CN107519867A - A kind of preparation method of the ruthenium catalyst for titanium dioxide loaded of α firpenes selective hydrogenation synthesizing cis pinane - Google Patents

A kind of preparation method of the ruthenium catalyst for titanium dioxide loaded of α firpenes selective hydrogenation synthesizing cis pinane Download PDF

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CN107519867A
CN107519867A CN201710825577.XA CN201710825577A CN107519867A CN 107519867 A CN107519867 A CN 107519867A CN 201710825577 A CN201710825577 A CN 201710825577A CN 107519867 A CN107519867 A CN 107519867A
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tio
pinane
titanium dioxide
australene
cis
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CN107519867B (en
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陈伟
胡银
宋卫国
巴明伟
刘铎
任向荣
周春荣
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Jiangxi Huachen Perfume Chemical Co ltd
Institute of Applied Chemistry Jiangxi Academy of Sciences
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Jiangxi Huachen Perfume Chemical Co ltd
Institute of Applied Chemistry Jiangxi Academy of Sciences
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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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • 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
    • 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
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
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    • C07B2200/09—Geometrical isomers

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Abstract

The invention discloses a kind of preparation method of the ruthenium catalyst for titanium dioxide loaded of α firpenes selective hydrogenation synthesizing cis pinane, using isopropyl titanate as presoma, hydrolyzed under acetic acid, nitric acid, sulfuric acid, hydrochloric acid, hydrofluoric acid effect, dispersed titanium dioxide nanoparticle is prepared by hydro-thermal method, and ruthenium load nano-titanium dioxide catalyst Ru/TiO is prepared using chemical reduction method2.It is 0.1~1 according to the mass ratio of catalyst and α firpenes:100, by α firpenes and Ru/TiO2Add in ptfe autoclave, wherein Ru and TiO2Mass ratio be 5:100；The catalyst has higher conversion ratio and cis-pinane selectivity, and without adding auxiliary agent, catalyst has the advantages that environment-friendly, degradable noxious pollutant in itself.

Description

A kind of ruthenium carried titanium dioxide catalysis of australene selective hydrogenation synthesizing cis pinane The preparation method of agent
Technical field
The present invention relates to a kind of system of the ruthenium catalyst for titanium dioxide loaded of australene selective hydrogenation synthesizing cis pinane Preparation Method, further relate to a kind of side that australene selective hydrogenation synthesizing cis pinane is carried out using ruthenium catalyst for titanium dioxide loaded Method, belong to catalyst technical field.
Background technology
China's turpentine oil aboundresources, terebinthine production and output occupy critical positions in the world.Australene is pine The main component of fuel-economizing, pinane can be made through catalytic hydrogenation reaction.Wherein, cis-pinane is that one kind is synthesizing dihydro laurene The important industrial chemicals intermediate of the spices such as alcohol, linalool, and production vitamin A and E important intermediate.Therefore, by α- Pinene hydrogenation prepares high content cis-pinane and had very important significance.
So far, domestic and international researchers have developed a series of australene catalytic hydrogenations and prepare cis-pinane Catalyst, mainly including noble metal, base metal etc. be homogeneous and heterogeneous catalysis.Some researchers utilize Raney nickel price The characteristics of cheap, prepares cis-pinane and achieves certain progress, and patent CN104001515A discloses a kind of load-type nickel Ni/TiO is made by the methods of roasting, hydrogen reducing in the preparation method of catalyst, the technology2-Al2O3Catalyst, australene Conversion ratio is 89.73%, and the selectivity of cis-pinane is 96.48%.It is not difficult to find out, it is low although Raney nickel cost is relatively low Conversion ratio and selectivity be still restrict its development bottleneck.At present, noble metal catalyst and its study on the modification Yin Qigao turn Rate and selectivity are still the emphasis of research.Patent CN105481633A discloses a kind of catalysis australene selective hydrogenation system The method of standby cis-pinane, the technology are prepared for carried noble metal Ru M-SiO2- APTES-Ru catalyst, the conversion of australene Rate is 99.4%, and the selectivity of cis-pinane is 96.3%.Patent discloses CN105566027A and discloses a kind of normal temperature and pressure Lower catalysis australene Hydrogenation is for the method for cis-pinane, technology polyethylene glycol 1000 vitamin E succinic acid ester (TPGS- 1000) the stable ruthenium nano particle glue beam prepared reacts 6h under the conditions of normal temperature (25 DEG C) normal pressure (0.1MPa), australene Conversion ratio can reach 99.9%, and the selectivity of cis-pinane is 99.1%.Nevertheless, but this homogeneous catalyst in reality Difficulty is reclaimed in production, influences secondary use.Therefore, research and develop for australene efficient selective hydrogenation preparing cis-pinane Heterogeneous catalysis has important realistic meaning.
The content of the invention
The purpose of the present invention is to propose to one kind is environment-friendly, catalytic performance is excellent, to australene hydrogenation synthesis cis-pinane Novel nano catalyst with high conversion and selectivity, therefore, providing a kind of australene selective hydrogenation synthesizing cis The preparation method of the ruthenium catalyst for titanium dioxide loaded of pinane, additionally provide one kind and utilize ruthenium catalyst for titanium dioxide loaded to carry out The method of australene selective hydrogenation synthesizing cis pinane,
The present invention is realized by following technical proposals.The present invention is using isopropyl titanate as presoma, in acetic acid, nitre Acid, sulfuric acid, hydrochloric acid, the lower hydrolysis of hydrofluoric acid effect, dispersed titanium dioxide nanoparticle are prepared by hydro-thermal method, and utilize Chemical reduction method prepares ruthenium load nano-titanium dioxide catalyst.
A kind of preparation method of the ruthenium catalyst for titanium dioxide loaded of australene selective hydrogenation synthesizing cis pinane, step It is as follows：
1. weigh 0.1g TiO2Add in conical flask, add 250mL deionized water, ultrasonic 1h thereto；
2. after ultrasound terminates, pH adjusting agent is added into conical flask, the pH=9-10 in conical flask is adjusted；
3. 35 DEG C are heated to, according to Ru and TiO2Mass ratio be 5:100 add 0.05mmol RuCl3, protected at 35 DEG C Hold 3h；
4. after keeping 3h to terminate at 35 DEG C, 95 DEG C are warming up to, adds 0.2-2mL 300mM sodium borohydride solution, then 0.5h is kept at 95 DEG C；
5. cooling down, filter, dry.
Further preferably, the pH adjusting agent is Na2CO3Solution.
Further preferably, the step 5. in, by step, 4. gained liquid cools to room temperature, centrifuges 3-4 times, then will be from Heart products therefrom dries 10-15h at 60 DEG C.
Further preferably, the TiO2Preparation process be：
1. measure 180mL water and 1.3mL acid forms mixed liquor；
2. 15mLTi (OC are added dropwise into mixed liquor3H7)4Suspension is formed, gained suspension is kept at 40 DEG C 24h, obtain the TiO of high degree of dispersion2Colloidal sol；
3. the TiO that will be obtained2Colloidal sol is transferred in 100mL ptfe autoclave, 24h is kept at 180 DEG C, then Spend ion-cleaning 3 times, 6h is dried at 80 DEG C and obtains product.
Further preferably, acid is CH used by configuring mixed liquor3COOH,HNO3,H2SO4, HF or HCl.
A kind of method that australene selective hydrogenation synthesizing cis pinane is carried out using ruthenium catalyst for titanium dioxide loaded, is urged Agent is support type Ru/TiO2, comprise the following steps that：
1. it is 0.1~1 according to the mass ratio of catalyst and australene:100, by 50g australenes and 0.05-0.5g Ru/ TiO2Add in ptfe autoclave, wherein Ru and TiO2Mass ratio be 5:100；
2. being replaced three to four times with hydrogen under gauge pressure 2.5-3.5MPa, leak detection, confirm that reactor sealing is intact；
3. opening hydrogen gas valve, it is 2-5MPa to adjust pressure in kettle, reactor heating controller is opened, in 100-140 DEG C, react 3-7h under mixing speed 500r/min.
It is still further preferred that step 3. in, save kettle in pressure be 3MPa, open reactor heating controller, in 120 DEG C, stir 5h is reacted under speed 500r/min.
Beneficial effects of the present invention：
1st, catalyst has higher conversion ratio and cis-pinane selectivity.Such catalyst is in australene selective hydrogenation The catalytic performance better than Raney's nickel is shown in the reaction of synthesizing cis pinane.
2nd, catalyst is using nano-titania particle load ruthenium, and without adding auxiliary agent, catalyst has environment friend in itself The advantages that good, degradable noxious pollutant.
3rd, product postprocessing is simple, and recovery is convenient, reusable edible, and accessory substance is few.
Embodiment
The method of the present invention is described further with reference to embodiment, is not limitation of the invention.
Embodiment 1：
TiO2Preparation：
1. measure 180mL water and 1.3mCH3COOH forms mixed liquor；
2. 15mLTi (OC are added dropwise into mixed liquor3H7)4Suspension is formed, gained suspension is kept at 40 DEG C 24h, obtain the TiO of high degree of dispersion2Colloidal sol；
3. the TiO that will be obtained2Colloidal sol is transferred in 100mL ptfe autoclave, 24h is kept at 180 DEG C, then Spend ion-cleaning 3 times, 6h is dried at 80 DEG C and obtains product.
Ru/TiO2Prepare：
1. weigh 0.1g TiO2Add in conical flask, add 250mL deionized water, ultrasonic 1h thereto；
After 2. ultrasound terminates, Na is added into conical flask2CO3Solution, adjust the pH=9 in conical flask；
3. 35 DEG C are heated to, according to Ru and TiO2Mass ratio be 5:100 add 0.05mmol RuCl3, protected at 35 DEG C Hold 3h；
4. after keeping 3h to terminate at 35 DEG C, 95 DEG C are warming up to, adds 0.2mL 300mM sodium borohydride solution, Ran Hou 0.5h is kept at 95 DEG C；
5. by step, 4. gained liquid cools to room temperature, centrifuges 3 times, then dries centrifugation products therefrom at 60 DEG C 10-15h。
Cis-pinane synthesizes
By 50g australenes and 0.05g Ru/TiO2(wherein TiO2Use CH3COOH processing, Ru and TiO2Mass ratio be 5: 100) add in ptfe autoclave, using being filled with 3.0MPa hydrogen after air 4 times in hydrogen displacement kettle, at 120 DEG C Heating stirring 5h, standing are cooled to room temperature.The conversion ratio of australene is 100%, and the selectivity of cis-pinane is 95.98%.
Embodiment 2：
TiO2Preparation：
1. measure 180mL water and 1.3m HNO3Form mixed liquor；
2. 15mLTi (OC are added dropwise into mixed liquor3H7)4Suspension is formed, gained suspension is kept at 40 DEG C 24h, obtain the TiO of high degree of dispersion2Colloidal sol；
3. the TiO that will be obtained2Colloidal sol is transferred in 100mL ptfe autoclave, 24h is kept at 180 DEG C, then Spend ion-cleaning 3 times, 6h is dried at 80 DEG C and obtains product.
Ru/TiO2Prepare：
1. weigh 0.1g TiO2Add in conical flask, add 250mL deionized water, ultrasonic 1h thereto；
After 2. ultrasound terminates, Na is added into conical flask2CO3Solution, adjust the pH=10 in conical flask；
3. 35 DEG C are heated to, according to Ru and TiO2Mass ratio be 5:100 add 0.05mmol RuCl3, protected at 35 DEG C Hold 3h；
4. after keeping 3h to terminate at 35 DEG C, 95 DEG C are warming up to, 2mL 300mM sodium borohydride solution is added, then 95 0.5h is kept at DEG C；
5. by step, 4. gained liquid cools to room temperature, centrifuges 4 times, then dries centrifugation products therefrom at 60 DEG C 10-15h。
Cis-pinane synthesizes
By 50g australenes and 0.05g Ru/TiO2(wherein TiO2Use HNO3Processing, Ru and TiO2Mass ratio be 5:100) Add in ptfe autoclave, using 3.0MPa hydrogen is filled with after air 4 times in hydrogen displacement kettle, heated at 120 DEG C 5h is stirred, standing is cooled to room temperature.The conversion ratio of australene is 98.65%, and the selectivity of cis-pinane is 95.68%.
Embodiment 3：
TiO2Preparation：
1. measure 180mL water and 1.3m H2SO4Form mixed liquor；
2. 15mLTi (OC are added dropwise into mixed liquor3H7)4Suspension is formed, gained suspension is kept at 40 DEG C 24h, obtain the TiO of high degree of dispersion2Colloidal sol；
3. the TiO that will be obtained2Colloidal sol is transferred in 100mL ptfe autoclave, 24h is kept at 180 DEG C, then Spend ion-cleaning 3 times, 6h is dried at 80 DEG C and obtains product.
Ru/TiO2Prepare：
1. weigh 0.1g TiO2Add in conical flask, add 250mL deionized water, ultrasonic 1h thereto；
After 2. ultrasound terminates, Na is added into conical flask2CO3Solution, adjust the pH=10 in conical flask；
3. 35 DEG C are heated to, according to Ru and TiO2Mass ratio be 5:100 add 0.05mmol RuCl3, protected at 35 DEG C Hold 3h；
4. after keeping 3h to terminate at 35 DEG C, 95 DEG C are warming up to, adds 0.2mL 300mM sodium borohydride solution, Ran Hou 0.5h is kept at 95 DEG C；
5. by step, 4. gained liquid cools to room temperature, centrifuges 4 times, then dries centrifugation products therefrom at 60 DEG C 10-15h。
Cis-pinane synthesizes：
By 50g australenes and 0.05g Ru/TiO2(wherein TiO2Use H2SO4Processing, Ru and TiO2Mass ratio be 5:100) Add in ptfe autoclave, using 3.0MPa hydrogen is filled with after air 4 times in hydrogen displacement kettle, heated at 120 DEG C 5h is stirred, standing is cooled to room temperature.The conversion ratio of australene is 100%, and the selectivity of cis-pinane is 96.20%.
Embodiment 4：
TiO2Preparation：
1. measure 180mL water and 1.3m HF form mixed liquor；
2. 15mLTi (OC are added dropwise into mixed liquor3H7)4Suspension is formed, gained suspension is kept at 40 DEG C 24h, obtain the TiO of high degree of dispersion2Colloidal sol；
3. the TiO that will be obtained2Colloidal sol is transferred in 100mL ptfe autoclave, 24h is kept at 180 DEG C, then Spend ion-cleaning 3 times, 6h is dried at 80 DEG C and obtains product.
Ru/TiO2Prepare：
1. weigh 0.1g TiO2Add in conical flask, add 250mL deionized water, ultrasonic 1h thereto；
After 2. ultrasound terminates, Na is added into conical flask2CO3Solution, adjust the pH=10 in conical flask；
3. 35 DEG C are heated to, according to Ru and TiO2Mass ratio be 5:100 add 0.05mmol RuCl3, protected at 35 DEG C Hold 3h；
4. after keeping 3h to terminate at 35 DEG C, 95 DEG C are warming up to, 1mL 300mM sodium borohydride solution is added, then 95 0.5h is kept at DEG C；
5. by step, 4. gained liquid cools to room temperature, centrifuges 4 times, then dries centrifugation products therefrom at 60 DEG C 10-15h。
Cis-pinane synthesizes：
By 50g australenes and 0.05g Ru/TiO2(wherein TiO2With HF processing, Ru and TiO2Mass ratio be 5:100) add Enter in ptfe autoclave, using 3.0MPa hydrogen is filled with after air 4 times in hydrogen displacement kettle, heats and stir at 120 DEG C 5h is mixed, standing is cooled to room temperature.The conversion ratio of australene is 100%, and the selectivity of cis-pinane is 96.48%.
Embodiment 5：
TiO2Preparation：
1. measure 180mL water and 1.3m HCl form mixed liquor；
2. 15mLTi (OC are added dropwise into mixed liquor3H7)4Suspension is formed, gained suspension is kept at 40 DEG C 24h, obtain the TiO of high degree of dispersion2Colloidal sol；
3. the TiO that will be obtained2Colloidal sol is transferred in 100mL ptfe autoclave, 24h is kept at 180 DEG C, then Spend ion-cleaning 3 times, 6h is dried at 80 DEG C and obtains product.
Ru/TiO2Prepare：
1. weigh 0.1g TiO2Add in conical flask, add 250mL deionized water, ultrasonic 1h thereto；
After 2. ultrasound terminates, Na is added into conical flask2CO3Solution, adjust the pH=10 in conical flask；
3. 35 DEG C are heated to, according to Ru and TiO2Mass ratio be 5:100 add 0.05mmol RuCl3, protected at 35 DEG C Hold 3h；
4. after keeping 3h to terminate at 35 DEG C, 95 DEG C are warming up to, 1mL 300mM sodium borohydride solution is added, then 95 0.5h is kept at DEG C；
5. by step, 4. gained liquid cools to room temperature, centrifuges 4 times, then dries centrifugation products therefrom at 60 DEG C 10-15h。
Cis-pinane synthesizes：
By 50g australenes and 0.05g Ru/TiO2(wherein TiO2With HCl processing, Ru and TiO2Mass ratio be 5:100) Add in ptfe autoclave, using 3.0MPa hydrogen is filled with after air 4 times in hydrogen displacement kettle, heated at 120 DEG C 5h is stirred, standing is cooled to room temperature.The conversion ratio of australene is 96.15%, and the selectivity of cis-pinane is 96.35%.
Embodiment 6：
TiO2Preparation：
1. measure 180mL water and 1.3m HF form mixed liquor；
2. 15mLTi (OC are added dropwise into mixed liquor3H7)4Suspension is formed, gained suspension is kept at 40 DEG C 24h, obtain the TiO of high degree of dispersion2Colloidal sol；
3. the TiO that will be obtained2Colloidal sol is transferred in 100mL ptfe autoclave, 24h is kept at 180 DEG C, then Spend ion-cleaning 3 times, 6h is dried at 80 DEG C and obtains product.
Ru/TiO2Prepare：
1. weigh 0.1g TiO2Add in conical flask, add 250mL deionized water, ultrasonic 1h thereto；
After 2. ultrasound terminates, Na is added into conical flask2CO3Solution, adjust the pH=10 in conical flask；
3. 35 DEG C are heated to, according to Ru and TiO2Mass ratio be 3:100 add 0.03mmol RuCl3, protected at 35 DEG C Hold 3h；
4. after keeping 3h to terminate at 35 DEG C, 95 DEG C are warming up to, 1mL 300mM sodium borohydride solution is added, then 95 0.5h is kept at DEG C；
5. by step, 4. gained liquid cools to room temperature, centrifuges 4 times, then dries centrifugation products therefrom at 60 DEG C 10-15h。
Cis-pinane synthesizes：
By 50g australenes and 0.0502gRu/TiO2(wherein TiO2With HF processing, Ru and TiO2Mass ratio be 3:100) Add in ptfe autoclave, using 3.0MPa hydrogen is filled with after air 4 times in hydrogen displacement kettle, heated at 120 DEG C 5h is stirred, standing is cooled to room temperature.The conversion ratio of australene is 48.87%, and the selectivity of cis-pinane is 96.52%.
Embodiment 7：
TiO2Preparation：
1. measure 180mL water and 1.3m HF form mixed liquor；
2. 15mLTi (OC are added dropwise into mixed liquor3H7)4Suspension is formed, gained suspension is kept at 40 DEG C 24h, obtain the TiO of high degree of dispersion2Colloidal sol；
3. the TiO that will be obtained2Colloidal sol is transferred in 100mL ptfe autoclave, 24h is kept at 180 DEG C, then Spend ion-cleaning 3 times, 6h is dried at 80 DEG C and obtains product.
Ru/TiO2Prepare：
1. weigh 0.1g TiO2Add in conical flask, add 250mL deionized water, ultrasonic 1h thereto；
After 2. ultrasound terminates, Na is added into conical flask2CO3Solution, adjust the pH=10 in conical flask；
3. 35 DEG C are heated to, according to Ru and TiO2Mass ratio be 10:100 add 0.1mmol RuCl3, protected at 35 DEG C Hold 3h；
4. after keeping 3h to terminate at 35 DEG C, 95 DEG C are warming up to, 1mL 300mM sodium borohydride solution is added, then 95 0.5h is kept at DEG C；
5. by step, 4. gained liquid cools to room temperature, centrifuges 4 times, then dries centrifugation products therefrom at 60 DEG C 10-15h。
Cis-pinane synthesizes：
By 50g australenes and 0.0502gRu/TiO2(wherein TiO2With HF processing, Ru and TiO2Mass ratio be 10:100) Add in ptfe autoclave, using 3.0MPa hydrogen is filled with after air 4 times in hydrogen displacement kettle, heated at 120 DEG C 5h is stirred, standing is cooled to room temperature.The conversion ratio of australene is 100%, and the selectivity of cis-pinane is 95.89%.
Embodiment 8：
TiO2Preparation：
1. measure 180mL water and 1.3m HCl form mixed liquor；
2. 15mLTi (OC are added dropwise into mixed liquor3H7)4Suspension is formed, gained suspension is kept at 40 DEG C 24h, obtain the TiO of high degree of dispersion2Colloidal sol；
3. the TiO that will be obtained2Colloidal sol is transferred in 100mL ptfe autoclave, 24h is kept at 180 DEG C, then Spend ion-cleaning 3 times, 6h is dried at 80 DEG C and obtains product.
Ru/TiO2Prepare：
1. weigh 0.1g TiO2Add in conical flask, add 250mL deionized water, ultrasonic 1h thereto；
After 2. ultrasound terminates, Na is added into conical flask2CO3Solution, adjust the pH=10 in conical flask；
3. 35 DEG C are heated to, according to Ru and TiO2Mass ratio be 5:100 add 0.05mmol RuCl3, protected at 35 DEG C Hold 3h；
4. after keeping 3h to terminate at 35 DEG C, 95 DEG C are warming up to, 1mL 300mM sodium borohydride solution is added, then 95 0.5h is kept at DEG C；
5. by step, 4. gained liquid cools to room temperature, centrifuges 4 times, then dries centrifugation products therefrom at 60 DEG C 10-15h。
Cis-pinane synthesizes：
By 50g australenes and 0.5g Ru/TiO2(wherein TiO2With HCl processing, Ru and TiO2Mass ratio be 5:100) add Enter in ptfe autoclave, using 2.5MPa hydrogen is filled with after air 4 times in hydrogen displacement kettle, adjusting pressure in kettle is 2MPa, the heating stirring 7h at 100 DEG C, standing are cooled to room temperature.The conversion ratio of australene is 98.11%, the choosing of cis-pinane Selecting property is 96.47%.
Embodiment 9：
TiO2Preparation：
1. measure 180mL water and 1.3m HCl form mixed liquor；
2. 15mLTi (OC are added dropwise into mixed liquor3H7)4Suspension is formed, gained suspension is kept at 40 DEG C 24h, obtain the TiO of high degree of dispersion2Colloidal sol；
3. the TiO that will be obtained2Colloidal sol is transferred in 100mL ptfe autoclave, 24h is kept at 180 DEG C, then Spend ion-cleaning 3 times, 6h is dried at 80 DEG C and obtains product.
Ru/TiO2Prepare：
1. weigh 0.1g TiO2Add in conical flask, add 250mL deionized water, ultrasonic 1h thereto；
After 2. ultrasound terminates, Na is added into conical flask2CO3Solution, adjust the pH=10 in conical flask；
3. 35 DEG C are heated to, according to Ru and TiO2Mass ratio be 5:100 add 0.05mmol RuCl3, protected at 35 DEG C Hold 3h；
4. after keeping 3h to terminate at 35 DEG C, 95 DEG C are warming up to, 1mL 300mM sodium borohydride solution is added, then 95 0.5h is kept at DEG C；
5. by step, 4. gained liquid cools to room temperature, centrifuges 4 times, then dries centrifugation products therefrom at 60 DEG C 10-15h。
Cis-pinane synthesizes：
By 50g australenes and 0.5g Ru/TiO2(wherein TiO2With HCl processing, Ru and TiO2Mass ratio be 5:100) add Enter in ptfe autoclave, using 3.5MPa hydrogen is filled with after air 4 times in hydrogen displacement kettle, adjusting pressure in kettle is 5MPa, the heating stirring 3h at 140 DEG C, standing are cooled to room temperature.The conversion ratio of australene is 99.93%, the choosing of cis-pinane Selecting property is 97.12%.
Comparative example 1-9, Ru and TiO in embodiment 62Mass ratio be 3:100 Ru/TiO2Selected as australene Property hydrogenation synthesis cis-pinane catalyst australene conversion ratio be 48.87%, transformation efficiency is very low.And in embodiment 7 The selectivity of cis-pinane is relatively low, but in embodiment 1-5 and 8-8, Ru and TiO2Mass ratio be 5:When 100, australene Conversion ratio is very high, reaches 96.15-100%, and selectivity is good, up to more than 95.98%, this show Ru prepared by the present invention with TiO2Mass ratio be 5:100 Ru/TiO2Catalyst has higher conversion ratio and cis-pinane selectivity.Such catalyst The catalytic performance better than Raney's nickel is shown in the reaction of australene selective hydrogenation synthesizing cis pinane.
Embodiment described above is a kind of preferable scheme of the present invention, not the present invention is made any formal Limitation, there are other variants and remodeling on the premise of without departing from the technical scheme described in claim.

Claims (10)

1. a kind of preparation method of the ruthenium catalyst for titanium dioxide loaded of australene selective hydrogenation synthesizing cis pinane, its feature It is：Step is as follows：
1. weigh 0.1g TiO2Add in conical flask, add 250mL deionized water, ultrasonic 1h thereto；
2. after ultrasound terminates, pH adjusting agent is added into conical flask, the pH=9-10 in conical flask is adjusted；
3. 35 DEG C are heated to, according to Ru and TiO2Mass ratio be 5:100 add 0.05mmol RuCl3, kept at 35 DEG C 3h；
4. after keeping 3h to terminate at 35 DEG C, 95 DEG C are warming up to, 0.2-2mL 300mM sodium borohydride solution is added, then 95 0.5h is kept at DEG C；
5. cooling down, filter, dry.
A kind of 2. ruthenium carried titanium dioxide catalysis of australene selective hydrogenation synthesizing cis pinane according to claim 1 The preparation method of agent, it is characterized in that：The pH adjusting agent is Na2CO3Solution.
A kind of 3. ruthenium carried titanium dioxide catalysis of australene selective hydrogenation synthesizing cis pinane according to claim 1 The preparation method of agent, it is characterized in that：The step 5. in, by step, 4. gained liquid cools to room temperature, centrifuges 3-4 times, then Centrifugation products therefrom is dried into 10-15h at 60 DEG C.
A kind of 4. ruthenium carried titanium dioxide catalysis of australene selective hydrogenation synthesizing cis pinane according to claim 1 The preparation method of agent, it is characterized in that：The TiO2Preparation process be：
1. measure 180mL water and 1.3mL acid forms mixed liquor；
2. 15mLTi (OC are added dropwise into mixed liquor3H7)4Suspension is formed, gained suspension keeps 24h at 40 DEG C, obtained To the TiO of high degree of dispersion2Colloidal sol；
3. the TiO that will be obtained2Colloidal sol is transferred in 100mL ptfe autoclave, and 24h is kept at 180 DEG C, is then spent Ion-cleaning 3 times, dry 6h obtains product at 80 DEG C.
A kind of 5. ruthenium carried titanium dioxide catalysis of australene selective hydrogenation synthesizing cis pinane according to claim 4 The preparation method of agent, it is characterized in that：Acid is CH used by configuring mixed liquor3COOH,HNO3,H2SO4, HF or HCl.
6. a kind of method that australene selective hydrogenation synthesizing cis pinane is carried out using ruthenium catalyst for titanium dioxide loaded, it is special Sign is：Catalyst is support type Ru/TiO2, comprise the following steps that：
1. it is 0.1~1 according to the mass ratio of catalyst and australene:100, by 50g australenes and 0.05-0.5g Ru/TiO2Add Enter in ptfe autoclave, wherein Ru and TiO2Mass ratio be 5:100；
2. being replaced three to four times with hydrogen under gauge pressure 2.5-3.5MPa, leak detection, confirm that reactor sealing is intact；
3. open hydrogen gas valve, adjust kettle in pressure be 2-5MPa, open reactor heat up controller, in 100-140 DEG C, stir Mix and react 3-7h under speed 500r/min.
7. one kind according to claim 6 utilizes ruthenium catalyst for titanium dioxide loaded to carry out australene selective hydrogenation synthesis The method of cis-pinane, it is characterized in that：Step 3. in, save kettle in pressure be 3MPa, open reactor heat up controller, in 120 DEG C, react 5h under mixing speed 500r/min.
8. one kind according to claim 6 utilizes ruthenium catalyst for titanium dioxide loaded to carry out australene selective hydrogenation synthesis The method of cis-pinane, it is characterized in that：Ru/TiO2Preparation process it is as follows：
1. weigh 0.1g TiO2Add in conical flask, add 250mL deionized water, ultrasonic 1h thereto；
After 2. ultrasound terminates, Na is added into conical flask2CO3Solution, adjust the pH=9-10 in conical flask；
3. 35 DEG C are heated to, according to Ru and TiO2Mass ratio be 5:100 add 0.05mmol RuCl3, kept at 35 DEG C 3h；
4. after keeping 3h to terminate at 35 DEG C, 95 DEG C are warming up to, 0.2-2mL 300mM sodium borohydride solution is added, then 95 0.5h is kept at DEG C；
5. by step, 4. gained liquid cools to room temperature, centrifuges 3-4 times, centrifugation products therefrom is then dried into 10- at 60 DEG C 15h。
9. one kind according to claim 8 utilizes ruthenium catalyst for titanium dioxide loaded to carry out australene selective hydrogenation synthesis The method of cis-pinane, it is characterized in that：
The TiO2Preparation process be：
1. measure 180mL water and 1.3mL acid forms mixed liquor；
2. 15mLTi (OC are added dropwise into mixed liquor3H7)4Suspension is formed, gained suspension keeps 24h at 40 DEG C, obtained To the TiO of high degree of dispersion2Colloidal sol；
3. the TiO that will be obtained2Colloidal sol is transferred in 100mL ptfe autoclave, and 24h is kept at 180 DEG C, is then spent Ion-cleaning 3 times, dry 6h obtains product at 80 DEG C.
10. one kind according to claim 9 utilizes ruthenium catalyst for titanium dioxide loaded to carry out australene selective hydrogenation conjunction Into the method for cis-pinane, it is characterized in that：Acid is CH used by configuring mixed liquor3COOH,HNO3,H2SO4, HF or HCl.
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