CN110694626B - Composite catalyst for synthesizing 2-pentanone from ethanol and preparation method thereof - Google Patents
Composite catalyst for synthesizing 2-pentanone from ethanol and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a composite catalyst for synthesizing 2-pentanone from ethanol, which is prepared from Al 2 O 3 And ZrO 2 Is used as a carrier, supports an active component CuO, is modified by an alkaline oxide assistant M and is expressed as M-CuO/ZrO 2 /Al 2 O 3 Wherein the basic oxide auxiliary agent M is selected from MgO, caO and K 2 And one or more of O. The method takes ethanol as a raw material, uses the composite catalyst of the invention in a fixed bed reactor, prepares 2-pentanone by a one-step method at 250-350 ℃ and normal pressure, the highest ethanol conversion rate can reach 100 percent, and the highest selectivity of the 2-pentanone can reach 68.0 percent.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and relates to ZrO for synthesizing 2-pentanone by ethanol in one step 2 A base catalyst, in particular to ZrO modified by non-noble metal Cu 2 A base catalyst, and a method for preparing the catalyst.
Background
2-pentanone, an important organic chemical raw material, is increasingly used as an industrial solvent and an intermediate for preparing medicines and pesticides. Especially as dewaxing solvents for high boiling petroleum fractions, such as those boiling in the lubricant oil range.
Currently, 2-pentanone is prepared by oxidative dehydrogenation of 2-sec-amyl alcohol or 2-pentanone is prepared by the co-thermal reaction of butyrylacetic acid ethyl ester and water. The methods have higher production cost, can generate more three-waste products in the production process, and are not environment-friendly.
CN 1660750A discloses a catalyst for synthesizing 2-pentanone from ethanol and a preparation method thereof, wherein the catalyst is composed of a mixed oxide of zirconium oxide, manganese oxide and zinc oxide loaded noble metal and an auxiliary agent and is used for catalyzing ethanol to synthesize 2-pentanone in a multiphase one-step manner. However, the catalyst is complex in composition and uses a noble metal. Meanwhile, the reaction conditions of the catalyst for catalyzing ethanol to synthesize 2-pentanone are harsh, the reaction temperature is close to 400 ℃, and the reaction needs to be carried out under a certain pressure (1-5 MPa).
CN 106478393A relates to a method for synthesizing 2-pentanone by ethanol in one step, which takes ethanol as a raw material, metal-doped cerium oxide as a catalyst, inert gas as carrier gas, and the 2-pentanone is prepared by reaction at 250-550 ℃ under normal pressure. The catalyst of the method is simple to prepare, can efficiently convert ethanol with rich sources into 2-pentanone in one step, and has the ethanol conversion rate as high as 94.8 percent, but the selectivity of the 2-pentanone is low and is only 41.8 percent.
Disclosure of Invention
The invention aims to provide a cheap and easily-obtained composite catalyst for synthesizing 2-pentanone from ethanol, which is simple to prepare, and the composite catalyst can be used in the reaction of synthesizing 2-pentanone from ethanol in one step and improve the conversion rate of ethanol and the selectivity of 2-pentanone.
The composite catalyst of the invention is Al 2 O 3 And ZrO 2 Is used as a carrier, supports an active component CuO, is modified by an alkaline oxide assistant M and is expressed as M-CuO/ZrO 2 /Al 2 O 3 . In the composite catalyst, carrier Al 2 O 3 And ZrO 2 The mass ratio of the CuO to the carrier is 0.1-1: 1, and the active component CuO accounts for 5-15 wt% of the total mass of the carrier.
Wherein, the alkaline oxide auxiliary agent M in the catalyst is selected from MgO, caO and K 2 And one or more of O.
Furthermore, the alkaline oxide auxiliary agent M accounts for 0.2-5 wt% of the total mass of the composite catalyst.
The invention also provides a preparation method of the composite catalyst, which comprises the steps of preparing soluble salt solution of soluble salts of Cu, zr and Al, taking alkali solution as a precipitator, simultaneously dropwise adding the alkali solution and the soluble salt solution for coprecipitation, washing, drying and roasting the precipitate to obtain the unmodified catalyst CuO/ZrO 2 /Al 2 O 3 (ii) a Then a soluble salt solution of an alkaline oxide assistant is introduced by adopting an impregnation method for modification; drying and roasting to obtain the composite catalyst M-CuO/ZrO 2 /Al 2 O 3 。
Wherein, in the raw materials for preparing the catalyst, the soluble salt of Cu is selected from copper nitrate trihydrate, copper acetate or copper chloride; the soluble salt of Zr is selected from zirconium nitrate pentahydrate, zirconyl nitrate dihydrate or zirconyl chloride octahydrate; the soluble salt of Al is selected from aluminum nitrate nonahydrate or aluminum chloride.
In the invention, the alkali solution used as the precipitant can be one or more aqueous solutions of sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide.
Correspondingly, the soluble salt of the alkaline oxide auxiliary agent is one or more of calcium nitrate, calcium chloride, magnesium nitrate, magnesium chloride, potassium nitrate and potassium chloride.
In the above method of the present invention, the pH of the reaction system should be controlled within a range of 8 to 11 during the coprecipitation.
More specifically, the invention is that under the air atmosphere, the precipitated product is dried for 12 to 24h at the temperature of 100 to 120 ℃ and roasted for 4 to 10h at the temperature of 400 to 650 ℃ to obtain the unmodified catalyst.
And then, soaking the unmodified catalyst in a soluble salt solution of an alkaline oxide assistant to obtain a soaked product, drying the soaked product at the temperature of 100-110 ℃ for 15-20 h, and roasting the dried product at the temperature of 500-600 ℃ for 5-8 h in an air atmosphere to obtain the composite catalyst.
The composite catalyst prepared by the invention is ground, tableted, crushed and sieved, and then 20-40 mesh catalyst particles are selected for filling, and the specific surface area of the catalyst is 80-100 m 2 g -1 。
The composite catalyst can be used for catalyzing the preparation reaction of preparing 2-pentanone by an ethanol one-step method after being activated.
Specifically, absolute ethyl alcohol is used as a raw material, the activated composite catalyst is adopted, and inert gas (Ar or N) is used in a fixed bed reactor 2 ) Is used as carrier gas, and reacts at 250-350 ℃ under normal pressure to obtain 2-pentanol.
In the reaction, the feeding airspeed of the ethanol is 0.5-5 h -1 The space velocity of the carrier gas is 1000 to 4000h -1 。
Preferably, the reaction temperature is 300 to 350 ℃,
more preferably, the ethanol feeding space velocity is 1-3 h -1 The space velocity of carrier gas is 2000-3000 h -1 。
In particular, the invention is H at 350 ℃ 2 /N 2 And activating the composite catalyst in a mixed atmosphere.
More specifically, the H 2 /N 2 H in a mixed atmosphere 2 The volume percentage content is 10 percent.
In the composite catalyst prepared by the invention, the Cu component has the main function of dehydrogenation, so that ethanol is dehydrogenated into acetaldehyde. The aldehyde formed is directly subjected to a condensation reaction to give the product, zrO 2 By itself having an acid-base property, the condensation reaction can be catalyzed, but ZrO due to 2 Is amphoteric oxide, and has weak acidity and alkalinity, so the invention further introduces alkali metal to modify the amphoteric oxide, so as to enhance the alkalinity of the catalyst and promote the condensation reaction. The Al component is added to stabilize the Cu substance and increase the specific surface area of the catalyst. The Cu component is easy to sinter, so that the catalyst is deactivated, the service life of the catalyst is shortened, and the Al component is introduced to disperse the Cu component and inhibit the aggregation of Cu, so that the catalyst has better stability.
The composite catalyst has the advantages of low reaction temperature not higher than 350 ℃, normal pressure, loose reaction conditions and high selectivity.
The composite catalyst has the other advantages that Cu is used as a dehydrogenation component, the raw materials are cheap and easy to obtain, and the precious metal Pd is avoided being used as the dehydrogenation component.
The invention adopts a composite catalyst M-CuO/ZrO modified by an alkaline oxide auxiliary agent 2 /Al 2 O 3 The catalyst is used, the 2-pentanone is prepared by the ethanol one-step method in the fixed bed reactor at 250-350 ℃ and normal pressure, the highest ethanol conversion rate can reach 100%, and the highest selectivity of the 2-pentanone can reach 68.0%. The composite catalyst of the invention is used for catalyzing the reaction, the reaction process is easy to operate, the catalyst raw materials are cheap and easy to obtain, the preparation method is simple, the catalyst activity is high, and the composite catalyst has better stability.
Detailed Description
The following examples are only preferred embodiments of the present invention and are not intended to limit the present invention in any way. Various modifications and alterations to this invention will become apparent to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Example 1.
8.9g of copper nitrate trihydrate, 79.9g of zirconium nitrate pentahydrate and 23.3g of aluminum nitrate nonahydrate are weighed and dissolved in 350ml of deionized water to obtain a salt solution.
50.2g of potassium hydroxide was weighed and dissolved in 400ml of deionized water to obtain an alkali solution.
Adding 1L of deionized water into a precipitation beaker, respectively dripping the salt solution and the alkali solution into the precipitation beaker with mechanical stirring through a peristaltic pump for coprecipitation, and controlling the pH value of a reaction system to be 11 in the dripping process.
And after the precipitation is completed, continuously stirring for 1h, standing for 3h, and performing suction filtration to obtain a precipitate. Washing the precipitate to neutrality, drying at 120 deg.c for 12 hr, heating to 500 deg.c in air atmosphere and roasting for 4 hr to obtain the unmodified catalyst.
0.02g of potassium carbonate was added to 10ml of water, and after complete dissolution, 5g of unmodified catalyst was weighed out and added thereto for excess impregnation. Ultrasonically evaporating the solvent to dryness, drying for 15h at 100 ℃, heating to 500 ℃ and roasting for 4h under an air atmosphere, tabletting, and crushing to 20-40 meshes to obtain the composite catalyst K 2 O-CuO/ZrO 2 /Al 2 O 3 Composition of 0.3% K 2 O，10.0% CuO，78.8% ZrO 2 ，10.9% Al 2 O 3 。
Taking 1ml of the composite catalyst prepared above, loading into a tubular fixed bed reactor with the inner diameter of 8mm and the inlet and outlet filled with magnetic rings, and introducing H at the flow rate of 20ml/min 2 H with 10 percent of volume percentage 2 /N 2 And (3) heating the mixed gas from room temperature to 350 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 3 hours, and reducing the composite catalyst.
Switching the carrier gas to Ar gas, and settingThe space velocity of the carrier gas is 1000h -1 At the temperature of 350 ℃, absolute ethyl alcohol is fed at the space velocity of 0.5h -1 Directly introducing the mixture into a tubular fixed bed reactor, preheating the mixture by a magnetic ring, and reacting the ethanol steam generated by the reaction through a fixed bed filled with a composite catalyst to prepare the 2-pentanone.
And condensing and collecting reaction products led out of the tubular fixed bed reactor, performing qualitative identification by using GC-MS, and performing gas chromatography quantitative analysis by using an FID detector. The detection result shows that the conversion per pass of the ethanol is 100 percent, and the selectivity of the 2-pentanone is 68.0 percent.
Example 2.
16.2g of copper nitrate trihydrate, 106.5g of zirconium nitrate pentahydrate and 46.5g of aluminum nitrate nonahydrate are weighed and dissolved in 350ml of deionized water to obtain a salt solution.
78.9g of sodium carbonate was weighed and dissolved in 400ml of deionized water to obtain an alkali solution.
And adding 1L of deionized water into the precipitation beaker, respectively and dropwise adding the salt solution and the alkali solution into the precipitation beaker with mechanical stirring for coprecipitation through a peristaltic pump, and controlling the pH value of a reaction system to be 11 in the dropwise adding process.
And after the precipitation is completed, continuously stirring for 1h, standing for 3h, and performing suction filtration to obtain a precipitate. Washing the precipitate to neutrality, drying at 120 deg.c for 12 hr, heating to 500 deg.c in air atmosphere and roasting for 4 hr to obtain the unmodified catalyst.
0.04g of potassium carbonate was added to 10ml of water, and after complete dissolution, 5g of unmodified catalyst was weighed out and added thereto for excess impregnation. Ultrasonically evaporating the solvent to dryness, drying for 15h at 100 ℃, heating to 500 ℃ and roasting for 5h under the air atmosphere, tabletting, and crushing to 20-40 meshes to obtain the composite catalyst K 2 O-CuO/ZrO 2 /Al 2 O 3 Composition of 0.5% K 2 O，12.6% CuO，72.0% ZrO 2 ，14.9% Al 2 O 3 。
Taking 1ml of the composite catalyst prepared above, loading into a tubular fixed bed reactor with the inner diameter of 8mm and the inlet and outlet filled with magnetic rings, and introducing H at the flow rate of 20ml/min 2 H with 10 percent of volume percentage 2 /N 2 Mixed gas at a temperature rise rate of 2 ℃/minRaising the temperature to 350 ℃ at room temperature, keeping the temperature for 3 hours, and reducing the composite catalyst.
Switching the carrier gas to Ar gas, and setting the space velocity of the carrier gas to 2000h -1 At the temperature of 350 ℃, absolute ethyl alcohol is fed at the space velocity of 1.2h -1 Directly introducing the mixture into a tubular fixed bed reactor, preheating the mixture by a magnetic ring, and reacting the ethanol steam generated by the reaction through a fixed bed filled with a composite catalyst to prepare the 2-pentanone.
And condensing and collecting reaction products led out of the tubular fixed bed reactor, performing qualitative identification by using GC-MS, and performing gas chromatography quantitative analysis by using an FID detector. The detection result shows that the conversion per pass of the ethanol is 88.0 percent, and the selectivity of the 2-pentanone is 65.0 percent.
Example 3.
15.0g of copper acetate, 62.0g of zirconyl nitrate dihydrate, and 13.1g of aluminum chloride were weighed out and dissolved in 350ml of deionized water to obtain a salt solution.
30.8g of sodium carbonate was weighed and dissolved in 400ml of deionized water to obtain an alkali solution.
Adding 1L of deionized water into a precipitation beaker, respectively dripping the salt solution and the alkali solution into the precipitation beaker with mechanical stirring through a peristaltic pump for coprecipitation, and controlling the pH value of a reaction system to be 10 in the dripping process.
And after the precipitation is completed, continuously stirring for 1h, standing for 3h, and performing suction filtration to obtain a precipitate. Washing the precipitate to neutrality, drying at 110 deg.c for 20 hr, heating at 600 deg.c in air atmosphere and roasting for 6 hr to obtain the unmodified catalyst.
0.3g of magnesium nitrate was added to 10ml of water, and after complete dissolution, 5g of unmodified catalyst was weighed out and added thereto for excess impregnation. Ultrasonically evaporating the solvent to dryness, drying for 15h at 100 ℃, heating to 500 ℃ and roasting for 5h under air atmosphere, tabletting and crushing to 20-40 meshes to obtain the composite catalyst MgO-CuO/ZrO 2 /Al 2 O 3 The composition is 1.6 percent of MgO,36.8 percent of CuO and 30.7 percent of ZrO 2 ，30.9% Al 2 O 3 。
Taking 1ml of the prepared composite catalyst, loading the composite catalyst into a tubular fixed bed reactor with the inner diameter of 8mm and the inlet and the outlet filled with magnetic rings, and introducing H at the flow rate of 20ml/min 2 H with 10 percent of volume percentage 2 /N 2 And (3) heating the mixed gas from room temperature to 350 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 3 hours, and reducing the composite catalyst.
Switching the carrier gas to Ar gas, and setting the space velocity of the carrier gas to 1000h -1 At the temperature of 350 ℃, absolute ethyl alcohol is fed at the space velocity of 0.8h -1 Directly introducing the mixture into a tubular fixed bed reactor, preheating the mixture by a magnetic ring, and reacting the ethanol steam generated by the reaction through a fixed bed filled with a composite catalyst to prepare the 2-pentanone.
And condensing and collecting reaction products led out of the tubular fixed bed reactor, performing qualitative identification by using GC-MS, and performing gas chromatography quantitative analysis by using an FID detector. The detection result shows that the conversion per pass of the ethanol is 100%, and the selectivity of the 2-pentanone is 56.3%.
Example 4.
15.5g of copper nitrate trihydrate, 133.1g of zirconium nitrate pentahydrate and 23.3g of aluminum nitrate nonahydrate are weighed and dissolved in 350ml of deionized water to obtain a salt solution.
87.0g of potassium hydroxide was weighed and dissolved in 400ml of deionized water to obtain an alkali solution.
Adding 1L of deionized water into a precipitation beaker, respectively dripping the salt solution and the alkali solution into the precipitation beaker with mechanical stirring through a peristaltic pump for coprecipitation, and controlling the pH value of a reaction system to be 8 in the dripping process.
And after the precipitation is completed, continuously stirring for 1h, standing for 3h, and performing suction filtration to obtain a precipitate. Washing the precipitate to neutrality, drying at 120 deg.c for 24 hr, heating to 650 deg.c in air atmosphere and roasting for 6 hr to obtain the unmodified catalyst.
0.15g of magnesium nitrate was added to 10ml of water, and after complete dissolution, 5g of unmodified catalyst was weighed out and added thereto for excess impregnation. Ultrasonically evaporating the solvent to dryness, drying at 110 ℃ for 20h, heating to 600 ℃ and roasting for 8h under the air atmosphere, tabletting and crushing to 20-40 meshes to prepare the composite catalyst, wherein the composite catalyst comprises 0.8% of MgO,10.9% of CuO and 81.5% of ZrO 2 ，6.8% Al 2 O 3 。
Taking 1ml of the prepared composite catalyst, and filling the composite catalyst into a reactor with magnetic rings filled at the inlet and the outletIn a tubular fixed bed reactor with an internal diameter of 8mm, H is introduced at a flow rate of 20ml/min 2 H with 10 percent of volume percentage 2 /N 2 And (3) heating the mixed gas from room temperature to 350 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 3 hours, and reducing the composite catalyst.
Switching the carrier gas to Ar gas, and setting the space velocity of the carrier gas to 1500h -1 At the temperature of 350 ℃, absolute ethyl alcohol is fed at the space velocity of 1.0h -1 Directly introducing the mixture into a tubular fixed bed reactor, preheating the mixture by a magnetic ring, and reacting the ethanol steam generated by the reaction through a fixed bed filled with a composite catalyst to prepare the 2-pentanone.
And condensing and collecting reaction products led out of the tubular fixed bed reactor, performing qualitative identification by using GC-MS, and performing gas chromatography quantitative analysis by using an FID detector. The detection result shows that the conversion per pass of the ethanol is 95%, and the selectivity of the 2-pentanone is 66.0%.
Example 5.
18.1g of copper nitrate trihydrate, 106.5g of zirconium nitrate pentahydrate and 69.8g of aluminum nitrate nonahydrate are weighed and dissolved in 350ml of deionized water to obtain a salt solution.
93.9g of potassium hydroxide was weighed and dissolved in 400ml of deionized water to obtain an alkali solution.
Adding 1L of deionized water into a precipitation beaker, respectively dripping the salt solution and the alkali solution into the precipitation beaker with mechanical stirring through a peristaltic pump for coprecipitation, and controlling the pH value of a reaction system to be 9 in the dripping process.
And after complete precipitation, continuously stirring for 1h, standing for 3h, and performing suction filtration to obtain a precipitate. Washing the precipitate to neutrality, drying at 120 deg.c for 24 hr, heating to 650 deg.c in air atmosphere and roasting for 10 hr to obtain the unmodified catalyst.
0.6g of magnesium chloride is added to 10ml of water and, after complete dissolution, 5g of unmodified catalyst are weighed into it for excess impregnation. Ultrasonically evaporating the solvent to dryness, drying for 15h at 100 ℃, heating to 500 ℃ and roasting for 6h under air atmosphere, tabletting and crushing to 20-40 meshes to obtain the composite catalyst Mg-CuO/ZrO 2 /Al 2 O 3 The composition of the material is 4.8 percent of MgO,12.3 percent of CuO and 63.3 percent of ZrO 2 ，19.6% Al 2 O 3 。
Taking 1ml of the composite catalyst prepared above, loading into a tubular fixed bed reactor with the inner diameter of 8mm and the inlet and outlet filled with magnetic rings, and introducing H at the flow rate of 20ml/min 2 H with 10 percent of volume percentage 2 /N 2 And (3) heating the mixed gas from room temperature to 350 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 3 hours, and reducing the composite catalyst.
The carrier gas is switched to Ar gas, and the airspeed of the carrier gas is set to 2500h -1 At the temperature of 300 ℃, absolute ethyl alcohol is fed for 2.5h at a feed space velocity -1 Directly introducing the mixture into a tubular fixed bed reactor, preheating the mixture by a magnetic ring, and reacting the ethanol steam generated by the reaction through a fixed bed filled with a composite catalyst to prepare the 2-pentanone.
And condensing and collecting reaction products led out of the tubular fixed bed reactor, performing qualitative identification by using GC-MS, and performing gas chromatography quantitative analysis by using an FID detector. The detection result shows that the conversion per pass of the ethanol is 98%, and the selectivity of the 2-pentanone is 55.0%.
Example 6.
33.22g of copper nitrate trihydrate, 261.5g of zirconium oxychloride octahydrate and 69.8g of aluminum nitrate nonahydrate are weighed and dissolved in 350ml of deionized water to obtain a salt solution.
120.1g of sodium hydroxide was weighed and dissolved in 400ml of deionized water to obtain an alkali solution.
Adding 1L of deionized water into a precipitation beaker, respectively dripping the salt solution and the alkali solution into the precipitation beaker with mechanical stirring through a peristaltic pump for coprecipitation, and controlling the pH value of a reaction system to be 10 in the dripping process.
And after the precipitation is completed, continuously stirring for 1h, standing for 3h, and performing suction filtration to obtain a precipitate. Washing the precipitate to neutrality, drying at 100 deg.c for 24 hr, heating at 450 deg.c in air atmosphere, and roasting for 10 hr to obtain the unmodified catalyst.
0.4g of magnesium chloride is added to 10ml of water and, after complete dissolution, 5g of unmodified catalyst are weighed into it for excess impregnation. Ultrasonically evaporating the solvent to dryness, drying for 15h at 100 ℃, heating to 500 ℃ and roasting for 5h under air atmosphere, tabletting and crushing to 20-40 meshes to obtain the composite catalyst MgO-CuO/ZrO 2 /Al 2 O 3 The composition of the alloy is 3.3 percent of MgO,8.6 percent of CuO and 80.5 percent of ZrO 2 ，7.6% Al 2 O 3 。
Taking 1ml of the prepared composite catalyst, loading the composite catalyst into a tubular fixed bed reactor with the inner diameter of 8mm and the inlet and the outlet filled with magnetic rings, and introducing H at the flow rate of 20ml/min 2 H with 10 percent of volume percentage 2 /N 2 And (3) heating the mixed gas from room temperature to 350 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 3 hours, and reducing the composite catalyst.
Switching the carrier gas to Ar gas, and setting the space velocity of the carrier gas to 3500h -1 At the temperature of 300 ℃, absolute ethyl alcohol is fed for 2.8h at a feed space velocity -1 Directly introducing the mixture into a tubular fixed bed reactor, preheating the mixture by a magnetic ring, and reacting the ethanol steam generated by the reaction through a fixed bed filled with a composite catalyst to prepare the 2-pentanone.
And condensing and collecting reaction products led out of the tubular fixed bed reactor, performing qualitative identification by using GC-MS, and performing gas chromatography quantitative analysis by using an FID detector. The detection result shows that the conversion per pass of the ethanol is 72.3 percent, and the selectivity of the 2-pentanone is 52.9 percent.
Example 7.
15.0g of copper nitrate trihydrate, 133.1g of zirconium nitrate pentahydrate and 69.8g of aluminum nitrate nonahydrate are weighed and dissolved in 350ml of deionized water to obtain a salt solution.
132.8g of potassium carbonate was weighed and dissolved in 400ml of deionized water to obtain an alkali solution.
Adding 1L of deionized water into a precipitation beaker, respectively dripping the salt solution and the alkali solution into the precipitation beaker with mechanical stirring through a peristaltic pump for coprecipitation, and controlling the pH value of a reaction system to be 8 in the dripping process.
And after the precipitation is completed, continuously stirring for 1h, standing for 3h, and performing suction filtration to obtain a precipitate. Washing the precipitate to be neutral, drying the precipitate at 110 ℃ for 24h, heating the precipitate to 550 ℃ under an air atmosphere, and roasting the precipitate for 10h to prepare the unmodified catalyst.
0.6g of magnesium nitrate was added to 10ml of water, and after complete dissolution, 5g of unmodified catalyst was weighed out and added thereto for excess impregnation. Ultrasonic drying the solvent, and drying at 100 deg.CHeating to 500 ℃ for roasting for 7h under the air atmosphere, tabletting and crushing to 20-40 meshes to obtain the composite catalyst MgO-CuO/ZrO 2 /Al 2 O 3 The composition of the material is 3.2 percent of MgO,9.1 percent of CuO and 70.3 percent of ZrO 2 ，17.4% Al 2 O 3 。
Taking 1ml of the prepared composite catalyst, loading the composite catalyst into a tubular fixed bed reactor with the inner diameter of 8mm and the inlet and the outlet filled with magnetic rings, and introducing H at the flow rate of 20ml/min 2 H with 10 percent of volume percentage 2 /N 2 And (3) heating the mixed gas from room temperature to 350 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 3 hours, and reducing the composite catalyst.
Switching the carrier gas to Ar gas, and setting the space velocity of the carrier gas to 3500h -1 At the temperature of 340 ℃, absolute ethyl alcohol is fed for 3.5h at a space velocity of feed -1 Directly introducing the mixture into a tubular fixed bed reactor, preheating the mixture by a magnetic ring, and reacting the ethanol steam generated by the reaction through a fixed bed filled with a composite catalyst to prepare the 2-pentanone.
And condensing and collecting reaction products led out of the tubular fixed bed reactor, performing qualitative identification by using GC-MS, and performing gas chromatography quantitative analysis by using an FID detector. The detection result shows that the conversion per pass of the ethanol is 70.3 percent, and the selectivity of the 2-pentanone is 66.0 percent.
Example 8.
5.5g of copper acetate, 20.2g of zirconyl nitrate dihydrate and 10g of aluminum chloride were weighed out and dissolved in 350ml of deionized water to obtain a salt solution.
35.8g of sodium carbonate was weighed and dissolved in 400ml of deionized water to obtain an alkali solution.
Adding 1L of deionized water into a precipitation beaker, respectively dripping the salt solution and the alkali solution into the precipitation beaker with mechanical stirring through a peristaltic pump for coprecipitation, and controlling the pH value of a reaction system to be 8 in the dripping process.
And after complete precipitation, continuously stirring for 1h, standing for 3h, and performing suction filtration to obtain a precipitate. Washing the precipitate to neutrality, drying at 100 deg.c for 12 hr, heating at 400 deg.c in air atmosphere and roasting for 4 hr to obtain the unmodified catalyst.
0.15g of calcium nitrate was added to 10ml of water to be completely dissolvedThereafter, 5g of an unmodified catalyst was weighed into it for excess impregnation. Ultrasonically evaporating the solvent to dryness, drying for 15h at 100 ℃, heating to 500 ℃ and roasting for 5h under air atmosphere, tabletting and crushing to 20-40 meshes to obtain the composite catalyst Ca-CuO/ZrO 2 /Al 2 O 3 The composition of the alloy is 1.0 percent of Ca,14.2 percent of CuO and 60.1 percent of ZrO 2 ，24.7% Al 2 O 3 。
Taking 1ml of the prepared composite catalyst, loading the composite catalyst into a tubular fixed bed reactor with the inner diameter of 8mm and the inlet and the outlet filled with magnetic rings, and introducing H at the flow rate of 20ml/min 2 H with 10 percent of volume 2 /N 2 And (3) heating the mixed gas from room temperature to 350 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 3 hours, and reducing the composite catalyst.
Switching the carrier gas to Ar gas, and setting the space velocity of the carrier gas to 3800h -1 At the temperature of 300 ℃, absolute ethyl alcohol is fed for 3.8h at a feed space velocity -1 Directly introducing the mixture into a tubular fixed bed reactor, preheating the mixture by a magnetic ring, and reacting the ethanol steam generated by the reaction through a fixed bed filled with a composite catalyst to prepare the 2-pentanone.
And condensing and collecting reaction products led out of the tubular fixed bed reactor, performing qualitative identification by using GC-MS, and performing gas chromatography quantitative analysis by using an FID detector. The detection result shows that the conversion per pass of the ethanol is 78.5 percent, and the selectivity of the 2-pentanone is 56.2 percent.
Example 9.
5.0g of copper chloride, 36.2g of zirconium oxychloride octahydrate and 14.9g of aluminum chloride were weighed and dissolved in 350ml of deionized water to obtain a salt solution.
53.4g of sodium carbonate was weighed and dissolved in 400ml of deionized water to obtain an alkali solution.
And adding 1L of deionized water into the precipitation beaker, respectively and dropwise adding the salt solution and the alkali solution into the precipitation beaker with mechanical stirring through a peristaltic pump for coprecipitation, and controlling the pH value of a reaction system to be 9 in the dropwise adding process.
And after the precipitation is completed, continuously stirring for 1h, standing for 3h, and performing suction filtration to obtain a precipitate. Washing the precipitate to neutrality, drying at 110 deg.c for 24 hr, heating to 400 deg.c in air atmosphere, and roasting for 10 hr to prepare the unmodified catalyst.
0.75g of calcium nitrate was added to 10ml of water and after complete dissolution, 5g of unmodified catalyst was weighed into it for excess impregnation. Ultrasonically evaporating the solvent to dryness, drying for 15h at 100 ℃, heating to 500 ℃ and roasting for 4h under an air atmosphere, tabletting and crushing to 20-40 meshes to obtain the composite catalyst CaO-CuO/ZrO 2 /Al 2 O 3 The composition of the alloy is 4.9 percent of CaO,12.5 percent of CuO and 58.5 percent of ZrO 2 ，24.1% Al 2 O 3 。
Taking 1ml of the composite catalyst prepared above, loading into a tubular fixed bed reactor with the inner diameter of 8mm and the inlet and outlet filled with magnetic rings, and introducing H at the flow rate of 20ml/min 2 H with 10 percent of volume percentage 2 /N 2 And (3) heating the mixed gas from room temperature to 350 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 3 hours, and reducing the composite catalyst.
Switching the carrier gas to Ar gas, and setting the space velocity of the carrier gas to 3800h -1 At the temperature of 250 ℃, absolute ethyl alcohol is fed for 3.0h at the space velocity of feed -1 Directly introducing the mixture into a tubular fixed bed reactor, preheating the mixture by a magnetic ring, and reacting the ethanol steam generated by the reaction through a fixed bed filled with a composite catalyst to prepare the 2-pentanone.
And condensing and collecting reaction products led out of the tubular fixed bed reactor, performing qualitative identification by using GC-MS, and performing gas chromatography quantitative analysis by using an FID detector. The detection result shows that the conversion per pass of the ethanol is 69.2 percent, and the selectivity of the 2-pentanone is 65.8 percent.
Example 10.
11.4g of copper chloride, 60.5g of zirconyl nitrate dihydrate and 73.2g of aluminum chloride were weighed out and dissolved in 350ml of deionized water to obtain a salt solution.
100.6g of potassium carbonate was weighed and dissolved in 400ml of deionized water to obtain an alkali solution.
Adding 1L of deionized water into a precipitation beaker, respectively dripping the salt solution and the alkali solution into the precipitation beaker with mechanical stirring through a peristaltic pump for coprecipitation, and controlling the pH value of a reaction system to be 10 in the dripping process.
And after the precipitation is completed, continuously stirring for 1h, standing for 3h, and performing suction filtration to obtain a precipitate. Washing the precipitate to neutrality, drying at 120 deg.c for 20 hr, heating to 550 deg.c in air atmosphere and roasting for 10 hr to obtain the unmodified catalyst.
0.4g of calcium chloride is added to 10ml of water and, after complete dissolution, 5g of unmodified catalyst are weighed into it for excess impregnation. Ultrasonically evaporating the solvent to dryness, drying for 15h at 100 ℃, heating to 500 ℃ and roasting for 6h under air atmosphere, tabletting and crushing to 20-40 meshes to obtain the composite catalyst CaO-CuO/ZrO 2 /Al 2 O 3 Composition of 3.9% K 2 O，10.3% CuO，42.8% ZrO 2 ，43.0% Al 2 O 3 。
Taking 1ml of the prepared composite catalyst, loading the composite catalyst into a tubular fixed bed reactor with the inner diameter of 8mm and the inlet and the outlet filled with magnetic rings, and introducing H at the flow rate of 20ml/min 2 H with 10 percent of volume 2 /N 2 And (3) heating the mixed gas from room temperature to 350 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 3 hours, and reducing the composite catalyst.
Switching the carrier gas to Ar gas, and setting the space velocity of the carrier gas to 4000h -1 At the temperature of 350 ℃, absolute ethyl alcohol is fed for 4.5h at a feed space velocity -1 Directly introducing the mixture into a tubular fixed bed reactor, preheating the mixture by a magnetic ring, and reacting the ethanol steam generated by the reaction through a fixed bed filled with a composite catalyst to prepare the 2-pentanone.
And condensing and collecting reaction products led out of the tubular fixed bed reactor, performing qualitative identification by using GC-MS, and performing gas chromatography quantitative analysis by using an FID detector. The detection result shows that the conversion per pass of the ethanol is 89.2 percent, and the selectivity of the 2-pentanone is 60.5 percent.
Comparative example 1.
Weighing 26.6g of pentahydrate zirconium nitrate, and dissolving in 350ml of deionized water to obtain a salt solution; 29.5g of sodium carbonate was weighed and dissolved in 400ml of deionized water to obtain a base solution.
Adding 1L of deionized water into a precipitation beaker, respectively dripping the salt solution and the alkali solution into the precipitation beaker with mechanical stirring through a peristaltic pump for coprecipitation, and controlling the pH value of a reaction system to be 9 in the dripping process. Stirring for 1 hr after precipitation, standing for 3 hr, and vacuum filtering to obtain precipitateWashing the material to be neutral, drying the material for 15h at 100 ℃, heating the material to 500 ℃ in air atmosphere and roasting the material for 6h to prepare the catalyst ZrO 2 。
Taking 1ml of the catalyst prepared above, loading into a tubular fixed bed reactor with an inner diameter of 8mm and an inlet and an outlet filled with magnetic rings, and introducing H at a flow rate of 20ml/min 2 H with 10 percent of volume percentage 2 /N 2 The mixed gas is heated from room temperature to 350 ℃ at the heating rate of 2 ℃/min, and is kept for 3h, and the catalyst is reduced.
Switching the carrier gas to Ar gas, and setting the space velocity of the carrier gas to 3000h -1 At the temperature of 350 ℃, absolute ethyl alcohol is fed at the space velocity of 5.0h -1 Directly introducing the mixture into a tubular fixed bed reactor, preheating by a magnetic ring, and reacting the ethanol steam generated by the preheating by a fixed bed filled with a catalyst to prepare the 2-pentanone.
And condensing and collecting reaction products led out of the tubular fixed bed reactor, performing qualitative identification by using GC-MS, and performing gas chromatography quantitative analysis by using an FID detector. The detection result shows that the conversion per pass of the ethanol is 30.2 percent, and the selectivity of the 2-pentanone is 18.4 percent.
Comparative example 2.
Weighing 1.4g of copper nitrate trihydrate and 26.6g of zirconium nitrate pentahydrate, and dissolving the copper nitrate trihydrate and the zirconium nitrate pentahydrate in 350ml of deionized water to obtain a salt solution; 30.5g of sodium carbonate was weighed and dissolved in 400ml of deionized water to obtain an alkali solution.
Adding 1L of deionized water into a precipitation beaker, respectively dripping the salt solution and the alkali solution into the precipitation beaker with mechanical stirring through a peristaltic pump for coprecipitation, and controlling the pH value of a reaction system to be 9 in the dripping process. Stirring for 1h after complete precipitation, standing for 3h, suction-filtering to obtain precipitate, washing to neutrality, drying at 100 deg.C for 15h, heating to 500 deg.C under air atmosphere, calcining for 6h to obtain catalyst CuO/ZrO 2 The composition was 5.7% of CuO and 94.3% of ZrO 2 。
Taking 1ml of the catalyst prepared above, loading into a tubular fixed bed reactor with an inner diameter of 8mm and an inlet and an outlet filled with magnetic rings, and introducing H at a flow rate of 20ml/min 2 H with 10 percent of volume percentage 2 /N 2 Mixed gas, heating rate of 2 deg.C/minThe temperature is raised from room temperature to 350 ℃ and kept for 3h, and the catalyst is reduced.
Switching the carrier gas to Ar gas, and setting the space velocity of the carrier gas to 3000h -1 At the temperature of 350 ℃, absolute ethyl alcohol is fed for 4.0h at a feed space velocity -1 Directly introducing the mixture into a tubular fixed bed reactor, preheating the mixture by a magnetic ring, and reacting the ethanol steam generated by the reaction through a fixed bed filled with a catalyst to prepare the 2-pentanone.
And condensing and collecting reaction products led out of the tubular fixed bed reactor, performing qualitative identification by using GC-MS, and performing gas chromatography quantitative analysis by using an FID detector. The detection result shows that the conversion per pass of the ethanol is 42.3 percent, and the selectivity of the 2-pentanone is 36.0 percent.
Comparative example 3.
Weighing 1.4g of copper nitrate trihydrate and 26.6g of zirconium nitrate pentahydrate, and dissolving the copper nitrate trihydrate and the zirconium nitrate pentahydrate in 350ml of deionized water to obtain a salt solution; 30.5g of sodium carbonate was weighed and dissolved in 400ml of deionized water to obtain an alkali solution.
Adding 1L of deionized water into a precipitation beaker, respectively dripping the salt solution and the alkali solution into the precipitation beaker with mechanical stirring through a peristaltic pump for coprecipitation, and controlling the pH value of a reaction system to be 9 in the dripping process. And after the precipitation is completed, continuously stirring for 1h, standing for 3h, performing suction filtration to obtain a precipitate, washing to be neutral, drying for 15h at 100 ℃, heating to 500 ℃ under an air atmosphere, and roasting for 6h to obtain the unmodified catalyst.
0.015g of potassium hydroxide was added to 10ml of water and after complete dissolution, 5g of unmodified catalyst was weighed into it for excess impregnation. Drying the solvent by ultrasonic drying for 15h at 100 ℃, heating to 500 ℃ and roasting for 5h under air atmosphere, tabletting, crushing to 20-40 meshes, and preparing the modified catalyst with the composition of 0.2 percent K 2 O，5.7% CuO，94.1% ZrO 2 。
Taking 1ml of the modified catalyst prepared above, loading into a tubular fixed bed reactor with the inlet and outlet filled with magnetic rings and the inner diameter of 8mm, and introducing H at the flow rate of 20ml/min 2 H with 10 percent of volume 2 /N 2 And (3) heating the mixed gas from room temperature to 350 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 3 hours, and reducing the modified catalyst.
Switching the carrier gas to Ar gas, and setting the space velocity of the carrier gas to 3000h -1 At the temperature of 350 ℃, absolute ethyl alcohol is fed for 4.0h at a feed space velocity -1 Directly introducing the mixture into a tubular fixed bed reactor, preheating by a magnetic ring, and reacting the ethanol steam generated by the preheating by a fixed bed filled with a modified catalyst to prepare the 2-pentanone.
And condensing and collecting reaction products led out of the tubular fixed bed reactor, performing qualitative identification by using GC-MS, and performing gas chromatography quantitative analysis by using an FID detector. The detection result shows that the conversion per pass of the ethanol is 40.8 percent, and the selectivity of the 2-pentanone is 43.0 percent.
Claims (7)
1.M-CuO/ZrO 2 /Al 2 O 3 Application of the composite catalyst for preparing 2-pentanone by using ethanol one-step method, wherein the M-CuO/ZrO 2 /Al 2 O 3 Is prepared from Al 2 O 3 And ZrO 2 The composite catalyst is a carrier, supports an active component CuO, and is modified by an alkaline oxide assistant M: preparing soluble salt solution of soluble salts of Cu, zr and Al, and dropwise adding the soluble salt solution and aqueous alkali as a precipitator at the same time to perform coprecipitation; washing, drying and roasting the precipitate to obtain the unmodified catalyst CuO/ZrO 2 /Al 2 O 3 (ii) a Then adopting an impregnation method to introduce soluble salt solution of alkaline oxide auxiliary agent to the unmodified catalyst CuO/ZrO 2 /Al 2 O 3 Modifying; drying and roasting to obtain the composite catalyst M-CuO/ZrO 2 /Al 2 O 3 (ii) a Wherein, the carrier Al in the composite catalyst 2 O 3 And ZrO 2 The mass ratio of the alkali oxide auxiliary agent M to the carrier is 0.1-1: 1, the active component CuO accounts for 5-15 wt% of the total mass of the carrier, and the alkali oxide auxiliary agent M is selected from MgO, caO and K 2 One or more of O accounts for 0.2 to 5 weight percent of the total mass of the composite catalyst;
when in use, the activated M-CuO/ZrO is taken as the raw material of absolute ethyl alcohol 2 /Al 2 O 3 As catalyst, in a fixed bed reactor, using inert gas Ar or N 2 As carrier gas, the space velocity of feeding ethanol is controlledIs 0.5 to 5 hours -1 The space velocity of the carrier gas is 1000 to 4000h -1 Reacting at 250-350 deg.c under normal pressure to prepare 2-pentanone.
2. The use according to claim 1, wherein the soluble salt of Cu is selected from the group consisting of copper nitrate trihydrate, copper acetate or copper chloride; the soluble salt of Zr is selected from zirconium nitrate pentahydrate, zirconyl nitrate dihydrate or zirconyl chloride octahydrate; the soluble salt of Al is selected from aluminum nitrate nonahydrate or aluminum chloride.
3. The use according to claim 1, wherein the alkali solution is an aqueous solution of one or more of sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide.
4. The use as claimed in claim 1, wherein the alkali oxide adjuvant soluble salt is one or more of calcium nitrate, calcium chloride, magnesium nitrate, magnesium chloride, potassium nitrate and potassium chloride.
5. The method according to claim 1, wherein the pH of the reaction system is controlled to 8 to 11 during the coprecipitation.
6. The method as claimed in claim 1, wherein the precipitated product is dried at 100-120 ℃ for 12-24h and calcined at 400-650 ℃ for 4-10 h under air atmosphere to obtain the unmodified catalyst.
7. The use as claimed in claim 1, wherein the composite catalyst is obtained by impregnating the unmodified catalyst in a soluble salt solution of an alkaline oxide assistant to obtain an impregnated product, drying the impregnated product at 100-110 ℃ for 15-20 h, and calcining the dried product at 500-600 ℃ for 5-8 h in an air atmosphere.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101322938A (en) * | 2008-07-29 | 2008-12-17 | 福州大学 | Ruthenium-based ammonia synthetic catalyst and preparation thereof |
| CN104096566A (en) * | 2013-04-12 | 2014-10-15 | 中国石油化工股份有限公司 | Method for preparing copper series methanol synthesis catalyst through precipitation-impregnation process |
| CN104226316A (en) * | 2014-10-11 | 2014-12-24 | 吉林化工学院 | Preparation method and application of supported copper catalyst with ZrO2 as carrier and alkali metal/alkaline-earth metals as promoter |
| CN106513001A (en) * | 2016-10-14 | 2017-03-22 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesis of ethanol from synthetic gas, preparation method and application thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101322938A (en) * | 2008-07-29 | 2008-12-17 | 福州大学 | Ruthenium-based ammonia synthetic catalyst and preparation thereof |
| CN104096566A (en) * | 2013-04-12 | 2014-10-15 | 中国石油化工股份有限公司 | Method for preparing copper series methanol synthesis catalyst through precipitation-impregnation process |
| CN104226316A (en) * | 2014-10-11 | 2014-12-24 | 吉林化工学院 | Preparation method and application of supported copper catalyst with ZrO2 as carrier and alkali metal/alkaline-earth metals as promoter |
| CN106513001A (en) * | 2016-10-14 | 2017-03-22 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesis of ethanol from synthetic gas, preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 系列金属氧化物对CuO/ZrO2-Al2O3催化剂的改性;郑舒;《精细石油化工》;20130318;第10页左栏最后一段、右栏第一段，第11页左栏第二段，第10页右栏最后一段 * |
| 郑舒.系列金属氧化物对CuO/ZrO2-Al2O3催化剂的改性.《精细石油化工》.2013,第10-16页. * |
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