||
| 12 | 9.426 | 2667.3 | 1085.5 | 0.14769 | ||
| 13 | 9.84 | 1612.6 | 668.1 | 0.10167 | ||
| 14 | 9.934 | 22073.6 | 10177.9 | 1.74605 | % | 3EO |
| 15 | 12.468 | 4300.8 | 1199.1 | 0.27845 | % | 4EO |
| 16 | 15.813 | 1199.2 | 238.1 | 0.09735 | % | 5EO |
Embodiment 5
1. the preparation of catalyzer
Take 77gCa (NO3)2��4H2O crystal and 23gAl (NO3)3��9H2O crystal is dissolved in 1L deionized water, is made into Al (NO3)3With Mg (NO3)2Mixing solutions. The Na of 1.00mol/L2CO3Solution 300mL joins in above-mentioned mixing solutions. Drip in mixing solutions by the NaOH solution of 2.25mol/L again, regulate pH value to 10 �� 0.5 of solution. At room temperature continue to be uniformly mixed solution about 5��6 hours, then take out filter, washing to neutral, dry in 80 DEG C of baking ovens and spend the night, obtained LDH.
Get the sample 10g after oven dry, join in the alcoholic solution of n-Butyl Lithium that 400mL concentration is 0.0025g/mL, reflux at 130��140 DEG C about 2 hours, and then take out filter, washing to neutral, dry in 80 DEG C of baking ovens and spend the night. Last in retort furnace at 500 DEG C roasting 5 hours, namely obtain the layered bi-metal oxide catalyst of modification.
2. the preparation of 2-Butoxyethyl acetate
Above-mentioned to the butylacetate of 51.1g and 0.90g O composite metallic oxide catalyst is at room temperature added in the autoclave of dried and clean, after inspection resistance to air loss and nitrogen are replaced, reaction is warming up to 80��90 DEG C. Then continuing to lead in reactor by 38.7g oxyethane, be warming up to 150��160 DEG C, control reactor pressure is no more than 0.4MPa. Lead to and stir into during oxyethane, and the increase along with reinforced quality, improve agitation revolution (agitation revolution is increased to 280r/min gradually from 160r/min) gradually.After end to be fed, turning off feed valve, start aging, digestion time is 30min, stops heating, is cooled to 80��90 DEG C, by emptying for pressure in still, opens still discharging, elimination catalyzer, namely obtain 2-Butoxyethyl acetate. Its gas chromatogram is shown in Fig. 5, product content analysis in table 5.
Table 5
| Peak number | Retention time | Area | Peak height | Concentration | Unit | Component name |
| 1 | 2.837 | 102583.5 | 64442.7 | 5.23273 | % | Raw material |
| 2 | 5.004 | 2700.9 | 912.7 | 0.13763 | ||
| 3 | 6.242 | 6719.5 | 2732.6 | 0.32424 | % | Diox |
| 4 | 6.707 | 1615272.6 | 251196.2 | 83.23094 | % | 1EO |
| 5 | 7.194 | 11249.1 | 5232.3 | 0.75732 | % | EG |
| 6 | 7.49 | 2171.7 | 941.6 | 0.10106 | ||
| 7 | 11.339 | 4812.1 | 1910.8 | 0.12452 | ||
| 8 | 11.917 | 162981.1 | 53476.3 | 8.03050 | % | 2EO |
| 9 | 12.026 | 9524.6 | 3807 | 0.34853 | % | DE |
| 10 | 14.703 | 15073.4 | 6499.4 | 0.8768 | ||
| 11 | 15.201 | 2189.2 | 934.8 | 0.11151 | ||
| 12 | 15.266 | 20392.9 | 8346.6 | 1.10391 | % | 3EO |
| 13 | 17.477 | 2224.5 | 771.9 | 0.13133 | ||
| 14 | 18.338 | 4543.8 | 955.6 | 0.32315 | % | 4EO |
Comparative example 1
1. the preparation of catalyzer
Take 192gMg (NO3)2��6H2O crystal and 56gAl (NO3)3��9H2O crystal is dissolved in 1L deionized water, is made into Al (NO3)3With Mg (NO3)2Mixing solutions. The Na of 0.90mol/L2CO3Solution 300mL joins in above-mentioned mixing solutions. Drip in mixing solutions by the NaOH solution of 2.25mol/L again, regulate pH value to 10 �� 0.5 of solution. At room temperature continue to be uniformly mixed solution about 5��6 hours, then take out filter, washing to neutral, dry in 80 DEG C of baking ovens and spend the night.
Get the sample 10g after oven dry, join in the deionized water 400mL of triethylamine of 0.0025g/mL, boiling reflux about 2 hours, and then take out filter, washing to neutral, dry in 80 DEG C of baking ovens and spend the night. Last in retort furnace at 500 DEG C roasting 5 hours, namely obtain final O composite metallic oxide catalyst.
2. the preparation of 2-Butoxyethyl acetate
With reference to the preparation process of 2-Butoxyethyl acetate in embodiment 1. Its gas-chromatography product content analysis in table 6.
Table 6
Comparative example 2
1. the preparation of catalyzer
Take 192gMg (NO3)2��6H2O crystal and 56gAl (NO3)3��9H2O crystal is dissolved in 1L deionized water, is made into Al (NO3)3With Mg (NO3)2Mixing solutions. The Na of 0.90mol/L2CO3Solution 300mL joins in above-mentioned mixing solutions. Drip in mixing solutions by the NaOH solution of 2.25mol/L again, regulate pH value to 10 �� 0.5 of solution. At room temperature continue to be uniformly mixed solution about 5��6 hours, then take out filter, washing to neutral, dry in 80 DEG C of baking ovens and spend the night. Last in retort furnace at 500 DEG C roasting 5 hours, namely obtain final O composite metallic oxide catalyst.
2. the preparation of 2-Butoxyethyl acetate
With reference to the preparation process of 2-Butoxyethyl acetate in embodiment 2. Its gas-chromatography product content analysis in table 7.
Table 7
| Peak number | Retention time | Area | Peak height | Concentration | Unit | Component name |
| 1 | 1.054 | 5738.3 | 5128.8 | 0.32613 | ||
| 2 | 1.145 | 22277.8 | 18284.7 | 1.26614 | ||
| 3 | 1.254 | 649 | 519.1 | 0.03689 | % | Standard specimen determines ethylene glycol |
| 4 | 1.31 | 1684518 | 1133940 | 95.73803 | % | N-BUTYL ACETATE |
| 5 | 1.441 | 296.6 | 233.7 | 0.01686 | % | Standard specimen determines glycol ether |
| 6 | 1.51 | 2471.3 | 910.9 | 0.14045 | ||
| 7 | 1.713 | 554.9 | 368.4 | 0.03154 | ||
| 8 | 1.815 | 390.4 | 260.8 | 0.02219 | ||
| 9 | 2.034 | 323.7 | 170.2 | 0.0184 | ||
| 10 | 2.121 | 120.9 | 72.3 | 0.00687 | ||
| 11 | 2.253 | 26635.3 | 16288 | 1.51379 | % | 1EO |
| 12 | 2.911 | 147.3 | 77.6 | 0.00837 | ||
| 13 | 3.243 | 372.4 | 223.4 | 0.02117 | ||
| 14 | 3.399 | 494.2 | 285.6 | 0.02809 | ||
| 15 | 3.464 | 285.5 | 171 | 0.01623 | ||
| 16 | 3.964 | 4222.8 | 2510.6 | 0.24 | ||
| 17 | 4.077 | 467.1 | 220 | 0.02655 | ||
| 18 | 4.304 | 913.4 | 538.5 | 0.05191 | ||
| 19 | 4.974 | 1037.4 | 611.4 | 0.05896 | ||
| 20 | 5.412 | 1479.1 | 839 | 0.08406 | ||
| 21 | 5.55 | 129 | 54.1 | 0.00733 | ||
| 22 | 5.724 | 180.3 | 101.6 | 0.01025 | ||
| 23 | 6.236 | 1716.4 | 985.3 | 0.09755 | ||
| 24 | 6.619 | 550.3 | 319 | 0.03128 | ||
| 25 | 7.369 | 1590.9 | 847.8 | 0.09042 | ||
| 26 | 7.735 | 229.8 | 124.3 | 0.01306 | ||
| 27 | 8.459 | 918.4 | 463.5 | 0.0522 | ||
| 28 | 8.818 | 111.4 | 57.4 | 0.00633 | ||
| 29 | 9.599 | 470.5 | 185.1 | 0.02674 | ||
| 30 | 11.122 | 215.4 | 54.6 | 0.01224 |
The comparative result of above-described embodiment and comparative example catalyst activity is in table 8.
Table 8
From the content analysis of product listed in table 1 to table 7, in the product of embodiment 1 to 5, the content of 2-Butoxyethyl acetate is respectively 72.2%, 82.3%, 80.8%, 82.2%, 83.2%, and in the product of comparative example 1,2, the content of 2-Butoxyethyl acetate is respectively 9.7%, 1.51%. Above-mentioned data show that in products therefrom, the content of 2-Butoxyethyl acetate is obviously higher than comparative example taking the layered bi-metal oxide compound of the modification of the present invention as catalyst preparing 2-Butoxyethyl acetate. And the data display that table 8 provides, during the building-up reactions of the layered bi-metal oxide catalyst catalysis ethylene glycol carboxylicesters of modification provided by the invention, there is higher activity, make building-up reactions speed relatively comparative example have significant raising, simultaneously also there is higher feed stock conversion and selectivity of product. Wherein, catalytic activity is according to the Mass Calculation of the oxyethane that reaction occurs under (every minute) in the unit time 1 gram of catalyst action.
Can see from the TEM photo of synthetic catalyst, the catalyzer that embodiment 2 obtains is that the mixture with thin slice shape amorphous magnesium and aluminum oxide formation forms (Fig. 6 A), (Fig. 6 B) that the catalyzer that comparative example 1 obtains is made up of the similar spheroidal particle of about about the 10nm of diameter, and the catalyzer that comparative example 2 obtains is only containing a small amount of particle with regular shape, majority is the mixture (Fig. 6 C) being made up of cotton-shaped amorphous magnesium and aluminum oxide.From the result analysis of experiment, the catalyzer being made up of the particle of rule, activity and the selectivity of target product in the reaction are not high, and increase along with the mixture of thin slice shape unbodied in catalyzer, and selectivity that is active and target product significantly improves.
In Fig. 7 to 9, D1 represents the sign curve of comparative example 1, and S2 represents the sign curve of embodiment 2, and D2 represents the sign curve of comparative example 2.
As seen from Figure 7, O composite metallic oxide catalyst provided by the invention relatively disappears than some diffraction peak of unmodified catalyzer, and the intensity of main characteristic peak also significantly weakens. As seen from Figure 8, O composite metallic oxide catalyst provided by the invention relatively reduces than unmodified catalyzer absorption peak. By Fig. 7, Fig. 8 it will be seen that lose certain species in modified hydrotalcite catalyzed oxidant layer, this may cause one of O composite metallic oxide catalyst provided by the invention reason with higher reactive behavior and target product highly selective. As seen from Figure 9, the catalyzer of the 2-in-1 one-tenth of embodiment and comparative example 1,2-in-1 become catalyzer compare, all there is weakly alkaline, but alkalescence intensity is more moderate. And the difference of polarity may cause one of O composite metallic oxide catalyst provided by the invention reason with higher reactive behavior and target product highly selective between organic alcohol solvent and deionized water.
Unless limited otherwise, term used herein is the implication that those skilled in the art understand usually.
Enforcement mode described in the invention is only for exemplary purpose; and be not used to limit the scope of the invention, those skilled in the art can make various other replacement, changes and improvements within the scope of the invention, thus; the invention is not restricted to above-mentioned enforcement mode, and only it is defined by the claims.
Claims (10)
1. a preparation method for the layered bi-metal oxide compound of modification, comprising:
1) layered double hydroxide is prepared;
2) layered double-metal hydroxide and alkali are reacted in organic alcohol, the layered double hydroxide of obtained alkali modification;
3) by layered double hydroxide roasting below 800 DEG C of described alkali modification, the layered bi-metal oxide compound of obtained described modification.
2. method according to claim 1, the layered bi-metal oxide compound of wherein said modification comprises at least one the IIth A family metal oxide and at least one group IIIA metal oxide.
3. method according to claim 2, wherein said IIth A family metal oxide is the oxide compound of magnesium and/or calcium, and described group IIIA metal oxide is the oxide compound of aluminium and/or gallium.
4. method according to claim 2, the content of wherein said IIth A family metal oxide is 10��70wt%, and the content of described group IIIA metal oxide is 30��90wt%, taking the gross weight of the layered bi-metal oxide compound of described modification as benchmark.
5. method according to claim 1, wherein said organic alcohol is selected from C1��C6Saturated monohydroxy alcohol or polyvalent alcohol.
6. method according to claim 5, wherein said organic alcohol is selected from C1��C6Saturated monohydroxy alcohol or dibasic alcohol.
7. method according to claim 1, wherein said alkali is organic bases or mineral alkali, and its consumption is 0.01��0.1 times of layered double-metal hydroxide by weight.
8. method according to claim 7, wherein said organic bases be selected from sodium methylate, potassium ethylate, n-Butyl Lithium, Monomethylamine, diethylamine, triethylamine, urea, pyridine one or more; Described mineral alkali be selected from sodium hydroxide, potassium hydroxide, salt of wormwood, sodium carbonate, sodium bicarbonate one or more.
9. method according to claim 1, wherein said step 2) comprising: the layered double hydroxide that layered double-metal hydroxide and alkali are reacted in organic alcohol solvent at 100��150 DEG C 1��5 hour obtained described alkali modification;The layered double hydroxide of described alkali modification is filtered and is washed till neutrality, and at 60��80 DEG C dry 12��24 hours.
10. method according to claim 1, wherein said step 3) maturing temperature be 300��800 DEG C, roasting time is 3��6 hours.
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