CN106732800B - A kind of in-situ preparation method and application of lipophilic nano molybdenum disulfide catalyst - Google Patents
A kind of in-situ preparation method and application of lipophilic nano molybdenum disulfide catalyst Download PDFInfo
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- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/04—Oxides
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- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/24—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1033—Oil well production fluids
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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- C10G2300/1077—Vacuum residues
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Abstract
The present invention provides the in-situ preparation methods and application of a kind of lipophilic nano molybdenum disulfide catalyst, four thio ammonium molybdate and reducing agent are configured to aqueous solution by a certain percentage, then organic solvent and modified ligand not soluble in water is added, it is slowly stirred reaction certain time at a certain temperature, products therefrom obtains lipophilic nano molybdenum disulfide catalyst after centrifugation, washing, drying.Prepared nano molybdenum disulfide has fabulous dispersibility and stability in oily phase, and structure is amorphous structure, and molybdenum disulfide monolithic layer is decomposed into heavy oil floating bed hydrogenation reaction process.Amorphous nano molybdenum disulfide catalyst provided by the invention is demonstrated by high catalytic hydrogenation activity in the floating bed hydrogenation reaction of one or more of crude oil, reduced crude, decompression residuum, coal tar, deasphalted oil, oil sands bitumen, pitch, coal tar asphalt mixture and presses down burnt performance.
Description
Technical field
The present invention relates to a kind of in-situ preparation methods of lipophilic nano molybdenum disulfide catalyst, and its inferior heavy oil,
Application during hydrogenation of residual oil suspended bed belongs to the synthesis and catalytic applications of nano material.
Background technique
As high-quality crude constantly consumes, crude quality heaviness, the trend of high-sulfurized and high acidification are more and more obvious.This
Outside, a large amount of residual oil are also created in petroleum refining process, account for about 30~50wt% of crude oil.How to a large amount of crude oil with poor quality and
It is one of the problem that petrochemical industry faces at present that refinery residual oil, which carries out effective processing and utilization,.Suspension bed hydrogenation process is using poor quality
Crude oil, shale oil, oil sands bitumen, refinery residual oil liquid fuel was prepared oil advanced technologies.Suspension bed hydrogenation process is the most
Prominent feature is using unsupported disperse type catalyzer, and disperse type catalyzer high degree of dispersion in feedstock oil once passes through
It is not recycled after reactor.Therefore, for the disperse type catalyzer of suspension bed hydrogenation process require active height, good dispersion,
The features such as stability is high, dosage is small, at low cost.
Molybdenum disulfide is a kind of two-dimensional layer material with class graphene-structured, in catalysis, lubrication, microelectronics, is partly led
The fields such as body have a wide range of applications.Molybdenum disulfide can be used as the hydrogenation catalyst of PETROLEUM PROCESSING, be widely used in hydrotreating,
It is hydrocracked, hydrodesulfurization, hydrodenitrogeneration, the treatment processes such as hydrodemetallization.When being used for heavy oil floating bed hydrogenation technique
When, Ying Caiyong non-loading type molybdenum disulfide.The preparation method of molybdenum disulfide mainly has high temperature vulcanized method, presoma to decompose at present
Method, solvent-thermal method, electrochemical deposition method, template etc..But these preparation methods are more complicated, the molybdenum disulfide being prepared
Catalyst generally has the shortcomings that dispersion degree is poor, at high cost.
CN200710013466.5 discloses a kind of lyosol catalysis for inferior heavy oil, dreg-oil suspension bed hydrogenation cracking
Agent, the liquid sol catalyst are vulcanized by the transition-metal Fe that partial size is between 0.1 μm~100 μm, Co, Ni, Cr, Cu, Mn, Mo, W
Composition granule is dispersed in water phase and constitutes, and metal active constituent content is 2~25%.The catalyst is that transition metal is solvable
Property salt complex is formed with monodentate ligand or organic polydentate ligand in water phase, then carry out what vulcanization reaction obtained.
CN201410758657.4 discloses a kind of method that mos2 microsphere is prepared in Reverse Microemulsion System, should
Method passes through in hydrothermal reaction kettle in microemulsion system and vulcanizes, restores soluble molybdenum source, then separation, washing and drying
After obtain mos2 microsphere.But the mos2 microsphere of invention preparation is micron order, and size is larger, uses as catalyst
When, limited surface atom ratio limits its catalytic performance.In addition, the method that the invention prepares mos2 microsphere is more multiple
It is miscellaneous.
CN201010185621.3 discloses a kind of preparation method of nanoscale flaky molybdenum disulfide, and this method is with tetrathio
Ammonium molybdate is raw material, and using oxalic acid as reducing agent, the aqueous solution of the two is reacted under heating stirring, by reaction product further in
High-temperature process under nitrogen protection, finally obtains nanoscale flaky molybdenum disulfide.But the nano-grade curing of invention preparation
Molybdenum has apparent poly- and phenomenon, and a large amount of flaky nanometer structures gather and stack to form macroscopical block structure.
Currently, the preparation method of nano molybdenum disulfide catalyst is more complicated, and generally by high-temperature process to improve it
Crystallinity, but significantly poly- and phenomenon can occur for nano molybdenum disulfide catalyst while high-temperature process, when being used for heavy oil
Floating bed hydrogenation can reduce its dispersion degree in heavy oil feedstock when reacting, to influence its high active of hydrogenation catalysis and suppression coke
Energy.
Summary of the invention
The purpose of the present invention is to provide a kind of in-situ preparation method of lipophilic nano molybdenum disulfide catalyst, Yi Jiqi
Application during inferior heavy oil, hydrogenation of residual oil suspended bed.Lipophilic nano molybdenum disulfide catalyst useization of the invention
Learn the precipitation method be prepared, by in-situ surface finishing by lipophilic ligand molecular modify to generation nano molybdenum disulfide table
On the one hand face improves the compatibility of nano molybdenum disulfide with oily phase, on the other hand inhibit nano molybdenum disulfide product into
One step growth controls Product size in nanoscale；Prepared nano molybdenum disulfide catalyst have with raw material oil compatibility it is good,
The advantages that dispersion degree is high, synthesis technology is simple, for showing high catalysis in inferior heavy oil, hydrogenation of residual oil suspended bed reaction
Hydrogenation activity and the burnt performance of suppression.
To achieve the above object, the technical solution adopted by the present invention is that:
A kind of in-situ preparation method of lipophilic nano molybdenum disulfide catalyst, specifically includes the following steps: (1) is by four sulphur
It is in molar ratio that 1:1.5~2.5:50~300 are configured to aqueous solution for ammonium molybdate, reducing agent, deionized water；(2) Xiang Shangshu water
Be added organic solvent and modified ligand not soluble in water in solution, aqueous solution, organic solvent, modified ligand volume ratio be 100:
20~500:5~80；(3) 0.5~10h of reaction is slowly stirred at 40~80 DEG C, be then centrifuged for, wash, dry after obtain parent
The nano molybdenum disulfide of oiliness.
In above-mentioned preparation method, reducing agent described in step (1) is oxalic acid, tartaric acid, citric acid, one in hydroxylamine hydrochloride
Kind is several.
In above-mentioned preparation method, organic solvent described in step (2) is aliphatic hydrocarbon, halogenated aliphatic hydrocarbon, aromatic hydrocarbon, stone brain
One or more of oil, straight-run diesel oil.
In above-mentioned preparation method, modified ligand described in step (2) includes that (carbon of alkyl is former in its structure for carboxylic acid compound
One or more of subnumber >=7) and sulfhydryl compound.
In above-mentioned preparation method, it is 80~200rpm that rate is slowly stirred described in step (3).
The lipophilic nano molybdenum disulfide catalyst being prepared according to above-mentioned preparation method, it is characterised in that: lipophilic
Nano molybdenum disulfide catalyst is the irregular particle that partial size is located at 50~200nm, does not contain crystal of molybdenum disulfide in particle
Feature lamellar structure；There is no the strong diffraction maximum for occurring sharp in the XRD spectra of lipophilic nano molybdenum disulfide catalyst, 2 θ=
Occur the characteristic diffraction peak of wide in range and faint molybdenum disulfide (002) crystal face at 13 °~16 °, occurs at 2 θ=35 °~42 °
The characteristic diffraction peak of wide in range and faint molybdenum disulfide (103) crystal face.
The lipophilic nano molybdenum disulfide catalyst being prepared according to above-mentioned preparation method has fabulous in oily phase
Dispersibility and stability.This is because during the preparation process, lipophilic modified ligand directly passes through chemical bond and is adsorbed onto original position
The nano molybdenum disulfide particle surface of generation, changes the surface nature of nano molybdenum disulfide particle, to effectively increase it
Dispersibility and stability in oily phase.
The lipophilic nano molybdenum disulfide catalyst being prepared according to above-mentioned preparation method, it is characterised in that: lipophilic
Nano molybdenum disulfide catalyst is decomposed in inferior heavy oil, hydrogenation of residual oil suspended bed reaction process, with length for 2~20nm
Single layer molybdenum disulfide structure disperses in product.
Lipophilic nano molybdenum disulfide catalyst provided by the invention is in the floating bed hydrogenation reaction of inferior heavy oil, residual oil
It is demonstrated by high catalytic hydrogenation activity and presses down burnt performance.The present invention passes through the modification of lipophilic modified ligand molecule, institute
The lipophilic nano molybdenum disulfide catalyst of preparation has fabulous dispersibility and stability in oily phase, to effectively increase
A large amount of reactive hydrogens of dispersion degree of the lipophilic nano molybdenum disulfide catalyst in heavy-oil hydrogenation reaction process, generation can be rapid
Heavy oil reaction is participated in, and annihilation reaction occurs with the heavy oil macromolecular radical nearby generated rapidly, and then improves catalysis and adds
Hydrogen activity and inhibition green coke performance.
According to above-mentioned lipophilic nano molybdenum disulfide catalyst answering in inferior heavy oil, hydrogenation of residual oil suspended bed reaction
With, the inferior heavy oil, residual oil include crude oil, reduced crude, decompression residuum, coal tar, deasphalted oil, oil sands bitumen, pitch,
One or more of coal tar asphalt.
Detailed description of the invention
Fig. 1 is X-ray diffraction (XRD) spectrogram of lipophilic nano molybdenum disulfide catalyst produced by the present invention.
Fig. 2 is the TEM photo of lipophilic nano molybdenum disulfide catalyst produced by the present invention.
Fig. 3 is the HRTEM photo of lipophilic nano molybdenum disulfide catalyst produced by the present invention.
Fig. 4 is photo of the lipophilic nano molybdenum disulfide catalyst produced by the present invention after toluene disperses and stands 3 days.
Fig. 5 is the TEM of lipophilic nano molybdenum disulfide catalyst distribution situation in heavy oil floating bed hydrogenation reaction product
Photo.
Specific embodiment
The present invention is described in further details below with reference to embodiment and attached drawing, but the invention is not limited to below
Embodiment.
Embodiment 1
2.6g four thio ammonium molybdate and 1.5g oxalic acid are dissolved in 30mL deionized water；20mL is added into above-mentioned aqueous solution
Normal heptane and 5mL oleic acid；Speed at 70 DEG C with 100rpm is slowly stirred reaction 2h；After reaction, it is centrifugated out black
Color solid product is washed 3 times using deionized water and alcohol mixed solution, and the catalysis of lipophilic nano molybdenum disulfide is obtained after dry
Agent.Prepared product is the irregular particle that partial size is 50~110nm, has fabulous dispersibility and stabilization in oily phase
Property, it stands 3 days and does not settle.
Embodiment 2
3.1g four thio ammonium molybdate, 0.5g oxalic acid and 1.6g hydroxylamine hydrochloride are dissolved in 50mL deionized water；To above-mentioned water
30mL toluene and 8mL n- dodecyl mereaptan are added in solution；Speed at 60 DEG C with 80rpm is slowly stirred reaction 1.5h；Reaction
After, it is centrifugated out black solid product, is washed 3 times using deionized water and alcohol mixed solution, obtains parent after dry
Oiliness nano molybdenum disulfide catalyst.Prepared product is the irregular particle that partial size is 70~150nm, is had in oily phase
Fabulous dispersibility and stability stands 2 days and does not settle.
Embodiment 3
3.5g four thio ammonium molybdate and 5.2g citric acid are dissolved in 50mL deionized water；It is added into above-mentioned aqueous solution
80mL1,1- dichloroethanes and 15mL caprylic acid；Speed at 80 DEG C with 80rpm is slowly stirred reaction 0.5h；Reaction terminates
Afterwards, it is centrifugated out black solid product, is washed 3 times using deionized water and alcohol mixed solution, obtains lipophilicity after dry
Nano molybdenum disulfide catalyst.Prepared product is the irregular particle that partial size is 60~180nm, is had in oily phase fabulous
Dispersibility and stability, stand and do not settle for 3 days.
Embodiment 4
2.3g four thio ammonium molybdate and 6.1g tartaric acid are dissolved in 40mL deionized water；It is added into above-mentioned aqueous solution
20mL straight-run diesel oil and 15mL n-hexadecyl mercaptan；Speed at 40 DEG C with 200rpm is slowly stirred reaction 1.5h；Reaction
After, it is centrifugated out black solid product, is washed 3 times using deionized water and alcohol mixed solution, obtains parent after dry
Oiliness nano molybdenum disulfide catalyst.Prepared product is the irregular particle that partial size is 50~90nm, is had in oily phase
Fabulous dispersibility and stability stands 3 days and does not settle.
Embodiment 5
1.5g four thio ammonium molybdate, 1.2g citric acid and 0.8g hydroxylamine hydrochloride are dissolved in 30mL deionized water；To above-mentioned
40mL naphtha and 10mL capric acid are added in aqueous solution；Speed at 60 DEG C with 150rpm is slowly stirred reaction 2.0h；Reaction
After, it is centrifugated out black solid product, is washed 3 times using deionized water and alcohol mixed solution, obtains parent after dry
Oiliness nano molybdenum disulfide catalyst.Prepared product is the irregular particle that partial size is 80~150nm, is had in oily phase
Fabulous dispersibility and stability stands 2 days and does not settle.
Embodiment 6
2.6g four thio ammonium molybdate and 3.8g tartaric acid are dissolved in 40mL deionized water；It is added into above-mentioned aqueous solution
20mL dimethylbenzene and 8mL1- benzene ethyl mercaptan；Speed at 50 DEG C with 170rpm is slowly stirred reaction 10.0h；After reaction,
It is centrifugated out black solid product, is washed 3 times using deionized water and alcohol mixed solution, obtains lipophilic nano after dry
Molybdenum disulfide catalyst.Prepared product is the irregular particle that partial size is 100~180nm, is had in oily phase fabulous
Dispersibility and stability stand 3 days and do not settle.
Fig. 1 is the XRD spectra of lipophilic nano molybdenum disulfide catalyst produced by the present invention, is not occurred in XRD spectra
There is the characteristic diffraction peak of wide in range and faint molybdenum disulfide (002) crystal face at 2 θ=13 °~16 ° in sharp strong diffraction maximum,
Occurs the characteristic diffraction peak of wide in range and faint molybdenum disulfide (103) crystal face at 2 θ=35 °~42 °.Fig. 2 and Fig. 3 is obtained
Lipophilic nano molybdenum disulfide catalyst TEM and HRTEM photo, display products therefrom is that partial size 50~200nm not advised
There is not the feature lamellar structure of crystal of molybdenum disulfide in then particle, shows that prepared product is amorphous structure.
Fig. 4 is photo of the lipophilic nano molybdenum disulfide catalyst produced by the present invention after toluene disperses and stands 3 days,
Illustrate that lipophilic nano molybdenum disulfide catalyst obtained has fabulous dispersibility and stability in oily phase.
Embodiment 7-14
The heavy oil feedstock that following embodiment uses be Kelamayi super-viscous oil decompression residuum and Athabasca oil sands bitumen,
Concrete composition and property are shown in Table 1.Embodiment 7-12 use suspension bed hydrogenation process, with Kelamayi super-viscous oil decompression residuum,
Athabasca oil sands bitumen or both 1:1 mixed raw material oil is raw material, tests lipophilicity prepared by embodiment 1-6 respectively and receives
The catalytic activity of rice molybdenum disulfide catalyst and the burnt performance of suppression, test result are shown in Table 2.Embodiment 13 uses Chinese patent
Amphiphilic nano molybdenum disulfide hydrogenation catalyst in surface described in CN201410494946.8, embodiment 14 use Chinese patent
The nano molybdenum disulfide prepared described in CN201210097518.2 using microemulsion system, is tested both molybdenum disulfide and urged
Catalytic activity and suppression burnt performance of the agent in heavy oil floating bed hydrogenation reaction, test result are shown in Table 2.
In table 2 evaluation result can be seen that lipophilic nano molybdenum disulfide catalyst provided by the invention inferior heavy oil,
With high catalytic hydrogenation activity and the burnt performance of suppression in hydrogenation of residual oil suspended bed reaction.In catalyst amount lower than 200ppm's
In the case of, inferior heavy oil, residual oil conversion ratio be greater than 86%, light oil yield is not less than 75% in product, toluene insolubles yield
Lower than 0.4%.Illustrate the lipophilicity of nano molybdenum disulfide catalyst by improving the dispersion degree and stabilization that it disperses in heavy oil
Property, it significantly improves the catalytic hydrogenation activity of catalyst and presses down burnt performance.
Fig. 5 is the TEM of lipophilic nano molybdenum disulfide catalyst distribution situation in heavy oil floating bed hydrogenation reaction product
Photo.After reaction, amorphous molybdenum disulfide catalyst of the present invention is scattered in product with the single layer structure of 2~20nm of length
In, active site extremely abundant is provided for heavy oil catalytic hydrogenation reaction.It is corresponding, Chinese patent
Amphiphilic nano molybdenum disulfide hydrogenation catalyst in surface described in CN201410494946.8 is that having for partial size 200nm or so is certain
The molybdenum disulfide particles of hexagonal system structure, after the conditioned response according to embodiment 13, surface amphiphilic nano molybdenum disulfide adds hydrogen
Catalyst is still distributed in the product with original pattern, size.Micro emulsion is used described in Chinese patent CN201210097518.2
The hexagonal crystal system molybdenum disulfide spheric granules that the nano molybdenum disulfide of liquid system preparation is 60~90nm of diameter, according to embodiment 14
Conditioned response after, nano molybdenum disulfide catalyst gather and be the dispersion of micron-sized molybdenum disulfide particles in the product.
The composition and property of table 1 Kelamayi super-viscous oil decompression residuum and Athabasca oil sands bitumen
2 heavy oil floating bed hydrogenation test evaluation result of table
Claims (5)
1. a kind of in-situ preparation method of lipophilic nano molybdenum disulfide catalyst, it is characterised in that the following steps are included:
It (1) is in molar ratio that 1:1.5 ~ 2.5:50 ~ 300 are configured to aqueous solution by four thio ammonium molybdate, reducing agent, deionized water；
(2) organic solvent and modified ligand not soluble in water are added in Xiang Shangshu aqueous solution, aqueous solution, organic solvent, modification are matched
The volume ratio of body is 100:20 ~ 500:5 ~ 80；
(3) 0.5 ~ 10h of reaction is slowly stirred at 40 ~ 80 DEG C, be then centrifuged for, wash, dry after obtain lipophilic nanometer two
Molybdenum sulfide catalyst；
Wherein, reducing agent described in step (1) is one or more of oxalic acid, tartaric acid, citric acid, hydroxylamine hydrochloride；Step
(2) organic solvent described in is one or more of aliphatic hydrocarbon, halogenated aliphatic hydrocarbon, aromatic hydrocarbon, naphtha, straight-run diesel oil；Step
Suddenly modified ligand described in (2) includes one or more of carboxylic acid compound and sulfhydryl compound, wherein carboxylic acid compound
Carbon atom number >=7 of alkyl in structure；It is 80 ~ 200rpm that rate is slowly stirred described in step (3).
What 2. a kind of in-situ preparation method of lipophilic nano molybdenum disulfide catalyst according to claim 1 was prepared
Lipophilic nano molybdenum disulfide catalyst.
3. lipophilic nano molybdenum disulfide catalyst according to claim 2, which is characterized in that lipophilic nano curing
Molybdenum catalyst has fabulous dispersibility and stability in oily phase.
4. lipophilic nano molybdenum disulfide catalyst according to claim 2, which is characterized in that lipophilic nano curing
Molybdenum catalyst is decomposed in inferior heavy oil, hydrogenation of residual oil suspended bed reaction process, two sulphur of single layer for being 2 ~ 20nm with length
Change molybdenum structure to be scattered in product.
5. the described in any item lipophilic nano molybdenum disulfide catalysts of claim 2-4 inferior heavy oil, it is dreg-oil suspension bed plus
Application in hydrogen reaction, the inferior heavy oil, residual oil include crude oil, reduced crude, decompression residuum, coal tar, deasphalted oil, oil
One or more of sand pitch, coal tar asphalt.
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|---|---|---|---|---|
| CN101857273A (en) * | 2010-05-26 | 2010-10-13 | 上海大学 | Preparation method of nanoscale flaky molybdenum disulfide |
| CN104689836A (en) * | 2013-12-04 | 2015-06-10 | 中国科学院大连化学物理研究所 | Highly dispersed nano molybdenum disulfide catalyst synthetic method |
| CN105728000A (en) * | 2016-02-04 | 2016-07-06 | 台州天天环保科技有限公司 | Preparation method and application of oleophylic type nanoscaled molybdenum disulfide |
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2016
- 2016-11-25 CN CN201611053936.6A patent/CN106732800B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857273A (en) * | 2010-05-26 | 2010-10-13 | 上海大学 | Preparation method of nanoscale flaky molybdenum disulfide |
| CN104689836A (en) * | 2013-12-04 | 2015-06-10 | 中国科学院大连化学物理研究所 | Highly dispersed nano molybdenum disulfide catalyst synthetic method |
| CN105728000A (en) * | 2016-02-04 | 2016-07-06 | 台州天天环保科技有限公司 | Preparation method and application of oleophylic type nanoscaled molybdenum disulfide |
Non-Patent Citations (1)
| Title |
|---|
| Preparation and Enhancement of Thermal Conductivity of Heat Transfer Oil-Based MoS2 Nanofluids;Yuan-Xian Zeng，et.al.;《Journal of Nanomaterials》;20131231;第2013卷;第1页第2段，第2页第1段，第2页第2.2节 * |
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