CN105728000A - Preparation method and application of oleophylic type nanoscaled molybdenum disulfide - Google Patents
Preparation method and application of oleophylic type nanoscaled molybdenum disulfide Download PDFInfo
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 235000015393 sodium molybdate Nutrition 0.000 claims abstract description 31
- 239000011684 sodium molybdate Substances 0.000 claims abstract description 31
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000295 fuel oil Substances 0.000 claims abstract description 28
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 27
- 239000012153 distilled water Substances 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 230000000694 effects Effects 0.000 claims abstract description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 22
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 19
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 239000004094 surface-active agent Substances 0.000 claims abstract description 11
- 238000001291 vacuum drying Methods 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims description 35
- 238000007667 floating Methods 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 9
- 238000003916 acid precipitation Methods 0.000 claims description 8
- 239000012467 final product Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- JHJUUEHSAZXEEO-UHFFFAOYSA-M sodium;4-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 JHJUUEHSAZXEEO-UHFFFAOYSA-M 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002010 green coke Substances 0.000 abstract description 8
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 231100000614 poison Toxicity 0.000 abstract description 2
- 230000007096 poisonous effect Effects 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 abstract 1
- 230000020477 pH reduction Effects 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 7
- 229910052750 molybdenum Inorganic materials 0.000 description 7
- 239000011733 molybdenum Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005987 sulfurization reaction Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical compound O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012053 oil suspension Substances 0.000 description 1
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- 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
- 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
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- 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
- C10G47/06—Sulfides
-
- C—CHEMISTRY; METALLURGY
- 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
- C10G2300/70—Catalyst aspects
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- C—CHEMISTRY; METALLURGY
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
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- C—CHEMISTRY; METALLURGY
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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Abstract
The invention discloses a preparation method and application of oleophylic type nanoscaled molybdenum disulfide, and belongs to the technical field of inferior heavy oil suspended bed hydrocracking.The method comprises the following steps that under the protection of nitrogen, distilled water, sodium molybdate and hydroxylamine hydrochloride are sequentially added into a container, mixed to be uniform and then subjected to a reaction under the heating effect; sodium sulfide continues to be added into the container, mixed to be uniform and subjected to a reaction under the heating effect; a surface active agent is added into the container, stirred to be uniform and subjected to acidification precipitation by dropwisely adding hydrochloric acid under the heating effect; after the reactions are ended, sufficient cooling and centrifugal are performed, washing is performed with distilled water and ethyl alcohol three times, and drying is performed in a vacuum drying box, and the oleophylic type nanoscaled molybdenum disulfide is obtained.The obtained oleophylic type nanoscaled molybdenum disulfide is high in molybdenum metal raw material conversion rate, no poisonous or harmful raw materials are involved, and the oleophylic type nanoscaled molybdenum disulfide can remarkably restrain the green coke amount in the heavy oil suspended bed hydrocracking technology.
Description
Technical field
The present invention relates to coal Direct Hydrogenation liquefaction/coal tar hydrocracking/inferior heavy oil floating bed hydrocracking technical field, particularly to a kind of lipophilic nano molybdenum disulfide preparation method and application thereof.
Background technology
Heavy oil floating bed hydrocracking is the hydrocracking heavy oil under high temperature, high hydrogen pressure environment.The hydrogenation catalyst of trace wherein becomes complete mixing flow state with heavy oil and hydrogen in reflection, and the effect of catalyst mainly suppresses heavy oil green coke in the reaction, thus improving the service cycle of device.Urge crude oil in China degree of dependence on inport to increase and heavy oil account for the ratio of crude oil and is gradually increased, how to process these high metals, high asphalitine, high-sulfur nitrogen heavy oil become heavy oil deep processing urgent problem.
The catalyst being presently used for heavy oil floating bed hydrocracking mainly includes water-soluble catalyst and oil-soluble catalyst two kinds, and wherein owing to water-soluble catalyst dispersing technology is complicated, energy consumption is high, industrial applications difficulty.Therefore, the highly active oil-soluble catalyst of development of new, including aphthenic acids catalyst series, it disadvantage is that additional vulcanizing agent is unfavorable for industry's enlarging production.Sulfuration catalyst series, its shortcoming is in that synthesis step is relatively complicated and material toxicity is relatively strong, and the catalyst particle size after sulfuration is relatively low in the utilization rate of micron level catalyst.
Summary of the invention
The present invention provides a kind of lipophilic nano molybdenum disulfide preparation method, solves that existing sulfuration catalyst series synthesis step is loaded down with trivial details, material toxicity strong and as the catalyst utilization problem end of compared with.
Present invention also offers the application for the catalyst of heavy oil floating bed hydrocracking of the lipophilic nano molybdenum disulfide, this catalyst can significantly reduce heavy oil green coke amount in slurry-bed hydrocracking, improves the service cycle of device.
For solving above-mentioned technical problem, the technical solution used in the present invention is:
A kind of lipophilic nano molybdenum disulfide preparation method, the method adopts sodium molybdate to be molybdenum source, and adopting sodium sulfide is sulfur source, and employing oxammonium hydrochloride. is reducing agent, adds surfactant and improves the lipophilic of molybdenum bisuphide；Comprise the following steps:
(1) under the protection of nitrogen, it is sequentially added into distilled water, sodium molybdate and oxammonium hydrochloride. in container, reacts under heat effect after mix homogeneously；
(2) continue to add sodium sulfide in container, react under heat effect after mixing uniformly；
(3) in container, add surfactant, under heat effect, drip hydrochloric acid after stirring carry out acid precipitation；
(4) reaction is sufficiently cool after terminating, centrifugal, washs respectively three times with distilled water and ethanol, dry in vacuum drying oven, to obtain final product.
Wherein it is preferred to, described sodium molybdate concentration in distilled water is 0.2～0.5g ml-1, sodium molybdate, described oxammonium hydrochloride., described sodium sulfide mol ratio be 1:4～6:4～5.
Wherein, preferably, described surfactant be in cetyl trimethylammonium bromide, dodecylbenzene sodium sulfonate, triton x-100, Polyethylene Glycol any one or a few, surfactant concentration in distilled water is 0.005～0.5g (100ml)-1。
Wherein it is preferred to, the heating-up temperature in described step (1) is 70 DEG C～90 DEG C, and the response time is 60min～90min.
Wherein it is preferred to, the heating-up temperature in described step (2) is 60 DEG C～80 DEG C, and the response time is 60min～80min.
Wherein it is preferred to, the heating-up temperature in described step (3) is 30 DEG C～50 DEG C, and the response time is 20min～30min.
Wherein it is preferred to, in described step (3) after dropping hydrochloric acid, the pH value of solution is 0.8～1.2.
The diameter of the lipophilic nano molybdenum disulfide prepared by above method is between 150nm～200nm, and the dispersion in toluene and hexamethylene is high.
The present invention also provides the application for the catalyst of heavy oil floating bed hydrocracking of the lipophilic nano molybdenum disulfide.
Beneficial effects of the present invention:
(1) the molybdenum feed stock conversion used by lipophilic nano molybdenum disulfide of present invention synthesis is high, it is not related to poisonous and harmful raw material, the synthesis economic benefit that improves greatly and meet green chemistry process, is a kind of environmentally friendly heavy oil floating bed hydrocracking catalyst.
(2) the lipophilic nano molybdenum disulfide catalyst synthesized by the present invention has higher hydrogenation activity in heavy oil floating bed hydrocracking reacts, there is no this material at present and be applied to floating bed hydrocracking, use the lipophilic nano molybdenum disulfide catalyst of the present invention as heavy oil floating bed hydrocracking catalyst, green coke amount can be reduced, maintain device long-term operation (if green coke amount is high, then easily cause device blocking).
(3) catalyst synthesized by the present invention has lipophile, need not at additional any auxiliary agent in oil phase dispersive process.Simultaneously, the catalyst particle size of synthesis is Nano grade, has high specific surface area, can provide substantial amounts of hydroperoxyl radical in heavy oil floating bed hydrocracking process, significantly inhibit the green coke amount in heavy oil floating bed hydrocracking technique, improve the economic benefit of heavy oil floating bed hydrocracking greatly.
Detailed description of the invention
Below technical scheme is clearly and completely described, it is clear that described content is only one embodiment of the invention, rather than whole embodiments.Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art obtain under not making creative work premise, broadly fall into the scope of protection of the invention.
A kind of lipophilic nano molybdenum disulfide preparation method, the method adopts sodium molybdate to be molybdenum source, and adopting sodium sulfide is sulfur source, and employing oxammonium hydrochloride. is reducing agent, adds surfactant and improves the lipophilic of molybdenum bisuphide；Comprise the following steps:
(1) under the protection of nitrogen, it is sequentially added into distilled water, sodium molybdate and oxammonium hydrochloride. in container, reacts under heat effect after mix homogeneously；
(2) continue to add sodium sulfide in container, react under heat effect after mixing uniformly；
(3) in container, add surfactant, under heat effect, drip hydrochloric acid after stirring carry out acid precipitation；
(4) reaction is sufficiently cool after terminating, centrifugal, washs respectively three times with distilled water and ethanol, dry in vacuum drying oven, to obtain final product.
The method adopts sodium molybdate to be molybdenum source, and adopting sodium sulfide is sulfur source, and employing oxammonium hydrochloride. is reducing agent, adds surfactant and improves the lipophilic of molybdenum bisuphide；
Lipophilic nano molybdenum disulfide is for the application of the catalyst of heavy oil floating bed hydrocracking.
Embodiment 1
The present embodiment provides a kind of lipophilic nano molybdenum disulfide preparation method, comprises the following steps:
(1) adding 200ml distilled water under the protection of nitrogen in container, add sodium molybdate and oxammonium hydrochloride., wherein, sodium molybdate concentration in distilled water is 0.2g ml-1, the mol ratio of sodium molybdate and oxammonium hydrochloride. is 1:5, reacts after mix homogeneously, and reaction temperature is 80 DEG C, and the response time is 50min；
(2) continuation adds sodium sulfide in container, reacts after mixing uniformly under heat effect, and heating-up temperature is 70 DEG C, and the response time is 70min, and the mol ratio of sodium molybdate and sodium sulfide is 1:4.5；
(3) adding 0.01g cetyl trimethylammonium bromide in container, dripping hydrochloric acid to pH value after stirring under heat effect is 1.0, carries out acid precipitation, and heating-up temperature is 40 DEG C, and the response time is 25min；
(4) reaction is sufficiently cool after terminating, centrifugal, washs respectively three times with distilled water and ethanol, dry in vacuum drying oven, to obtain final product.
Lipophilic nano molybdenum disulfide is for the application of the catalyst of heavy oil floating bed hydrocracking.
Embodiment 2
The present embodiment provides a kind of lipophilic nano molybdenum disulfide preparation method, comprises the following steps:
(1) adding 200ml distilled water under the protection of nitrogen in container, add sodium molybdate and oxammonium hydrochloride., wherein, sodium molybdate concentration in distilled water is 0.3g ml-1, the mol ratio of sodium molybdate and oxammonium hydrochloride. is 1:6, reacts after mix homogeneously, and reaction temperature is 70 DEG C, and the response time is 90min；
(2) continuation adds sodium sulfide in container, reacts after mixing uniformly under heat effect, and heating-up temperature is 60 DEG C, and the response time is 80min, and the mol ratio of sodium molybdate and sodium sulfide is 1:5；
(3) adding 0.1g dodecylbenzene sodium sulfonate in container, dripping hydrochloric acid to pH value after stirring under heat effect is 0.8, carries out acid precipitation, and heating-up temperature is 30 DEG C, and the response time is 30min；
(4) reaction is sufficiently cool after terminating, centrifugal, washs respectively three times with distilled water and ethanol, dry in vacuum drying oven, to obtain final product.
Lipophilic nano molybdenum disulfide is for the application of the catalyst of heavy oil floating bed hydrocracking.
Embodiment 3
The present embodiment provides a kind of lipophilic nano molybdenum disulfide preparation method, comprises the following steps:
(1) adding 200ml distilled water under the protection of nitrogen in container, add sodium molybdate and oxammonium hydrochloride., wherein, sodium molybdate concentration in distilled water is 0.4g ml-1, the mol ratio of sodium molybdate and oxammonium hydrochloride. is 1:4, reacts after mix homogeneously, and reaction temperature is 90 DEG C, and the response time is 60min；
(2) continuation adds sodium sulfide in container, reacts after mixing uniformly under heat effect, and heating-up temperature is 80 DEG C, and the response time is 60min, and the mol ratio of sodium molybdate and sodium sulfide is 1:4；
(3) adding 0.03g triton x-100 in container, dripping hydrochloric acid to pH value after stirring under heat effect is 1.2, carries out acid precipitation, and heating-up temperature is 50 DEG C, and the response time is 20min；
(4) reaction is sufficiently cool after terminating, centrifugal, washs respectively three times with distilled water and ethanol, dry in vacuum drying oven, to obtain final product.
Lipophilic nano molybdenum disulfide is for the application of the catalyst of heavy oil floating bed hydrocracking.
Embodiment 4
The present embodiment provides a kind of lipophilic nano molybdenum disulfide preparation method, comprises the following steps:
(1) adding 200ml distilled water under the protection of nitrogen in container, add sodium molybdate and oxammonium hydrochloride., wherein, sodium molybdate concentration in distilled water is 0.5g ml-1, the mol ratio of sodium molybdate and oxammonium hydrochloride. is 1:4, reacts after mix homogeneously, and reaction temperature is 80 DEG C, and the response time is 70min；
(2) continuation adds sodium sulfide in container, reacts after mixing uniformly under heat effect, and heating-up temperature is 65 DEG C, and the response time is 75min, and the mol ratio of sodium molybdate and sodium sulfide is 1:4.2；
(3) adding 0.8g Polyethylene Glycol in container, dripping hydrochloric acid to pH value after stirring under heat effect is 0.9, carries out acid precipitation, and heating-up temperature is 45 DEG C, and the response time is 28min；
(4) reaction is sufficiently cool after terminating, centrifugal, washs respectively three times with distilled water and ethanol, dry in vacuum drying oven, to obtain final product.
Lipophilic nano molybdenum disulfide is for the application of the catalyst of heavy oil floating bed hydrocracking.
Embodiment 5
The present embodiment provides a kind of lipophilic nano molybdenum disulfide preparation method, comprises the following steps:
(1) adding 200ml distilled water under the protection of nitrogen in container, add sodium molybdate and oxammonium hydrochloride., wherein, sodium molybdate concentration in distilled water is 0.3g ml-1, the mol ratio of sodium molybdate and oxammonium hydrochloride. is 1:5, reacts after mix homogeneously, and hot temperature is 85 DEG C, and the response time is 75min；
(2) continuation adds sodium sulfide in container, reacts after mixing uniformly under heat effect, and heating-up temperature is 75 DEG C, and the response time is 65min, and the mol ratio of sodium molybdate and sodium sulfide is 1:4.7；
(3) in container, add cetyl trimethylammonium bromide and the dodecylbenzene sodium sulfonate of 0.16g altogether, the weight ratio of the two is 1:1, and dripping hydrochloric acid to pH value after stirring under heat effect is 1.1, carries out acid precipitation, heating: temperature is 45 DEG C, and the response time is 22min；
(4) reaction is sufficiently cool after terminating, centrifugal, washs respectively three times with distilled water and ethanol, dry in vacuum drying oven, to obtain final product.
Lipophilic nano molybdenum disulfide is for the application of the catalyst of heavy oil floating bed hydrocracking.
Application examples 1
The present invention also provides for the using method of a kind of lipophilic nanometer curing, described lipophilic nanometer curing catalyst adds the Kelamayi reduced crude containing high metal, high asphalitine, high-sulfur nitrogen, investigates its coke inhibiting and lighting ability in dreg-oil suspension bed hydrogenation cracking reacts.Wherein the metal in lipophilic nanometer curing catalyst is 50～2000 μ g g in the ratio of heavy oil feedstock-1.Use lipophilic nano molybdenum disulfide catalyst 150 μ g g-1Adding Kelamayi reduced crude, through 440 DEG C, after 12MPa hydrocracking reaction 1h, green coke amount is about 1.2%, and gasoline and diesel yield reach 39.61%.
Application examples 2
The present invention also provides for the using method of a kind of lipophilic nano molybdenum disulfide, and affiliated lipophilic nano molybdenum disulfide catalyst adds the FCC slurry that arene content is high, investigates its coke inhibiting and lighting ability in FCC slurry slurry-bed hydrocracking.Wherein the metal in lipophilic nanometer curing catalyst is 50～2000 μ g g in the ratio of FCC slurry raw material-1.Use lipophilic nano molybdenum disulfide catalyst 90 μ g g-1Adding in the refinery FCC slurry of Qingdao, through 440 DEG C, after 12MPa hydrocracking reaction 1h, green coke amount is about 0.1%, and gasoline and diesel yield can reach 38.65%.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all within the spirit and principles in the present invention, any amendment of making, equivalent replacement, improvement etc., should be included within protection scope of the present invention.
Claims (8)
1. a lipophilic nano molybdenum disulfide preparation method, it is characterised in that comprise the following steps:
(1) under the protection of nitrogen, it is sequentially added into distilled water, sodium molybdate and oxammonium hydrochloride. in container, reacts under heat effect after mix homogeneously；
(2) continue to add sodium sulfide in container, react under heat effect after mixing uniformly；
(3) in container, add surfactant, under heat effect, drip hydrochloric acid after stirring carry out acid precipitation；
(4) reaction is sufficiently cool after terminating, centrifugal, washs respectively three times with distilled water and ethanol, dry in vacuum drying oven, to obtain final product.
2. a kind of lipophilic nano molybdenum disulfide preparation method according to claim 1, it is characterised in that described sodium molybdate concentration in distilled water is 0.2～0.5g ml-1, described sodium molybdate, described oxammonium hydrochloride., described sodium sulfide mol ratio be 1:4～6:4～5.
3. a kind of lipophilic nano molybdenum disulfide preparation method according to claim 1, it is characterized in that, described surfactant be in cetyl trimethylammonium bromide, dodecylbenzene sodium sulfonate, triton x-100, Polyethylene Glycol any one or a few, surfactant concentration in distilled water is 0.005～0.5g (100ml)-1。
4. a kind of lipophilic nano molybdenum disulfide preparation method according to claim 1, it is characterised in that the heating-up temperature in described step (1) is 70 DEG C～90 DEG C, and the response time is 60min～90min.
5. a kind of lipophilic nano molybdenum disulfide preparation method according to claim 1, it is characterised in that the heating-up temperature in described step (2) is 60 DEG C～80 DEG C, and the response time is 60min～80min.
6. a kind of lipophilic nano molybdenum disulfide preparation method according to claim 1, it is characterised in that the heating-up temperature in described step (3) is 30 DEG C～50 DEG C, and the response time is 20min～30min.
7. a kind of lipophilic nano molybdenum disulfide preparation method according to claim 1, it is characterised in that in described step (3) after dropping hydrochloric acid, the pH value of solution is 0.8～1.2.
8. the lipophilic nano molybdenum disulfide described in any one of claim 1～7 is for the application of the catalyst of heavy oil floating bed hydrocracking.
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| CN106732800A (en) * | 2016-11-25 | 2017-05-31 | 青岛大学 | A kind of in-situ preparation method of lipophilic nano molybdenum disulfide catalyst and application |
| CN106732672A (en) * | 2017-02-23 | 2017-05-31 | 中国石油大学(华东) | It is a kind of to load catalyst with base of molybdenum for the coal that kerosene floating bed hydrogenation is refined altogether |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106544054A (en) * | 2016-11-25 | 2017-03-29 | 青岛大学 | A kind of Heavy oil hydrogenation method |
| CN106732800A (en) * | 2016-11-25 | 2017-05-31 | 青岛大学 | A kind of in-situ preparation method of lipophilic nano molybdenum disulfide catalyst and application |
| CN106544054B (en) * | 2016-11-25 | 2018-12-11 | 青岛大学 | A kind of Heavy oil hydrogenation method |
| CN106732800B (en) * | 2016-11-25 | 2019-06-11 | 青岛大学 | A kind of in-situ preparation method and application of lipophilic nano molybdenum disulfide catalyst |
| CN106732672A (en) * | 2017-02-23 | 2017-05-31 | 中国石油大学(华东) | It is a kind of to load catalyst with base of molybdenum for the coal that kerosene floating bed hydrogenation is refined altogether |
| CN106732672B (en) * | 2017-02-23 | 2020-05-01 | 中国石油大学(华东) | Coal-loaded molybdenum-based catalyst for coal-oil suspension bed hydrogenation co-refining |
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