CN107519867B - Preparation method of ruthenium-supported titanium dioxide catalyst for synthesizing cis-pinane by selective hydrogenation of α -pinene - Google Patents
Preparation method of ruthenium-supported titanium dioxide catalyst for synthesizing cis-pinane by selective hydrogenation of α -pinene Download PDFInfo
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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Abstract
The invention discloses a preparation method of ruthenium-supported titanium dioxide catalyst for synthesizing cis-pinane by selective hydrogenation of α -pinene, which comprises the steps of hydrolyzing isopropyl titanate serving as a precursor under the action of acetic acid, nitric acid, sulfuric acid, hydrochloric acid and hydrofluoric acid, preparing uniformly dispersed nano titanium dioxide particles by a hydrothermal method, and preparing ruthenium-supported nano titanium dioxide catalyst Ru/TiO by a chemical reduction method2According to the mass ratio of the catalyst to α -pinene of 0.1-1: 100, α -pinene and Ru/TiO are added2Adding into a polytetrafluoroethylene reaction kettle, wherein Ru and TiO2The mass ratio of (A) to (B) is 5: 100; the catalyst has the advantages of high conversion rate and cis-pinane selectivity, no need of adding an auxiliary agent, environmental friendliness, capability of degrading harmful pollutants and the like.
Description
Technical Field
The invention relates to a preparation method of a ruthenium-loaded titanium dioxide catalyst for synthesizing cis-pinane by selective hydrogenation of α -pinene, and also relates to a method for synthesizing cis-pinane by selective hydrogenation of α -pinene by using the ruthenium-loaded titanium dioxide catalyst, belonging to the technical field of catalysts.
Background
α -pinene is the main component of turpentine and can be used for preparing pinane by catalytic hydrogenation reaction, wherein, cis-pinane is an important chemical raw material intermediate for synthesizing dihydromyrcenol, linalool and other spices, and is also an important intermediate for producing vitamin A and E, therefore, the preparation of high-content cis-pinane by hydrogenation of α -pinene has very important significance.
Until now, researchers at home and abroad have developed a series of catalysts for preparing cis-pinane by catalytic hydrogenation of α -pinene, mainly comprising homogeneous and heterogeneous catalysts such as noble metals, non-noble metals and the like, some researchers have made some progress in preparing cis-pinane by using the characteristic of low price of nickel catalysts, and patent CN104001515A discloses a preparation method of a supported nickel catalyst, and the technology prepares Ni/TiO by roasting, hydrogen reduction and other methods2-Al2O3The catalyst, α -pinene conversion rate is 89.73%, cis-pinane selectivity is 96.48%, it is not hard to see, although nickel catalyst cost is lower, low conversion rate and selectivity are still bottle necks restricting its development, at present, noble metal catalyst and its modification research are still important for research because of its high conversion rate and selectivity, patent CN105481633A discloses a method for preparing cis-pinane by catalyzing α -pinene selective hydrogenation, said technology prepares M-SiO of supported noble metal Ru2The conversion rate of α -pinene is 99.4% and the selectivity of cis-pinene is 96.3% in the presence of APTES-Ru catalyst, and CN105566027A discloses a method for preparing cis-pinene by catalyzing α -pinene hydrogenation at normal temperature and pressure, wherein polyethylene glycol 1000 vitamin E succinate (TPGS) is used in the method-1000) the ruthenium nano particle water micelle prepared stably reacts for 6h under the conditions of normal temperature (25 ℃) and normal pressure (0.1MPa), the conversion rate of α -pinene can reach 99.9%, and the selectivity of cis-pinane is 99.1%.
Disclosure of Invention
The invention aims to provide a novel nano catalyst which is environment-friendly and has excellent catalytic performance and high conversion rate and selectivity for synthesizing cis-pinane by hydrogenating α -pinene, thereby providing a preparation method of a ruthenium-loaded titanium dioxide catalyst for synthesizing the cis-pinane by selectively hydrogenating α -pinene and a method for synthesizing the cis-pinane by selectively hydrogenating α -pinene by using the ruthenium-loaded titanium dioxide catalyst,
the invention is realized by the following technical scheme. According to the invention, isopropyl titanate is used as a precursor, hydrolysis is carried out under the action of acetic acid, nitric acid, sulfuric acid, hydrochloric acid and hydrofluoric acid, uniformly dispersed nano titanium dioxide particles are prepared by a hydrothermal method, and a ruthenium-loaded nano titanium dioxide catalyst is prepared by a chemical reduction method.
A preparation method of a ruthenium-supported titanium dioxide catalyst for synthesizing cis-pinane by selective hydrogenation of α -pinene comprises the following steps:
① weighing 0.1g of TiO2Adding the mixture into a conical flask, adding 250mL of deionized water into the conical flask, and performing ultrasonic treatment for 1 h;
② after the ultrasound is finished, adding a pH regulator into the conical flask, and regulating the pH value in the conical flask to 9-10;
③ heated to 35 deg.C according to Ru and TiO2In a mass ratio of 5:100, 0.05mmol of RuCl is added3Keeping the temperature at 35 ℃ for 3 h;
④ 35 ℃ for 3h, heating to 95 ℃, adding 0.2-2mL of 300mM sodium borohydride solution, and keeping at 95 ℃ for 0.5 h;
⑤ cooling, filtering, and drying.
Further preferably, theThe pH regulator is Na2CO3And (3) solution.
Further preferably, in the step ⑤, the liquid obtained in the step ④ is cooled to room temperature, centrifuged for 3-4 times, and then the centrifuged product is dried at 60 ℃ for 10-15 h.
Further preferably, the TiO is2The preparation steps are as follows:
① measuring 180mL of water and 1.3mL of acid to form a mixed solution;
② to the mixture was added 15mLTi (OC) dropwise3H7)4Forming a suspension, maintaining the obtained suspension at 40 ℃ for 24h to obtain highly dispersed TiO2Sol;
③ the TiO obtained2Transferring the sol into a 100mL polytetrafluoroethylene reaction kettle, keeping the temperature at 180 ℃ for 24h, then washing the sol for 3 times by using deionized water, and drying the sol at 80 ℃ for 6h to obtain a product.
More preferably, the acid used to prepare the mixed solution is CH3COOH,HNO3,H2SO4HF or HCl.
A method for synthesizing cis-pinane by α -pinene selective hydrogenation using ruthenium supported titanium dioxide catalyst, the catalyst is supported Ru/TiO2The method comprises the following specific steps:
① according to the mass ratio of the catalyst to α -pinene of 0.1-1: 100, 50g of α -pinene and 0.05-0.5g of Ru/TiO are mixed2Adding into a polytetrafluoroethylene reaction kettle, wherein Ru and TiO2The mass ratio of (A) to (B) is 5: 100;
② replacing three to four times with hydrogen under gauge pressure of 2.5-3.5MPa, detecting leakage, and determining that the reaction kettle is sealed;
③ opening a hydrogen inlet valve, adjusting the pressure in the kettle to 2-5MPa, opening the temperature controller of the reaction kettle, and reacting for 3-7h at 100-140 ℃ and a stirring speed of 500 r/min.
Preferably, in step ③, the pressure in the reactor is 3MPa, the temperature controller of the reactor is opened, and the reaction is carried out for 5h at 120 ℃ and a stirring speed of 500 r/min.
The invention has the beneficial effects that:
1. the catalyst has higher conversion rate and cis-pinane selectivity, and the catalyst shows better catalytic performance than raney nickel in the reaction of synthesizing cis-pinane by α -pinene selective hydrogenation.
2. The catalyst adopts the nanometer titanium dioxide particles to load ruthenium, no addition of an auxiliary agent is needed, and the catalyst has the advantages of environmental friendliness, capability of degrading harmful pollutants and the like.
3. The product has simple post-treatment, convenient recovery, recycling and less by-products.
Detailed Description
The process of the present invention is further illustrated by the following examples, which are not intended to limit the invention.
Example 1:
TiO2the preparation of (1):
① measuring 180mL of water and 1.3mCH3COOH to form a mixed solution;
② to the mixture was added 15mLTi (OC) dropwise3H7)4Forming a suspension, maintaining the obtained suspension at 40 ℃ for 24h to obtain highly dispersed TiO2Sol;
③ the TiO obtained2Transferring the sol into a 100mL polytetrafluoroethylene reaction kettle, keeping the temperature at 180 ℃ for 24h, then washing the sol for 3 times by using deionized water, and drying the sol at 80 ℃ for 6h to obtain a product.
Ru/TiO2Preparation:
① weighing 0.1g of TiO2Adding the mixture into a conical flask, adding 250mL of deionized water into the conical flask, and performing ultrasonic treatment for 1 h;
② after completion of sonication, Na was added to the flask2CO3Adjusting the pH value in the conical flask to 9;
③ heated to 35 deg.C according to Ru and TiO2In a mass ratio of 5:100, 0.05mmol of RuCl is added3Keeping the temperature at 35 ℃ for 3 h;
④ 35 ℃ for 3h, heating to 95 ℃, adding 0.2mL of 300mM sodium borohydride solution, and keeping at 95 ℃ for 0.5 h;
⑤ cooling the liquid obtained in step ④ to room temperature, centrifuging 3 times, and drying the centrifuged product at 60 deg.C for 10-15 h.
Cis-pinane synthesis
50g of α -pinene and 0.05g of Ru/TiO2(wherein the TiO is2By CH3COOH treatment, Ru and TiO2The mass ratio of 5:100) is added into a polytetrafluoroethylene reaction kettle, hydrogen is used for replacing the air in the kettle for 4 times, then 3.0MPa hydrogen is filled, the mixture is heated and stirred for 5 hours at the temperature of 120 ℃, the mixture is kept stand and cooled to the room temperature, the conversion rate of α -pinene is 100 percent, and the selectivity of cis-pinane is 95.98 percent.
Example 2:
TiO2the preparation of (1):
① weighing 180mL of water and 1.3m of HNO3Forming a mixed solution;
② to the mixture was added 15mLTi (OC) dropwise3H7)4Forming a suspension, maintaining the obtained suspension at 40 ℃ for 24h to obtain highly dispersed TiO2Sol;
③ the TiO obtained2Transferring the sol into a 100mL polytetrafluoroethylene reaction kettle, keeping the temperature at 180 ℃ for 24h, then washing the sol for 3 times by using deionized water, and drying the sol at 80 ℃ for 6h to obtain a product.
Ru/TiO2Preparation:
① weighing 0.1g of TiO2Adding the mixture into a conical flask, adding 250mL of deionized water into the conical flask, and performing ultrasonic treatment for 1 h;
② after completion of sonication, Na was added to the flask2CO3Adjusting the pH value in the conical flask to 10;
③ heated to 35 deg.C according to Ru and TiO2In a mass ratio of 5:100, 0.05mmol of RuCl is added3Keeping the temperature at 35 ℃ for 3 h;
④ 35 ℃ for 3h, heating to 95 ℃, adding 2mL of 300mM sodium borohydride solution, and keeping at 95 ℃ for 0.5 h;
⑤ cooling the liquid obtained in step ④ to room temperature, centrifuging for 4 times, and drying the centrifuged product at 60 deg.C for 10-15 h.
Cis-pinane synthesis
50g of α -pinene and 0.05g of Ru/TiO2(wherein the TiO is2With HNO3Treatment ofRu and TiO2The mass ratio of 5:100) is added into a polytetrafluoroethylene reaction kettle, hydrogen is used for replacing the air in the kettle for 4 times, then 3.0MPa hydrogen is filled, the mixture is heated and stirred for 5 hours at the temperature of 120 ℃, the mixture is kept stand and cooled to the room temperature, the conversion rate of α -pinene is 98.65 percent, and the selectivity of cis-pinane is 95.68 percent.
Example 3:
TiO2the preparation of (1):
① weighing 180mL of water and 1.3m H2SO4Forming a mixed solution;
② to the mixture was added 15mLTi (OC) dropwise3H7)4Forming a suspension, maintaining the obtained suspension at 40 ℃ for 24h to obtain highly dispersed TiO2Sol;
③ the TiO obtained2Transferring the sol into a 100mL polytetrafluoroethylene reaction kettle, keeping the temperature at 180 ℃ for 24h, then washing the sol for 3 times by using deionized water, and drying the sol at 80 ℃ for 6h to obtain a product.
Ru/TiO2Preparation:
① weighing 0.1g of TiO2Adding the mixture into a conical flask, adding 250mL of deionized water into the conical flask, and performing ultrasonic treatment for 1 h;
② after completion of sonication, Na was added to the flask2CO3Adjusting the pH value in the conical flask to 10;
③ heated to 35 deg.C according to Ru and TiO2In a mass ratio of 5:100, 0.05mmol of RuCl is added3Keeping the temperature at 35 ℃ for 3 h;
④ 35 ℃ for 3h, heating to 95 ℃, adding 0.2mL of 300mM sodium borohydride solution, and keeping at 95 ℃ for 0.5 h;
⑤ cooling the liquid obtained in step ④ to room temperature, centrifuging for 4 times, and drying the centrifuged product at 60 deg.C for 10-15 h.
Synthesizing cis-pinane:
50g of α -pinene and 0.05g of Ru/TiO2(wherein the TiO is2By H2SO4Treatment of Ru with TiO2The mass ratio of 5:100) is added into a polytetrafluoroethylene reaction kettle, the air in the kettle is replaced by hydrogen for 4 times, then 3.0MPa hydrogen is filled, and the reaction temperature is 120 DEGHeating and stirring for 5h at the temperature of room temperature, standing and cooling to room temperature, wherein the conversion rate of α -pinene is 100 percent, and the selectivity of cis-pinane is 96.20 percent.
Example 4:
TiO2the preparation of (1):
① measuring 180mL of water and 1.3m of HF to form a mixed solution;
② to the mixture was added 15mLTi (OC) dropwise3H7)4Forming a suspension, maintaining the obtained suspension at 40 ℃ for 24h to obtain highly dispersed TiO2Sol;
③ the TiO obtained2Transferring the sol into a 100mL polytetrafluoroethylene reaction kettle, keeping the temperature at 180 ℃ for 24h, then washing the sol for 3 times by using deionized water, and drying the sol at 80 ℃ for 6h to obtain a product.
Ru/TiO2Preparation:
① weighing 0.1g of TiO2Adding the mixture into a conical flask, adding 250mL of deionized water into the conical flask, and performing ultrasonic treatment for 1 h;
② after completion of sonication, Na was added to the flask2CO3Adjusting the pH value in the conical flask to 10;
③ heated to 35 deg.C according to Ru and TiO2In a mass ratio of 5:100, 0.05mmol of RuCl is added3Keeping the temperature at 35 ℃ for 3 h;
④ 35 ℃ for 3h, heating to 95 ℃, adding 1mL of 300mM sodium borohydride solution, and keeping at 95 ℃ for 0.5 h;
⑤ cooling the liquid obtained in step ④ to room temperature, centrifuging for 4 times, and drying the centrifuged product at 60 deg.C for 10-15 h.
Synthesizing cis-pinane:
50g of α -pinene and 0.05g of Ru/TiO2(wherein the TiO is2Treatment with HF, Ru and TiO2The mass ratio of 5:100) is added into a polytetrafluoroethylene reaction kettle, hydrogen is used for replacing the air in the kettle for 4 times, then 3.0MPa hydrogen is filled, the mixture is heated and stirred for 5 hours at the temperature of 120 ℃, the mixture is kept stand and cooled to the room temperature, the conversion rate of α -pinene is 100 percent, and the selectivity of cis-pinane is 96.48 percent.
Example 5:
TiO2the preparation of (1):
① measuring 180mL of water and 1.3m of HCl to form a mixed solution;
② to the mixture was added 15mLTi (OC) dropwise3H7)4Forming a suspension, maintaining the obtained suspension at 40 ℃ for 24h to obtain highly dispersed TiO2Sol;
③ the TiO obtained2Transferring the sol into a 100mL polytetrafluoroethylene reaction kettle, keeping the temperature at 180 ℃ for 24h, then washing the sol for 3 times by using deionized water, and drying the sol at 80 ℃ for 6h to obtain a product.
Ru/TiO2Preparation:
① weighing 0.1g of TiO2Adding the mixture into a conical flask, adding 250mL of deionized water into the conical flask, and performing ultrasonic treatment for 1 h;
② after completion of sonication, Na was added to the flask2CO3Adjusting the pH value in the conical flask to 10;
③ heated to 35 deg.C according to Ru and TiO2In a mass ratio of 5:100, 0.05mmol of RuCl is added3Keeping the temperature at 35 ℃ for 3 h;
④ 35 ℃ for 3h, heating to 95 ℃, adding 1mL of 300mM sodium borohydride solution, and keeping at 95 ℃ for 0.5 h;
⑤ cooling the liquid obtained in step ④ to room temperature, centrifuging for 4 times, and drying the centrifuged product at 60 deg.C for 10-15 h.
Synthesizing cis-pinane:
50g of α -pinene and 0.05g of Ru/TiO2(wherein the TiO is2Treatment with HCl, Ru and TiO2The mass ratio of 5:100) is added into a polytetrafluoroethylene reaction kettle, hydrogen is used for replacing the air in the kettle for 4 times, then 3.0MPa hydrogen is filled, the mixture is heated and stirred for 5 hours at the temperature of 120 ℃, the mixture is kept stand and cooled to the room temperature, the conversion rate of α -pinene is 96.15 percent, and the selectivity of cis-pinane is 96.35 percent.
Example 6:
TiO2the preparation of (1):
① measuring 180mL of water and 1.3m of HF to form a mixed solution;
② to the mixture was added 15mLTi (OC) dropwise3H7)4Forming a suspension, maintaining the obtained suspension at 40 ℃ for 24h to obtain highly dispersed TiO2Sol;
③ the TiO obtained2Transferring the sol into a 100mL polytetrafluoroethylene reaction kettle, keeping the temperature at 180 ℃ for 24h, then washing the sol for 3 times by using deionized water, and drying the sol at 80 ℃ for 6h to obtain a product.
Ru/TiO2Preparation:
① weighing 0.1g of TiO2Adding the mixture into a conical flask, adding 250mL of deionized water into the conical flask, and performing ultrasonic treatment for 1 h;
② after completion of sonication, Na was added to the flask2CO3Adjusting the pH value in the conical flask to 10;
③ heated to 35 deg.C according to Ru and TiO2In a mass ratio of 3:100, 0.03mmol of RuCl is added3Keeping the temperature at 35 ℃ for 3 h;
④ 35 ℃ for 3h, heating to 95 ℃, adding 1mL of 300mM sodium borohydride solution, and keeping at 95 ℃ for 0.5 h;
⑤ cooling the liquid obtained in step ④ to room temperature, centrifuging for 4 times, and drying the centrifuged product at 60 deg.C for 10-15 h.
Synthesizing cis-pinane:
50g of α -pinene and 0.0502gRu/TiO2(wherein the TiO is2Treatment with HF, Ru and TiO2The mass ratio of 3:100) is added into a polytetrafluoroethylene reaction kettle, hydrogen is used for replacing the air in the kettle for 4 times, then 3.0MPa hydrogen is filled, the mixture is heated and stirred for 5 hours at the temperature of 120 ℃, the mixture is kept stand and cooled to the room temperature, the conversion rate of α -pinene is 48.87 percent, and the selectivity of cis-pinane is 96.52 percent.
Example 7:
TiO2the preparation of (1):
① measuring 180mL of water and 1.3m of HF to form a mixed solution;
② to the mixture was added 15mLTi (OC) dropwise3H7)4Forming a suspension, maintaining the obtained suspension at 40 ℃ for 24h to obtain highly dispersed TiO2Sol;
③ the TiO obtained2Transferring the sol into a 100mL polytetrafluoroethylene reaction kettle, keeping the temperature at 180 ℃ for 24h, then washing the sol for 3 times by using deionized water, and drying the sol at 80 ℃ for 6h to obtain a product.
Ru/TiO2Preparation:
① weighing 0.1g of TiO2Adding the mixture into a conical flask, adding 250mL of deionized water into the conical flask, and performing ultrasonic treatment for 1 h;
② after completion of sonication, Na was added to the flask2CO3Adjusting the pH value in the conical flask to 10;
③ heated to 35 deg.C according to Ru and TiO2In a mass ratio of 10:100, 0.1mmol of RuCl is added3Keeping the temperature at 35 ℃ for 3 h;
④ 35 ℃ for 3h, heating to 95 ℃, adding 1mL of 300mM sodium borohydride solution, and keeping at 95 ℃ for 0.5 h;
⑤ cooling the liquid obtained in step ④ to room temperature, centrifuging for 4 times, and drying the centrifuged product at 60 deg.C for 10-15 h.
Synthesizing cis-pinane:
50g of α -pinene and 0.0502gRu/TiO2(wherein the TiO is2Treatment with HF, Ru and TiO2The mass ratio of 10:100) is added into a polytetrafluoroethylene reaction kettle, hydrogen is used for replacing the air in the kettle for 4 times, then 3.0MPa hydrogen is filled, the mixture is heated and stirred for 5 hours at the temperature of 120 ℃, the mixture is kept stand and cooled to the room temperature, the conversion rate of α -pinene is 100 percent, and the selectivity of cis-pinane is 95.89 percent.
Example 8:
TiO2the preparation of (1):
① measuring 180mL of water and 1.3m of HCl to form a mixed solution;
② to the mixture was added 15mLTi (OC) dropwise3H7)4Forming a suspension, maintaining the obtained suspension at 40 ℃ for 24h to obtain highly dispersed TiO2Sol;
③ the TiO obtained2Transferring the sol into a 100mL polytetrafluoroethylene reaction kettle, keeping the temperature at 180 ℃ for 24h, then washing the sol for 3 times by using deionized water, and drying the sol at 80 ℃ for 6h to obtain a product.
Ru/TiO2Preparation:
① weighing 0.1g of TiO2Adding the mixture into a conical flask, adding 250mL of deionized water into the conical flask, and performing ultrasonic treatment for 1 h;
② after completion of sonication, Na was added to the flask2CO3Adjusting the pH value in the conical flask to 10;
③ heated to 35 deg.C according to Ru and TiO2In a mass ratio of 5:100, 0.05mmol of RuCl is added3Keeping the temperature at 35 ℃ for 3 h;
④ 35 ℃ for 3h, heating to 95 ℃, adding 1mL of 300mM sodium borohydride solution, and keeping at 95 ℃ for 0.5 h;
⑤ cooling the liquid obtained in step ④ to room temperature, centrifuging for 4 times, and drying the centrifuged product at 60 deg.C for 10-15 h.
Synthesizing cis-pinane:
50g of α -pinene and 0.5g of Ru/TiO2(wherein the TiO is2Treatment with HCl, Ru and TiO2The mass ratio of 5:100) is added into a polytetrafluoroethylene reaction kettle, hydrogen is used for replacing the air in the kettle for 4 times, then 2.5MPa hydrogen is filled, the pressure in the kettle is adjusted to be 2MPa, the kettle is heated and stirred for 7 hours at 100 ℃, the kettle is kept still and cooled to room temperature, the conversion rate of α -pinene is 98.11 percent, and the selectivity of cis-pinane is 96.47 percent.
Example 9:
TiO2the preparation of (1):
① measuring 180mL of water and 1.3m of HCl to form a mixed solution;
② to the mixture was added 15mLTi (OC) dropwise3H7)4Forming a suspension, maintaining the obtained suspension at 40 ℃ for 24h to obtain highly dispersed TiO2Sol;
③ the TiO obtained2Transferring the sol into a 100mL polytetrafluoroethylene reaction kettle, keeping the temperature at 180 ℃ for 24h, then washing the sol for 3 times by using deionized water, and drying the sol at 80 ℃ for 6h to obtain a product.
Ru/TiO2Preparation:
① weighing 0.1g of TiO2Adding the mixture into a conical flask, adding 250mL of deionized water into the conical flask, and performing ultrasonic treatment for 1 h;
② after completion of sonication, Na was added to the flask2CO3Adjusting the pH value in the conical flask to 10;
③ heated to 35 deg.C according to Ru and TiO2In a mass ratio of 5:100, 0.05mmol of RuCl is added3Keeping the temperature at 35 ℃ for 3 h;
④ 35 ℃ for 3h, heating to 95 ℃, adding 1mL of 300mM sodium borohydride solution, and keeping at 95 ℃ for 0.5 h;
⑤ cooling the liquid obtained in step ④ to room temperature, centrifuging for 4 times, and drying the centrifuged product at 60 deg.C for 10-15 h.
Synthesizing cis-pinane:
50g of α -pinene and 0.5g of Ru/TiO2(wherein the TiO is2Treatment with HCl, Ru and TiO2The mass ratio of 5:100) is added into a polytetrafluoroethylene reaction kettle, hydrogen is used for replacing the air in the kettle for 4 times, then 3.5MPa hydrogen is filled, the pressure in the kettle is adjusted to be 5MPa, the kettle is heated and stirred for 3 hours at 140 ℃, the kettle is kept still and cooled to room temperature, the conversion rate of α -pinene is 99.93 percent, and the selectivity of cis-pinane is 97.12 percent.
Comparative examples 1 to 9, example 6 Ru and TiO2Ru/TiO with a mass ratio of 3:1002The conversion rate of α -pinene used as a catalyst for synthesizing cis-pinane by selective hydrogenation of α -pinene is 48.87%, and the conversion efficiency is very low, while the selectivity of cis-pinane is low in example 7, but Ru and TiO are mixed in examples 1-5 and 8-82When the mass ratio of the alpha-pinene to the alpha-pinene is 5:100, the conversion rate of α -pinene is high and reaches 96.15-100%, the selectivity is good and reaches more than 95.98%, which shows that the Ru and TiO prepared by the invention are mixed2Ru/TiO with a mass ratio of 5:1002The catalyst has higher conversion rate and cis-pinane selectivity, and the catalyst shows better catalytic performance than raney nickel in the reaction of synthesizing cis-pinane by α -pinene selective hydrogenation.
The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (4)
1. A method for synthesizing cis-pinane by α -pinene selective hydrogenation by using a ruthenium-supported titanium dioxide catalyst is characterized by comprising the following steps:
the preparation steps of the catalyst are as follows:
① measuring 180mL of water and 1.3mL of acid to form a mixed solution, wherein the acid used for preparing the mixed solution is CH3COOH,HNO3,H2SO4HF or HCl; to the mixture was added dropwise 15mLTi (OC)3H7)4Forming a suspension, maintaining the obtained suspension at 40 ℃ for 24h to obtain highly dispersed TiO2Sol, TiO obtained2Transferring the sol into a 100mL polytetrafluoroethylene reaction kettle, keeping the reaction kettle at 180 ℃ for 24h, washing the sol for 3 times by using deionized water, and drying the sol at 80 ℃ for 6h to obtain a product; 0.1g of TiO was weighed2Adding the mixture into a conical flask, adding 250mL of deionized water into the conical flask, and performing ultrasonic treatment for 1 h;
② after the ultrasound is finished, adding a pH regulator into the conical flask, and regulating the pH value in the conical flask to 9-10;
③ heated to 35 deg.C according to Ru and TiO2In a mass ratio of 5:100, 0.05mmol of RuCl is added3Keeping the temperature at 35 ℃ for 3 h;
④ 35 ℃ for 3h, heating to 95 ℃, adding 0.2-2mL of 300mM sodium borohydride solution, and keeping at 95 ℃ for 0.5 h;
⑤ cooling, filtering and drying to obtain the supported Ru/TiO2A catalyst,
the synthesis of cis-pinane comprises the following steps:
① according to the mass ratio of the catalyst to α -pinene of 0.1-1: 100, 50g of α -pinene and 0.05-0.5g of Ru/TiO are mixed2Adding into a polytetrafluoroethylene reaction kettle, wherein Ru and TiO2The mass ratio of (A) to (B) is 5: 100;
② replacing three to four times with hydrogen under gauge pressure of 2.5-3.5MPa, detecting leakage, and determining that the reaction kettle is sealed;
③ opening a hydrogen inlet valve, adjusting the pressure in the kettle to 2-5MPa, opening the temperature controller of the reaction kettle, and reacting for 3-7h at 100-140 ℃ and a stirring speed of 500 r/min.
2. The method for synthesizing cis-pinane by selective hydrogenation of α -pinene using the ruthenium supported titanium dioxide catalyst as claimed in claim 1, wherein in the step ③ of synthesizing cis-pinane, the pressure in the reaction kettle is 3MPa, the temperature controller of the reaction kettle is opened, and the reaction is carried out at 120 ℃ and a stirring speed of 500r/min for 5 hours.
3. The method for synthesizing cis-pinane by selective hydrogenation of α -pinene using the ruthenium-supported titanium dioxide catalyst as claimed in claim 1, wherein the pH regulator is Na2CO3And (3) solution.
4. The method for synthesizing cis-pinane by α -pinene selective hydrogenation according to claim 1, wherein the step ⑤ of catalyst preparation comprises cooling the liquid obtained in step ④ to room temperature, centrifuging the liquid for 3-4 times, and drying the centrifuged product at 60 ℃ for 10-15 h.
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