CN104096559A - Multiwalled carbon nanotube (MCNTs)-supported platinum grease hydrogenation catalyst - Google Patents
Multiwalled carbon nanotube (MCNTs)-supported platinum grease hydrogenation catalyst Download PDFInfo
- Publication number
- CN104096559A CN104096559A CN201410302108.6A CN201410302108A CN104096559A CN 104096559 A CN104096559 A CN 104096559A CN 201410302108 A CN201410302108 A CN 201410302108A CN 104096559 A CN104096559 A CN 104096559A
- Authority
- CN
- China
- Prior art keywords
- mcnts
- catalyst
- platinum
- hydrogenation
- carrier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention provides a multiwalled carbon nanotube (MCNTs)-supported platinum grease hydrogenation catalyst, belongs to the field of catalysts, and relates to a platinum catalyst loaded on the MCNTs. The catalyst is formed by the active component platinum loaded on the MCNTs, the actual loading amount of platinum is 1.73% (the carrier weight is used as the benchmark), the specific surface area of the catalyst is 412.12 m<2>g<-1>, the specific pore volume is 0.462 cm<3>g<-1>, the average pore diameter is 4.48436 nanometer, and the platinum particle diameter ranges from 2.5 nanometers to 5.5 nanometers. According to the platinum grease hydrogenation catalyst provided by the invention, the preparation technology is classic and simple, the carrier material is novel, and the catalytic activity of the hydrogenated soybean oil is extremely high; moreover, compared with the industrial nickel catalyst, the catalyst provided by the invention has the advantages that less trans fatty acids are generated, the selectivity is good, the quality of the hydrogenated oil is good, and the hydrogenation effect is excellent.
Description
Technical field
The invention belongs to catalyst field, relate in particular to a kind of noble metal support type oil hydrogenation catalyst.
Background technology
20 beginnings of the century are since Germany scientist Wilhelm adopts Raney nickel to grease catalytic hydrogenation first, HYDROGENATION OF OILS AND FATS has had the developing history of last 100 years, hydrogenation has become in oil modification industry most widely used at present, also be a most important technique, also increase year after year of the demand of hydrogenated oil and fat.After edible oil hydrogenation, can reduce the degree of unsaturation of grease, improve fusing point, increase the content of hard fat; Improve edible oil and fat to oxygen and hot stability; Color and luster, fragrance and the mouthfeel etc. of improving edible oil and fat, expanded the purposes in food, generally can be used as the raw material of shortening, margarine or substitute of cocoa fat, has higher economic worth.
The high temperature of hydrogenation process, high pressure, catalytic condition will cause a large amount of trans-fatty acid (trans fatty acids, TFA) to produce, and in different hydrogenated vegetable oil, the content of trans-fatty acid has very big-difference because of the difference of processing technology.Research shows, TFA can increase the danger that people suffer from angiocardiopathy and type II diabetes, affects upgrowth and development of children, increases risk of cancer etc.Due to health is existed to harm, TFA has become the hot issue that government, academia, food processing industry and the general common people pay close attention to.Lot of domestic and foreign research is all devoted to seek to reduce in hydrogenation process the method for TFA growing amount.By controlling suitable hydroprocessing condition (temperature, pressure, mixing speed), select suitable noble metal catalyst, additive as amine substance, inorganic phosphate, free fatty etc., or adopt the methods such as supercritical fluid hydrogenation and electrochemistry hydrogenation reaction, all can reduce the content of trans-fatty acid in hydrogenated oil and fat.Researcher by selecting suitable hydrogenation conditions (as pressure, temperature, mixing speed and catalyst) thus change after hydrogenation the formation volume of trans-fatty acid in grease, and a large amount of foreign studies all focus on the optimization of probing into of preparation to all kinds of catalyst in catalytic hydrogenation and performance and hydrogenation conditions, thereby set up the rule model between hydrogenation processing conditions and trans-fatty acid formation.
Because catalyst is the key of HYDROGENATION OF OILS AND FATS, therefore since oil hydrogenation is realized suitability for industrialized production, people always in the exploitation to oil hydrogenation catalyst, modification, improve and application is studied.In traditional industry, the hydrogenated oil and fat of large-scale production is mainly taking metallic nickel, copper as catalyst at present, and because nickel catalyst has carcinogenicity, and Cu-series catalyst can produce a large amount of trans-fatty acids, and grease oxidation rancid is accelerated in the trace copper meeting of existence.
Summary of the invention
The invention provides a kind of carbon multi-wall nano tube loaded platinum oil hydrogenation catalyst.Selecting the noble metal platinum of high activity, low trans fatty acid generation is active component, is carried on artificial synthetic carrier multi-walled carbon nano-tubes and prepares carried noble metal platinum catalyst.Show that by the hydrogenation experimental evaluation of soybean oil catalyst of the present invention is high activity, the content of trans fatty acids producing is low, active metal component few catalyst that runs off, and observe by the quality of grease after hydrogenation, this catalyst is compared commercial nickel catalyst and is more suitable for production hydrogenated edible oil.
The object of the invention is to be achieved through the following technical solutions:
The carbon multi-wall nano tube loaded platinum oil hydrogenation catalyst that the present invention synthesizes, is made up of noble metal platinum and carrier multi-walled carbon nano-tubes MCNTs; Platinum particle size is about 4.0 ± 1.5 nm, is dispersed on carrier multi-walled carbon nano-tubes, and actual negative carrying capacity is that 1.73%(is taking vehicle weight as benchmark); Carrier multi-walled carbon nano-tubes is through the processing of red fuming nitric acid (RFNA) active oxidation, and the specific area of carrier MCNTs is 454.92 m
2g
-1, specific pore volume is 0.563 cm
3g
-1, average pore size is 4.95431 nm.
The preparation method of catalyst comprises following concrete steps:
(1) activation processing of carrier multi-walled carbon nano-tubes MCNTs: take the MCNTs of 3 g, first carry out purification process; To in MCNTs, add 68 % red fuming nitric acid (RFNA)s, under normal temperature, stir 24 h, centrifugal, after filtering and wash for several times, dry 12 h in 80 ° of C baking ovens;
(2) oxidation processes of MCNTs: after the purified MCNTs handling well is ground with mortar, add the rare nitric acid of 34 %, under normal temperature, stir 12 h, equally through centrifugal, filter, washing is to being neutral, in 80 ° of C baking ovens, dry 12 h, for subsequent use; It is that carrier surface is carried out to chemical modification effect that this process is used concentrated acid to carry out active oxidation object, make functional group certain on its surface or lumen wall band as the hydrophilic radical such as carboxyl and hydroxyl, just can be combined with noble metal in a certain way, be beneficial to the dipping of metallic solution, complete loading process;
(3) preparation of precious metals pt loading multi-wall carbon nanotubes catalyst: then by MCNTs after treatment, add the ethanol of 5 mL, add under the ultra-pure water room temperature of 25 mL and mix, ultrasonic dispersion 30 min, disperse noble metal granule to avoid the reunion of carrier better; After stirring, be heated to 80 ° of C, keep temperature 30 min, add H
2ptCl
66H
2o solution, adds the formalin of 35 mLs as reducing agent after stirring 15 min under constant temperature, and condensing reflux 8 h under 80 ° of C still stir 24 h after being cooled to room temperature.Finally that it is centrifugal, after washing for several times, in baking oven, after dry 12 h, make the catalyst Pt/MCNTs containing active component Pt; The catalyst preparing uses nitrogen to preserve.
The catalyst that uses above method to prepare, carrier load of metal after activation processing is easier, and uses the operation of formaldehyde wet reducing easier, and cost is lower compared with hydrogen reducing; The present invention uses novel carrier multi-wall carbon nano-tube tube material, metal platinum raw material sources are abundant, the activity of synthetic catalyst oil with hydrogenated soybean is high, metal component number of dropouts is few, the content of trans fatty acids low (28.59 g/100g soybean oil) that contrast Raney nickel produces in the time of iodine number 70, the stay in grade of hydrogenated oil and fat.The hydrogenation catalyst that the present invention is synthetic, is made up of noble metal platinum and carrier multi-walled carbon nano-tubes MCNTs; Platinum particle size is about 4.0 ± 1.5 nm, is dispersed on carrier multi-walled carbon nano-tubes, and actual negative carrying capacity is that 1.73%(is taking vehicle weight as benchmark); Carrier multi-walled carbon nano-tubes is through the processing of red fuming nitric acid (RFNA) active oxidation, and the specific area of carrier MCNTs is 454.92 m
2g
-1, specific pore volume is 0.563 cm
3g
-1, average pore size is 4.95431 nm.
On carrier is selected, through invention lot of experiments, select artificial synthetic vectors as CNT, activated alumina, titanium dioxide, zeolite loaded metal platinum respectively, the catalyst of making carries out activity and contrast experiment optionally.Research finds, activated alumina, zeolite cannot load on metal ingredient platinum, therefore active almost nil.Titania support is reunited more serious.And the catalyst of CNT, titanium dichloride load metal platinum has carried out sign and hydrogenation experiment, TEM characterization result shows Pt/TiO
2be respectively 2.5 ± 0.25 nm, 4.0 ± 1.5 nm with the upper platinum grain size of Pt/MCNTs.Observe platinum grain in carbon nanotube carrier larger, metal platinum decentralization is the highest, is evenly distributed, and is typical mesoporous material.
The feature of the synthetic catalyst of the present invention is: the step of synthetic catalyst is simple, and after formaldehyde reduction, active metal is stable, and reduction cost is relatively low, and raw material sources are abundant.With commercial nickel catalyst contrast, the catalyst activity that this law makes is higher, and in the time that iodine number is 70-90, trans-fatty acid growing amount is lower, and after hydrogenation, the quality of grease is fine: acid value is stable and be less than 1.0 mg (KOH)/g; The slip point value of grease significantly rises, finally up to 45.08 DEG C; Solid fats content (SFC) value of grease increases in time and significantly rises, and the SFC value of Raney nickel is only just 6 % left and right in the time that hydrogenation time reaches 240 min.
Brief description of the drawings
The iodine number decline curve of Fig. 1 Raney Ni and 1.73%Pt/MCNTs oil with hydrogenated soybean 4h
The C18:0 that when Fig. 2 IV ≈ 70, catalyst produces,
transc18:1 and total trans content
The fusing point of grease after Fig. 3 1.73%Pt/MCNTs and the hydrogenation of Raney Ni catalyst
After the hydrogenation of Fig. 4 1.73%Pt/MCNTs catalyst, grease solid fats content (SFC) changes
After the hydrogenation of Fig. 5 Raney Ni catalyst, grease solid fats content (SFC) changes
The acid value of Fig. 6 1.73%Pt/MCNTs oil with hydrogenated soybean
The acid value of Fig. 7 Raney Ni oil with hydrogenated soybean.
Detailed description of the invention
Example is described further:
Embodiment 1
The preparation condition of catalyst:
(1) activation processing of carrier MCNTs---take the carrier multi-walled carbon nano-tubes of approximately 3 g, first carry out purification process.The round-bottomed flask that MCNTs is placed in to 250 mL adds the red fuming nitric acid (RFNA) of a certain amount of 68 %, stirs 24 h under normal temperature, centrifugal, after filtering and wash for several times, and dry 12 h in 80 ° of C baking ovens;
(2) oxidation processes of MCNTs: the round-bottomed flask of putting into 250 mL after the purified MCNTs carrier mortar of handling well is ground, add the rare nitric acid of a certain amount of 34 %, under normal temperature, stir 12 h, same through centrifugal, filter, washing is to being neutral, in 80 ° of C baking ovens, dry 12 h, for subsequent use.It is that carrier surface is carried out to chemical modification effect that this process is used concentrated acid to carry out active oxidation object, make functional group certain on its surface or lumen wall band as the hydrophilic radical such as carboxyl and hydroxyl, just can be combined with noble metal in a certain way, be beneficial to the dipping of metallic solution, complete loading process;
(3) preparation of precious metals pt loading multi-wall carbon nanotubes catalyst: by a certain amount of multi-walled carbon nano-tubes carrier after treatment flask that is placed in, add the ethanol of 5 mL, add under the ultra-pure water room temperature of 25 mL and mix, ultrasonic dispersion 30 min, disperse noble metal granule to avoid the reunion of carrier better.Stir after a period of time, be heated to 80 ° of C, keep temperature 30 min, add the H that calculates concentration
2ptCl
66H
2o solution, adds the formalin of 35 mLs as reducing agent after stirring 15 min under constant temperature, and condensing reflux 8 h under 80 ° of C still stir 24 h after being cooled to room temperature.Finally that it is centrifugal, after washing for several times, in baking oven, after dry 12 h, make the catalyst Pt/MCNTs containing active component Pt.The catalyst preparing uses nitrogen to preserve.
Parametric measurement: the hydrogenation catalyst that the present invention is synthetic, is made up of noble metal platinum and carrier multi-walled carbon nano-tubes MCNTs; Platinum particle size is about 4.0 ± 1.5 nm, is dispersed on carrier multi-walled carbon nano-tubes, and actual negative carrying capacity is that 1.73%(is taking vehicle weight as benchmark); Carrier multi-walled carbon nano-tubes is through the processing of red fuming nitric acid (RFNA) active oxidation, and the specific area of carrier MCNTs is 454.92 m
2g
-1, specific pore volume is 0.563 cm
3g
-1, average pore size is 4.95431 nm.
Embodiment 2
Catalyst effect evaluation experimental of the present invention:
Hydrogenation process condition: measure the soybean oil of 300 mL, take catalyst 150 mg(that embodiment 1 prepares and ensure that catalyst amount is 5%, taking the weight of feedstock oil as benchmark) be placed in clean clean reactor, by reactor sealing, put heating jacket.Until temperature rise arrive approach setting value 170 DEG C after, pass into flowing nitrogen 5-10 minute to get rid of oxygen in still, then start to pass into pure hydrogen, introduce hydrogen and after nitrogen, maintain Hydrogen Vapor Pressure 3 bar to get rid of in still about 5 minutes, access condensed water also starts agitating device and makes rotating speed maintain 400 r/min, and now recording hydrogenation time is 0 h.Sample once every 0.5 h afterwards, hydrogenation 4 h, carry out determination of iodine value to oil sample after hydrogenation altogether, each sample are carried out to vapor detection analysis simultaneously.After hydrogenation stops, closing in time hydrogen gas cylinder and air intake valve, stop stirring, close condensed water and stop heating.Naturally after cooling, valve is driven in pressure release, pours residual hydrogen carburetion into waste liquid cylinder, cleans clean kettle with for subsequent use.Using conventional commercial catalysts---Raney's nickel is as reference, and it is a kind of solid-state different-phase catalyst being made up of the small grains of the nickel alumin(i)um alloy with loose structure.
In Fig. 2, add up iodine number content of trans fatty acids of grease after each catalyst hydrogenation in the time of 70-90, the trans C18:1 content that when data are presented at IV ≈ 72.6,1.73%Pt/MCNTs produces is 27.04 g/100 g soybean oils, is significantly less than the trans-fatty acid content (31.42 g/100 g soybean oil) that Raney Ni produces.And a little higher than Raney's nickel of stearic acid (C18:0) content that the 1.73%Pt/MCNTs catalyst of preparation produces reaches 17.51 g/100 g soybean oils.This is that the hole geometric configuration of multi-walled carbon nano-tubes carrier can promote the hydrogenation saturated reaction of polyunsaturated triglyceride because have the Pt/MCNTs catalyst of huge pore volume and micro-aperture.Because the carrier of this platinum catalyst has darker hole, the time of staying of polyunsaturated triglyceride in hole extended, thereby promote its hydrogenation saturated reaction, the saturated acid content therefore generating is higher.
the aliphatic acid of each catalyst oil with hydrogenated soybean composition when table 1 IV ≈ 70
?aS
1?=?(C18:1-C18:1
0)/(C18:2
0-?C18:2)
bS
2?=?(C18:0-C18:0
0)/(?C18:1-C18:1
0)
cΔDB?=?∑(ΔC18:1+?2ΔC18:2+3ΔC18:3)
Isomerization index (isomerization index, SI) definition in table 1 is: in aliphatic acid, carbon-carbon double bond isomery turns to the content double bond content more saturated than upper hydrogenation of anti-configuration.The isomery index SI of Pt/MCNTs catalyst is respectively 0.276, and the isomery index SI of Raney nickel is up to 0.476.Can infer, being that the isomery index SI of platinum catalyst under iodine number is lower in specific saturation degree shows that frequency that its isomerization reaction occurs still less, means the trans-fatty acid of Pt/MCNTs catalyst generation compared with Raney nickel still less.Because the industrial selective good catalyst of seeking is to produce lower monoene isomers (antiform oleic acid) content, therefore select the content of antiform oleic acid as the contrast index of catalyst selectivity quality, can find out that the antiform oleic acid content that 1.73%Pt/MCNTs catalyst produces is starkly lower than Raney nickel.
What table 1 was added up is that S is compared in content and the selection that two kinds of catalyst are approximately 70 o'clock each fatty acid compositions in iodine number
1, S
2.Statistics demonstration, S is compared in the selection of 1.73%Pt/MCNTs catalyst
1be 0.72 to compare S with the selection of Raney nickel
1close (0.87), and S is compared in its selection
2be 0.32, higher than Raney nickel, imply that C18:1 in its hydrogenation process is converted into the content of C18:0 more.
What Fig. 1 showed is the iodine number decline curve of grease after catalyst hydrogenation, and result shows that the double bond conversion rate of 1.73%Pt/MCNTs catalyst is 49.3 %, and iodine number drops to 71 from 140, and the double bond conversion rate of commercial nickel catalyst is 29.7%.Can obviously find out that the catalytic activity of 1.73%Pt/MCNTs catalyst is apparently higher than common commercial Raney nickel.Therefore on the whole, 1.73%Pt/MCNTs catalyst has greater activity compared with business nickel, lower selective generation antiform oleic acid (C18:1), and high selectivity generates saturated fatty acid (C18:0).
The variation of oil quality after contrast 1.73%Pt/MCNTs catalyst and Raney nickel hydrogenation, after Fig. 3 shows loaded platinum catalyst hydrogenation the rising of grease fusing point very obvious, finally up to 42.48 DEG C, and after Raney nickel hydrogenation, grease fusing point only approaches room temperature; What Fig. 4 and Fig. 5 showed is under different temperatures after catalyst hydrogenation, and the solid fats content of grease, with the variation diagram of hydrogenation time, can be found out under same temperature, along with the obviously increase of SFC value of carrying out (30-240 min) grease of hydrogenation.After Fig. 4 shows the hydrogenation of 1.73%Pt/MCNTs catalyst, grease has the highest SFC value, is being hydrogenated to increase fast after 90 min; And the SFC value of grease is only just 6 % left and right (20 ° of C) in the time that hydrogenation time reaches 240 min after the hydrogenation of Raney Ni catalyst.
After the hydrogenation of 1.73%Pt/MCNTs catalyst, the acid value of grease changes littlely and all lower than 1.0 mg (KOH)/g as can be seen from Figure 6, is applicable to grease selective hydration, and after hydrogenation, oil quality is good.And grease fusing point approaches room temperature after the hydrogenation of commercial nickel catalyst, solid fats content is very low, and acid value fluctuation is large, and hydrogenated oil and fat poor quality, is not suitable for producing hydrogenated oil and fat.
Claims (2)
1. carbon multi-wall nano tube loaded platinum oil hydrogenation catalyst, is characterized in that: be made up of platinum and carrier multi-walled carbon nano-tubes MCNTs; Platinum particle size is about 4.0 ± 1.5 nm, is dispersed on carrier multi-walled carbon nano-tubes, taking vehicle weight as benchmark load capacity is as 1.73%; Carrier multi-walled carbon nano-tubes is through the processing of red fuming nitric acid (RFNA) active oxidation, and the specific area of carrier MCNTs is 454.92 m
2g
-1, specific pore volume is 0.563 cm
3g
-1, average pore size is 4.95431 nm.
2. the preparation method of the carbon multi-wall nano tube loaded platinum oil hydrogenation catalyst of claim 1, is characterized in that comprising the steps:
1) activation processing of carrier multi-walled carbon nano-tubes MCNTs: take the MCNTs of 3 g, first carry out purification process; To in MCNTs, add 68 % red fuming nitric acid (RFNA)s, under normal temperature, stir 24 h, centrifugal, after filtering and wash for several times, dry 12 h in 80 ° of C baking ovens;
2) oxidation processes of MCNTs: after the purified MCNTs handling well is ground with mortar, add the rare nitric acid of 34 %, under normal temperature, stir 12 h, equally through centrifugal, filter, washing is to being neutral, in 80 ° of C baking ovens, dry 12 h, for subsequent use;
3) preparation of precious metals pt loading multi-wall carbon nanotubes catalyst: then by MCNTs after treatment, add the ethanol of 5 mL, add under the ultra-pure water room temperature of 25 mL and mix, ultrasonic dispersion 30 min, disperse noble metal granule to avoid the reunion of carrier better; After stirring, be heated to 80 ° of C, keep temperature 30 min, the H adding
2ptCl
66H
2o solution, adds the formalin of 35 mLs as reducing agent after stirring 15 min under constant temperature, and condensing reflux 8 h under 80 ° of C still stir 24 h after being cooled to room temperature; Finally that it is centrifugal, after washing for several times, in baking oven, after dry 12 h, make the catalyst Pt/MCNTs containing active component Pt; The catalyst preparing uses nitrogen to preserve.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410302108.6A CN104096559A (en) | 2014-06-30 | 2014-06-30 | Multiwalled carbon nanotube (MCNTs)-supported platinum grease hydrogenation catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410302108.6A CN104096559A (en) | 2014-06-30 | 2014-06-30 | Multiwalled carbon nanotube (MCNTs)-supported platinum grease hydrogenation catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104096559A true CN104096559A (en) | 2014-10-15 |
Family
ID=51665333
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410302108.6A Pending CN104096559A (en) | 2014-06-30 | 2014-06-30 | Multiwalled carbon nanotube (MCNTs)-supported platinum grease hydrogenation catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104096559A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106607018A (en) * | 2015-10-23 | 2017-05-03 | 中国石油化工股份有限公司 | Low carbon alkane dehydrogenation catalyst, and preparation method and applications thereof |
| CN107088435A (en) * | 2017-04-26 | 2017-08-25 | 东北农业大学 | A kind of preparation method of Ni Pt bimetallic catalysts |
| CN107099383A (en) * | 2017-04-26 | 2017-08-29 | 东北农业大学 | A kind of bimetallic supported catalyst is used for the method for oil with hydrogenated soybean |
| CN109234044A (en) * | 2018-09-20 | 2019-01-18 | 陈琪峰 | A kind of preparation method of high-effective cleansing anticorrosion type automobile cleaning agent |
| CN109395719A (en) * | 2018-11-05 | 2019-03-01 | 江苏大学 | A method of in multi-wall carbon nano-tube pipe surface controllable load noble metal nanometer material |
| CN109395744A (en) * | 2018-11-07 | 2019-03-01 | 江苏大学 | A kind of Ag2O quantum dot hydridization ZnIn2S4The preparation method of nanometer sheet p-n junction composite photo-catalyst |
| CN113457672A (en) * | 2021-08-18 | 2021-10-01 | 南京工业大学 | Multi-walled carbon nanotube supported platinum-based catalyst and preparation method and application thereof |
| CN116005184A (en) * | 2022-12-19 | 2023-04-25 | 东北农业大学 | Method for chemically modifying fullerene C60 carrier and application of fullerene C60 carrier in electrochemical hydrogenation of soybean oil |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798548A (en) * | 2010-04-08 | 2010-08-11 | 东北农业大学 | Method for developing lube base oil with hydrogenated soybean oil under supercritical CO2 state |
-
2014
- 2014-06-30 CN CN201410302108.6A patent/CN104096559A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798548A (en) * | 2010-04-08 | 2010-08-11 | 东北农业大学 | Method for developing lube base oil with hydrogenated soybean oil under supercritical CO2 state |
Non-Patent Citations (1)
| Title |
|---|
| 李艳: "CNTs负载Pt、Pd催化剂制备及α，β-不饱和醛选择性加氢反应性能的研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》, no. 11, 15 November 2008 (2008-11-15) * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106607018A (en) * | 2015-10-23 | 2017-05-03 | 中国石油化工股份有限公司 | Low carbon alkane dehydrogenation catalyst, and preparation method and applications thereof |
| CN106607018B (en) * | 2015-10-23 | 2019-07-23 | 中国石油化工股份有限公司 | A kind of catalyst for dehydrogenation of low-carbon paraffin and preparation method and application |
| CN107088435A (en) * | 2017-04-26 | 2017-08-25 | 东北农业大学 | A kind of preparation method of Ni Pt bimetallic catalysts |
| CN107099383A (en) * | 2017-04-26 | 2017-08-29 | 东北农业大学 | A kind of bimetallic supported catalyst is used for the method for oil with hydrogenated soybean |
| CN109234044A (en) * | 2018-09-20 | 2019-01-18 | 陈琪峰 | A kind of preparation method of high-effective cleansing anticorrosion type automobile cleaning agent |
| CN109395719A (en) * | 2018-11-05 | 2019-03-01 | 江苏大学 | A method of in multi-wall carbon nano-tube pipe surface controllable load noble metal nanometer material |
| CN109395744A (en) * | 2018-11-07 | 2019-03-01 | 江苏大学 | A kind of Ag2O quantum dot hydridization ZnIn2S4The preparation method of nanometer sheet p-n junction composite photo-catalyst |
| CN109395744B (en) * | 2018-11-07 | 2021-05-25 | 江苏大学 | Ag2O quantum dot hybrid ZnIn2S4Preparation method of nanosheet p-n type composite photocatalyst |
| CN113457672A (en) * | 2021-08-18 | 2021-10-01 | 南京工业大学 | Multi-walled carbon nanotube supported platinum-based catalyst and preparation method and application thereof |
| CN116005184A (en) * | 2022-12-19 | 2023-04-25 | 东北农业大学 | Method for chemically modifying fullerene C60 carrier and application of fullerene C60 carrier in electrochemical hydrogenation of soybean oil |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104096559A (en) | Multiwalled carbon nanotube (MCNTs)-supported platinum grease hydrogenation catalyst | |
| CN104437572B (en) | A kind of preparation method of graphene-supported nano nickel phosphide hydrogenation catalyst | |
| CN105218289B (en) | A kind of method that unrighted acid original position hydrogenation decarboxylation prepares long chain alkane | |
| CN102728359B (en) | Cobalt-base catalyst adopting silicon oxide mesoporous foam as carrier, and application thereof | |
| CN103801295B (en) | The Catalysts and its preparation method of aviation kerosine prepared by castor oil | |
| CN103691432B (en) | A kind of ruthenium/aluminium oxide catalyst, method for making and application thereof | |
| Cepeda et al. | Hydrogenation of sunflower oil over M/SiO2 and M/Al2O3 (M= Ni, Pd, Pt, Co, Cu) catalysts | |
| CN105237319A (en) | Method for preparation of long-chain alkane from unsaturated fatty acid at zero hydrogen consumption | |
| CN103657726A (en) | Preparation method and application of silica-microsphere-immobilized nanometer metal compound catalyst | |
| Zhao et al. | Preparation of hydrogenated soybean oil of high oleic oil with supported catalysts | |
| CN107500296A (en) | A kind of bar-shaped β Mo2C controlledly synthesis and its application in inverse water gas shift reation | |
| Wang et al. | Preparation and hydrodeoxygenation properties of Co–Mo–O–B amorphous catalyst | |
| CN105733646B (en) | A kind of method of high-grade aliphatic ester Hydrogenation hydrocarbon | |
| CN103721368A (en) | Hydrodechlorination method of trichloro ethylene | |
| CN107935816A (en) | A kind of method for being catalyzed guaiacol hydrogenation deoxidation and preparing cyclohexanol | |
| CN102534687B (en) | PdNiCu ternary nanoporous metal and preparation and application thereof | |
| CN102600900A (en) | Load-type gold-palladium bimetallic catalyst and preparation method thereof | |
| CN101829567A (en) | Preparation method and application of load type nano-gold catalyst | |
| CN104084232B (en) | A kind of preparation method of catalyst of biological fatty alcohol deoxidation | |
| KR101655764B1 (en) | Nickel catalyst and Hydrogenated Castor oil produced by this Nickel catalyst | |
| CN103752308A (en) | Preparation method of nano gold/carbon catalyst | |
| CN103657642A (en) | Grease hydrogenation catalyst | |
| CN102671711A (en) | Supported nano amorphous alloy catalyst and preparation method and application | |
| CN107262143A (en) | Hydrogenation catalyst suitable for producing aviation kerosine and its preparation method and application | |
| CN106064089B (en) | A kind of Regenrable catalyzed and preparation method thereof for catalyzing and reforming biologic oil hydrogen manufacturing |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20141015 |