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CN111992213B - Preparation method of core-shell catalyst for preparing cyclohexanol by catalytic hydrogenation and deoxidation of guaiacol - Google Patents

Preparation method of core-shell catalyst for preparing cyclohexanol by catalytic hydrogenation and deoxidation of guaiacol Download PDF

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CN111992213B
CN111992213B CN202010961675.8A CN202010961675A CN111992213B CN 111992213 B CN111992213 B CN 111992213B CN 202010961675 A CN202010961675 A CN 202010961675A CN 111992213 B CN111992213 B CN 111992213B
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catalyst
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guaiacol
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CN111992213A (en
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鲁墨弘
赵梦阳
胡双进
陈晨
李明时
张伟
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Changzhou University
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • 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
    • B01J23/74—Iron group metals
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    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • C07C29/19—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings
    • C07C29/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings in a non-condensed rings substituted with hydroxy groups
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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Abstract

The invention belongs to the field of preparation of catalysts, and particularly relates to a preparation method of a core-shell type catalyst for preparing cyclohexanol by catalyzing hydrogenation and deoxidation of guaiacol. Firstly, preparing cobalt nano-particles by using a solvent reduction method, and then preparing the cobalt nano-particles by using a post-synthesis method to obtain the cobalt nano-particles taking Co as a core and M as a core x O y ‑SiO 2 Co @ M being a shell x O y ‑SiO 2 Core-shell catalysts, wherein M = Ce, ti, al. The catalyst has the advantages of simple preparation process, low cost, low energy consumption and low reaction pressure and temperature. In addition, the prepared core-shell catalyst shows good reaction activity in the guaiacol hydrodeoxygenation reaction, has good stability, can be roasted and recycled after reaction, and has good economic benefit.

Description

Preparation method of core-shell catalyst for preparing cyclohexanol by catalytic hydrogenation and deoxidation of guaiacol
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a preparation method of a core-shell type catalyst for preparing cyclohexanol by catalyzing hydrogenation and deoxidation of guaiacol.
Background
Cyclohexanol is an important chemical raw material and is widely applied to a plurality of industrial production fields. Can be used for producing adipic acid, hexamethylene diamine, caprolactam and the like, can also be used as a raw material for fuel production, and cyclohexane prepared by hydrogenation and dehydration is one of main components of gasoline. Furthermore, cyclohexanol is also used in solvents, paints, pharmaceuticals, plasticizers, and the like. Currently, the industrial production of cyclohexanol is mainly realized by oxidation of cyclohexane and hydrogenation of phenol, which is not in accordance with the strategy of sustainable development and increases the consumption of fossil energy.
Guaiacol has a high proportion in phenolic compounds obtained by pyrolysis of lignin, and lignin has a wide reserve in nature. The method for preparing cyclohexanol by using guaiacol hydrodeoxygenation has low production cost and saves energy. Recently, the transition metal catalyst shows better reaction activity in the guaiacol hydrodeoxygenation reaction, has unique advantages compared with catalysts such as noble metals, sulfides and the like, and is low in cost, green and clean.
In patent CN107649169A, a catalyst prepared by loading any two or three active components of Ni, co, cu, mg, al and Fe on a molecular sieve is used for catalyzing guaiacol to perform hydrodeoxygenation to prepare cyclohexanol, the reaction occurs under the conditions of high pressure (3-6 MPa) and long reaction time (6-10 h), and the conversion rate of guaiacol to cyclohexanol is low in selectivity.
Disclosure of Invention
The invention aims to improve the catalytic activity of a Co-based catalyst, improve the yield of cyclohexanol and reduce the reaction energy consumption, and a core-shell type catalyst with high catalytic activity for catalyzing hydrogenation and deoxidation of guaiacol to prepare cyclohexanol is prepared, and in order to realize the aim, the technical scheme of the invention is as follows:
a preparation method of a core-shell type catalyst for catalyzing hydrogenation deoxidation of guaiacol to prepare cyclohexanol comprises the following steps:
(1) Preparing two parts of hexadecyl trimethyl ammonium bromide (CTAB) aqueous solutions with the same volume, wherein one part contains hydrazine hydrate, and the other part contains a cobalt source precursor and a sodium hydroxide solution in a metered manner;
wherein the concentration of Cetyl Trimethyl Ammonium Bromide (CTAB) in the solution is 0.1mol/L; the precursor of the cobalt source is Co (NO) 3 ) 2 ·6H 2 O, the concentration of the sodium hydroxide solution is 1mol/L;
(2) Mixing the prepared two parts of Cetyl Trimethyl Ammonium Bromide (CTAB) aqueous solutions, and mechanically stirring for 1-2 h at 80 ℃;
(3) And (3) taking out the product obtained in the step (2), alternately washing the product with ethanol and deionized water for 2 to 3 times, and carrying out vacuum drying at 50 ℃ overnight to obtain the Co nanoparticles.
(4) Dispersing the Co nano particles obtained in the step (3) in a mixed solution of deionized water and ethanol;
(5) Preparing a metal carrier precursor and a silicon source precursor into a mixed solution, adding the mixed solution and an alkali solution into the suspension obtained in the step (4) in a parallel flow manner under mechanical stirring at the temperature of between 60 and 80 ℃, and stirring for 0.5 hour;
wherein the metal carrier precursor is nitrate, acetate or chloride of M, wherein M = Ce, ti and Al; the precursor of the silicon source is Na 2 SiO 3 ·9H 2 O; the alkali solution is (NH) 4 ) 2 CO 3 Solution, na 2 CO 3 One of the solutions;
(6) Taking out the obtained precipitate, filtering, washing to neutrality, placing in n-butanol at 50 deg.C, stirring, evaporating to dryness, placing in oven at 100 deg.C for 12 hr, and reducing in hydrogen flow at 400-450 deg.C for 3-4 hr before use to obtain core-shell catalyst Co @ M x O y -SiO 2 ；
The mass fraction of Co in the obtained core-shell type catalyst is 10 percent, and M is x O y :SiO 2 The mass ratio of (A) is 1:2-3.
The invention also provides an application of the core-shell catalyst, which comprises the following specific steps:
adding 0.2-0.4 g of catalyst into a fixed bed tubular reactor, then introducing guaiacol raw material and hydrogen, reacting at 160-220 ℃, under the reaction pressure of 2MPa for 2-4 h, and collecting generated cyclohexanol, wherein the catalyst is the core-shell catalyst.
Wherein hydrogen gas Volume of Raw materials Volume of Space velocity of 0.7h and 800L/L -1 。
The preparation method of the core-shell catalyst has the beneficial effects that:
the invention firstly utilizes a solvent reduction method to prepare cobalt nano-particles, and then utilizes a post-synthesis method to prepare the cobalt nano-particles which take Co as a core and M as a core x O y -SiO 2 Co @ M being a shell x O y -SiO 2 A core-shell catalyst. The purpose of introducing silica into the shell is to increase the specific surface area of the support, and more lewis acid sites can be obtained by calcination. The purpose of introducing the M oxide is to ensure that the catalyst can form more oxygen vacancies after roasting reduction, which is beneficial to the breaking of C-O bonds and improves the yield of cyclohexanol.
The catalyst has low cost and simple preparation method, and the prepared core-shell catalyst has good stability, can still keep good catalytic activity after a long-time reaction, and obtains cyclohexanol with higher yield in the hydrogenation and deoxidation reaction of guaiacol.
Drawings
Figure 1 is a graph of the conversion of guaiacol over time for two different catalysts.
FIG. 2 shows Co @ CeO catalyst 2 -SiO 2 Transmission electron micrograph (D).
FIG. 3 is catalyst Co @ TiO 2 -SiO 2 Transmission electron micrograph (D).
Detailed Description
The present invention is further described below with reference to examples, but is not limited thereto.
Example 1
A preparation method of a core-shell type catalyst comprises the following steps:
(1) Two portions of a 20mL,0.1mol/L aqueous solution of cetyltrimethylammonium bromide (CTAB) were prepared. Wherein one part contains 6g hydrazine hydrate and one part contains 0.54g Co (NO) 3 ) 2 ·6H 2 O and 1.8mL of 1mol/L NaOH;
(2) Mixing the prepared two CTAB solutions, and sealing for 2h at 80 ℃;
(3) Taking out the product obtained in the step (2), alternately washing the product for 2 to 3 times by using ethanol and deionized water, and carrying out vacuum drying overnight at the temperature of 50 ℃ to obtain 0.11g of Co nanoparticles;
(4) Preparing Co nanoparticles for many times, and dispersing 0.31g of Co nanoparticles in a mixed solution of 80mL of deionized water and 20mL of ethanol;
(5) 1.724g Ce (CH) 3 COO) 3 、8.83g Na 2 SiO 3 ·9H 2 O was dissolved in 50mL of deionized water to obtain 6.5g (NH) 4 ) 2 CO 3 Dissolving in 50mL of deionized water, adding the two into the suspension in the step (4) in a parallel flow manner under the condition of mechanical stirring at 60 ℃, and keeping for 0.5h;
(6) Taking out the precipitate obtained in step (5), filtering, washing to neutral, placing in n-butanol at 50 deg.C, stirring, evaporating to dryness, placing in oven at 100 deg.C for 12 hr, and reducing in hydrogen flow at 400 deg.C for 3 hr before use to obtain Co @ CeO 2 -SiO 2 The core-shell catalyst has an active component Co mass fraction of 10 percent and m CeO2 :m SiO2 ＝1:2。
The core-shell catalyst was used as follows:
in a fixed bed tubular reactor, 0.2g of Co @ CeO was added 2 -SiO 2 (1:2) catalyst, reaction temperature is 220 ℃, reaction pressure is 2MPa, reaction time is 2h, and hydrogen gas Volume of Raw materials Volume of Space velocity of 0.7h and 800L/L -1 And collecting the generated mixed products of cyclohexanol and the like, wherein the conversion rate of the guaiacol is 100%, and the yield of the cyclohexanol is 94.5%. After 480h, the guaiacol conversion was 97.2%.
Example 2
(1) - (3) same as in example 1;
(4) Co nanoparticles are prepared for multiple times, 0.187g of Co is taken, and the rest is the same as that in the example 1 (4);
(5) 1.32g of TiCl 4 、5.30g Na 2 SiO 3 ·9H 2 Dissolving O in 50mL deionized water, and taking 5g of Na 2 CO 3 Dissolving in 50mL of deionized water, adding the two into the suspension in the step (4) in a parallel flow manner under the condition of mechanical stirring at 80 ℃, and keeping for 0.5h;
(6) Taking out the precipitate obtained in step (5), filtering, washing to neutrality, adding into n-butanol, stirring at 50 deg.C, evaporating to dryness, placing in oven at 100 deg.C for 12 hr, and reducing in hydrogen flow at 400 deg.C for 3 hr to obtain Co @ TiO 2 -SiO 2 The core-shell catalyst has an active component Co mass fraction of 10 percent and m TiO2 :m SiO2 ＝1:2。
The core-shell catalyst was used as follows:
in a fixed bed tubular reactor, 0.2g of Co @ TiO is added 2 -SiO 2 (1:2) catalyst, reaction temperature is 220 ℃, reaction pressure is 2MPa, reaction time is 2h, hydrogen Volume of Raw materials Volume of Space velocity of 0.7h and 800L/L -1 And collecting the generated mixed products of cyclohexanol and the like, wherein the conversion rate of the guaiacol is 99.4%, and the yield of the cyclohexanol is 92.3%. After 480h, the guaiacol conversion was 95.8%.
Example 3
(1) - (3) same as in example 1;
(4) Co nanoparticles were prepared several times, taking 0.125g Co, the rest being the same as example (1);
(5) 2.72g of Al (NO) 3 ) 3 ·9H 2 O、3.5g Na 2 SiO 3 ·9H 2 Dissolving O in 50mL deionized water, and taking 5g of Na 2 CO 3 Dissolving in 50mL of deionized water, adding the two into the suspension in the step (4) in a parallel flow manner under the condition of mechanical stirring at 60 ℃, and keeping for 0.5h;
(6) Taking out the precipitate obtained in the step (5), filtering, washing to neutrality, placing in n-butanol at 50 deg.C, stirring, evaporating to dryness, placing in oven at 100 deg.C for 12 hr, and reducing in hydrogen flow at 400 deg.C for 3 hr before use to obtain Co @ Al 2 O 3 -SiO 2 The core-shell catalyst comprises an active component Co with the mass fraction of 10 percent, mAl2O3, mSiO2=1:2.
The core-shell catalyst was used as follows:
in a fixed bed tubular reactor, 0.2g of Co @ Al is added 2 O 3 -SiO 2 (1:2) catalyst, reaction temperature is 220 ℃, reaction pressure is 2MPa, reaction time is 2h, and hydrogen gas Volume of Raw materials Volume of Space velocity of 0.7h and 800L/L -1 And collecting the generated mixed products such as cyclohexanol and the like, wherein the conversion rate of the guaiacol is 95.6%, and the yield of the cyclohexanol is 87.8%. After 480h, the guaiacol conversion was 91.5%.
Example 4
(1) - (3) same as in example 1;
(4) Preparing Co nano particles for many times, taking 0.32g of Co nano particles, and the rest is the same as the example (1);
(5) 1.33g of Ce (CH) 3 COO) 3 、10.22g Na 2 SiO 3 ·9H 2 Dissolving O in 50mL deionized water, and taking 8g of Na 2 CO 3 Dissolving in 50mL of deionized water, adding the two into the suspension in the step (4) in a parallel flow manner under the condition of mechanical stirring at 60 ℃, and keeping for 0.5h;
(6) Taking out the precipitate obtained in step (5), filtering, washing to neutral, placing in n-butanol at 50 deg.C, stirring, evaporating to dryness, placing in oven at 100 deg.C for 12 hr, and reducing in hydrogen flow at 400 deg.C for 3 hr before use to obtain Co @ CeO 2 -SiO 2 The core-shell catalyst has an active component Co mass fraction of 10 percent and m Al2O3 :m SiO2 ＝1:3。
The core-shell catalyst was used as follows:
in a fixed bed tubular reactor, 0.2g of Co @ CeO was added 2 -SiO 2 (1:3) catalyst, reaction temperature is 220 ℃, reaction pressure is 2MPa, reaction time is 2h, and hydrogen gas Volume of Raw material Volume of Space velocity of 0.7h and 800L/L -1 And collecting the generated mixed products of cyclohexanol and the like, wherein the conversion rate of the guaiacol is 99.1%, and the yield of the cyclohexanol is 92.9%.
Example 5
(1) - (3) same as example 1;
(4) Preparing Co nano particles for many times, taking 0.25g of Co nano particles, and the rest is the same as the example (1);
(5) 1.32g of TiCl 4 、7.95g Na 2 SiO 3 ·9H 2 Dissolving O in 50mL deionized water, and taking 6g of Na 2 CO 3 Dissolving in 50mL of deionized water, adding the two into the suspension in the step (4) in a parallel flow manner under the condition of mechanical stirring at 80 ℃, and keeping for 0.5h;
(6) Taking out the precipitate obtained in the step (5), filtering, washing to neutrality, placing in n-butanol, stirring at 50 deg.C, evaporating to dryness, placing in oven at 100 deg.C for 12 hr, and reducing the catalyst in hydrogen flow at 400 deg.C before use3h, co @ TiO obtained 2 -SiO 2 The core-shell catalyst has an active component Co mass fraction of 10 percent and m TiO2 :m SiO2 ＝1:3。
The core-shell catalyst was used as follows:
in a fixed bed tubular reactor, 0.2g of Co @ TiO is added 2 -SiO 2 (1:3) catalyst, reaction temperature is 220 ℃, reaction pressure is 2MPa, reaction time is 2h, hydrogen Volume of Raw materials Volume of Space velocity of 0.7h and 800L/L -1 And collecting the generated mixed products such as cyclohexanol and the like, wherein the conversion rate of the guaiacol is 98.5%, and the yield of the cyclohexanol is 91.8%.
Example 6
(1) - (3) same as in example 1;
(4) Co nanoparticles were prepared several times, and 0.164g of Co nanoparticles was collected, and the remainder was the same as in example (1)
(5) 2.72g of Al (NO) 3 ) 3 ·9H 2 O、5.25g Na 2 SiO 3 ·9H 2 Dissolving O in 50mL deionized water, and taking 5g of Na 2 CO 3 Dissolving in 50mL of deionized water, adding the two into the suspension obtained in the step (4) together in a concurrent flow manner under the condition of mechanical stirring at 60 ℃, and keeping for 0.5h;
(6) Taking out the precipitate obtained in the step (5), filtering, washing to neutrality, placing in n-butanol at 50 deg.C, stirring, evaporating to dryness, placing in oven at 100 deg.C for 12 hr, and reducing in hydrogen flow at 400 deg.C for 3 hr before use to obtain Co @ Al 2 O 3 -SiO 2 The core-shell catalyst has an active component Co mass fraction of 10 percent and m Al2O3 :m SiO2 ＝1:3。
The application of the core-shell type catalyst is as follows:
in a fixed bed tubular reactor, 0.2g of Co @ Al is added 2 O 3 -SiO 2 (1:3) catalyst, reaction temperature is 220 ℃, reaction pressure is 2MPa, reaction time is 2h, and hydrogen gas Volume of Raw materials Volume of Space velocity of 0.7h and 800L/L -1 And collecting the generated mixed products of cyclohexanol and the like, wherein the conversion rate of the guaiacol is 94.7%, and the yield of the cyclohexanol is 86.7%.
Example 7
(1) - (6) same as in example 1.
The core-shell catalyst was used as follows:
in a fixed bed tubular reactor, 0.2g of Co @ CeO was added 2 -SiO 2 (1:2) catalyst, reaction temperature of 220 ℃, reaction pressure of 2MPa, reaction time of 4h, hydrogen Volume of Raw material Volume of Space velocity of 0.7h and 800L/L -1 And collecting the generated mixed products such as cyclohexanol and the like, wherein the conversion rate of the guaiacol is 100%, and the yield of the cyclohexanol is 95.7%.
Example 8
(1) - (6) same as in example 2.
The core-shell catalyst was used as follows:
in a fixed bed tubular reactor, 0.2g of Co @ TiO was added 2 -SiO 2 (1:2) catalyst, reaction temperature is 220 ℃, reaction pressure is 2MPa, reaction time is 2h, hydrogen Volume of Raw materials Volume of Space velocity of 0.7h and 800L/L -1 And collecting the generated mixed products of cyclohexanol and the like, wherein the conversion rate of the guaiacol is 99.5%, and the yield of the cyclohexanol is 92.3%.
Example 9
(1) - (6) same as in example 3;
the core-shell catalyst was used as follows:
in a fixed bed tubular reactor, 0.2g of Co @ Al is added 2 O 3 -SiO 2 (1:2) catalyst, reaction temperature is 220 ℃, reaction pressure is 2MPa, reaction time is 2h, and hydrogen gas Volume of Raw materials Volume of Space velocity of 0.7h and 800L/L -1 And collecting the generated mixed products of cyclohexanol and the like, wherein the conversion rate of the guaiacol is 96.3%, and the yield of the cyclohexanol is 88.9%.
Comparative example 1
(1) - (4) same as in example 1;
(5) No Na addition 2 SiO 3 ·9H 2 O，Ce(CH 3 COO) 3 Mass 5.16g (NH) 4 ) 2 CO 3 The mass is 3g, and the rest is carried outExample 1;
(6) Co @ CeO was prepared as in example 1 2 A core-shell catalyst.
The core-shell catalyst was used as follows:
in a fixed bed tubular reactor, 0.2g of Co @ CeO was added 2 Catalyst, reaction temperature is 220 ℃, reaction pressure is 2MPa, reaction time is 2h, and hydrogen is used Volume of Raw materials Volume of Space velocity of 0.7h and 800L/L -1 And collecting the generated mixed products of cyclohexanol and the like, wherein the conversion rate of the guaiacol is 97.8%, and the yield of the cyclohexanol is 90.9%.
Comparative example 2
(1) - (4) same as in example 1;
(5) No addition of Ce (CH) 3 COO) 3 ，Na 2 SiO 3 ·9H 2 The mass of O is 13.25g 2 CO 3 Mass 6.5g, the rest being as in example 1;
(6) Co @ SiO was prepared as in example 3 2 A core-shell catalyst.
The core-shell catalyst was used as follows:
in a fixed bed tubular reactor, 0.2g of Co @ SiO is added 2 Catalyst, reaction temperature is 220 ℃, reaction pressure is 2MPa, reaction time is 2h, and hydrogen is used Volume of Raw materials Volume of Space velocity of 0.7h and 800L/L -1 And collecting the generated mixed products such as cyclohexanol, wherein the conversion rate of the guaiacol is 93.7%, and the yield of the cyclohexanol is 85.6%.
Comparative example 3
(1) 1.724g Ce (CH) 3 COO) 3 、8.83g Na 2 SiO 3 ·9H 2 O was dissolved in 50mL of deionized water to obtain 6.5g (NH) 4 ) 2 CO 3 Dissolving in 50ml deionized water to prepare a solution;
(2) Under the condition of stirring at 60 ℃, dropwise adding the two into 100mL of deionized water at the same time, and stirring for 0.5h;
(3) Taking out the product obtained in the step (2) for filtration and washing until the product is neutral;
(4) Dispersing the precipitate obtained in step (3) into 100mL of n-butanol at 50 deg.CStirring and evaporating to dryness, placing in an oven for drying overnight at 100 ℃, and preparing to obtain CeO 2 -SiO 2 (1:2) a carrier;
(2) Weighing 1.53g Co (NO) 3 ) 2 ·6H 2 O, prepared into an equal volume of solution to be impregnated into CeO 2 -SiO 2 In a carrier, and then dried at 100 ℃;
(3) The catalyst was calcined at 400 ℃ for 3h, followed by reduction in a hydrogen stream for 3h, to prepare 10% Co/CeO 2 -SiO 2 (1:2) catalyst.
The application of the catalyst is as follows:
in a fixed bed tubular reactor, 0.2g of Co/CeO was added 2 -SiO 2 (1:2) catalyst, reaction temperature of 220 ℃, reaction pressure of 2MPa, reaction time of 2.5h, hydrogen Volume of Raw material Volume of =800L/L and airspeed of 0.7h -1 And collecting the generated mixed products of cyclohexanol and the like, wherein the conversion rate of the guaiacol is 99.3%, and the yield of the cyclohexanol is 93.6%. After 480h, the guaiacol conversion was 85.5%.
Table 1 shows cyclohexanol yield data over 220 ℃ catalyst.
Figure BDA0002680790750000101

Claims (3)

1. A preparation method of a core-shell catalyst for preparing cyclohexanol by hydrogenation and deoxidation of guaiacol is characterized by comprising the following steps:
(1) Preparing two parts of hexadecyl trimethyl ammonium bromide aqueous solution with the same volume; one part of the hydrazine hydrate and the other part of the hydrazine hydrate contain metered cobalt source precursor and sodium hydroxide solution;
the cobalt source precursor is Co (NO) 3 ) 2 ·6H 2 O, the concentration of the sodium hydroxide solution is 1mol/L, and the concentration of cetyl trimethyl ammonium bromide in the solution is 0.1mol/L;
(2) Mixing two parts of the hexadecyl trimethyl ammonium bromide solution prepared in the step (1), and mechanically stirring for 1-2h at 80 ℃;
(3) Taking out the product obtained in the step (2), alternately washing 2~3 times by using ethanol and deionized water, and carrying out vacuum drying overnight at 50 ℃ to obtain Co nanoparticles;
(4) Dispersing the Co nano particles obtained in the step (3) in a mixed solution of deionized water and ethanol to obtain a suspension;
(5) Preparing a metal carrier precursor and a silicon source precursor into a mixed solution, and under the condition of mechanical stirring at 60-80 ℃, adding the mixed solution and an alkali solution into the suspension in the step (4) in a parallel flow manner, and keeping the mixed solution for 0.5h;
the metal carrier precursor is nitrate, acetate or chloride of metal M, wherein M = Ce, ti and Al; the precursor of the silicon source is Na 2 SiO 3 ·9H 2 O；
The alkali solution is (NH) 4 ) 2 CO 3 Solution, na 2 CO 3 One of the solutions;
(6) Taking out the precipitate obtained in the step (5), filtering, washing to neutrality, placing in n-butanol at 50 deg.C, stirring, evaporating to dryness, placing in oven at 100 deg.C for 12 hr, and reducing in hydrogen gas flow before use to obtain Co @ M x O y -SiO 2 A core-shell catalyst;
the reduction temperature is 400 to 450 ℃, and the reduction time is 3 to 4 hours;
in the preparation of Co @ M x O y -SiO 2 In the core-shell type catalyst, the mass fraction of Co is 10%, M x O y :SiO 2 The mass ratio of (A) to (B) is 1.
2. Use of a core-shell catalyst prepared according to claim 1, wherein the catalyst is introduced into a fixed bed tubular reactor, followed by feeding the guaiacol feedstock and hydrogen gas as formulated, and collecting the resulting product.
3. The use of the core-shell catalyst according to claim 2, wherein the amount of the catalyst used is 0.2 to 0.4g, and the hydrogen is used in the amount of the catalyst Volume of Raw materials Volume of =800L/L and space velocity of 0.7h -1 The reaction temperature is 160 to 220 ℃, the reaction pressure is 2MPa, and the reaction time is 2 to 4h.
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