CN115382556B - Cu-Ru bimetal doped titanium-silicon metal composite oxide catalyst and application thereof in catalytic hydrogenation of triacetonamine - Google Patents

Cu-Ru bimetal doped titanium-silicon metal composite oxide catalyst and application thereof in catalytic hydrogenation of triacetonamine Download PDF

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CN115382556B
CN115382556B CN202211208409.3A CN202211208409A CN115382556B CN 115382556 B CN115382556 B CN 115382556B CN 202211208409 A CN202211208409 A CN 202211208409A CN 115382556 B CN115382556 B CN 115382556B
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triacetonamine
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ruthenium
copper
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CN115382556A (en
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唐天地
刘宬宏
傅雯倩
刘长俊
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Changzhou University
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    • 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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8926—Copper and noble metals
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/617—500-1000 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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    • B01J35/633—Pore volume less than 0.5 ml/g
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D211/40—Oxygen atoms
    • C07D211/44—Oxygen atoms attached in position 4
    • C07D211/46—Oxygen atoms attached in position 4 having a hydrogen atom as the second substituent in position 4
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
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    • Y02P20/584—Recycling of catalysts

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Abstract

The invention belongs to the technical field of catalytic hydrogenation of triacetonamine, and discloses a Cu-Ru bimetal doped titanium-silicon metal composite oxide catalyst and application thereof in catalytic hydrogenation of triacetonamine. The invention prepares the Cu-Ru bimetallic doped titanium silicon metal composite oxide (Cu-Ru/TiSiO) x ) The catalyst is used for synthesizing tetramethyl piperidinol by hydrogenation reduction of triacetonamine, can perform high-yield synthesis at low temperature, simultaneously inhibit hydrogenation of amine in triacetonamine molecules, prevent C-N bond from breaking, avoid byproduct generation, and improve reaction yield. The catalyst prepared by the method has mild preparation conditions, is simple to operate, accords with the aim of green chemistry, has large specific surface area and strong hydrogenation reduction capability, and has obviously improved service life and reactivity in the reaction of preparing tetramethyl piperidinol by triacetonamine.

Description

Cu-Ru bimetal doped titanium-silicon metal composite oxide catalyst and application thereof in catalytic hydrogenation of triacetonamine
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a Cu-Ru bimetal doped titanium silicon oxide catalyst and a method for synthesizing tetramethyl piperidinol by high-efficiency catalytic hydrogenation reduction of triacetonamine.
Background
Hindered Amine Light Stabilizers (HALS) are aids that inhibit or slow the degradation of polymeric materials due to photooxidation, which do not color resins, are low-toxic or nontoxic, and can meet the requirements of film products, fiber products and food packaging materials, so HALS have been a research hotspot in the field of polymer stabilization aids since the 70 th century. 2, 6-tetramethyl piperidinol (piperidinol for short) is a key intermediate for preparing various HALS with excellent performance, and the effect of the key intermediate is multiple times that of the traditional stabilizer, so that the efficient synthesis of the piperidinol has important significance.
At present, the current time of the process,the synthesis of the piperidinol mainly takes the triacetonamine as a raw material and is prepared by methods such as an autoclave hydrogenation method, a chemical reduction method, an electrochemical reduction method, a fixed bed hydrogenation method and the like, wherein the fixed bed hydrogenation method has a far development prospect due to the characteristics of continuous feed production, green and safe performance and simple operation. However, the current report on the catalyst used for preparing piperidinol by the fixed bed hydrogenation method of triacetonamine is single, and most of the report is through gamma-Al 2 O 3 The catalyst has short service life, high reaction energy consumption and poor catalytic activity, deamination easily occurs in the hydrogenation process of the triacetonamine, and firstly, carbon-nitrogen bonds are weakened due to the fact that N-H forms bonds with two tertiary carbon atoms, and the carbon-nitrogen bonds are easily broken when the reaction temperature is high. Secondly, when the acid center of the carrier is stronger, the carrier is easy to adsorb triacetonamine molecules, so that the C-N bond is broken by the catalyst with stronger reducibility. Therefore, in the triacetonamine hydrogenation reaction, the reaction process is complex, more hydrogenation catalysts can generate C=O bond hydrogenation to become C-OH, N hydrogenation can also generate N-C bond rupture to generate a series of side reactions, and the yield is difficult to improve. These problems have prompted the search for alternative catalysts with high selectivity combined with improved long term stability.
Disclosure of Invention
In order to solve the problems in the background technology, the invention takes nano rutile as a titanium source and water glass as a silicon source to prepare the titanium-silicon metal composite oxide with high specific surface area, adopts the titanium-silicon metal composite oxide as a carrier to load copper-ruthenium bimetallic, and prepares Cu-Ru/TiSiO x The catalyst is used for synthesizing tetramethyl piperidinol by the hydrogenation reduction of triacetonamine, and the tetramethyl piperidinol can be synthesized in high yield at low temperature.
The preparation method of the Cu-Ru supported bimetallic hydrogenation catalyst comprises the following steps:
weighing potassium hydroxide at room temperature, uniformly mixing with quantitative deionized water, adding into water glass, adding nano rutile powder into the water glass under the stirring condition, adding copper and ruthenium metal mixed solution, uniformly stirring to obtain gel precursor, and transferring into a polytetrafluoroethylene lining reaction kettle for static hydrothermal reaction (the hydrothermal condition is 210 ℃ and 48 h). And then washing and filtering the obtained solid, drying the solid in an oven at 110 ℃ overnight, and finally gradually heating and calcining the solid in a muffle furnace to obtain the target catalyst.
As an improvement of the invention, the gel system mole ratio is TiO 2 :SiO 2 :K 2 O:H 2 O, cu, ru=1:8:1-2:120-200:0.04-0.6:0.0005-0.03. Preferably the gel system has a molar ratio of TiO 2 :SiO 2 :K 2 O:H 2 O:Cu:Ru＝1:8:1.2～1.7:165.3～185.6:0.085～0.42:0.0054～0.016。
As an improvement of the invention, the calcination temperature in the preparation of the catalyst is 300-600 ℃ and the calcination time is 2-10 h. Preferably, the calcination temperature is 450-550 ℃ and the calcination time is 4-6 h in the preparation method.
As an improvement of the invention, the mass fractions of copper and ruthenium in the catalyst are respectively 0.5-7 wt.% and 0.01-0.5 wt.%. Preferably, the mass fractions of copper and ruthenium in the catalyst are respectively 1-5 wt.% and 0.1-0.3 wt.%.
As an improvement of the invention, the catalyst is required to be pressed into tablets and sieved to finally collect particles with 40-60 meshes.
The catalyst is used for catalyzing the reaction of preparing piperidinol by the hydrogenation of triacetonamine, and the application method comprises the following steps: weighing catalyst, filling it in fixed bed microreactor, and adding it in H 2 Reducing for 3-5 h at 200-220 ℃ under the atmosphere, reducing the temperature to the reaction temperature after the activation is completed, inputting the reaction liquid through a flow pump under the hydrogen condition, and analyzing the collected product liquid by adopting a gas chromatography after the reaction system is stable.
Wherein the dosage of the catalyst is 0.5-1.5 g; the reaction solution is a mixed solution of triacetonamine and isopropanol (the molar ratio is 1:3-10); the flow rate of the raw material liquid is 12mL/h; the reaction temperature is 60-80 ℃; the total pressure is 1MPa; the hydrogen flow is 0.5-2L/h.
The beneficial effects are that: the titanium-silicon metal composite oxide prepared by the hydrothermal synthesis method is an amorphous carrier, almost has no acid sites, and is beneficial to improving the selectivity of the target product tetramethyl piperidinol; the distribution of a small amount of active components is uniform, the binding force between the carrier and the active components is strong, and the titanium-silicon metal composite oxide serving as the carrier has larger specific surface area and pore volume, more active centers and stronger adsorption and mass transfer capacity, so that the thermal stability and the service life of the catalyst are obviously improved, and the reaction temperature and the use amount of metal are reduced.
Drawings
FIG. 1 is a scanning electron microscope image of the catalyst obtained in example 1.
Detailed Description
The invention is further described below in connection with examples, but is not limited thereto.
Example 1
(1) 20.636g of water glass are weighed and stirred in a 150mL beaker, followed by the addition of potassium hydroxide solution (2.110 g KOH+20g H) 2 O) stirring for 30min in the beaker, adding 0.8848g of TiO after the system is uniformly stirred 2 After stirring for 1h, a mixed metal salt solution (0.6843 g of copper nitrate trihydrate and 0.03764g of ruthenium nitrate are dissolved in 2g of deionized water; the mass fractions of copper and ruthenium in the catalyst are respectively 3wt.% and 0.2 wt.%) is added, and after stirring for 1h, the mixture is put into a 100mL polytetrafluoroethylene lining kettle for static hydrothermal reaction at 210 ℃ for 48 h. Washing and suction filtering, drying the obtained solid in an oven at 110 ℃ overnight, calcining at 500 ℃ for 5 hours, tabletting and forming by using a self-made tablet press, and sieving to obtain 40-60 mesh particle species to obtain the corresponding catalyst.
(2) Hydrogenation reduction of triacetonamine: weighing 1.0g of the catalyst and 1.0g of 40-60 mesh quartz sand, uniformly mixing, filling into a fixed bed reactor, and adding into H 2 Reducing for 5h at 220 ℃ in atmosphere, cooling to 70 ℃ at a hydrogen flow rate of 1L/h and a reaction pressure of 1MPa, adding a mixture of reactants (isopropanol triacetonamine molar ratio of 3:1) into a reactor at a flow rate of 12mL/h, and starting the reaction, wherein the contact time of the reactants and the catalyst is 2 seconds. After the reaction is stable, the reaction product is collected and analyzed by gas chromatography, and the product yield is 98.6% after continuous operation for 360 hours.
Example 2
The procedure of example 1 was repeated except that 2.110g of KOH in step (1) was changed to 1.489g of KOH. After the reaction is stable, the reaction product is collected and analyzed by gas chromatography, and the product yield is 97.6% after continuous operation for 360 hours.
Example 3
The procedure of example 1 was repeated except that the calcination temperature in step (1) was changed to 450 ℃. After the reaction is stable, the reaction product is collected and analyzed by gas chromatography, and the product yield is 97.3% after continuous operation for 360 hours.
Example 4
The procedure of example 1 was repeated except that the calcination temperature in step (1) was changed to 550 ℃. After the reaction is stable, the reaction product is collected and analyzed by gas chromatography, and the product yield is 97.5% after continuous operation for 360 hours.
Example 5
The procedure of example 1 was repeated except that the calcination time in step (1) was changed to 4 hours. After the reaction is stable, the reaction product is collected and analyzed by gas chromatography, and the product yield is 97.1% after continuous operation for 360 hours.
Example 6
0.6843g of copper nitrate trihydrate in the step (1) is changed to 1.1405g of copper nitrate trihydrate, and the mass fractions of copper and ruthenium in the catalyst are 5wt.% and 0.2wt.%, respectively, and the other operations are the same as in the example 1. After the reaction is stable, the reaction product is collected and analyzed by gas chromatography, and the product yield is 98.9% after continuous operation for 360 hours.
Example 7
0.6843g of copper nitrate trihydrate in the step (1) is changed to 0.2281g of copper nitrate trihydrate, and the mass fractions of copper and ruthenium in the catalyst are respectively 1wt.% and 0.2wt.%, and the other operations are the same as in the example 1. After the reaction is stable, the reaction product is collected and analyzed by gas chromatography, and the product yield is 96.3% after continuous operation for 360 hours.
Example 8
0.03764g of ruthenium nitrate in the step (1) is changed to 0.01882g of ruthenium nitrate, and the mass fractions of copper and ruthenium in the catalyst are 3wt.% and 0.1wt.%, respectively, and the other operations are the same as in example 1. The reaction product was collected and analyzed by gas chromatography, and the product yield was 97.1% by continuous operation for 360 hours.
Example 9
0.03764g of ruthenium nitrate in the step (1) is changed to 0.05646g of ruthenium nitrate, and the mass fractions of copper and ruthenium in the catalyst are 3wt.% and 0.3wt.%, respectively, and the other operations are the same as in example 1. After the reaction is stable, the reaction product is collected and analyzed by gas chromatography, and the product yield is 99.0% after continuous operation for 360 hours.
Example 10
The procedure of example 1 was repeated except that 1g of the catalyst in step (2) was changed to 0.5g of the catalyst. After the reaction is stable, the reaction product is collected and analyzed by gas chromatography, and the product yield is 97.1% after continuous operation for 360 hours.
Example 11
The procedure of example 1 was repeated except that 1g of the catalyst in step (2) was changed to 1.5g of the catalyst. After the reaction is stable, the reaction product is collected and analyzed by gas chromatography, and the product yield is 98.8% after continuous operation for 360 hours.
Example 12
The procedure of example 1 was followed except that the molar ratio of isopropyl alcohol to triacetonamine in the reactant mixture in step (2) was changed to 6:1. After the reaction is stable, the reaction product is collected and analyzed by gas chromatography, and the product yield is 99.1% after continuous operation for 360 hours.
Example 13
The procedure of example 1 was repeated except that the reaction temperature in step (3) was changed to 70℃and 60 ℃. After the reaction was stabilized, the reaction product was collected and analyzed by gas chromatography, and the product yield was 97.0% by continuous operation for 360 hours.
Comparative example 1
(1) And (3) preparing a catalyst: preparing Cu-Ru/gamma-Al by adopting isovolumetric impregnation method 2 O 3 Firstly, preparing copper and ruthenium metal precursor impregnating solution (0.2316 g of copper nitrate trihydrate and 0.012g of ruthenium nitrate are dissolved in 0.651g of deionized water), taking 2g of gamma-Al sold in the market 2 O 3 Soaking the sample in equal volume, standing at room temperature, drying for 12h, drying overnight in a 110 ℃ oven, calcining at 450 ℃ for 5h, tabletting by a self-made tabletting machine, and sieving to obtain 40-60 mesh particle species to obtain corresponding Cu-Ru/gamma-Al 2 O 3 The mass fractions of copper and ruthenium in the catalyst are 3wt.% and 0 respectively.2wt.％。
(2) Hydrogenation reduction of triacetonamine: 1g of the Cu-Ru/gamma-Al is weighed 2 O 3 Uniformly mixing catalyst and 1g of quartz sand with 40-60 meshes, filling the mixture into a fixed bed reactor, and filling the mixture into H 2 Reducing for 5h at 220 ℃ in atmosphere, cooling to 70 ℃ at a hydrogen flow rate of 1L/h and a reaction pressure of 1MPa, adding a mixture of reactants (isopropanol triacetonamine molar ratio of 3:1) into a reactor at a flow rate of 12mL/h, and starting the reaction, wherein the contact time of the reactants and the catalyst is 2 seconds. After the reaction is stable, collecting reaction products, analyzing the reaction products by gas chromatography, wherein the yield of the tetramethyl piperidinol is extremely low<5％)。
Comparative example 2
Changing the reaction temperature in the step (2) to 120 ℃ and the reaction pressure to 3MPa, and other operations are the same as in the comparative example 1, collecting reaction products after the reaction is stable, analyzing the reaction products by gas chromatography, and continuously running for 360 hours, wherein the product yield is 38.4 percent
Comparative example 3
(1) And (3) preparing a catalyst: preparing Cu-Ru/SiO by adopting isovolumetric impregnation method 2 Firstly preparing copper and ruthenium metal precursor impregnating solution (0.2316 g of copper nitrate trihydrate and 0.012g of ruthenium nitrate are dissolved in 0.32g of deionized water), taking 2g of commercial nano silicon dioxide powder for isovolumetric impregnation, standing and drying for 12h at room temperature, drying overnight in a 110 ℃ oven, calcining for 5h at 450 ℃, tabletting by a self-made tablet press, and sieving to obtain 40-60 meshes of particles to obtain corresponding Cu-Ru/SiO 2 The mass fractions of copper and ruthenium in the catalyst are 3wt.% and 0.2wt.%, respectively.
(2) Hydrogenation reduction of triacetonamine: weighing 1.0g of the catalyst and 1.0g of 40-60 mesh quartz sand, uniformly mixing, filling into a fixed bed reactor, and adding into H 2 Reducing for 5h at 220 ℃ in atmosphere, cooling to 70 ℃ at a hydrogen flow rate of 1L/h and a reaction pressure of 1MPa, adding a mixture of reactants (isopropanol triacetonamine molar ratio of 3:1) into a reactor at a flow rate of 12mL/h, and starting the reaction, wherein the contact time of the reactants and the catalyst is 2 seconds. After the reaction is stable, the reaction product is collected and analyzed by gas chromatography, and the product yield is 13 after continuous operation for 360 hours.2％。
Comparative example 4
(1) And (3) preparing a catalyst: preparing Cu-Ru/TiO by adopting isovolumetric impregnation method 2 Firstly preparing copper and ruthenium metal precursor impregnating solution (0.2316 g of copper nitrate trihydrate and 0.012g of ruthenium nitrate are dissolved in 0.32g of deionized water), taking 2g of commercial titanium dioxide (rutile) powder for isovolumetric impregnation, standing and drying at room temperature for 12h, drying overnight in a 110 ℃ oven, calcining at 450 ℃ for 5h, tabletting by a self-made tablet press, and sieving to obtain 40-60 meshes of particles to obtain corresponding Cu-Ru/TiO 2 The mass fractions of copper and ruthenium in the catalyst are 3wt.% and 0.2wt.%, respectively.
(2) Hydrogenation reduction of triacetonamine: weighing 1.0g of the catalyst and 1.0g of 40-60 mesh quartz sand, uniformly mixing, filling into a fixed bed reactor, and adding into H 2 Reducing for 5h at 220 ℃ in atmosphere, cooling to 70 ℃ at a hydrogen flow rate of 1L/h and a reaction pressure of 1MPa, adding a mixture of reactants (isopropanol triacetonamine molar ratio of 3:1) into a reactor at a flow rate of 12mL/h, and starting the reaction, wherein the contact time of the reactants and the catalyst is 2 seconds. After the reaction is stable, the reaction product is collected and analyzed by gas chromatography, and the product yield is 15.6% after continuous operation for 360 hours.
Comparative example 5
(1) When the titanium-silicon ratio is increased, the titanium-silicon ratio is in direct proportion to the number of acid sites and the acid strength of the synthesized titanium-silicon composite metal oxide in a certain range. A composite metal oxide having a high titanium to silicon ratio of 0.25 was prepared. 20.672g of water glass was weighed into a 150mL beaker and stirred, followed by the addition of potassium hydroxide solution (2.5054g KOH+20g H 2 O) stirring for 30min in the beaker, adding 1.7696g of TiO after the system is uniformly stirred 2 After stirring for 1h, a mixed metal salt solution (0.7849 g of copper nitrate trihydrate, 0.04317g of ruthenium nitrate dissolved in 2.3g of deionized water) was added, stirred for 1h, and then the mixture was placed in a 100mL polytetrafluoroethylene liner kettle for a static hydrothermal reaction at 210℃for 48 h. Washing, suction filtering, drying the obtained solid in a 110 ℃ oven overnight, calcining at 500 ℃ for 5 hours, tabletting and forming by using a self-made tablet press, and sieving to obtain 40-60 mesh particle species to obtain the corresponding catalystThe mass fractions of copper and ruthenium in the catalyst are 3wt.% and 0.2wt.%, respectively.
(2) Hydrogenation reduction of triacetonamine: 1g of the Cu-Ru/TiSiO is weighed x Uniformly mixing catalyst and 1g of quartz sand with 40-60 meshes, filling the mixture into a fixed bed reactor, and filling the mixture into H 2 Reducing for 5h at 220 ℃ in atmosphere, cooling to 70 ℃ at a hydrogen flow rate of 1L/h and a reaction pressure of 1MPa, adding a mixture of reactants (isopropanol triacetonamine molar ratio of 3:1) into a reactor at a flow rate of 12mL/h, and starting the reaction, wherein the contact time of the reactants and the catalyst is 2 seconds. After the reaction was stabilized, the reaction product was collected and analyzed by gas chromatography, and the product yield was 58.4% by continuous operation for 360 hours.
Table one: comparison of texture Property parameters of example catalysts and comparative example catalysts
The bimetallic Cu-Ru/TiSiO prepared by the invention x The catalyst overcomes the defects of small specific surface area, low thermal stability, low activity and the like of the catalyst such as Raney nickel and the like. The catalyst has higher specific surface area and pore volume, more active centers and stronger adsorption and mass transfer capacity, and obviously improves the thermal stability and service life of the catalyst. Improves the conversion rate of the triacetonamine and the selectivity of the tetramethyl piperidinol.

Claims (8)

1. The application of the Cu-Ru bimetal doped titanium-silicon metal composite oxide catalyst in preparing tetramethyl piperidinol by catalyzing triacetonamine hydrogenation is characterized in that the preparation method of the Cu-Ru bimetal doped titanium-silicon metal composite oxide catalyst is as follows:
weighing potassium hydroxide at room temperature, uniformly mixing with quantitative deionized water, adding into water glass, adding nano rutile powder under stirring, adding copper and ruthenium metal salt mixed solution, uniformly stirring to obtain a catalyst precursor, transferring the catalyst precursor into a reaction kettle for static hydrothermal reaction, and performing suction filtration and washing after the reaction to obtain a solidDrying and calcining the body to obtain the catalyst Cu-Ru/TiSiO x ；
Molar ratio of the respective components in the catalyst precursor TiO 2 :SiO 2 :K 2 O:H 2 O:Cu:Ru=1:8:1~2:120~200:0.04~0.6:0.0005~0.03。
2. The use according to claim 1, wherein the molar ratio of the respective constituents of the catalyst precursor TiO 2 :SiO 2 :K 2 O:H 2 O:Cu:Ru=1:8:1.2~1.7:165.3~185.6:0.085~0.42:0.0054~0.016。
3. The use according to claim 1, wherein the catalyst is prepared at a calcination temperature of 300-600 ℃ for a calcination time of 2-10 hours.
4. The use according to claim 1, wherein the copper source and the ruthenium source in the copper and ruthenium metal mixed solution are respectively from copper nitrate trihydrate and ruthenium nitrate, and the mass fraction of copper and ruthenium in the catalyst is respectively 0.5-7 wt.% and 0.01-0.5 wt.%.
5. The use according to claim 1, wherein the mass fraction of copper and ruthenium in the catalyst is 1-5 wt.%, 0.1-0.3 wt.%, respectively.
6. The use according to claim 1, wherein the catalyst is subjected to tabletting and sieving to finally collect particles of 40-60 meshes.
7. The application according to claim 1, wherein the application method is: weighing catalyst, filling it in fixed bed microreactor, and adding it in H 2 And (3) carrying out high-temperature reduction under the atmosphere, after the activation is completed, reducing the temperature to the reaction temperature, inputting a raw material liquid of triacetonamine and isopropanol through a flow pump, and carrying out gas chromatographic analysis after the reaction system is stable.
8. The use according to claim 7, wherein the catalyst is used in an amount of 0.5 to 1.5g; the mol ratio of the triacetonamine to the isopropanol in the raw material liquid is 1:3-10; the flow rate of the raw material liquid is 12mL/h; the reaction temperature is 60-80 ℃; the total pressure is 1MPa; the hydrogen flow is 0.5-2L/h.
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