CN109590012B - Nitrogen-doped carbon-coated double-nano metal catalyst and preparation method and application thereof - Google Patents
Nitrogen-doped carbon-coated double-nano metal catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a nitrogen-doped carbon-coated double-nano metal catalyst, and a preparation method and application thereof. The catalyst greatly improves the selectivity of the catalyst to beta-phenethyl alcohol and the service life of the catalyst through the modification of the auxiliary agent and the carrier and the coating of the nitrogen-doped carbon compound. The catalyst prepared by the invention is simple in process for preparing beta-phenethyl alcohol by hydrogenation of styrene oxide, can continuously and stably run under the mild conditions of 70-80 ℃ and 3-4 MPa, and has the conversion rate of styrene oxide>99.8%, selectivity to beta-phenylethyl alcohol>99.5 percent, no other auxiliary agent or solvent is needed to be added in the reaction process, the product separation is simple, and the unit consumption of the catalyst is as low as 0.8Kg(CAT)/t(PEA)And is beneficial to industrial scale-up production.
Description
Technical Field
The invention relates to a nitrogen-doped carbon-coated double-nano metal catalyst, a preparation method thereof and application of the nitrogen-doped carbon-coated double-nano metal catalyst in preparation of beta-phenylethyl alcohol from styrene oxide.
Background
Beta-phenylethyl alcohol is a simple aromatic primary alcohol, has elegant, fine and lasting rose fragrance, and is widely applied to daily chemical products, such as astringent, soap, shampoo and the like; also used in edible essence and tobacco essence, and is the main raw material for preparing rose-flavor food additive and rose-flavor essence; in addition, the beta-phenethyl alcohol can also be used in chemical production, such as drug intermediates, fuel intermediates, advanced perfume intermediates and the like, and the production condition of the beta-phenethyl alcohol is closely related to human life.
Natural phenethyl alcohol has a softer and longer-lasting aroma and higher commercial value, but the resource of the natural phenethyl alcohol in the nature is very limited. Therefore, the beta-phenylethyl alcohol on the market is basically synthesized industrially. The main method for industrially producing the beta-phenylethyl alcohol is sequentially optimized by a toluene method, an ethylene oxide method (Friedel-Crafts reaction) and a styrene oxide hydrogenation method, and as the main method for preparing the beta-phenylethyl alcohol at present, a homogeneous phase method and a heterogeneous phase method for preparing the beta-phenylethyl alcohol by hydrogenating the styrene oxide are reported in documents. Homogeneous processes are hardly used because of the great difficulty of product separation. Among heterogeneous catalysts, skeletal Ni is the most commonly used catalyst.
US3579593 describes a method for preparing beta-phenylethyl alcohol by using frameworks Ni and Pd as catalysts respectively, and when Ni is used alone as a catalyst, the content of a byproduct, namely ethylbenzene is up to 11%; when Pd is used as a catalyst alone, the content of the byproduct phenylacetaldehyde reaches 10 percent, and the yield of beta-phenethyl alcohol is low.
By adding alkaline assistants such as NaOH and the like into the reaction system, the conversion rate of styrene oxide and the selectivity of beta-phenethyl alcohol both reach 99 percent, but the addition of the alkali assistant causes the problems of tower blockage and the like during the separation of the later-stage products.
In CN1111169A, although the yield of beta-phenethyl alcohol is high, the auxiliary agents added in the process are organic amine and alkaline substances, have toxicity and equipment corrosivity, and have great influence on aroma.
US2822403 proposes to prepare beta-phenylethyl alcohol under alkaline conditions with water as solvent and Raney Ni or Co as catalyst, but this process requires a large amount of water and the addition of an emulsifier to adjust the compatibility of water and styrene oxide, which all bring great difficulties for the separation of the later products.
In the technology, the defects of low product yield, difficult product separation, addition of an auxiliary agent alkali, short service life of the catalyst, poor product fragrance and the like exist, so that the development of a high-efficiency and high-selectivity catalyst, the avoidance of addition of the auxiliary agent and the improvement of the service life of the catalyst have important significance.
Disclosure of Invention
The invention aims to provide a catalyst for preparing beta-phenethyl alcohol, which has excellent activity and selectivity and longer catalytic life.
According to a first aspect of the present invention, there is provided a nitrogen-doped carbon-coated double nano metal catalyst, comprising catalyst active components of Ni and Co and an auxiliary agent, which are supported in an amine-modified MCM-41 mesoporous molecular sieve carrier, and a nitrogen-doped carbon compound which is dispersed in the amine-modified MCM-41 mesoporous molecular sieve carrier and forms a coating layer for the active components, wherein,
ni element: the content is 10-25 wt%, preferably 15-20 wt%, calculated by element Ni;
co element: the content is 5-20 wt%, preferably 10-15 wt%, calculated by element Co;
auxiliary agent: the content of the metal element is 2-10 wt%, preferably 4-5 wt%, and the metal element comprises one or more of Zn, Mg, La and Ce, preferably comprises Zn and Ce, and more preferably the molar ratio of Zn to Ce is 1-2: 1;
coating: the content of the nitrogen-doped carbon compound is 15-30 wt%, preferably 20-25 wt%, calculated by carbon nitride;
carrier: 15-68 wt%, preferably 35-51 wt% of amine modified MCM-41 mesoporous molecular sieve, and SiO2Counting;
all based on the weight of the catalyst.
In the catalyst, the active component and the auxiliary component exist in oxide form, and exist in element form after being reduced, and the measurement is based on the element.
Wherein the nitrogen-doped carbon compound is a product formed by roasting a nitrogen-doped carbon compound precursor, for example, one or more of compounds containing carbon and nitrogen elements, such as melamine, urea and uracil, in an inert gas atmosphere (for example, roasting at 350-450 ℃ for 6-15 hours). It can be expressed as N-C3N4, which is different from C3N4 in that the C/N ratio is only 0.6 or less of the ideal C3N4 ratio, i.e. N is generally 0.4-0.6, and the specific ratio is related to the post-firing environment. The higher the post-firing temperature, the higher the n value.
The active components Ni and Co of the catalyst are loaded in an amine modified MCM-41 mesoporous molecular sieve carrier, and a coating structure is formed on the active components by introducing a nitrogen-doped carbon compound.
According to a second aspect of the present invention, there is further provided a process for preparing the above catalyst, comprising the steps of:
(A) preparing amine modified MCM-41 mesoporous molecular sieve mother liquor;
(B) mixing an active component precursor and an auxiliary agent precursor with MCM-41 mesoporous molecular sieve mother liquor;
(C) heating a nitrogen-doped carbon compound precursor, for example, one or more of a compound containing carbon and nitrogen elements such as melamine, urea and uracil in an inert gas atmosphere to obtain a nitrogen-doped carbon compound, dispersing the nitrogen-doped carbon compound in a molecular sieve by an impregnation method, and forming a coating structure on an active component;
(D) and (C) forming the product obtained in the step (C).
In a more specific embodiment, the above catalyst is prepared by a process comprising the steps of:
1) dissolving precursors (usually Ni salt and Co salt) of Ni and Co elements serving as active components and an auxiliary agent precursor (salt of one or more elements of Zn, Mg, La and Ce) in water, preferably deionized water to form an aqueous solution, preferably adding all the precursors into the water together to form the aqueous solution, and also preparing the aqueous solution of each precursor, wherein the concentration of each precursor salt in the aqueous solution is 1-30 wt%, preferably 3-15 wt%;
2) adding the aqueous solution obtained in the step 1) into the amine modified MCM-41 mesoporous molecular sieve mother solution for mixing (for example, continuously stirring);
3) heating (such as in a crucible with a cover) a nitrogen-doped carbon compound precursor (such as a compound containing carbon and nitrogen elements, such as one or more of melamine, urea and uracil, preferably melamine or melamine) in an inert environment (such as in a crucible with a cover) for 6-15 hours to obtain a solid, and grinding into powder;
4) adding the powder obtained in the step 3) into the mixed solution obtained in the step 2) under strong stirring, and preferably enhancing the powder to penetrate into the active component by an ultrasonic mode;
5) removing the solvent from the mixed solution obtained in the step 4) (for example, by moving the mixed solution into a vacuum freeze drying box), and then roasting the solid powder (for example, transferring the solid powder into a crucible);
6) using a binder to obtain spherical particles (the particle size ranges from 10 meshes to 100 meshes) of the catalyst for later use by using the solid powder obtained in the step 5) through a rolling ball forming mode.
The active component precursor, the amine modified MCM-41 mesoporous molecular sieve and the nitrogen-doped carbon compound precursor are respectively used in such amounts that in the prepared catalyst, based on the content of metal elements, Ni element accounts for 10-35 wt%, preferably 20-25 wt%, Co element accounts for 5-20 wt%, preferably 10-15 wt%, auxiliary agent content is 2-10 wt%, preferably 4-6 wt%, and the nitrogen-doped carbon compound content is 20-35 wt%, preferably 25-30 wt%, based on carbon nitride; 15-68 wt%, preferably 35-51 wt% of amine modified MCM-41 mesoporous molecular sieve.
Preferably, in step 1) of the preparation method of the catalyst, the active component precursor is Ni (NO)3)2·6H2O and Co (NO)3)2·6H2O, the promoter precursor is selected from Zn (NO)3)2·6H2O、Mg(NO3)2·6H2O、La(NO3)3·6H2O、Ce(NO3)3·6H2One or more of O, preferably including Zn (NO)3)2·6H2O and Ce (NO)3)3·6H2O, more preferably Zn and Ce, with the molar ratio of 1-2: 1; the total content of Zn and Ce elements accounts for 2-10 wt%, preferably 4-6 wt% of the prepared catalyst.
In the invention, the dosage of water in the aqueous solution in the step 1) is active component precursor Ni (NO)3)2·6H2O and Co (NO)3)2·6H21.5 to 10 times, preferably about 2 times of the total mass of O; in order to ensure the full mixing of the active component precursor and the auxiliary agent precursor, the mixing time of the active component precursor and the auxiliary agent precursor in the step 1) of the preparation method of the catalyst is preferably controlled to be 2-5 h, and preferably 3-4 h.
In the step (A) or the step 2) of the preparation method of the catalyst, the preparation method of the amine modified MCM-41 mesoporous molecular sieve mother liquor comprises the following steps: tetraethyl orthosilicate is dropwise added into Cetyl Trimethyl Ammonium Bromide (CTAB) aqueous solution (the concentration range is 10-40 wt%, and the preferred concentration range is 15-25 wt%) under strong stirring, so that the concentration of the ethyl orthosilicate in the CTAB aqueous solution is 50-80 wt%, preferably 65-75 wt%, and added into CTAB water solution to reach 5-15 wt%, preferably 8-12 wt%, for example, 10wt% of triethylene diamine is fully dissolved, then alkali, preferably NaOH aqueous solution (the concentration is 5-20 wt%, preferably about 10 wt%) is added to adjust the pH value to 9-11, and the temperature is kept for a period of time (for example, in an autogenous pressure hydrothermal reaction kettle (the temperature is 40-100 ℃, preferably 60-80 ℃, the pressure is 0.1-0.5 MPa, preferably about 0.2-0.4MPa), the temperature is kept for 5-24 hours, preferably 12 hours), so that the amine modified MCM-41 mesoporous molecular sieve mother liquor (the solid content in the mother liquor is generally 10-50 wt%) is obtained.
In the invention, the water solution obtained in the step 2) and the amine modified MCM-41 mesoporous molecular sieve mother liquor are mixed and stirred for 3-8 hours, preferably 4-5 hours.
In the step 3) of the preparation method of the catalyst, the heating temperature is 400-600 ℃, preferably 500-550 ℃, and the heating time is 4-10 hours, preferably 6-8 hours.
In the preparation method of the catalyst, in the step 4), the ultrasonic temperature is 40-80 ℃, preferably 50-60 ℃; the ultrasonic time is 1-4 h, preferably 2-3 h.
In the step 5) of the preparation method of the catalyst, the drying temperature of the vacuum freeze drying oven is 90-120 ℃, preferably 100-110 ℃, and the drying time is 12-24 hours, preferably 15-20 hours; the roasting mode is that the mixture is heated to 800-1000 ℃, preferably 850-900 ℃ at the speed of 2.5 ℃/min in the nitrogen atmosphere and is kept for 1-4 hours, preferably 2-3 hours.
In the step 6) of the preparation method of the catalyst, the binder is alumina or silica sol, preferably silica sol; the particle size of the catalyst is preferably 40-60 meshes, and the amount of the binder is 10-40%, preferably 20-25 wt% of the solid powder in the step 5).
According to the third aspect of the invention, the invention also provides the application of the nitrogen-doped carbon-coated double-nano metal catalyst in preparing beta-phenylethyl alcohol by hydrogenating styrene oxide.
According to a fourth aspect of the present invention, the present invention provides a method for preparing β -phenylethyl alcohol by hydrogenation of styrene oxide using the above nitrogen-doped carbon-coated double nano-metal catalyst, comprising the following steps:
1) filling a catalyst in the fixed bed, filling 20-40 meshes of quartz sand in the upper layer and the lower layer, and introducing hydrogen to reduce the catalyst;
2) pumping the raw material styrene oxide into the reactor at a hydrogenation reaction temperature of 60-90 ℃, preferably 70-80 ℃ and a hydrogen pressure (absolute pressure) of 1-5 MPa, preferably 3-4 MPa to perform hydrogenation reaction to generate beta-phenylethyl alcohol.
The reactor used in the invention is a fixed bed reactor, and the space velocity of styrene oxide in the reaction process is 1-10 h-1Preferably 5 to 7.5-1。
The invention has the beneficial effects that:
the nitrogen-doped carbon-coated double-nano metal catalyst ensures the activity of the catalyst through the synergistic effect of double-active-component nano metal; meanwhile, a coating structure of nitrogen-doped carbon compounds is introduced into the catalyst, so that the phenomenon that epoxy groups in styrene oxide are directly connected with active sites of the catalyst to trigger a deoxidation reaction to generate a large amount of styrene and then the styrene is hydrogenated to generate ethylbenzene is avoided; the possibility of hydrogenation reaction of the benzene ring is reduced and the possibility of further hydrogenation of the beta-phenethyl alcohol is reduced by adjusting the auxiliary agent and the amine modified carrier. Therefore, while the introduction of an alkaline assistant is avoided, the selectivity of the beta-phenethyl alcohol is greatly improved through the modification and coating structure of the assistant and the carrier.
The catalyst effectively inhibits the loss of active components by coating the nitrogen-doped carbon compound, has long service life and low unit consumption, and greatly reduces the production cost.
The process for preparing the beta-phenethyl alcohol by hydrogenating the styrene oxide is simple, does not need to add any other auxiliary agent or solvent in the reaction process, has mild reaction conditions and simple product separation, and is easy for industrial amplification production.
Detailed Description
Example 1
49.3g of Ni (NO) were weighed3)2·6H2O, 98.6g of Co (NO)3)2·6H2O, 11.4g ZnNO3)2·6H2O, 26.7g Mg (NO)3)2·6H2O, 7.8g of La (NO)3)3·6H2O and 7.8g Ce (NO)3)3·6H2Adding 295.9g of deionized water into the solution to prepare a solution, and fully stirring the solution for 2 hours to form a solution 1; adding 156.0g of TEOS (tetraethyl orthosilicate) into 222g of 10wt% CTAB (cetyltrimethylammonium bromide) solution, adding 22.2g of triethylene diamine into the CTAB solution to form MCM-41 mesoporous molecular sieve mother liquor, and fully mixing and stirring the solution 1 and the molecular sieve mother liquor for 3 hours; weighing 18.9g of melamine, heating at 400 ℃ for 10h under an argon atmosphere to form solid powder, adding the fixed powder into the mixed solution, performing ultrasonic treatment at 40 ℃ for 4h, taking out the mixed solution, transferring the mixed solution to a vacuum freeze drying oven, drying at 90 ℃ for 24h, heating to 800 ℃ at the speed of 2.5 ℃/min under the nitrogen atmosphere, and roasting for 4h to obtain a solid catalyst primary product. Taking 50g of solid catalyst powder, taking 5g of alumina as a binder, and carrying out ball rolling molding on a primary catalyst product to obtain a 40-60-mesh spherical particle catalyst for later use, wherein the catalyst is named as CAT1-Al, and the Ni content in the final catalyst is 10wt%The catalyst comprises 20wt% of Co, 2.5 wt% of Zn, 2.5 wt% of Mg, 2.5 wt% of La, 2.5 wt% of Ce, 15wt% of nitrogen-doped carbon compound and the balance of amine modified MCM-41 mesoporous molecular sieve.
The catalyst CAT1-Al is used in a fixed bed process for preparing beta-phenethyl alcohol by hydrogenation of styrene oxide: weighing 20g of the catalyst, filling the catalyst into the middle part of a reactor, filling 20-40 meshes of quartz sand into the upper layer and the lower layer, introducing hydrogen to reduce the catalyst, wherein the reduction temperature is 550 ℃, the reduction time is 5h, the set temperature is 60 ℃, the pressure is 5MPa, and the space velocity of styrene oxide is 10h-1Continuous stable operation was carried out.
Example 2
123.3g of Ni (NO) were weighed3)2·6H2O, 24.7g of Co (NO)3)2·6H2O and 9.1g ZnNO3)2·6H2Adding 295.9g of deionized water into the solution to prepare a solution, and fully stirring the solution for 5 hours to form a solution 1; adding 131.7g of TEOS into 188g of 40% CTAB solution, adding 18.8g of triethylene diamine into the CTAB solution to form MCM-41 mesoporous molecular sieve mother liquor, and fully mixing and stirring the solution 1 and the molecular sieve mother liquor for 8 hours; 37.8g of melamine is weighed and heated for 4h at 600 ℃ under the argon atmosphere to form solid powder, the fixed powder is added into the mixed solution and is subjected to ultrasonic treatment for 1h at 80 ℃, the mixed solution is taken out and is transferred to a vacuum freeze drying box to be dried for 12h at 120 ℃, and then the mixed solution is heated to 1000 ℃ at the speed of 2.5 ℃/min under the nitrogen atmosphere to be roasted for 1h to obtain a solid catalyst primary product. Taking 50g of solid catalyst powder, and taking 20g of alumina as a binder to obtain a 40-60-mesh spherical particle catalyst for later use by a rolling ball molding mode of a primary catalyst product, wherein the catalyst is named as CAT 2-Al.
The final catalyst contains 25wt% of Ni, 5wt% of Co, 2wt% of Zn, 30wt% of nitrogen-doped carbon compound and the balance of amine modified MCM-41 mesoporous molecular sieve.
The catalyst CAT2-Al is used in a fixed bed process for preparing beta-phenethyl alcohol by hydrogenation of styrene oxide: weighing 20g of the catalyst, filling the catalyst into the middle part of a reactor, filling 20-40 meshes of quartz sand into the upper layer and the lower layer, introducing hydrogen to reduce the catalyst, wherein the reduction temperature is 200 ℃, and the reduction time isThe reaction time is 1h, the set temperature is 90 ℃, the pressure is 1MPa, and the space velocity of styrene oxide is 1h-1Continuous stable operation was carried out.
Example 3
74.0g of Ni (NO) was weighed3)2·6H2O, 74.0g of Co (NO)3)2·6H2O and 15.6g of LaNO3)3·6H2Adding 295.9g of deionized water into the solution to prepare a solution, and fully stirring the solution for 2.5 hours to form a solution 1; adding 156.0g of TEOS into 222g of 20% CTAB solution, adding 22.2g of triethylene diamine into the CTAB solution to form MCM-41 mesoporous molecular sieve mother liquor, and fully mixing and stirring the solution 1 and the molecular sieve mother liquor for 4 hours; weighing 25.2g of melamine, heating the melamine at 450 ℃ for 5h under the argon atmosphere to form solid powder, adding the solid powder into the mixed solution, carrying out ultrasonic treatment at 50 ℃ for 1.5h, taking out the mixed solution, transferring the mixed solution to a vacuum freeze drying oven, drying the mixed solution at 95 ℃ for 14h, and then heating the mixed solution to 850 ℃ at the speed of 2.5 ℃/min under the nitrogen atmosphere to roast the mixed solution for 1.5h to obtain a solid catalyst primary product. Taking 50g of solid catalyst powder, and taking 10g of alumina as a binder to obtain a 40-60 mesh spherical particle catalyst for later use by a rolling ball molding mode of a primary catalyst product, wherein the catalyst is named as CAT 3-Al.
The final catalyst contains 15wt% of Ni, 15wt% of Co, 5wt% of La, 20wt% of nitrogen-doped carbon compound and the balance of amine modified MCM-41 mesoporous molecular sieve.
The catalyst CAT3-Al is used in a fixed bed process for preparing beta-phenethyl alcohol by hydrogenation of styrene oxide: weighing 20g of the catalyst, filling the catalyst into the middle part of a reactor, filling 20-40 meshes of quartz sand into the upper layer and the lower layer, introducing hydrogen to reduce the catalyst, wherein the reduction temperature is 300 ℃, the reduction time is 3h, the set temperature is 70 ℃, the pressure is 4MPa, and the space velocity of styrene oxide is 7.5h-1Continuous stable operation was carried out.
Example 4
123.3g of Ni (NO) were weighed3)2·6H2O, 49.3g of Co (NO)3)2·6H2O and 15.5g Ce (NO)3)3·6H2Adding 345.3g of deionized water into the solution to prepare a solution, and fully stirring the solution for 4.5 hours to form a solution 1; will be provided with104.0g of TEOS is added into 148g of 20% CTAB solution, 14.8g of triethylene diamine is added into the CTAB solution to form MCM-41 mesoporous molecular sieve mother liquor, and the solution 1 and the molecular sieve mother liquor are fully mixed and stirred for 7 hours; 37.8g of melamine is weighed and heated at 550 ℃ for 9h under the argon atmosphere to form solid powder, the solid powder is added into the mixed solution and is subjected to ultrasonic treatment at 70 ℃ for 3.5h, the mixed solution is taken out and is transferred to a vacuum freeze drying oven to be dried at 115 ℃ for 20h, and then the mixed solution is heated to 950 ℃ under the nitrogen atmosphere at the speed of 2.5 ℃/min and is roasted for 3.5h to obtain a solid catalyst initial product. Taking 50g of solid catalyst powder, and taking 10g of alumina as a binder to obtain a 40-60 mesh spherical particle catalyst for later use by a rolling ball molding mode of a primary catalyst product, wherein the catalyst is named as CAT 4-Al.
The final catalyst contains 25wt% of Ni, 10wt% of Co, 5wt% of Ce, 30wt% of nitrogen-doped carbon compound and the balance of amine modified MCM-41 mesoporous molecular sieve.
The catalyst CAT4-Al is used in a fixed bed process for preparing beta-phenethyl alcohol by hydrogenation of styrene oxide: weighing 20g of the catalyst, filling the catalyst into the middle part of a reactor, filling 20-40 meshes of quartz sand into the upper layer and the lower layer, introducing hydrogen to reduce the catalyst, wherein the reduction temperature is 400 ℃, the reduction time is 2h, the set temperature is 80 ℃, the pressure is 2MPa, and the space velocity of styrene oxide is 5h-1Continuous stable operation was carried out.
Example 5
74.0g of Ni (NO) was weighed3)2·6H2O, 74.0g of Co (NO)3)2·6H2O, 13.7g ZnNO3)2·6H2O, 16.0g Mg (NO)3)2·6H2O and 4.7g Ce (NO)3)3·6H2Adding 295.9g of deionized water into the solution to prepare a solution, and fully stirring the solution for 3 hours to form a solution 1; adding 135.2g of TEOS into 193g of 20% CTAB solution, adding 19.3g of triethylene diamine into the CTAB solution to form MCM-41 mesoporous molecular sieve mother liquor, and fully mixing and stirring the solution 1 and the molecular sieve mother liquor for 5 hours; weighing 31.5g melamine, heating at 500 deg.C for 6 hr under argon atmosphere to obtain solid powder, adding the solid powder into the above mixed solution, performing ultrasonic treatment at 55 deg.C for 2 hr, taking out, and mixingTransferring the solution to a vacuum freeze drying oven, drying at 100 deg.C for 15h, heating to 900 deg.C at 2.5 deg.C/min under nitrogen atmosphere, and calcining for 2h to obtain solid catalyst. Taking 50g of solid catalyst powder, and taking 10g of alumina as a binder to obtain a 40-60 mesh spherical particle catalyst for later use by a rolling ball molding mode of a primary catalyst product, wherein the catalyst is named as CAT 5-Al.
The final catalyst contains 15wt% of Ni, 15wt% of Co, 3 wt% of Zn, 1.5 wt% of Mg, 1.5 wt% of Ce, 25wt% of nitrogen-doped carbon compound and the balance of amine modified MCM-41 mesoporous molecular sieve.
The catalyst CAT5-Al is used in a fixed bed process for preparing beta-phenethyl alcohol by hydrogenation of styrene oxide: weighing 20g of the catalyst, filling the catalyst into the middle part of a reactor, filling 20-40 meshes of quartz sand into the upper layer and the lower layer, introducing hydrogen to reduce the catalyst, wherein the reduction temperature is 350 ℃, the reduction time is 3h, the set temperature is 70 ℃, the pressure is 3MPa, and the space velocity of styrene oxide is 5h-1Continuous stable operation was carried out.
Example 6
74.0g of Ni (NO) was weighed3)2·6H2O, 49.3g of Co (NO)3)2·6H2O, 15.4g Mg (NO)3)2·6H2O and 5.0g Ce (NO)3)3·6H2Adding 246.6g of deionized water into the solution to prepare a solution, and fully stirring the solution for 4 hours to form a solution 1; adding 176.8g of TEOS into 252g of 20% CTAB solution, adding 25.2g of triethylene diamine into the CTAB solution to form MCM-41 mesoporous molecular sieve mother liquor, and fully mixing and stirring the solution 1 and the molecular sieve mother liquor for 6 hours; weighing 25.2g of melamine, heating at 550 ℃ for 8h under argon atmosphere to form solid powder, adding the solid powder into the mixed solution, performing ultrasonic treatment at 65 ℃ for 2.5h, taking out the mixed solution, transferring the mixed solution to a vacuum freeze drying box, drying at 110 ℃ for 18h, heating to 850 ℃ at the speed of 2.5 ℃/min under nitrogen atmosphere, and roasting for 3h to obtain a solid catalyst primary product. Taking 50g of solid catalyst powder, and taking 10g of alumina as a binder to obtain a 40-60 mesh spherical particle catalyst for later use by a rolling ball molding mode of a primary catalyst product, wherein the catalyst is named as CAT 6-Al.
The final catalyst contains 15wt% of Ni, 10wt% of Co, 2.4 wt% of Mg, 1.6 wt% of Ce, 20wt% of nitrogen-doped carbon compound and the balance of amine modified MCM-41 mesoporous molecular sieve.
The catalyst CAT6-Al is used in a fixed bed process for preparing beta-phenethyl alcohol by hydrogenation of styrene oxide: weighing 20g of the catalyst, filling the catalyst into the middle part of a reactor, filling 20-40 meshes of quartz sand into the upper layer and the lower layer, introducing hydrogen to reduce the catalyst, wherein the reduction temperature is 350 ℃, the reduction time is 3h, the set temperature is 70 ℃, the pressure is 4MPa, and the space velocity of styrene oxide is 5h-1Continuous stable operation was carried out.
Example 7
98.6g of Ni (NO) were weighed3)2·6H2O, 74.0g of Co (NO)3)2·6H2O, 11.4g Zn (NO)3)2·6H2O and 7.8g of La (NO)3)3·6H2Adding 345.3g of deionized water into the solution to prepare a solution, and fully stirring the solution for 3.5 hours to form a solution 1; adding 121.3g of TEOS into 173g of 20% CTAB solution, adding 17.3g of triethylene diamine to form MCM-41 mesoporous molecular sieve mother liquor, and fully mixing and stirring the solution 1 and the molecular sieve mother liquor for 4 hours; 31.5g of melamine is weighed and heated at 500 ℃ for 7h under the argon atmosphere to form solid powder, the fixed powder is added into the mixed solution and is subjected to ultrasonic treatment at 60 ℃ for 3h, the mixed solution is taken out and is transferred to a vacuum freeze drying box to be dried at 105 ℃ for 16h, and then the mixed solution is heated to 850 ℃ under the nitrogen atmosphere at the speed of 2.5 ℃/min and is roasted for 2.5h to obtain a solid catalyst primary product. Taking 50g of solid catalyst powder, and taking 10g of alumina as a binder to obtain a 40-60 mesh spherical particle catalyst for later use by a rolling ball molding mode of a primary catalyst product, wherein the catalyst is named as CAT 7-Al.
In the final catalyst, the Ni content is 20wt%, the Co content is 15wt%, the Zn content is 2.5 wt%, the La content is 2.5 wt%, the nitrogen-doped carbon compound content is 25wt%, and the balance is the amine modified MCM-41 mesoporous molecular sieve.
The catalyst CAT7-Al is used in a fixed bed process for preparing beta-phenethyl alcohol by hydrogenation of styrene oxide: weighing 20g of the catalyst, filling the catalyst into the middle part of a reactor, and filling 20-40 meshes of quartz sand into the upper layer and the lower layerIntroducing hydrogen to reduce the catalyst at 350 deg.C for 3 hr, setting the temperature at 80 deg.C, the pressure at 3MPa and the space velocity of styrene oxide at5 hr-1Continuous stable operation was carried out.
Example 8
98.6g of Ni (NO) were weighed3)2·6H2O, 49.3g of Co (NO)3)2·6H2O, 13.7g Zn (NO)3)2·6H2O and 6.2g Ce (NO)3)3·6H2Adding 295.9g of deionized water into the solution to prepare a solution, and fully stirring the solution for 3.5 hours to form a solution 1; adding 156.0g of TEOS into 222g of 20% CTAB solution, adding 22.2g of triethylene diamine into the CTAB solution to form MCM-41 mesoporous molecular sieve mother liquor, and fully mixing and stirring the solution 1 and the molecular sieve mother liquor for 4.5 hours; weighing 25.2g of melamine, heating at 550 ℃ for 7h under argon atmosphere to form solid powder, adding the solid powder into the mixed solution, performing ultrasonic treatment at 60 ℃ for 3h, taking out the mixed solution, transferring the mixed solution to a vacuum freeze drying oven, drying at 105 ℃ for 16h, heating to 900 ℃ at the speed of 2.5 ℃/min under nitrogen atmosphere, and roasting for 2.5h to obtain a solid catalyst primary product. Taking 50g of solid catalyst powder, and taking 10g of alumina as a binder to obtain a 40-60 mesh spherical particle catalyst for later use by a rolling ball molding mode of a primary catalyst product, wherein the catalyst is named as CAT 8-Al.
In the final catalyst, the Ni content is 20wt%, the Co content is 10wt%, the Zn content is 3 wt%, the Ce content is 2wt%, the nitrogen-doped carbon compound content is 20wt%, and the balance is the amine modified MCM-41 mesoporous molecular sieve.
The catalyst CAT8-Al is used in a fixed bed process for preparing beta-phenethyl alcohol by hydrogenation of styrene oxide: weighing 20g of the catalyst, filling the catalyst into the middle part of a reactor, filling 20-40 meshes of quartz sand into the upper layer and the lower layer, introducing hydrogen to reduce the catalyst, wherein the reduction temperature is 350 ℃, the reduction time is 3h, the set temperature is 70 ℃, the pressure is 4MPa, and the space velocity of styrene oxide is 5h-1Continuous stable operation was carried out.
Comparative examples 1 to 8
The rolling ball forming binders of the embodiments 1 to 8 are respectively changed into silica sol, and the catalysts are sequentially named as CAT 1-8-Si and are used in the fixed bed process for preparing the beta-phenethyl alcohol by hydrogenating styrene oxide under the corresponding equivalent conditions.
The results of the experimental evaluation are shown in Table 1.
TABLE 1 evaluation results of continuous and batch processes for preparing phenethyl alcohol
The modified catalyst can be used for obtaining the beta-phenethyl alcohol with high selectivity under the condition of using an optimized fixed bed process without adding an auxiliary agent and a solvent additionally. Compared with other catalysts, the modified catalyst has the synergistic effect of double active components, namely nano metal, so that the activity of the catalyst is guaranteed; meanwhile, the selectivity of the beta-phenethyl alcohol is greatly improved through the modification of the auxiliary agent and the carrier and the coating structure of the nitrogen-doped carbon compound.
Compared with a comparative example, the catalyst obtained by optimizing the binder has longer service life and lower unit consumption of the catalyst, and the minimum consumption can reach 0.8Kg(CAT)/t(PEA)。
Claims (26)
1. A nitrogen-doped carbon-coated double nano metal catalyst comprises active components Ni and Co and an auxiliary agent which are loaded in an amine modified MCM-41 mesoporous molecular sieve carrier, and a nitrogen-doped carbon compound which is dispersed in the amine modified MCM-41 mesoporous molecular sieve carrier and forms a coating layer for the active components, wherein,
ni element: the content is 10-25 wt% calculated by element Ni;
co element: the content is 5-20 wt%, calculated by element Co;
auxiliary agent: the content is 2-10 wt%, and the metal element comprises one or more of Zn, Mg, La and Ce;
coating: a nitrogen-doped carbon compound in an amount of 15 to 30wt% based on carbon nitride;
carrier: 15-68 wt% of amine modified MCM-41 mesoporous molecular sieve, and SiO2Counting;
the above wt% are based on the weight of the catalyst.
2. The nitrogen-doped carbon-coated double nanometal catalyst of claim 1, wherein,
ni element: the content is 15-20 wt% calculated by element Ni;
co element: the content is 10-15 wt%, calculated by element Co;
auxiliary agent: the content of the metal element is 4-5 wt%, and the metal element comprises one or more of Zn, Mg, La and Ce;
coating: a nitrogen-doped carbon compound in an amount of 20 to 25wt% based on carbon nitride;
carrier: 35-51 wt% of amine modified MCM-41 mesoporous molecular sieve, and SiO2And (6) counting.
3. The nitrogen-doped carbon-coated double-nanometal catalyst according to claim 1, wherein the promoter is an element comprising Zn and Ce.
4. The nitrogen-doped carbon-coated double-nano metal catalyst according to claim 3, wherein the molar ratio of Zn and Ce as auxiliaries is 1-2: 1.
5. The nitrogen-doped carbon-coated double nanometal catalyst according to any one of claims 1 to 4, wherein the nitrogen-doped carbon compound is a product formed by firing a nitrogen-doped carbon compound precursor under an inert gas atmosphere.
6. The nitrogen-doped carbon-coated double nanometal catalyst of claim 5, wherein the nitrogen-doped carbon compound precursor is a carbon nitrogen element containing compound.
7. The nitrogen-doped carbon-coated double-nano metal catalyst according to claim 6, wherein the compound containing carbon and nitrogen is one or more of melamine, urea and uracil.
8. The nitrogen-doped carbon-coated double-nano metal catalyst according to claim 5, wherein the roasting is carried out at 350-450 ℃ for 6-15 hours.
9. The method of any one of claims 1-8 for preparing a nitrogen doped carbon coated dual nanometal catalyst, comprising the steps of:
(A) preparing amine modified MCM-41 mesoporous molecular sieve mother liquor;
(B) mixing an active component precursor and an auxiliary agent precursor with MCM-41 mesoporous molecular sieve mother liquor;
(C) heating the nitrogen-doped carbon compound precursor in an inert gas atmosphere to obtain a nitrogen-doped carbon compound, dispersing the nitrogen-doped carbon compound in the molecular sieve by an impregnation method, and forming a coating structure on the active component;
(D) and (C) forming the product obtained in the step (C).
10. The method of any one of claims 1-8 for preparing a nitrogen doped carbon coated dual nanometal catalyst, comprising the steps of:
1) dissolving precursors of Ni and Co elements serving as active components and an auxiliary agent precursor in water to form a water solution;
2) adding the aqueous solution obtained in the step 1) into the amine modified MCM-41 mesoporous molecular sieve mother liquor for mixing;
3) heating the nitrogen-doped carbon compound precursor in an inert environment to obtain a solid, and grinding the solid into powder;
4) adding the powder obtained in the step 3) into the mixed solution obtained in the step 2) under the condition of strong stirring;
5) removing the solvent from the mixed solution obtained in the step 4), and then roasting the solid powder;
6) using a binder to obtain spherical particle catalyst by rolling ball molding of the solid powder obtained in the step 5) for later use.
11. The preparation method according to claim 10, wherein in step 1), the precursors of the active components, i.e., Ni and Co, are Ni salts and Co salts, the promoter precursor is one or more of Zn, Mg, La and Ce, and water is deionized water;
in step 4), the penetration of the powder into the active ingredient is intensified by means of ultrasound.
12. The production method according to claim 11, wherein in the step 1), the concentration of each precursor salt in the aqueous solution is 1 to 30 wt%.
13. The preparation method according to claim 12, wherein in the step 1), the concentration of each precursor salt in the aqueous solution is 3 to 15 wt%.
14. The production method according to any one of claims 10 to 13, wherein, in step 1), the active component precursor is Ni (NO)3)2·6H2O and Co (NO)3)2·6H2O, the promoter precursor is selected from Zn (NO)3)2·6H2O、Mg(NO3)2·6H2O、La(NO3)3·6H2O、 Ce(NO3)3·6H2One or more of O; the total content of Zn and Ce elements accounts for 2-10 wt% of the prepared catalyst; and/or
Step 1) the water solution takes the amount of water as an active component precursor Ni (NO)3)2·6H2O and Co (NO)3)2·6H21.5-10 times of the total mass of O.
15. The preparation method of claim 14, wherein in the step 1), the total content of Zn and Ce elements accounts for 4-6 wt% of the prepared catalyst; and/or
Step 1) the water solution takes the amount of water as an active component precursor Ni (NO)3)2·6H2O and Co (NO)3)2·6H22 times of the total mass of O.
16. The production method according to claim 14, wherein, in step 1), the auxiliary agent precursor is a precursor including Zn (NO)3)2·6H2O and Ce (NO)3)3·6H2O。
17. The preparation method of claim 16, wherein in the step 1), the molar ratio of Zn and Ce elements in the auxiliary agent precursor is 1-2: 1.
18. The preparation method according to claim 9 or 10, wherein in the step (a) or 2), the amine modified MCM-41 mesoporous molecular sieve mother liquor is prepared by: dropwise adding tetraethyl orthosilicate into a Cetyl Trimethyl Ammonium Bromide (CTAB) aqueous solution under strong stirring, adding triethylene diamine which accounts for 5-15 wt% of the CTAB aqueous solution, fully dissolving, then adding alkali to adjust the pH value to 9-11, and preserving the temperature for a period of time to obtain the amine modified MCM-41 mesoporous molecular sieve mother liquor.
19. The method according to claim 18, wherein the concentration of cetyltrimethylammonium bromide (CTAB) aqueous solution is 10 to 40 wt%;
adding 8-12 wt% of triethylene diamine in a CTAB aqueous solution for full dissolution;
the alkali is NaOH aqueous solution;
the heat preservation is carried out in an autogenous pressure hydrothermal reaction kettle at the temperature of 40-100 ℃ and the pressure of 0.1-0.5 MPa for 5-24 hours;
the amine modified MCM-41 mesoporous molecular sieve mother liquor has solid content of 10-50 wt%.
20. The method of claim 19, wherein the concentration of cetyltrimethylammonium bromide (CTAB) in water is 15-25 wt%;
adding triethylene diamine which is 10wt% in CTAB aqueous solution for full dissolution;
the concentration of the NaOH aqueous solution is 5-20 wt%;
the heat preservation is carried out in an autogenous pressure hydrothermal reaction kettle at the temperature of 60-80 ℃, the pressure of 0.2-0.4MPa and the constant temperature for 12 hours.
21. The method of claim 20, wherein the aqueous NaOH solution has a concentration of 10 wt%.
22. The preparation method according to claim 11, wherein the aqueous solution in the step 2) is mixed with the amine modified MCM-41 mesoporous molecular sieve mother liquor for 3-8 h; and/or
In the step 3), the heating temperature is 400-600 ℃, and the heating time is 4-10 h; and/or
In the step 4), the ultrasonic temperature is 40-80 ℃; the ultrasonic time is 1-4 h; and/or
In the step 5), removing the solvent in a vacuum freeze drying oven, wherein the drying temperature is 90-120 ℃, and the drying time is 12-24 hours; the roasting mode is that the mixture is heated to 800-1000 ℃ at the speed of 2.5 ℃/min under the nitrogen atmosphere and is kept for 1-4 hours; and/or
In the step 6), the binder is alumina or silica sol; the amount of the binder is 10-40 wt% relative to the solid powder in the step 5).
23. The preparation method according to claim 22, wherein the aqueous solution in the step 2) is mixed with the amine modified MCM-41 mesoporous molecular sieve mother liquor for 4-5 h; and/or
In the step 3), the heating temperature is 500-550 ℃, and the heating time is 6-8 h; and/or
In the step 4), the ultrasonic temperature is 50-60 ℃; the ultrasonic time is 2-3 h; and/or
In the step 5), removing the solvent in a vacuum freeze drying oven, wherein the drying temperature is 100-110 ℃, and the drying time is 15-20 h; the roasting mode is heating to 850-900 ℃ at the speed of 2.5 ℃/min in the nitrogen atmosphere, and keeping for 2-3 h; and/or
In the step 6), the binder is silica sol; the particle size of the catalyst is 40-60 meshes, and the using amount of the binder is 20-25 wt% relative to the solid powder in the step 5).
24. Use of a nitrogen-doped carbon-coated double nanometal catalyst according to any one of claims 1 to 8 or obtained by the production method according to any one of claims 9 to 23 for the production of a catalystPreparation of styrene oxide by hydrogenationβ-use of phenethyl alcohol.
25. Styrene oxide hydrogenation preparationβ-a process for the production of phenethyl alcohol, comprising the following steps:
1) filling the nitrogen-doped carbon-coated double-nano metal catalyst of any one of claims 1 to 8 or the nitrogen-doped carbon-coated double-nano metal catalyst obtained by the preparation method of any one of claims 9 to 23 in a fixed bed, filling 20-40 meshes of quartz sand in the upper and lower layers, and introducing hydrogen to reduce the catalyst;
2) pumping the raw material styrene oxide into the reactor at a hydrogenation reaction temperature of 60-90 ℃ and a hydrogen absolute pressure of 1-5 MPa for hydrogenation reaction to generateβ-phenyl ethanol.
26. The method as claimed in claim 25, wherein in the step 2), the styrene oxide raw material is pumped in at a hydrogenation reaction temperature of 70-80 ℃ and a hydrogen absolute pressure of 3-4 MPa for hydrogenation reaction to generateβ-phenyl ethanol.
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