CN112547069B - Nickel-copper catalyst and preparation method thereof as well as method for preparing methyl isobutyl alcohol - Google Patents
Nickel-copper catalyst and preparation method thereof as well as method for preparing methyl isobutyl alcohol Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
- C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
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Abstract
The invention belongs to the technical field of catalyst preparation, and relates to a nickel-copper catalyst, a preparation method thereof and a method for preparing methyl isobutyl alcohol. The nickel copper catalyst comprises, based on 100 parts by weight of the catalyst: 2-10 parts by weight of nickel; 5-15 parts by weight of copper; and 75-93 parts by weight of a boron modified alumina carrier; wherein at least a part of the alumina carrier is theta-crystal type alumina carrier. The nickel-copper catalyst prepared by the method has high conversion rate to MIBK, high selectivity to MIBC and high stability.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and in particular relates to a nickel-copper catalyst, a preparation method thereof and a method for preparing methyl isobutyl alcohol.
Background
Methyl isobutyl alcohol, also called 4-methyl-2-pentanol, abbreviated as MIBC, is a medium boiling point solvent with excellent performance and is widely used in the fields of mineral flotation, paint, pesticide, medicine, synthetic resin, cellulose, binder and the like. In mineral flotation, MIBC is used as a foaming and flotation solvent, so that the ore processing capacity can be improved, and the consumption of foaming agent can be reduced. MIBC is used as a foaming agent instead of T-80 in the Nikola Yeast concentrating mill, so that the ore processing capacity can be remarkably improved, the recovery rate of copper and zinc in the single-metal concentrate can be improved, the consumption of the foaming agent can be greatly reduced, and the production cost can be saved.
Existing routes to methyl isobutyl alcohol generally include: the anti-aging agent 6PPD is obtained as a byproduct, and is obtained by co-production when the methyl isobutyl ketone (MIBK) is synthesized through catalytic hydrogenation of acetone/mesityl oxide. However, the product obtained by the former method has low purity, is mixed with a large amount of impurities, is difficult to separate and purify, and is not suitable for industrial production. The process route for co-producing MIBC in the process of synthesizing MIBK through catalytic hydrogenation of acetone/mesityl oxide has the problem of low MIBC selectivity and low yield, and cannot meet the increasing industrial demands.
With the continued improvement of domestic MIBK production units, MIBK-only units have not been profitable, and most units are either off-stream or in low load operation. Manufacturers are looking for downstream products that expand MIBK to increase the profitability level and risk resistance of devices that produce methyl isobutyl ketone (MIBK), one of the important products being MIBC, with better market prospects. However, a key problem in the hydrogenation of MIBK to MIBC is the catalytic capability of the catalyst.
Patent document CN101765577a discloses a method for preparing MIBC and/or IBHK plus TMN using a copper-based catalyst. A copper-based catalyst is disclosed therein for catalyzing MIBK to prepare MIBC. The catalyst contains Cr, and because Cr contains extremely toxic substances, the catalyst has great hidden trouble in safety and environmental protection.
Patent document CN107930640a discloses a catalyst for co-production of MIBK and MIBC in a one-step process. The catalyst takes copper, alkaline earth metal, cerium and chromium as load components, and the alkaline earth metal exists in the form of oxide. The catalyst has ideal stability by taking acetone as a raw material, the catalyst cost is obviously lower than that of the existing palladium catalyst, and the catalyst has better economic benefit. However, the selectivity of the catalyst to MIBC is too low, and the problem of gradually excessive MIBK productivity is not solved.
The paper literature (methyl isobutyl carbinol [ J ]. Tong Mengliang, etc. prepared by liquid phase catalytic hydrogenation of skeleton nickel, petrochemical industry, 2006,35 (7): 661-664) uses skeleton nickel as a catalyst, MIBC is prepared by liquid phase hydrogenation of MIBK, and the optimal activation condition of the skeleton nickel is that the mass fraction of alkali liquor is 20.00%, the activation temperature is 90 ℃ and the activation time is 3 hours; under the conditions of 105-115 ℃ and hydrogen pressure of 1.2MPa and stirring rotation speed of 1000r/min, the conversion rate of MIBK can reach 100 percent, and the yield of MIBC is 99 percent. The method is complex in process and complex in operation. Moreover, the nickel component of the skeletal nickel catalyst has poor dispersity and low effective utilization rate, and greatly influences the activity of the catalyst.
In summary, the existing catalysts for producing MIBC have their own problems. Therefore, there is a need to develop a catalyst for preparing MIBC with high activity and high selectivity.
Disclosure of Invention
The invention aims to provide a nickel-copper catalyst with high activity and high selectivity, a preparation method thereof and a method for preparing methyl isobutyl alcohol.
In order to achieve the above object, a first aspect of the present invention provides a nickel copper catalyst. The nickel-copper catalyst comprises, based on 100 parts by weight of the total weight of the nickel-copper catalyst:
2-10 parts by weight of nickel;
5-15 parts by weight of copper; and
75-93 parts by weight of a boron modified alumina carrier;
wherein at least a part of the alumina carrier is theta-crystal type alumina carrier.
Preferably, the nickel is 2 to 8 parts by weight, the copper is 6 to 12 parts by weight, and the boron-modified alumina support is 80 to 92 parts by weight.
Preferably, the boron is present in the boron modified alumina support in an amount of from 0.5wt% to 3wt%, preferably from 0.5wt% to 2wt%.
Preferably, the mass fraction of the theta-crystal form of aluminum oxide in the aluminum oxide is 75% -100%; further preferably, the mass fraction of the theta-crystal form of alumina in the alumina is 90% -100%. Most preferably, the mass fraction of the theta-crystalline form of alumina in the alumina is 100%.
According to the invention, the particle size of the nickel copper catalyst is 0.3-15mm. Preferably, the particle size of the nickel copper catalyst is 0.5-5mm.
The present invention is not limited to the shape of the nickel-copper catalyst, and for example, the shape of the nickel-copper catalyst includes: sphere, bar, column, and ring.
A second aspect of the present invention provides a method of preparing the nickel copper catalyst of the first aspect.
The method comprises the following steps:
i) preparing the boron modified alumina carrier;
II) immersing the boron modified alumina carrier in a mixed solution of nickel salt and copper salt, or spraying the mixed solution of nickel salt and copper salt on the boron modified alumina carrier, and then drying and thermally decomposing to obtain the nickel-copper catalyst in an oxidation state.
In one embodiment of the invention, step i) comprises the steps of:
mixing alumina powder with an additive, adding water for kneading, granulating, drying and roasting to obtain an alumina carrier;
ii) mixing the alumina carrier prepared in the step i) with a boron-containing aqueous solution, and then drying and thermally decomposing to obtain the boron-modified alumina carrier.
In another embodiment of the invention, step i) comprises the steps of:
a) Mixing the alumina powder, boride and additives, adding water for kneading, and then granulating, drying and roasting to obtain the boron modified alumina carrier.
Specifically, in step i) and step a), the roasting temperatures are each 600 to 950 ℃ and the roasting times are each 2 to 6 hours.
Specifically, in step ii), the aqueous boron-containing solution is an aqueous boric acid solution.
Specifically, in step ii), the thermal decomposition temperature is 300 to 450, and the thermal decomposition time is 2 to 4 hours.
In particular, in step a), the boride is preferably boric acid.
Specifically, the additive comprises: at least one of starch, sesbania powder, citric acid and methyl cellulose.
In one embodiment of the present invention, in step ii), the thermal decomposition temperature is 300 to 450 ℃ and the thermal decomposition time is 2 to 4 hours.
In a specific embodiment of the invention, in step ii), the alumina support prepared in step 1) is immersed in an aqueous boron-containing solution or the aqueous boron-containing solution is sprayed onto the alumina support prepared in step 1).
In a preferred embodiment of the present invention, the method further comprises: repeating step ii) to obtain the boron modified alumina carrier. The number of repetitions is 2 to 4 times depending on the amount of boron to be loaded.
In a preferred embodiment of the present invention, the method further comprises: repeating the step II) to obtain the nickel-copper catalyst in the oxidation state.
Preferably, in the step II), the thermal decomposition temperature is 300-450 ℃, and the thermal decomposition time is 2-4 hours.
In the present invention, nickel salts and copper salts are used to provide active components nickel and copper, and thus the present invention is not particularly limited in the kinds of nickel salts and copper salts. Preferably, the solubility of the nickel salt and copper salt in water is high, e.g. in step ii), the nickel salt comprises: at least one of nickel nitrate, nickel chloride, nickel sulfate, nickel acetate and nickel oxalate; the copper salt comprises: at least one of copper nitrate, copper chloride, copper oxalate, copper sulfate and copper acetate. More preferably, the nickel salt comprises: at least one of nickel nitrate, nickel acetate and nickel oxalate. More preferably, the copper salt comprises: at least one of copper nitrate, copper acetate and copper oxalate.
According to the invention, the method further comprises: III) reducing the oxidized nickel-copper catalyst to obtain a reduced nickel-copper catalyst.
Specifically, step iii) comprises the steps of: placing the nickel-copper catalyst in the oxidation state on a catalyst bed, and introducing reducing gas into the catalyst bed; the reducing gas is hydrogen or a mixed gas of hydrogen and nitrogen;
raising the temperature of the catalyst bed at a first preset heating rate until a first preset temperature is reached, and maintaining the first preset time;
continuously increasing the temperature of the catalyst bed at a second preset heating rate until the temperature reaches a second preset temperature, and keeping the second preset time;
and reducing the temperature of the catalyst bed at a preset cooling rate.
Preferably, the space velocity of the reducing gas is 300-5000 m 3 /m 3 ·h -1 。
Preferably, the first preset heating rate is 5-20 ℃/h; the first preset temperature is 160+/-10 ℃; the first preset time is 2-8 hours. More preferably, the first preset heating rate is 5-10 ℃/h.
Preferably, the second preset heating rate is 5-20 ℃/h; the second preset temperature is 250-500 ℃; the second preset time is 2-48 hours. More preferably, the second preset heating rate is 5-10 ℃/h.
Preferably, the preset cooling rate is 5-20 ℃/h.
According to the present invention, when the temperature of the catalyst bed is lowered to below 50 ℃, the introduction of the reducing gas into the catalyst bed is stopped, while the inert gas or nitrogen is introduced into the catalyst bed, followed by the introduction of air into the catalyst bed, and the proportion of air is gradually increased, while the temperature of the catalyst bed is maintained not to exceed 50 ℃.
A third aspect of the invention provides the use of the nickel copper catalyst according to the first aspect.
Preferably, the nickel copper catalyst related to the first aspect is used for preparing methyl isobutyl alcohol by hydrogenating methyl isobutyl ketone.
In a fourth aspect, the invention provides a method for preparing methyl isobutyl alcohol by hydrogenating methyl isobutyl ketone. The method comprises the following steps:
adding a nickel-copper catalyst related to the first aspect onto a catalyst bed of a reactor, introducing preheated methyl isobutyl ketone and preheated hydrogen into the reactor for hydrogenation reaction, and keeping the temperature in the reactor at 90-150 ℃, preferably at 100-140 ℃; the pressure is 0.5-3.5 MPa, preferably 0.8-2.8 MPa; the liquid hourly space velocity of the methyl isobutyl ketone is 0.1 to 1.0h -1 Preferably 0.2 to 0.8h -1 。
According to the present invention, preferably, the molar ratio of the preheated hydrogen to the preheated methyl isobutyl ketone is 1.1:1 to 10:1.
More preferably, the temperature of the preheating is 80-120 ℃.
Preferably, the reactor is a fixed bed reactor.
The invention provides a nickel-copper catalyst, which adopts a boron modified alumina carrier, so that the number of medium-strength acid centers of alumina can be greatly increased, the addition of boron can improve the surface acidity of the alumina and the nickel-copper catalyst, especially the proportion of B acid in the acid position on the surface of the nickel-copper catalyst, so that the hydrogenation performance of the nickel-copper catalyst is improved; the interaction between the active component and the boron modified alumina carrier can be enhanced, the dispersity of the active component is further improved, migration, agglomeration and sintering of the active component in the catalytic process can be prevented, and the boron modified alumina carrier still has rich pore channels due to the fact that the alumina contains theta-crystal form alumina, so that outward diffusion and movement of generated macromolecule product molecules are facilitated, the pore channel blocking and thinning of the carrier are slowed down as much as possible, and the activity and stability of the nickel-copper catalyst are improved; the active components are nickel and copper, so that the selectivity of the nickel-copper catalyst in the preparation of methyl isobutyl alcohol is enhanced.
Compared with a gamma-crystal type alumina carrier, the theta-crystal type alumina carrier provided by the invention has a unique crystal face structure, the pore size distribution is more favorable for the reaction of the system, and the theta-crystal type alumina has rich pore channels and rich macropores, so that the outwards diffusion and movement of the generated macromolecule product molecules are facilitated, and the pore channel blockage and thinning of the carrier are slowed down as much as possible. The boron modification of the alumina carrier containing the theta crystal form can minimize the negative influence of boron addition on the pore size distribution of the alumina carrier because the theta crystal form alumina has rich pore channels, and simultaneously improves the specific surface area of the nickel-copper catalyst, so that the catalytic performance and the service life of the nickel-copper catalyst are obviously improved.
According to the method for preparing the nickel-copper catalyst, the active components (nickel and copper) are highly dispersed, so that the utilization rate of the active components is improved, and the activity of the nickel-copper catalyst is enhanced; the surface acidity of the nickel-copper catalyst is improved, the specific surface of the nickel-copper catalyst is increased, the pore size distribution of the nickel-copper catalyst is improved, and the selectivity and stability of the nickel-copper catalyst are greatly improved; the interaction between the active component and the boron modified alumina carrier is enhanced, the dispersity of the active component is further improved, meanwhile, the migration, loss, agglomeration and sintering of the active component in the catalysis process of the nickel-copper catalyst are effectively avoided, and the service life of the nickel-copper catalyst is remarkably prolonged.
The method for preparing the methyl isobutyl alcohol by hydrogenating the methyl isobutyl ketone provided by the invention has high conversion rate to MIBK and high selectivity to MIBC.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention are described below, it should be understood that the present invention may be embodied in various forms and should not be limited to the embodiments set forth herein.
Example 1
(1) Forming an alumina carrier: mixing 300g of alumina powder and 6g of sesbania powder in a kneader, adding 280g of water, kneading for 20min, extruding into 2mm coarse clover by using a strip extruder, drying at 120 ℃, and roasting at 800 ℃ for 4 hours to obtain an alumina carrier, wherein the content of theta-crystal form alumina is 100wt%.
(2) Boron modified alumina carrier: 2.83g of boric acid was weighed, dissolved in 80g of water, and 100g of the carrier was then weighed, immersed in a boric acid solution, dried at 120℃for 4 hours, and then thermally decomposed at 360℃for 4 hours.
(3) Loading active components: 12.22g Ni (NO) 3 ) 2 ·6H 2 O、70.27g Cu(NO 3 ) 2 ·3H 2 O is dissolved in 80ml of water, the carrier obtained in the step (2) is poured into the solution, shaken well, then dried at 100 ℃ for 4 hours, and thermally decomposed at 350 ℃ for 3 hours, thus obtaining the nickel-copper catalyst in an oxidation state.
(4) Nickel copper catalyst in reduced oxidation state: reducing the nickel-copper catalyst in the oxidation state obtained in the step (3) by using a mixed gas of 25vol% of hydrogen and 75vol% of nitrogen, wherein the reduction heating rate is 10 ℃/h, the reduction heating time is 450 ℃, the reduction heating time is 8 hours, and the temperature is reduced to room temperature, thereby obtaining the nickel-copper catalyst C-1 in the reduction state.
Example 2
(1) Forming an alumina carrier: mixing 300g of alumina powder with 6g of citric acid in a kneader, adding 280g of water, kneading for 20min, extruding into coarse clover with the thickness of 2mm by using a strip extruder, drying at 120 ℃, and roasting at 800 ℃ for 4 hours to obtain an alumina carrier, wherein the content of theta-crystal form alumina is 90wt% and the balance is gamma-crystal form alumina.
(2) Boron modified alumina carrier: weighing 5.69g of boric acid, dissolving in 160g of water, and equally dividing the dissolved solution into two parts; weighing 100g of carrier, immersing the carrier in one part of boric acid solution, drying at 120 ℃ for 4 hours, and thermally decomposing at 360 ℃ for 4 hours; then immersing in the other boric acid solution, drying at 120deg.C for 4 hr, and thermal decomposing at 360 deg.C for 4 hr.
(3) Loading active components: 61.33g Ni (NO) 3 ) 2 ·6H 2 O、23.51g Cu(NO 3 ) 2 ·3H 2 O is dissolved in 80ml of water, the carrier obtained in the step (2) is poured into the solution, shaken uniformly, then dried for 4 hours at 100 ℃, and thermally decomposed for 3 hours at 350 DEG CObtaining the nickel copper catalyst in an oxidation state.
(4) Nickel copper catalyst in reduced oxidation state: reducing the nickel copper catalyst in the oxidation state obtained in the step (3) by using a mixed gas of 25vol% of hydrogen and 75vol% of nitrogen, wherein the reduction heating rate is 10 ℃/h, the temperature is raised to 170 ℃ and stays for 4 hours, then the reduction heating rate is 10 ℃/h, the temperature is raised to 450 ℃, the temperature stays for 8 hours at the temperature, and then the temperature is reduced to room temperature, so that the nickel copper catalyst C-2 in the reduction state is obtained.
Example 3
(1) Forming an alumina carrier: mixing 300g of alumina powder with 6g of methylcellulose in a kneader, adding 280g of water, kneading for 20min, extruding into 2mm coarse clover by using a strip extruder, drying at 120 ℃, and roasting at 800 ℃ for 4 hours to obtain an alumina carrier, wherein the content of theta-crystal alumina is 95wt% and the balance is gamma-crystal alumina.
(2) Boron modified alumina carrier: 17.42g boric acid was mixed into the alumina powder during the carrier molding in step (1), and the other operations were unchanged.
(3) Loading active components: 57.91g Ni (NO) 3 ) 2 ·6H 2 O、66.60g Cu(NO 3 ) 2 ·3H 2 O is dissolved in 80ml of water, the carrier obtained in the step (2) is poured into the solution, shaken well, then dried at 100 ℃ for 4 hours, and thermally decomposed at 350 ℃ for 3 hours, thus obtaining the nickel-copper catalyst in an oxidation state.
(4) Nickel copper catalyst in reduced oxidation state: reducing the nickel-copper catalyst in the oxidation state obtained in the step (3) by using a mixed gas of 25vol% of hydrogen and 75vol% of nitrogen, wherein the reduction heating rate is 10 ℃/h, the reduction heating time is 450 ℃, the reduction heating time is 8 hours, and the temperature is reduced to room temperature, thereby obtaining the nickel-copper catalyst C-3 in the reduction state.
Example 4
(1) Forming an alumina carrier: mixing 300g of alumina powder with 6g of starch in a kneader, adding 280g of water, kneading for 20min, extruding into coarse clover with the thickness of 2mm by using a strip extruder, drying at 120 ℃, and roasting at 800 ℃ for 4 hours to obtain an alumina carrier, wherein the content of theta-crystal alumina is 75wt% and the balance is gamma-crystal alumina.
(2) Boron modified alumina carrier: weighing 5.69g of boric acid, dissolving in 160g of water, and equally dividing the dissolved solution into two parts; weighing 100g of carrier, immersing the carrier in one part of boric acid solution, drying at 120 ℃ for 4 hours, and thermally decomposing at 360 ℃ for 4 hours; then immersing in the other boric acid solution, drying at 120deg.C for 4 hr, and thermal decomposing at 360 deg.C for 4 hr.
(3) Loading active components: 30.66g Ni (NO) 3 ) 2 ·6H 2 O、47.02g Cu(NO 3 ) 2 ·3H 2 O is dissolved in 80ml of water, the carrier obtained in the step (2) is poured into the solution, shaken well, then dried at 100 ℃ for 4 hours, and thermally decomposed at 350 ℃ for 3 hours, thus obtaining the nickel-copper catalyst in an oxidation state.
(4) Nickel copper catalyst in reduced oxidation state: reducing the nickel-copper catalyst in the oxidation state obtained in the step (3) by using a mixed gas of 25vol% of hydrogen and 75vol% of nitrogen, wherein the reduction heating rate is 10 ℃/h, the reduction heating time is 450 ℃, the reduction heating time is 8 hours, and the temperature is reduced to room temperature, thereby obtaining the nickel-copper catalyst C-4 in the reduction state.
Example 5
(1) Forming an alumina carrier: mixing 300g of alumina powder and 6g of sesbania powder in a kneader, adding 280g of water, kneading for 20min, extruding into 2mm coarse clover by using a strip extruder, drying at 120 ℃, and roasting at 800 ℃ for 4 hours to obtain an alumina carrier, wherein the content of theta-crystal alumina is 95wt% and the balance is gamma-crystal alumina.
(2) Boron modified alumina carrier: weighing 5.69g of boric acid, dissolving in 160g of water, and equally dividing the dissolved solution into two parts; weighing 100g of carrier, immersing the carrier in one part of boric acid solution, drying at 120 ℃ for 4 hours, and thermally decomposing at 360 ℃ for 4 hours; then immersing in the other boric acid solution, drying at 120deg.C for 4 hr, and thermal decomposing at 360 deg.C for 4 hr.
(3) Loading active components: 49.65g of Ni (NO) 3 ) 2 ·6H 2 O、38.06g Cu(NO 3 ) 2 ·3H 2 O is dissolved in 80ml of water, the carrier obtained in the step (2) is poured into the solution, shaken well, then dried at 100 ℃ for 4 hours, and thermally decomposed at 350 ℃ for 3 hours, thus obtaining the nickel-copper catalyst in an oxidation state.
(4) Nickel copper catalyst in reduced oxidation state: reducing the nickel-copper catalyst in the oxidation state obtained in the step (3) by using a mixed gas of 25vol% of hydrogen and 75vol% of nitrogen, wherein the reduction heating rate is 10 ℃/h, the reduction heating time is 450 ℃, the reduction heating time is 8 hours, and the temperature is reduced to room temperature, thereby obtaining the nickel-copper catalyst C-5 in the reduction state.
Example 6
(1) Forming an alumina carrier: mixing 300g of alumina powder and 6g of sesbania powder in a kneader, adding 280g of water, kneading for 20min, extruding into 2mm coarse clover by using a strip extruder, drying at 120 ℃, and roasting at 800 ℃ for 4 hours to obtain an alumina carrier, wherein the content of theta-crystal alumina is 20wt% and the balance is gamma-crystal alumina.
(2) Boron modified alumina carrier: weighing 5.69g of boric acid, dissolving in 160g of water, and equally dividing the dissolved solution into two parts; weighing 100g of carrier, immersing the carrier in one part of boric acid solution, drying at 120 ℃ for 4 hours, and thermally decomposing at 360 ℃ for 4 hours; then immersing in the other boric acid solution, drying at 120deg.C for 4 hr, and thermal decomposing at 360 deg.C for 4 hr.
(3) Loading active components: 49.65g of Ni (NO) 3 ) 2 ·6H 2 O、38.06g Cu(NO 3 ) 2 ·3H 2 O is dissolved in 80ml of water, the carrier obtained in the step (2) is poured into the solution, shaken well, then dried at 100 ℃ for 4 hours, and thermally decomposed at 350 ℃ for 3 hours, thus obtaining the nickel-copper catalyst in an oxidation state.
(4) Nickel copper catalyst in reduced oxidation state: reducing the nickel-copper catalyst in the oxidation state obtained in the step (3) by using a mixed gas of 25vol% of hydrogen and 75vol% of nitrogen, wherein the reduction heating rate is 10 ℃/h, the reduction heating time is 450 ℃, the reduction heating time is 8 hours, and the temperature is reduced to room temperature, thereby obtaining the nickel-copper catalyst C-6 in the reduction state.
Example 7
(1) Forming an alumina carrier: mixing 300g of alumina powder and 6g of sesbania powder in a kneader, adding 280g of water, kneading for 20min, extruding into 2mm coarse clover by using a strip extruder, drying at 120 ℃, and roasting at 800 ℃ for 4 hours to obtain an alumina carrier, wherein the content of theta-crystal alumina is 60wt% and the balance is gamma-crystal alumina.
(2) Boron modified alumina carrier: weighing 5.69g of boric acid, dissolving in 160g of water, and equally dividing the dissolved solution into two parts; weighing 100g of carrier, immersing the carrier in one part of boric acid solution, drying at 120 ℃ for 4 hours, and thermally decomposing at 360 ℃ for 4 hours; then immersing in the other boric acid solution, drying at 120deg.C for 4 hr, and thermal decomposing at 360 deg.C for 4 hr.
(3) Loading active components: 49.65g of Ni (NO) 3 ) 2 ·6H 2 O、38.06g Cu(NO 3 ) 2 ·3H 2 O is dissolved in 80ml of water, the carrier obtained in the step (2) is poured into the solution, shaken well, then dried at 100 ℃ for 4 hours, and thermally decomposed at 350 ℃ for 3 hours, thus obtaining the nickel-copper catalyst in an oxidation state.
(4) Nickel copper catalyst in reduced oxidation state: reducing the nickel-copper catalyst in the oxidation state obtained in the step (3) by using a mixed gas of 25vol% of hydrogen and 75vol% of nitrogen, wherein the reduction heating rate is 10 ℃/h, the reduction heating time is 450 ℃, the reduction heating time is 8 hours, and the temperature is reduced to room temperature, thereby obtaining the nickel-copper catalyst C-7 in the reduction state.
Comparative example 1
(1) Forming an alumina carrier: mixing 300g of alumina powder and 6g of sesbania powder in a kneader, adding 280g of water, kneading for 20min, extruding into 2mm coarse clover by using a strip extruder, drying at 120 ℃, and roasting at 800 ℃ for 4 hours to obtain an alumina carrier, wherein the alumina carrier is gamma-crystal alumina.
(2) Boron modified alumina carrier: weighing 5.69g of boric acid, dissolving in 160g of water, and equally dividing the dissolved solution into two parts; weighing 100g of carrier, immersing the carrier in one part of boric acid solution, drying at 120 ℃ for 4 hours, and thermally decomposing at 360 ℃ for 4 hours; then immersing in the other boric acid solution, drying at 120deg.C for 4 hr, and thermal decomposing at 360 deg.C for 4 hr.
(3) Loading active components: 49.65g of Ni (NO) 3 ) 2 ·6H 2 O、38.06g Cu(NO 3 ) 2 ·3H 2 O is dissolved in 80ml of water, the carrier obtained in the step (2) is poured into the solution, shaken well, then dried at 100 ℃ for 4 hours, and thermally decomposed at 350 ℃ for 3 hours, thus obtaining the nickel-copper catalyst in an oxidation state.
(4) Nickel copper catalyst in reduced oxidation state: reducing the nickel-copper catalyst in the oxidation state obtained in the step (3) by using a mixed gas of 25vol% of hydrogen and 75vol% of nitrogen, wherein the reduction heating rate is 10 ℃/h, the reduction heating time is 450 ℃, the reduction heating time is 8 hours, and the temperature is reduced to room temperature, thereby obtaining the nickel-copper catalyst DC-1 in the reduction state.
Test example 1
This test example is used to illustrate the use of the nickel copper catalysts prepared in examples 1-7 and comparative example 1 in methyl isobutyl ketone hydrogenation reactions.
The nickel-copper catalyst is filled in a fixed bed reactor, methyl isobutyl ketone is metered into a preheater thereof by a metering pump, hydrogen is metered into the hydrogen preheater by a gas mass flowmeter, then the nickel-copper catalyst and the hydrogen are mixed and sent into the upper end of the reactor to enter a catalyst bed layer for hydrogenation reaction under the following reaction conditions: the reaction temperature is 120 ℃, the reaction pressure is 1.6MPa, and the space velocity is 0.5h -1 The molar ratio of hydrogen to acetone was 5:1. The test results are shown in Table 1.
TABLE 1 hydrogenation test results
| Nickel copper catalyst | MIBK conversion% | MIBC Selectivity% | |
| Example 1 | C-1 | 99.8 | 100 |
| Example 2 | C-2 | 99.8 | 100 |
| Example 3 | C-3 | 99.6 | 100 |
| Example 4 | C-4 | 99.4 | 100 |
| Example 5 | C-5 | 99.8 | 100 |
| Example 6 | C-6 | 91.2 | 98.85 |
| Example 7 | C-7 | 95.1 | 99.15 |
| Comparative example 1 | DC-1 | 89.7 | 98.53 |
As can be seen from Table 1, the nickel copper catalysts prepared in examples 1 to 7 had a conversion rate of MIBK to the nickel copper catalyst gradually increased as the content of the theta alumina in the alumina carrier increased, and the conversion rate of MIBK to the nickel copper catalyst was 99.4% or more and the MIBC selectivity reached 100% when the content of the theta alumina in the alumina carrier was 75wt% or more, relative to the nickel copper catalyst prepared in comparative example without the theta alumina. Therefore, the nickel-copper catalyst provided by the invention has good conversion rate of MIBK and high selectivity to MIBC.
Test example 2
This test example is used to illustrate the use of the nickel copper catalyst prepared in example 5 in the hydrogenation of methyl isobutyl ketone under different reaction conditions.
The nickel-copper catalyst is filled in a fixed bed reactor, methyl isobutyl ketone is metered into a preheater thereof by a metering pump, hydrogen is metered into the hydrogen preheater by a gas mass flowmeter, and then the hydrogen and the hydrogen are mixed and sent into the upper end of the reactor to enter a catalyst bed layer for hydrogenation reaction. The reaction conditions were changed and the test results are shown in Table 2.
TABLE 2 hydrogenation test results
| Temperature (temperature) | Pressure of | Ratio of hydroketones | Airspeed of (space velocity) | MIBK conversion | MIBC selectivity |
| 110℃ | 2.6MPa | 6:1 | 0.5h -1 | 99.78％ | 100％ |
| 130℃ | 1.7MPa | 6:1 | 0.5h -1 | 99.81％ | 100％ |
| 130℃ | 3.5MPa | 4:1 | 0.6h -1 | 99.63％ | 100％ |
| 90℃ | 3.2MPa | 6:1 | 0.4h -1 | 99.83％ | 100％ |
| 140℃ | 0.8MPa | 2:1 | 0.2h -1 | 99.67％ | 100％ |
| 130℃ | 2.0MPa | 4:1 | 0.8h -1 | 99.55％ | 100％ |
From examples 6 and 7, the nickel copper catalyst provided by the invention has high conversion rate of MIBK and selectivity of MIBC. Under the above reaction conditions, the conversion rate of MIBK can be more than 99%, and the MIBC selectivity can be kept at 100%.
Test example 3
This test example was used to examine the stability of the catalyst.
The nickel-copper catalyst C-4 is selected to be filled, the methyl isobutyl ketone hydrogenation reaction is carried out according to the reaction condition of the test example 1, the evaluation test is carried out for 1500 hours, and the activity and the selectivity of the nickel-copper catalyst are not obviously changed, and the specific expression is as follows: the conversion of MIBK was 99.37% and the MIBC selectivity was 100%. Therefore, the nickel-copper catalyst provided by the invention has excellent stability.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described.
Claims (12)
1. The application of a nickel-copper catalyst in preparing methyl isobutyl alcohol by hydrogenating methyl isobutyl ketone is characterized in that the nickel-copper catalyst comprises, based on 100 parts by weight of the total weight of the nickel-copper catalyst:
2-10 parts by weight of nickel;
5-15 parts by weight of copper; and
75-93 parts by weight of a boron modified alumina carrier;
wherein at least one part of the alumina carrier is an alumina carrier in a theta crystal form;
the mass fraction of the theta-crystal form aluminum oxide in the aluminum oxide is 75% -100%;
the content of the boron in the boron modified alumina carrier is 0.5wt percent to 3wt percent;
the method for preparing methyl isobutyl alcohol by catalyzing methyl isobutyl ketone hydrogenation by using the nickel-copper catalyst comprises the following steps:
adding the nickel-copper catalyst to a catalyst bed of a reactor, introducing preheated methyl isobutyl ketone and preheated hydrogen into the reactor, and carrying out hydrogenation reaction, wherein the temperature in the reactor is kept at 90-150 ℃ and the pressure is kept at 0.5-3.5 MPa; the liquid hourly space velocity of the methyl isobutyl ketone is 0.1-1.0 h -1 。
2. The use according to claim 1, wherein the temperature is 100-140 ℃;
the pressure is 0.8-2.8 MPa;
the liquid hourly space velocity of the methyl isobutyl ketone is 0.2-0.8 h -1 ；
The molar ratio of the preheated hydrogen to the preheated methyl isobutyl ketone is 1.1:1-10:1;
the reactor is a fixed bed reactor.
3. Use according to claim 1, characterized in that the nickel is 2-8 parts by weight, the copper is 6-12 parts by weight and the boron-modified alumina support is 80-92 parts by weight.
4. Use according to claim 1, characterized in that the boron content in the boron-modified alumina support is between 0.5% and 2% by weight.
5. The use according to claim 1, wherein the mass fraction of the alumina in the form θ is 90% -100% in the alumina.
6. The use according to any one of claims 1 to 5, wherein the preparation method of the nickel copper catalyst comprises the following steps:
i) preparing the boron modified alumina carrier;
II) immersing the boron modified alumina carrier in a mixed solution of nickel salt and copper salt, or spraying the mixed solution of nickel salt and copper salt on the boron modified alumina carrier, and then drying and thermally decomposing to obtain the nickel-copper catalyst in an oxidation state.
7. The use of claim 6, wherein the method of preparing further comprises: III) reducing the oxidized nickel-copper catalyst to obtain a reduced nickel-copper catalyst.
8. The use according to claim 7, wherein step i) comprises the steps of:
mixing alumina powder with an additive, adding water for kneading, granulating, drying and roasting to obtain an alumina carrier;
ii) mixing the alumina carrier prepared in the step i) with a boron-containing aqueous solution, and then drying and thermally decomposing to obtain the boron-modified alumina carrier; or alternatively
Step I) comprises the steps of:
a) Mixing the alumina powder, boride and additives, adding water for kneading, and then granulating, drying and roasting to obtain the boron modified alumina carrier.
9. The use according to claim 8, wherein in step i) and step a) the calcination temperatures are each 600-950 ℃ and the calcination times are each 2-6 hours;
in step ii), the aqueous boron-containing solution is an aqueous boric acid solution;
in step ii), the thermal decomposition temperature is 300-450 ℃, and the thermal decomposition time is 2-4 hours;
the additive comprises: at least one of starch, sesbania powder, citric acid and methyl cellulose.
10. Use according to claim 9, wherein in step a) the boride is boric acid.
11. The use according to claim 6, wherein in step ii) the thermal decomposition temperature is 300-450 ℃ and the thermal decomposition time is 2-4 hours;
in the step II), the nickel salt is at least one selected from nickel nitrate, nickel chloride, nickel sulfate, nickel acetate and nickel oxalate; the copper salt is at least one selected from copper nitrate, copper chloride, copper oxalate, copper sulfate and copper acetate.
12. The use according to claim 11, wherein the nickel salt is selected from at least one of nickel nitrate, nickel acetate and nickel oxalate;
the copper salt is at least one selected from copper nitrate, copper acetate and copper oxalate.
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